materials

Article
Co-Bonded Hybrid Thermoplastic-Thermoset Composite
Interphase: Process-Microstructure-Property Correlation
Jamal Seyyed Monfared Zanjani * and Ismet Baran *

Faculty of Engineering Technology, University of Twente, 7500AE Enschede, The Netherlands

* Correspondence: j.seyyedmonfaredzanjani@utwente.nl (J.S.M.Z.); i.baran@utwente.nl (I.B.)

Abstract: Co-bonding is an effective joining method for fiber-reinforced composites in which a

prefabricated part bonds with a thermoset resin during the curing process. Manufacturing of co-
bonded thermoset-thermoplastic hybrid composites is a challenging task due to the complexities of
the interdiffusion of reactive thermoset resin and thermoplastic polymer at the interface between two
plies. Herein, the interphase properties of co-bonded acrylonitrile butadiene styrene thermoplastic to
unsaturated polyester thermoset are investigated for different processing conditions. The effect of
processing temperature on the cure kinetics and interdiffusion kinetics are studied experimentally.
The interphase thickness and microstructure are linked to the chemo-rheological properties of the
materials. The interdiffusion mechanisms are explored and models are developed to predict the
interphase thickness and microstructure for various process conditions. The temperature-dependent
diffusivities were estimated by incorporating an inverse diffusion model. The mechanical response
of interphases was analyzed by the Vickers microhardness test and was correlated to the processing
condition and microstructure. It was observed that processing temperature has significant effect
on the interdiffusion process and, consequently, on the interphase thickness, its microstructure and
mechanical performance.



Keywords: polymer interdiffusion; co-bonding; interphase; thermoplastics; thermosets curing;

 microhardness; hybrid composites
Citation: Zanjani, J.S.M.; Baran, I.
Co-Bonded Hybrid Thermoplastic-
Thermoset Composite Interphase:
Process-Microstructure-Property 1. Introduction
Correlation. Materials 2021, 14, 291.
Advanced fiber-reinforced polymeric composites have emerged as structural materials
https://doi.org/10.3390/ma14020291
with a very wide range of applications due to their significant weight reduction, extended
durability, and higher design flexibility compared to other traditional material alternatives.
Received: 3 December 2020
However, there are ever-pressing industrial needs for further improving the performance
Accepted: 29 December 2020
of polymeric composites and to meet the requirements of demanding and cutting edge
Published: 8 January 2021
applications. Combining various advanced materials and creating hybrid or multi-material
Publisher’s Note: MDPI stays neu-
composites (MMCs) have the potential to push forward the mechanical performance of the
tral with regard to jurisdictional clai-
manufactured part. The laminated MMCs consist of two or more different combinations of
ms in published maps and institutio- layers, which offer a design versatility to place each specific material, where they can exploit
nal affiliations. their best characteristics and properties to the benefit of the overall integrity of the structure.
Hence, it is considered that the laminated MMCs have the potential to develop future
structural materials with high performance [1,2]. Thermoplastic-thermoset hybrid polymer-
based composites are one of the possibilities of MMCs with significant potential to address
Copyright: © 2021 by the authors. Li- challenges for many state of the art applications [3]. Thermoplastic-thermoset MMCs
censee MDPI, Basel, Switzerland.
combine the damage tolerance characteristics, and welding capability of thermoplastics
This article is an open access article
with the strength and stiffness of thermoset composites resulting in more reliable structures
distributed under the terms and con-
with an extended lifetime [4–6]. However, joining thermoplastics to thermosets remains a
ditions of the Creative Commons At-
challenging step despite the development of various joining technologies for composite
tribution (CC BY) license (https://
structures including (i) mechanical fastening [7–9], (ii) welding [10–13], (iii) adhesive
creativecommons.org/licenses/by/
bonding [14–16], (iv) co-curing (parts are cured at the same time) [17,18], and (v) hybrid
4.0/).

Materials 2021, 14, 291. https://doi.org/10.3390/ma14020291 https://www.mdpi.com/journal/materials

Materials 2021, 14, 291 2 of 17

joints (combination of two or more of previous methods) [19–21]. Nevertheless, all these
joining methods have disadvantages in terms of being unreliable, labour-intensive, time-
consuming and expensive [22].
An alternative and effective joining method for composites is co-bonding (an uncured
part is joined with one or more cured parts) [23,24]. The co-bonding method can be applied
for jointing both similar or dissimilar materials including thermoplastics to thermosets.
Co-bonding eliminates the needs for mechanical fasteners, and adhesives resulting in a
more effective and applicable joining method for many applications. The interface between
two parts in the co-bonding process is controlled by thermodynamic affinity and physical
interactions in between and also the curing process of the reactive resin [10]. Several studies
have been conducted on co-bonding process of thermoplastic-thermoset for epoxy ther-
moset resins and various thermoplastics. In [25], the difference in diffusion of a bisphenol
A type epoxy resin and the corresponding diamine curing agent into polysulfone (PSU)
was studied. The diffusivity of amine was found to be an order of magnitude larger than
that for epoxy at different temperatures. As an extension to the aforementioned study,
Rajagopalan et al. [26] showed that the amine enhanced the epoxy diffusivity into PSU by
a factor of three due to amine swelling effect. In addition, they identified three chrono-
logical processes of diffusion, reaction, and phase separation which derive the interphase
formation. In another study, Sonnenfeld et al. [27] improved the damage tolerance of epoxy
matrix composites through manufacturing of thermoplastic/thermoset multilayer com-
posites using semi-crystalline poly-ether-ether-ketone (PEEK) and polyphenylene sulfide
(PPS). They demonstrated that the introduction of a layer which was compatible with both
thermoplastic and thermoset sections such as poly-ether-imide (PEI) increased the adhesion
energy by a factor of 15. Velthem et al. [28] studied the influence of the interdiffusion of
two thermoplastics of poly(ether sulfone) (PES) and phenoxy in the epoxy system and they
correlated the resulting interphase morphologies to the interlaminar fracture toughness.
Nevertheless, all these studies were limited to epoxy as the thermoset resin and focused on
the interdiffusion process and morphology of interphase.
Processing condition plays an essential role in interphase formation between ther-
mosets and thermoplastics during co-bonding by altering the cure reaction kinetics, and
interdiffusion process. The curing reaction of a thermosetting resin is a multi-stage complex
and highly temperature-dependent process. In the curing of a thermoset resin, many
reactions take place simultaneously such as the decomposition of the initiator, the poly-
merization of different monomers and oligomers, and termination reactions with changes
in the physical behaviour of the resin. All these reactions influence the interdiffusion
process and interphase formation since the degree of cure or degree of cross linking of
the molecules increases as a function of process time and temperature as shown in [29,30].
Therefore, the interdiffusion kinetics and, consequently, the interdiffusion termination
time as determining parameters on the interphase formation are closely linked to curing
kinetics of the thermoset resin [31]. More specifically, as the cure reaction progresses the
molecular weight and crosslinking density of the resin increase after which no polymer
interdiffusion takes place. Regarding the cessation of the polymer interdiffusion at the
thermoset-thermoplastic interface, the most accepted assumption is that diffusivity of the
reacting resins terminates at the gel point defined as a time in which the resin switches
its state from a viscous liquid to a semi-solid rubbery gel and loses its fluidity [12,32–34].
Accordingly, the kinetics of curing and interdiffusion determines the interphase thickness,
its quality, and the microstructure. It is known that the mechanical performance and
strength of interphase in hybrid composites are primarily determined by the interphase
thickness [35,36]. Therefore, a physical and mechanical understanding of the interphase
is critical to determine the load transfer efficiency across dissimilar materials and to over-
see the overall integrity of the structure. To the best of the authors’ knowledge, there
is no comprehensive study elaborating on the effect of processing conditions and cure
kinetics on the micro-structure and mechanical response of the interphases in co-bonded
thermoplastic-thermoset parts in the literature.
Materials 2021, 14, 291 3 of 17

In this study, unsaturated polyester resin (UPR) for the first time is used to be co-
bonded to a thermoplastic part. UPR is one of the widespread used thermoset resins in
various industry due to its low cost and excellent processability in many applications
such as wind energy and ship manufacturing industries [37,38]. On the other hand, a
terpolymer of acrylonitrile, butadiene, and styrene with commercial name of acrylonitrile
butadiene styrene (ABS) known to have excellent mechanical properties including high
toughness, ductility, and very high impact strength is selected as the thermoplastic ma-
terial [39]. Herein, the effect of processing temperature on the co-bonding of ABS and
UPR and resultant interphase morphology and mechanical response are investigated. The
interdiffusion kinetics and mechanisms during co-bonding are explained and linked to
the chemo-rheological properties of UPR. Models are developed and utilized to predict
the interphase thickness at various processing conditions and to provide information on
interphase microstructure. The experimentally characterized gel time and interdiffusion
thickness are used in a one-dimensional (1D) inverse diffusion model to estimate the diffu-
sivity at different temperatures. Subsequently, the diffusivities are fit to an Arrhenius type
of model. Vickers’ microhardness test was used to study the mechanical behaviour at the
interphase of the specimens at various temperatures. Finally, a methodology is provided to
assemble process-microstructure-property correlations at interphases which are essential
to the design and manufacturing of reliable thermoplastic -thermoset MMCs.

2. Materials and Methods

2.1. Materials
An industrial medium reactive orthophthalic unsaturated polyester resin (UPR) de-
signed for resin transfer moulding and vacuum injection moulding processes as described
in [40] was used as thermoset resin. This resin contained 45% styrene with an acid number
of 25 mgKOH/g. A liquid peroxide system specialized for curing of the unsaturated
polyester and vinyl ester resins at room temperature with low peak exotherm, and long
working time (gel time) was used as an initiator. ABS in the sheet form with grade name of
VIKUREEN ABS PLAAT GLANS WIT 0291 (Epsotech, Jülich Kirchberg, Germany), with
strong resistance to corrosive chemicals and/or physical impacts, was used as thermoplastic
material in this study.

2.2. Interphase between Thermoset and Thermoplastic

To study the interdiffusion of thermoset resin into thermoplastic, ABS specimens
were prepared by cutting them using a wet saw into parts with estimated dimensions
of 15 mm × 15 mm × 3 mm followed by edge sanding with #500 SiC foil to remove
any debris. Next, an isopropyl alcohol and a mixture of water were utilized to wash
ABS specimens to remove any remaining particles and contamination. Specimens were
dried in the oven at a temperature of 60 ◦ C for 24 h and then left in a desiccator to reach
room temperature. Afterward, ABS specimens were placed vertically in the middle of
a cylindrical embedding mould with a diameter of 25 mm by using a couple of metallic
clamping rings. The degassed UPR resin mixture was poured onto the ABS specimens until
the resin completely covered them. Effect of temperature on the interphase was studied
by preparing the samples and placing of the moulds in the preheated oven fixed at the
set temperatures of 25 ◦ C, 35 ◦ C, 40 ◦ C, 50 ◦ C, and 60 ◦ C and curing for 24 h followed
by a post-curing process at 60 ◦ C for 24 h. After the de-moulding of samples, Struers
polishing system (Teramin-30, Struers, Cleveland, OH, USA) was employed to polish the
cross-sections of specimens with SiC foil of #500, #1000, #2000 and #4000, in the given
order. The final polishing of the embedded specimens were done by using OP-S NonDry.
A schematic view of the cross-section for the co-bonded ABS-UPR sample and the resulting
interphase due to polymer interdiffusion are shown in Figure 1.
 Materials 2021, 14, 291 4 of 17
Materials 2021, 14, x FOR PEER REVIEW 4 of 17

UPR
Interphase UPR
thickness

25 mm
3 mm
ABS ABS
Polymer
interdiffusion
.
Figure
Figure 1.
1. Schematic
Schematic view of the interphase region
region in
in the
the acrylonitrile
acrylonitrile butadiene
butadienestyrene-unsaturated
styrene-unsatu-
rated polyester
polyester resin (ABS-UPR)
resin (ABS-UPR) co-bonded
co-bonded specimen
specimen [31]. [31].

2.3. Characterizations
2.3. Characterizations
2.3.1. Microscopic Analysis of Unsaturated Polyester Resin-Acrylonitrile Butadiene
2.3.1. Microscopic Analysis of Unsaturated Polyester Resin-Acrylonitrile Butadiene
Styrene (UPR-ABS) Interphase+
Styrene (UPR-ABS) Interphase+
The polished cross-section of interphases formed between the co-bonded ABS and
UPRThe polished
systems cross-section
at various of conditions
processing interphases formed
were between
analysed the aco-bonded
by using ABS and
Keyence VHX-5000
UPR systems at various processing conditions were analysed by using a
digital microscope (Keyence, Osaka, Japan) equipped with a VH-100UR lens. 2D stitchingKeyence VHX-
5000 digital microscope (Keyence, Osaka, Japan) equipped with a VH-100UR
function of the microscope software was used to joint several captured images to obtain lens. 2D
stitching function
a sufficiently largeofcross-section
the microscope software
of the was The
interface. usedinterphase
to joint several captured
thickness valuesimages
were
to obtain a sufficiently large cross-section of the interface. The interphase thickness
reported for each temperature as the average measurements at mid-section of the interface values
were reported
far from for each
the clamps andtemperature
obtained from as at
the average
least three measurements
specimens for eachat mid-section
temperature.of the
interface far from the clamps and obtained from at least three specimens for each temper-
ature.
2.3.2. Surface Swelling Measurements
Furthermore, the surface swelling of ABS by UPR resin were examined at room
2.3.2. Surface Swelling
temperature. For this,Measurements
a parallel plate apparatus of the rheometer (in stationary mode)
(AntonFurthermore,
Paar Germany the surface
GmbH,swelling of ABS
Ostfildern, by UPRwas
Germany) resinemployed
were examined
to confineat room tem-
the resin
perature.
between the For head
this, aplate
parallel
andplate
ABS apparatus
sheet (as theof the rheometer
bottom plate) (in stationary
as shown mode) 2a.
in Figure (Anton
The
nominal
Paar normalGmbH,
Germany force was set to 0.1 Germany)
Ostfildern, N in the rheometer.
was employedThe normal force the
to confine wasresin
kept between
constant
to ensure
the the contact
head plate and ABS of resin
sheet to(asthe
therheometer headas
bottom plate) and surface
shown of the specimen
in Figure and to
2a. The nominal
prevent force
normal resin starvation
was set todue 0.1 Nto diffusion at the study
in the rheometer. Thesurface.
normalThe capillary
force was kept forces between
constant to
UPR and the plates which might cause a possible resin flow out was
ensure the contact of resin to the rheometer head and surface of the specimen and to pre- prevented by the
plate-plate
vent configuration.
resin starvation Herein,
due to diffusion50 mm × 50
at the mmsurface.
study ABS plates Thewere cut, edge
capillary forcessanded
between as
mentioned
UPR and the in plates
detail in Section
which 2.2, cause
might and then were glued
a possible resinonflowthe surface
out wasofprevented
the bottombyplate the
of the rheometer.
plate-plate The plate-plate
configuration. Herein,distance
50 mm ×was 50 set
mmtoABS0.5 mm andwere
plates was cut,
fillededge
withsanded
UPR, i.e., as
without mixing
mentioned it with
in detail the liquid
in Section peroxide
2.2, and system,
then were gluedandonkept the for 60 min.
surface of theNext, Keyence
bottom plate
VK-9700
of confocalThe
the rheometer. microscope was
plate-plate used towas
distance capture
set tothe
0.5changes
mm andinwas thefilled
surface withtopology
UPR, i.e., of
ABS due to swelling by UPR. The height and spatial resolutions
without mixing it with the liquid peroxide system, and kept for 60 min. Next, Keyencewere 1 and 120 nm in the
confocal confocal
VK-9700 microscope which had
microscope wasa laser
usedwith 408 nmthe
to capture wavelength.
changes in As theseen
surfacefrom Figure 2b,
topology of
the confocal microscopy measurements were performed on the
ABS due to swelling by UPR. The height and spatial resolutions were 1 and 120 nm5 in
Materials 2021, 14, x FOR PEER REVIEW
path which covered the
of the
17
region with
confocal and without
microscope whichUPRhad to define
a laser the408
with surface swelling of As
nm wavelength. APB.seenThefromlength
Figureof the
2b,
scanned length by the confocal microscopy was approximately
the confocal microscopy measurements were performed on the path which covered the 8 mm.
region with and without UPR to define the surface swelling of APB. The length of the
scanned length by 25 mm
the confocal microscopy was approximately In contact 8 mm.Measurement length
to UPR

0.5 mm thick Rheometer head

UPR ABS
ABS

(a) (b)
Figure
Figure2.2.(a)
(a)Schematic
Schematicview
viewofofthe
therheometer
rheometersetup
setupfor
forthe
the swelling
swelling experiments
experiments by
by placing UPR on
placing UPR
on ABS surface, and (b) measurement direction in confocal microscopy.
ABS surface, and (b) measurement direction in confocal microscopy.

2.3.3. Chemo-Rheology of UPR

The chemo-rheological properties of the UPR were characterized by using the Anton
Paar-Physica MCR 501 rheometer (Anton Paar Germany GmbH, Ostfildern, Germany) in
“plate–plate” mode. The effect of processing temperature on the viscosity, storage modu-
lus (G′) and loss modulus (G″) were investigated. All the measurements were performed
by using circular aluminium plates of 25 mm diameter in oscillatory mode at a 0.5% strain
Materials 2021, 14, 291 5 of 17

2.3.3. Chemo-Rheology of UPR

The chemo-rheological properties of the UPR were characterized by using the Anton
Paar-Physica MCR 501 rheometer (Anton Paar Germany GmbH, Ostfildern, Germany) in
“plate–plate” mode. The effect of processing temperature on the viscosity, storage modulus
(G0 ) and loss modulus (G”) were investigated. All the measurements were performed by
using circular aluminium plates of 25 mm diameter in oscillatory mode at a 0.5% strain and
a 1 Hz with a plate-plate spacing of 0.3 mm. The temperature-dependent gel time of the
resin, as an indication of the cure kinetics of UPR resin, was estimated from the crossing
point of storage modulus (G0 ) and loss modulus (G”) of UPR mixture including the liquid
peroxide [41]. The rheometer measurements were performed at seven different isothermal
temperatures of 25 ◦ C, 35 ◦ C, 40 ◦ C, 50 ◦ C, 60 ◦ C, 80 ◦ C and 100 ◦ C and final gel time at
each temperature was reported as the average of at least three repetitions. In the gel-time
measurements, the rheometer was maintained at the set temperature for 30 min before
placing the resin to achieve a uniform and stabilised temperature in the measurement
chamber. The relation between temperature-dependent gel time values and temperature
was describe by employing an Arrhenius relationship as [42]:

−∆E
     
1 1
= exp (1)
tG t0 RT

where tG was gel time, t0 was the pre-exponential time constant, R was the universal gas
constant, and ∆E is the activation energy of the gelation. Herein, gel time as an index
of cure kinetics was employed to monitor the changes during the curing reaction and to
determine the cure kinetics effect on interphase formation. The viscosity measurement
was performed on the UPR (without initiator) with a ramp of 1.5 ◦ C/min between room
temperature to 85 ◦ C where measurements were taken every 10 s and resulted in 240
measurement points.

2.3.4. Diffusivity Coefficient of UPR in ABS

1D Inverse Diffusion Model
The 1D interdiffusion of the UPR into ABS as schematically shown in Figure 3 was
modelled using the Fick’s second law [43] as:

∂c( x, t) ∂2 c( x, t)
=D (2)
∂t ∂x2
where c( x, t) was the UPR concentration in ABS, D was the diffusivity or coefficient of
diffusion. By assuming D is constant at a certain temperature and the volume of ABS does
not change with the diffusion of UPR into ABS, Equation (2) can be solved analytically
as [44]:
c( x, t) − c(0, t)
 
x
= erf √ (3)
c( x, 0) − c(0, t) 2 Dt
where erf was the error function, c(0, t) was the concentration at x = 0 and c( x, 0) was the
initial concentration. Since the interdiffusion distance (xint ) was experimentally determined,
the corresponding D can be obtained from Equation (3) by considering the conditions in
the following:
• c(0, t) = 1 for t ≤ t gel and c(0, t) = 0 for t > t gel where t gel was the gelation time of the
polyester resin which was determined experimentally in Section 2.3.3.
• The concentration was assumed to be relatively small by using a value of 10−5 at
 
t = t gel and at x = xint , i.e., c xint , t gel = 10−5 (see Figure 3).
 and at = , i.e., , = 10 (see Figure 3).
Accordingly, was obtained using Equation (4). Note that was estimated for dif-
ferent and which were obtained at different process temperatures.

Materials 2021, 14, 291 1 6 of 17

= (4)
2erf (1 − , )

Figure3.
Figure 3. Schematic
Schematic view
view of
of the
the 1D
1D diffusion
diffusionof
ofUPR
UPRinto
intoABS
ABS(left).
(left).The
Theresulting concentration
resulting concentration
distribution(right).
distribution (right).

Temperature
Accordingly,Dependent
D was Diffusivity Model
obtained using Equation (4). Note that D was estimated for
different t and
The obtained
gel x which were obtained at different
int values from the 1D inverse process
diffusion temperatures.
model for different tempera-
tures were fit with an Arrhenius type of equation as follows [44]:
  2
1  x −
 expint
t gel 2erf=
D= ( )   (4)
(5)
−1
1 − c xint , t gel
which was the diffusivity model also used in [25,26,44]. In Equation (4), D0 was the pre-
Temperature Dependent
exponential constant, Diffusivity
E1 was Model energies, R was the universal gas constant and
the activation
T wasThethe temperature
obtained in K.
D values A linear
from the 1Dregression was employed
inverse diffusion model forfordifferent
the fitting procedure
temperatures
by transforming
were the non-linear
fit with an Arrhenius relation
type of in Equation
equation (5)[44]:
as follows into a linear one as:

( D) =exp − E)1−
 
Dln= 0
ln ( (6)
(5)
RT

which was the

2.3.5. Resin diffusivity model also used in [25,26,44]. In Equation (4), D0 was the pre-
Uptake
exponential constant, E1 was the activation energies, R was the universal gas constant and
The kinetics of the interdiffusion was investigated by resin uptake experiments
T was the temperature in K. A linear regression was employed for the fitting procedure by
where ABS specimens were immersed into a UPR bath (without initiator) and the weight
transforming the non-linear relation in Equation (5) into a linear one as:
of the absorbed resin by specimens were measured at different times of 60, 300, 600, 1200,
1800, 3600 and 7200 s after immersion and temperatures
E of 25 °C, 35 °C, 40 °C, 50 °C, and
ln( D ) = ln( D0 ) − 1 (6)
60 °C. The nominal dimensions of the ABS specimens RTwere 30 mm × 30 mm which were

2.3.5. Resin Uptake

The kinetics of the interdiffusion was investigated by resin uptake experiments where
ABS specimens were immersed into a UPR bath (without initiator) and the weight of the
absorbed resin by specimens were measured at different times of 60, 300, 600, 1200, 1800,
3600 and 7200 s after immersion and temperatures of 25 ◦ C, 35 ◦ C, 40 ◦ C, 50 ◦ C, and
60 ◦ C. The nominal dimensions of the ABS specimens were 30 mm × 30 mm which were
measured by using a micrometre with a precision of ±0.01 mm. An analytical balance
was used to measure the dry weight of specimens. The immersion of the specimens in to
the resin was carried out by using the metallic clamps. The excess resin on the specimen
surface after the immersion step was washed by using an ethanol. In addition, non-sticking
and absorbent fabrics were used to clean the specimen surfaces. After drying, resin uptake
Materials 2021, 14, 291 7 of 17

weight were measured by the analytical balance and the uptake values per contact area
(M*) were calculated using the below formula:

Wi − Wd
M∗ = (7)
A
where Wi and Wd were the resin uptake weight and dry ABS specimen weight, respectively,
M* was the mass uptake per unit area and A was the surface area. As the length and
width of specimens were considerably (over 10 times) larger than the thickness, the resin
uptake from the edges of ABS samples was neglected. The measured data were fitted to
Equation (8) in order to evaluate the transport type and associated diffusion kinetics (resin
uptake) [45].
M∗ = ktn (8)
where k was an empirical rate constant, t was the time and n was the transport exponent of
diffusion. The type of diffusion is indicated by n in Equation (8), i.e., n = 0.5 for Fickian
diffusion, 0.5 < n<1 for an anomalous diffusion, and n = 1 for Case II diffusion [45].
Nevertheless, to obtain a kinetics model for a continuous range of temperatures based
on Equation (8), it was needed to have a model for n and k over experimental temperatures.
Herein, n and k are approximated by Equations (9) and (10) as:
 
N0
n = An exp (9)
T

k = k1 + k2 T (10)
where An , N0 , k1 , k2 were defined as constants to be determined through fitting of experi-
mental results.

2.3.6. Resin Volume Fraction at Interphase

To correlate the diffusion kinetics to resin curing kinetics and consequently interphase
formation, Equations (1) and (8)–(10) are combined into Equation (11). This eliminated
the time term from resin uptake equation (Equation (8)) for the reactive resin and yield
to a model for amount of diffused reactive resin per unit area (M*) into ABS at given
temperature.
N0
t ( An exp ( T ))
M∗ = (k1 + k2 T )( 0 ) (11)
exp −∆E
RT

Moreover, the relation between M* and Vr (the volume of the diffused resin) was
obtained by using the following relation:

M ρVr
M∗ = = = ρVr∗ (12)
A A

where ρ and A were the density of uncured resin (1.05 gr/cm3 ) and contact surface area,
respectively. Herein, Vr * was defined as Vr∗ = VAr and so-called reduced resin volume
(diffused volume per unit of contact area). Vr * values at any given temperature were
obtained from combining Equations (11) and (12) as:
N0
1 t ( An exp ( T ))
Vr∗ = ( )(k1 + k2 T )( 0 ) (13)
ρ exp −∆E RT
Materials 2021, 14, x FOR PEER REVIEW 8 of 17
Materials 2021, 14, 291 8 of 17

Accordingly, the ratio of Vr* to reduced volume of interface Vint* which corresponds
Accordingly,
to interphase the ratio
thickness of Vr * the
provided to reduced
volume volume
fractionof
ofinterface Vintinterphase
resin at the * which corresponds
(φ) as an
to interphase
essential thickness provided
microstructure indicator inthebinary
volume fraction of
interphases resin atas:
defined the interphase (ϕ) as an
essential microstructure indicator in binary interphases
∗ defined as:
= ∗∗ (14)
V
ϕ = ∗r (14)
Vint
2.3.7. Hardness Measurement at Interphase
2.3.7. Hardness Measurement at Interphase
The Vickers microhardness test was employed to analyse the changes in the mechan-
The Vickers microhardness test was employed to analyse the changes in the mechanical
ical response at the UPR-ABS interphase. The hardness obtained by this method was de-
response at the UPR-ABS interphase. The hardness obtained by this method was described
scribed as the resistance of the surface to indentation [46]. Vickers microhardness map-
as the resistance of the surface to indentation [46]. Vickers microhardness mapping was
ping was conducted using the LECO LM100AT micro-hardness tester by applying a load
conducted using the LECO LM100AT micro-hardness tester by applying a load of 10 gr and
of 10 gr and an indent spacing of 100 µm. The Vickers diamond pyramid hardness num-
an indent spacing of 100 µm. The Vickers diamond pyramid hardness number, HV , was
ber, HV, was defined as the ratio of the applied load, P, to the pyramidal contact area of
defined as the ratio of the applied load, P, to the pyramidal contact area of the indentation:
the indentation:
P
Hv == α 2 (15)
(15)
d
whereddwas
where wasthe
thediagonal
diagonallength
lengthofofthe
theresultant
resultantimpression,
impression,andandαα was
wasdefined
defined asas 1.8544
1.8544
forthe
for theVickers
Vickersindenter
indenter[47].
[47].Figure
Figure44shows
showsananexample
examplepattern
patternandandsample
sampleconfiguration
configuration
usedin
used in the
the microhardness
microhardness measurements
measurements in inthe
thevicinity
vicinityofofinterphase
interphasefor forABS
ABSandandUPR.
UPR. A
total of 25 indentations for each line were conducted
A total of 25 indentations for each line were conducted with with 100 µm
µm intervals in the width
the width
ofinterphase
of interphaseas asshown
shownin
inFigure
Figure11in
inwhich
whichthe
theinitial
initial1000
1000µm was for
µm was for the
the UPR
UPR and
and the
the
restcovered
rest coveredthetheinterphase
interphaseand
andABS
ABSregions.
regions.The
Thehardness
hardnessprofiles
profileswere
werereported
reported for
foreach
each
temperaturedetermined
temperature determinedfromfrom the
the average
average measurements
measurements for for at
at least
least three
three specimens.
specimens.

Vickersmicrohardness
Figure4.4.Vickers
Figure microhardnessmeasurement
measurement pattern
pattern and
and sample
sample configuration.
configuration.

3. Results and Discussion

3. Results and Discussion
3.1. Interphase Formation and Processing Temperature Effect
3.1. Interphase Formation and Processing Temperature Effect
Figure 5 reveals the optical microscopic observations of ABS-UPR interphases indi-
Figure
cating 5 revealsinterphase
the average the opticalthickness
microscopic observations
formed at different of ABS-UPR
temperatures interphases
ranging indi-
from
cating
◦ the average
◦ interphase thickness formed at different
25 C to 60 C. It was observed that an interphase was formed between ABS and UPRtemperatures ranging fromat 25
all
°C to 60 °C. It was observed that an interphase was formed between
temperature ranges with no visible gradient of diffusion. Nonetheless, the interdiffusion ABS and UPR at all
temperature
fronts in bothranges with
sides of no visible
formed gradient
interphases wereof slightly
diffusion. Nonetheless,
different from inner the sections
interdiffusion
which
fronts
implies inthe
both sides of formed
contribution interphases
of various phenomena wereinslightly
interphasedifferent from inner
formation. sections
Therefore, an
which implies the contribution of various phenomena in interphase
overview image of interphase formed around the ABS specimen at 25 C was constructed formation.
◦ Therefore,
an
by overview image overlapping
stitching several of interphasemicroscopic
formed around images theasABS
shown specimen
in Figure at 625 to°C was con-
illustrate the
structed by stitching several overlapping microscopic images as
effect of boundary conditions and constraints such as metallic clamps on the interphase shown in Figure 6 tofor-
il-
lustrate
mation.the effect of
In Figure 6, boundary
a dash-lined conditions and constraints
frame is inserted such to
in the image as estimate
metallic the clamps on the
boundaries
interphase formation.
of the original In Figurebefore
ABS specimen 6, a dash-lined
interactions frame
withisUPR.
inserted
Theinframe
the image
size and to estimate
location
the
wereboundaries
approximated,of thebased
original
on ABS specimen
the location before interactions
of metallic clamping rings withand
UPR. The frame
nominal size
thickness
and location
of the ABS samplewere approximated,
before embedding. based on the
Figure location
6 reveals of the
that metallic clamping
interphase formed rings and
around
nominal
the ABS thickness
noticeablyof the ABSthe
exceeded sample beforeofembedding.
boundaries the originalFigure 6 reveals
ABS sample (dashedthat frame).
the inter-To
phase formed
elaborate, it wasaround
expectedthe to
ABS
have noticeably
the diffusionexceeded
in boththe boundaries
directions of UPRof into
the original
ABS andABS ABS
sample
into UPR.(dashed frame). To
Nevertheless, elaborate,
diffusion it was
of ABS expected
into UPR was to have the diffusion
at a much lower level in both direc-
compared
tions
to UPRof UPR into ABS
into ABS due toandtheABS intomolecule
higher UPR. Nevertheless,
size and lower diffusion of ABS
molecular into UPR
mobility was at
of ABS as
compared with liquid UPR [48,49]. However, the difference in the interphase thicknesses
Materials 2021, 14, x FOR PEER REVIEW 9 of 17
Materials 2021, 14, x FOR PEER REVIEW 9 of 17

Materials 2021, 14, 291 9 of 17

a much lower level compared to UPR into ABS due to the higher molecule size and lower
a much lower level compared to UPR into ABS due to the higher molecule size and lower
molecular mobility of ABS as compared with liquid UPR [48,49]. However, the difference
molecular mobility of ABS as compared with liquid UPR [48,49]. However, the difference
in the interphase thicknesses inside and outside of the frame was not as significant as it
in the and
inside interphase
outside thicknesses
of the frame inside
wasofand
not outside
as of the as
significant frame was not as significant as it
was anticipated. Therefore, swelling ABS with UPR wasitawas anticipated.
contributing Therefore,
parameter in
was anticipated.
swelling of ABS withTherefore,
UPR was swelling of ABS with
a contributing UPR was
parameter a contributing
in the parameterInin
interphase thickness.
the interphase thickness. In this regard, the swelling behaviour of ABS in contact with
the regard,
this interphase thickness.
the swelling In this regard,
behaviour of ABS the swelling
in contact behaviour
with UPR wasof ABS in
studied bycontact
placingwith
the
UPR was studied by placing the UPR on the surface of the ABS sample in the rheometer
UPRon
UPR was
thestudied
surfacebyof placing
the ABS the UPRinonthe
sample therheometer
surface ofasthe ABS sample
mentioned. in the
Figure rheometer
7 depicts the
as mentioned. Figure 7 depicts the confocal microscopy results of the surface profile of
as mentioned.
confocal Figure
microscopy 7 depicts
results of thethe confocal
surface microscopy
profile of ABS after results
beingofinthe surface
contact withprofile
UPR inof
ABS after being in contact with UPR in the rheometer. It is clearly seen that the ABS sur-
the
ABS rheometer. It in
after being is clearly
contactseen
withthat
UPRtheinABS surface wasItswelled
the rheometer. and
is clearly its height
seen that theincreased
ABS sur-
face was swelled and its height increased approximately 70 µm as compared with the rest
approximately
face was swelled 70 and
µm as
itscompared with the
height increased rest of the specimen.
approximately 70 µm asThe increasewith
compared in the
theABS
rest
of the specimen. The increase in the ABS sheet thickness confirmed the swelling behaviour
sheet
of thethickness
specimen. confirmed the in
The increase swelling
the ABS behaviour of ABSconfirmed
sheet thickness in contactthewith UPR. behaviour
swelling
of ABS in contact with UPR.
of ABS in contact with UPR.
25 °C 35 °C
25 °C 35 °C

40 °C 50 °C 60 °C
40 °C 50 °C 60 °C

Figure
Figure5.5.Micrographs
Micrographsshowing
showingthe
theinterphase
interphaseformation
formationbetween
betweenABS
ABSand
andUPR
UPRat
atdifferent
differenttemperatures.
temperatures.
Figure 5. Micrographs showing the interphase formation between ABS and UPR at different temperatures.

Figure 6. Overall view of the interphase formed between ABS and UPR at 25 °C.
Figure6.6.Overall
Figure Overallview
viewof
ofthe
theinterphase
interphaseformed
formedbetween
betweenABS
ABSand
andUPR
UPRatat25
25◦°C.
C.
Moreover,
Moreover, it can bebeseen
seenininFigure 5 that thethe
process temperature influenced the in-
Moreover, itit can
can be seen in Figure
Figure 55that
that process
the process temperature
temperature influenced
influenced thethe
in-
terphase
interphasethickness
thickness considerably.
considerably. Figure
Figure8 8displays
displays the
thechanges
changes inininterphase
interphase thickness
thickness
terphase thickness considerably. Figure 8 displays the changes in interphase thickness
with
with respect totothetheprocess
process temperature. It is Itseen
is seenthethat the thickest interphase was
withrespect
respect to the temperature.
process temperature. It isthat thickest
seen that the interphase was achieved
thickest interphase was
achieved
for for
specimen specimen prepared
prepared prepared ◦ at
at 25 C with25 °C with
an with an
interphaseinterphase thickness
thickness of
of 710 ± 710 ±
20 µm 20 µm while
while the
achieved for specimen at 25 °C
◦ C35
an interphase thickness of 710 ± 20 µm while
the thinnest
thinnest interphase
interphase waswas observed
observed at 35at °C as±635 ± 10Itµm. It can beinseen in Figure 8
the thinnest interphase was observed at as
35635°C as10 µm.
635 ± 10 can
µm.beItseen
can be Figure
seen◦ in8 Figure
that the
◦
8
that the interphase thickness sharply decreased by increasing the temperature
interphase thickness sharply decreased by increasing the temperature from 25 C to 35 C from 25 °C
that the interphase thickness sharply decreased ◦ C up by increasing the temperature from 25 °C
to 35 °C followed
followed by a gradual
by a gradual increaseincrease
after 35after 35 °C up◦to
to 50 50 °Cslightly
C and and slightly
dropsdrops 50 ◦ C50
from from to
to◦35 °C followed by a gradual increase after 35 °C up to 50 °C and slightly drops from◦ 50
°C
60 toC.60 °C.
The The controversy
controversy effect ofeffect of temperature
temperature on interphaseon interphase
thickness underthickness under35
and above andC
°C to 60 °C. The controversy effect of temperature on interphase thickness under and
can be described by the effect of temperature on the cure kinetics and diffusion kinetics
of the resin. An increase in temperature was expected to accelerate the curing kinetics
leading to a decrease in the time available for the interdiffusion process (decreasing factor
for interphase thickness). However, the rate of change in the cure kinetic is different at low
Materials
Materials2021,
2021,14,
14,x xFOR
FORPEER
PEERREVIEW
REVIEW 1010ofof1717

above
above35 35°C°Ccan
canbe bedescribed
describedby bythe
theeffect
effectofoftemperature
temperatureon onthe
thecure
curekinetics
kineticsand
anddiffu-
diffu-
Materials 2021, 14, 291 sion kinetics of the resin. An increase in temperature was expected to accelerate
sion kinetics of the resin. An increase in temperature was expected to accelerate the curing the curing
10 of 17
kinetics
kineticsleading
leadingtotoaadecrease
decreaseininthe
thetime
timeavailable
availablefor forthetheinterdiffusion
interdiffusionprocess
process(decreas-
(decreas-
ing
ingfactor
factorforforinterphase
interphasethickness).
thickness).However,
However,the therate
rateofofchange
changeininthe
thecure
curekinetic
kineticisisdif-
dif-
ferent
ferentatatlowlowandandhigh
hightemperatures.
temperatures.At Athigher
highertemperature,
temperature,the theperoxide
peroxidewaswasalready
already
and high temperatures. At higher temperature, the peroxide was already over its thermal
over
overitsitsthermal
thermalactivation
activationtemperature
temperaturethreshold
threshold(the (theemployed
employedinitiator
initiatorwas
wasdesigned
designed
activation temperature threshold (the employed initiator was designed for application in
for
for application in room temperature and above it). Therefore, the acceleration ratewas
application in room temperature and above it). Therefore, the acceleration rate was
room temperature and above it). Therefore, the acceleration rate was lower while at the
lower
lowerwhile
whileatatthethelower
lowertemperature
temperaturean anincrease
increaseinintemperature
temperaturecan canprovide
providethe
theneces-
neces-
lower temperature an increase in temperature can provide the necessary activation energy
sary
saryactivation
activationenergy
energyforforperoxides
peroxidesand andboost
boostthe thereaction
reactionkinetics
kineticssignificantly
significantly[50].
[50].To
To
for peroxides and boost the reaction kinetics significantly [50]. To obtain a comprehensive
obtain
obtainaacomprehensive
comprehensiveunderstanding
understandingofofthe theeffect
effectofoftemperature
temperatureon onthe
theinterphase
interphasefor-for-
understanding of the effect of temperature on the interphase formation, cure kinetics and its
mation,
mation,curecure kinetics
kineticsandand its mechanical
mechanicalproperties, and interdiffusion process were
werein-
mechanical properties, anditsinterdiffusion properties,
process wereand interdiffusion
investigated processdescribed
and further in-
vestigated
vestigated and further described in the next section.
in the next and further described in the next section.
section.

8080

6060

4040

2020

00
00 22 44 66 88
Lenght
Lenght[mm]
[mm]
Figure
Figure7.7.
Figure 7.Confocal
Confocalmicroscopy
Confocal microscopymeasurement
microscopy measurementofof
measurement ofsurface
surfaceswelling
surface swellingof
swelling ofABS
of ABSin
ABS incontact
in contactwith
contact withUPR.
with UPR.
UPR.
Interphase thickness [ m]
Interphase thickness [ m]

Figure
Figure8.8.
Figure 8.Interphase
Interphasethickness
Interphase thicknessformation
thickness formationbetween
formation between
betweenABS
ABS
ABSand
andUPR
andUPRfor
UPRfordifferent
fordifferentprocessing
differentprocessingtempera-
processingtempera-
tempera-
tures.
tures.
tures.

3.2.
3.2.Resin
ResinCuring
Curingand andDiffusion
DiffusionKinetics
Kinetics
Figure9a
Figure 9ashows
showsthe
shows thegel
the geltime
gel time
time obtained
obtained
obtained withwith
with respect
respect
respecttototo isothermal
isothermal
isothermal rheometer
rheometer
rheometer tests.tests.
tests. ItIt
isIt is
isseen
seenseen
that that
that thethe
the gel gel
geltime
timetime changed
changed
changed linearly
linearly
linearly inintheinlogarithmic
the the logarithmic
logarithmic scale scale
scalewith with temperature
withtemperature
temperature indi-
indi-
indicating
cating
catingthat
thatthethat
thegel the
gel timegelwas
time time
was was considerably
considerably
considerably shortened
shortenedshortened
by
byan by an increase
anincrease
increase in temperature.
inintemperature.
temperature. Herein,
Herein,
Herein,
Equation
Equation(1)Equation (1)
(1)isisreorganizedis reorganized
reorganizedasasEquation as Equation
Equation(16) (16) to
(16)totodetermine determine
determinethe the
theconstants constants
constantsfromfromthe from thein
thefitfitline
line fit
in
line
the in
thegraph the
graphln(t graph
ln(tG)G)vs.ln(t )
vs.1000/T
1000/T
G vs. 1000/T
graph graph
graphasaspresented as presented
presentedininFigure in Figure
Figure9b.
9b. 9b.

111 = ln ( 111) − ∆ /
(ln( ))=
lnln( ) =lnln( ( ) )−−∆E/RT
∆ / (16)
(16)
(16)
tG t0
The
Theslope
slopeand
andintercept
interceptfor
forEquation
Equation(16)
(16)ofofthe
thefitfitline
linewere
werecalculated
calculatedtotobe
be−8.005
−8.005
KKandand17.77,
17.77,respectively,
respectively,which
whichcorrespond
correspondtotothethepre-exponential
pre-exponentialtime timeconstant
constantofof22××
10
10−8−8s sand
andactivation
activationenergy
energyofof66.5
66.5kJ/mol.
kJ/mol.
 40 °C and 50 °C was only about 900 s and it further declined from 50 °C to 60 °C as the gel
time difference was obtained as approximately 360 s. On the other hand, at higher tem-
peratures viscosity of the resin dropped to much lower values compared to the viscosity
at lower temperatures. This low viscosity at high temperatures promoted the interdiffu-
Materials 2021, 14, 291
sion process with limited change in the gel time leading to a gradual increase in the inter-
11 of 17
phase thickness between 35 °C to 50 °C. Furthermore, the significantly shorter gel time at
60 °C compared to 50 °C is the reason to its lower interphase thickness.

Gel time tG [Sec]

ln (1/tG)
(a) (b)
1
10
[Pa.s]

100
Viscosity

10-1

10-2
20 40 60 80 100
Temperature [°C]
(c)
Figure
Figure9.9.(a)
(a)change
changeiningel
geltime
time vs.
vs. temperature,
temperature,(b)
(b) ln(1/t
ln(1/tG)Gvs.
) vs.1000/T
1000/Tand fitted
and line
fitted based
line ononEquation
based Equation(16),
(16),and
and(c)(c)
viscosity
viscositychange
changeasasaafunction
functionofoftemperature
temperaturefor
forUPR.
UPR.

The slopeCoefficient
3.3. Diffusivity and intercept for Equation (16) of the fit line were calculated to be −8.005 K
and Model
andThe
17.77, respectively, which
diffusivity of UPR into correspond to the pre-exponential
ABS was estimated time constant
by using Equation 2×
(4) andofthe 10−8 s
results
and activation
obtained energy
are shown of 66.5 10.
in Figure kJ/mol.
The inverse diffusion model resulted in an exact value
for the interdiffusion thickness asthe
Moreover, the changes in seentemperature
in Figure 10b were associated
for the with the
corresponding alterations
diffusivity val-in
interdiffusion kinetics by increasing the molecular mobilities indicated by a reduction
ues. It can be seen in Figure 10a that the fitted diffusivity was found to be in the range of in the
viscosity of the resin as seen in Figure 9c [28,51]. In Figure 9c, it was found that
10−12–10−10 (m2/s) for the temperature range of 25–60 °C. The estimated magnitudes of the the viscosity
of UPR changed linearly with temperature in logarithmic scale and a small increase in
diffusivities matched with the reported diffusivities of other systems such as epoxy-PSU
temperature reduces the viscosity considerably which can promote the interdiffusion and
result in thicker interphase. It is worth noting that to eliminate the effect of curing on
the viscosity of the resin, initiator was not added to the resin in viscosity measurement
tests [30].
These observations regarding the changes in cure kinetics via the gel time and resin
viscosity by temperature clearly described the drop in the interphase thickness between
25 ◦ C and 35 ◦ C, i.e., the gel time decreased significantly in this region. On the other hand,
after 35 ◦ C the change in gel time took place at much lower levels. To elaborate, the gel time
dropped approximately from 12500 s at 25 ◦ C to 4000 s at 35 ◦ C. This indicated that 8500 s
less time was available for the polymer diffusion. The gel time difference between 40 ◦ C
and 50 ◦ C was only about 900 s and it further declined from 50 ◦ C to 60 ◦ C as the gel time
difference was obtained as approximately 360 s. On the other hand, at higher temperatures
viscosity of the resin dropped to much lower values compared to the viscosity at lower
temperatures. This low viscosity at high temperatures promoted the interdiffusion process
with limited change in the gel time leading to a gradual increase in the interphase thickness
between 35 ◦ C to 50 ◦ C. Furthermore, the significantly shorter gel time at 60 ◦ C compared
to 50 ◦ C is the reason to its lower interphase thickness.

3.3. Diffusivity Coefficient and Model

The diffusivity of UPR into ABS was estimated by using Equation (4) and the results
obtained are shown in Figure 10. The inverse diffusion model resulted in an exact value
for the interdiffusion thickness as seen in Figure 10b for the corresponding diffusivity
values. It can be seen in Figure 10a that the fitted diffusivity was found to be in the range
Materials 2021, 14, 291 12 of 17

Materials 2021, 14, x FOR PEER REVIEW 12 of 17

of 10−12 –10−10 (m2 /s) for the temperature range of 25–60 ◦ C. The estimated magnitudes of
the diffusivities matched with the reported diffusivities of other systems such as epoxy-
[26,52], amine-PSU
PSU [26,52], [26,52],
amine-PSU toluene-PEEK
[26,52], toluene-PEEK(for 0% initial
(for crystallinity
0% initial of PEEK)
crystallinity [53], CS2-
of PEEK) [53],
PEEK (for 0%
CS2-PEEK (forinitial crystallinity
0% initial of PEEK)
crystallinity of PEEK)[53] [53]
and and
toluene-PVAc
toluene-PVAc (for(for
mass fraction
mass fractionof
toluene
of tolueneof 0.1) [54] [54]
of 0.1) as seen in Figure
as seen 10a. The
in Figure 10a. trend of the of
The trend temperature dependent
the temperature diffu-
dependent
sivity was captured
diffusivity was capturedwell well
with with
the temperature
the temperature dependent
dependentmodel given
model in Equation
given in Equation (5)
(5) with =
with D01.69 × 10× 10
= 1.69 1
m /smand
2 2 /s and= E7.52
1 =× 10 ×cal/mol.
7.52 4
10 cal/mol.The diffusivity coefficient
The diffusivity mag-
coefficient
nitude obtained
magnitude and its
obtained andtrend with temperature
its trend with temperature was inwas conformity with available
in conformity litera-
with available
ture. The relation
literature. between
The relation the experimentally
between the experimentally obtained viscosity
obtained and the
viscosity andtemperature
the temperature de-
pendent
dependent diffusivity obtained
diffusivity obtained by the inverse
by the diffusion
inverse model
diffusion is shown
model in Figure
is shown 10c. 10c.
in Figure It canIt
canseen
be be seen
that that the diffusivity
the diffusivity was wasfound found
to betoinversely
be inversely proportional
proportional whichwhich supported
supported the
the aforementioned
aforementioned observations
observations regarding
regarding the interdiffusion
the interdiffusion thickness
thickness and and viscosity.
viscosity. In ad-In
addition
dition thethe
trendtrend obtained
obtained for for
thethe diffusivity
diffusivity vs viscosity
vs viscosity alsoalso matches
matches withwith
thethe findings
findings in
in [55]
[55] for for
thethe diffusion
diffusion of organic
of organic molecules
molecules in sucrose–water
in sucrose–water solutions.
solutions.
Interdiffusion thickness [ m]
Diffusivity [m 2/s]

Diffusivity [m 2/s]

(a) (b) (c)

Figure
Figure 10.
10. (a)
(a) Diffusivity
Diffusivity vs
vs temperature
temperature for
for UPR-ABS
UPR-ABS inin comparison
comparison toto material
material pairs
pairs from
from literature,
literature, (b)
(b) interphase
interphase
thickness change by temperature through fitted inverse model, and (c) viscosity dependency of the diffusivity for UPR-
thickness change by temperature through fitted inverse model, and (c) viscosity dependency of the diffusivity for UPR-ABS.
ABS.

3.4. Kinetics of Interdiffusion and Its Correlation to Interphase Microstructure

3.4. Kinetics of Interdiffusion and Its Correlation to Interphase Microstructure
Figure 11a depicts the resin uptake per surface area (M*) vs. time at the different
Figure 11a depicts the resin uptake per surface area (M*) vs. time at the different
temperatures ranging from 25 ◦ C to 60 ◦ C. It can be seen that increasing the temperature
temperatures ranging from 25 °C to 60 °C. It can be seen that increasing the temperature
enhanced the resin uptake value for all the measurement times. A line fitting was employed
enhanced the resin uptake value for all the measurement times. A line fitting was em-
for the relation between Ln (M*) and Ln (t) seen in Figure 11b to determine k and n (see
ployed for the relation between Ln (M*) and Ln (t) seen in Figure 11b to determine k and
Equation (8)) and the results obtained are listed in Table 1. It was observed that n value
n (see Equation (8)) and the results obtained are listed in Table 1. It was observed that n
changed with a change in temperature however it remained between 0.5 and 1 which
value changed with a change in temperature however it remained between 0.5 and 1
indicated the anomalous nature of the diffusion process. More specifically, the value of n
which indicated
in Equation the anomalous
(8) sharply dropped nature of theatdiffusion
from 0.7001 process.
25 ◦ C to 0.5717 More
at 35 specifically,
◦ C and thereaftertheit
value of na in
followed Equation
gradually (8) sharply
decreasing dropped
trend from 0.7001
by an increase attemperature
in the 25 °C to 0.5717down at to350.5251
°C and at
thereafter
◦ it followed a gradually decreasing trend by an increase in the
60 C. Herein, An and N0 as the constants in Equation (9) were calculated as 0.048 and 775 K, temperature
down to 0.5251
respectively by at 60 °C.
linear Herein,
fitting An and
on the N0 as the
projection constants
of n values on inLn
Equation (9) were
(n) vs 1/T graphcalculated
as shown
as
in Figure 12a. Similarly, k values at any given temperature in our experimentalon
0.048 and 775 K, respectively by linear fitting on the projection of n values Ln (n)
range vs
were
1/T graph as shown in Figure 12a. Similarly, k values at any given
evaluated by Equation (10) where k1 and k2 were calculated to be −4.13 × 10 gr/mm . sntemperature
− 5 in our
2
experimental
and 3.86 × 10range were2evaluated
−7 gr/mm by Equation
·sn . K by line fitting on(10)
the kwhere
vs. T kgraph
1 and k2 were calculated to be
as shown in Figure 12b.
−4.13 × 10−5 gr/mm2. sn and 3.86 × 10−7 gr/mm2·sn. K by line fitting on the k vs. T graph as
shown in Figure 12b.
 Materials2021,
Materials 2021,14,
14,291
x FOR PEER REVIEW 13ofof1717
13
Materials 2021, 14, x FOR PEER REVIEW 13 of 17

10-4 -7
6
-4
ABS-25°C
10 -7
6 ABS-35°C
5 ABS-25°C -8
ABS-40°C
5 ABS-35°C
ABS-50°C -8
] ]

4
2 2

ABS-40°C
M* [gr/mm

ABS-60°C -9

Ln*)(M*)
4 ABS-50°C
3
M* [gr/mm

ABS-60°C -9

Ln (M
3 -10
2 ABS-25°C
-10 ABS-35°C
2 ABS-25°C
ABS-40°C
1 -11 ABS-35°C
ABS-50°C
-11 ABS-40°C
ABS-60°C
1
0 -12 ABS-50°C
0 2000 4000 6000 8000 4 5 6 7 8
ABS-60°C9
0 time [Sec] -12
0 2000 4000 6000 8000 5 4 6 Ln(t) 7 8 9
(a)
time [Sec] (b)
Ln(t)
Figure11.
Figure 11.(a)
(a)Resin (a)
Resinuptake
uptakevs.
vs.time
timefor
forABS,
ABS,and
and(b)
(b)Ln(M*)
Ln(M*)vs.
vs.Ln(t)
Ln(t)based
basedon (b)
onEquations
Equations (7)and
(7) and(8).
(8).
Figure 11. (a) Resin uptake vs. time for ABS, and (b) Ln(M*) vs. Ln(t) based on Equations (7) and (8).
Table 1. Empirical rate constant (k), and transport exponent (n) for ABS-UPR at different tempera-
Table 1. Empirical rate constant (k), and transport exponent (n) for ABS-UPR at different tempera-
tures.
Table 1. Empirical rate constant (k), and transport exponent (n) for ABS-UPR at different tempera-
tures.
tures.
Temperature (°C) 25 35 40 50 60
Temperature (◦ C) 25 35 40 50 60
n
Temperature (°C) 0.7002
25 0.5717
35 0.5538
40 0.5254
50 0.5251
60
n 2 n 0.7002 −7 0.5717−6 0.5538 0.5254 0.5251
k (gr/mm
n ·s ) 3.86 × 10
0.7002 1.88 × 10
0.5717 2.62 × 10
0.5538 −6 4.12 × 10
0.5254 −6 5.25 × 10−6
0.5251
2 n
k (gr/mm 2·s n) 3.86 × 10 − 7 1.88 × 10 − 6 2.62 × 10 − 6 4.12 × 10 − 6 5.25 × 10−6
k (gr/mm ·s ) 3.86 × 10−7 1.88 × 10−6 2.62 × 10−6 4.12 × 10−6 5.25 × 10−6
s ]s ]
-2 -n-2 -n
Ln(n)

[gr mm
Ln(n)

k [grk mm

(a) (b)
Figure 12. Line fitting on (a)(a)
n and (b) k changes by temperature to obtain predictive models (b)based on Equations (9) and
(10).
Figure 12. Line fitting on (a) n and (b) k changes by temperature to obtain predictive models based on Equations (9) and
Figure 12. Line fitting on (a) n and (b) k changes by temperature to obtain predictive models based on Equations (9) and (10).
(10).
Table 2 summaries the φ vales calculated based on Equation (14) for ABS-UPR inter-
Table 2 summaries the ϕ vales calculated based on Equation (14) for ABS-UPR inter-
phases obtained at different φtemperatures. It can be seen that the volume fraction of inter-
resin
phasesTable 2 summaries
obtained thetemperatures.
at different vales calculated
It canbased on that
be seen Equation (14) forfraction
the volume ABS-UPR of resin
at the interface decreases by increasing the process temperature. This can be explained by
atphases obtained
the interface at different
decreases temperatures.
by increasing It can be
the process seen that the
temperature. volume
This can befraction of resin
explained by
aatdifference in
the interface the progress
decreases of diffusion front line which was accelerated by an increase in
a difference in the progressbyofincreasing the process
diffusion front temperature.
line which This can
was accelerated bybeanexplained
increase inby
the temperature
a difference in thewhile such
progress an increase
ofincrease
diffusion in temperature led to a faster curing and, there-
the temperature while such an infront line which
temperature ledwas
to a accelerated
faster curingbyand,
an increase
therefore,in
fore,
the lower diffusion
temperature time
while limiting
such an the volume
increase in of diffusedled
temperature resin
to ainfaster
the interphase
curing area.
and, there-
lower diffusion time limiting the volume of diffused resin in the interphase area.
fore, lower diffusion time limiting the volume of diffused resin in the interphase area.
Table 2. Volume fraction of UPR (φ) at the ABS/ UPR interphase obtained from Equation (14).
Table 2. Volume fraction of UPR (ϕ) at the ABS/ UPR interphase obtained from Equation (14).
Table 2. Volume
Temperature fraction25
(°C) of UPR (φ) at 35
the ABS/ UPR interphase
40 obtained
50from Equation60(14).
Temperature (◦ C) 25 35 40 50 60
Temperature (°C) 0.40
25 0.34
35 0.26
40 0.21
50 0.20
60
ϕ 0.40 0.34 0.26 0.21 0.20
0.40 0.34 0.26 0.21 0.20
 bers at the interphase for all the samples were lower than for both pure UPR and ABS. It
can also be seen that there was a transition region from the UPR to ABS (between 1000 µm
and 1200 µm) as a sharp drop in the hardness value followed by a minimum value plateau
indicating the interphase area and ended by an increase to ABS hardness value. The plat-
Materials 2021, 14, 291 14 of 17
eau lengths were correlated with interphase thicknesses obtained by the microscopic ob-
servations. The drop in the hardness at the interphase regions can be explained by the
plasticizing effect of unreacted UPR monomers due to the limited access to reaction com-
ponents at the interphase
3.5. Interphase’s Mechanicalarea. It canby
Response beMicrohardness
seen from Figure 13a that the interphase hardness
is correlated with the processed temperature science a higher cure temperature results in
Figure 13a shows the variations of Vickers microhardness numbers in the vicinity
an increase in interphase hardness.
of the interphase prepared at different temperatures. It was observed that the hardness
To relate the microhardness at the interphase to the processing condition and micro-
numbers at the interphase for all the samples were lower than for both pure UPR and
structure of interphase, Figure 13b exhibits the averaged harness at the interphase (aver-
ABS. It can also be seen that there was a transition region from the UPR to ABS (between
age
1000ofµm1200
andµm–1700
1200 µm)µm) as aand volume
sharp fraction
drop in of resinvalue
the hardness at thefollowed
interphase
by a(φ) calculated
minimum by
value
Equation (14) on different processing temperatures. It can be seen that samples
plateau indicating the interphase area and ended by an increase to ABS hardness value. The prepared
at higherlengths
plateau temperatures had a lower
were correlated withφinterphase
and hence thicknesses
a less resin presence
obtained atbyinterphase to act
the microscopic
as a plasticizer and consequently this resulted in a higher hardness values
observations. The drop in the hardness at the interphase regions can be explained by compared to
specimens prepared at lower temperatures. On the other hand, samples prepared
the plasticizing effect of unreacted UPR monomers due to the limited access to reaction at lower
temperatures
components at showed a lower hardness
the interphase duebe
area. It can to seen
higher volume
from Figure fraction
13a thatof resin at the in-
the interphase
terphase. Figure 13b provides a clear correlation on the process-microstructure
hardness is correlated with the processed temperature science a higher cure temperature and prop-
erties
resultsrelation at the interphase
in an increase of ABS
in interphase with UPR.
hardness.

16 9
Average Interphase Hardness #, H
v 0.4
Resin volume fraction
Vickers Hardness #, Hv

Vickers Hardness #, H v
14 8.5
0.35
8
12
0.3

[]
7.5
10 0.25
25 °C 7
35 °C
8 40 °C 0.2
50 °C
6.5
60 °C
6 6 0.15
0 500 1000 1500 2000 2500 20 30 40 50 60
L [ m] Temperature [°C]
(a) (b)
Figure 13.
Figure 13. (a)
(a) Vickers
Vickers microhardness
microhardness values
values at
at the
the interphase
interphase vicinity
vicinity for
for UPR-ABS
UPR-ABS interphase,
interphase, and
and (b)
(b) correlation
correlation between
between
interphase hardness and resin volume fraction.
interphase hardness and resin volume fraction.

4. Conclusions andmicrohardness
To relate the Future Work at the interphase to the processing condition and mi-
crostructure of interphase,
The interphase Figure 13b
of a co-bonded exhibits
ABS-UPR theinvestigated
was averaged harness at theby
in this work interphase
critically
(average of the
correlating 1200processing
µm–1700 µm) and volume
conditions, fraction of resin
chemo-rheological at the interphase
behaviour, resulting(ϕ)microstruc-
calculated
by Equation
ture (14) on different
and mechanical processing
performance. temperatures.
The swelling of ABSIt with
can beUPRseenwas
thatidentified
samples prepared
as a con-
at higher temperatures had a lower ϕ and hence a less resin presence
tributing parameter to the interphase size. It was observed that the interphase size at interphase to
act as a plasticizer and consequently this resulted in a higher hardness
changed with the processing temperature and it was correlated with thermal changes in values compared
to specimens
the prepared
viscosity and at lower
cure kinetics oftemperatures.
UPR through the On the other The
gel time. hand, samples of
diffusivity prepared
UPR intoat
lowerwas
ABS temperatures
estimated by showed a lower
using the hardness
1D inverse due tomodel
diffusion higherinvolume
which thefraction of resin at
experimentally
the interphase. Figure 13b provides a clear correlation on the process-microstructure
characterized temperature-dependent gelation time and interdiffusion thicknesses were and
properties relation at the interphase of ABS with UPR.
utilized. The diffusivities obtained were fit to an Arrhenius relationship which can be used
further for process simulations with various temperature ranges. More characterization
4. Conclusions and Future Work
experiments must be carried out to validate the diffusivities obtained and the developed
The interphase of a co-bonded ABS-UPR was investigated in this work by critically
correlating the processing conditions, chemo-rheological behaviour, resulting microstruc-
ture and mechanical performance. The swelling of ABS with UPR was identified as a
contributing parameter to the interphase size. It was observed that the interphase size
changed with the processing temperature and it was correlated with thermal changes in
the viscosity and cure kinetics of UPR through the gel time. The diffusivity of UPR into
ABS was estimated by using the 1D inverse diffusion model in which the experimentally
characterized temperature-dependent gelation time and interdiffusion thicknesses were
utilized. The diffusivities obtained were fit to an Arrhenius relationship which can be used
further for process simulations with various temperature ranges. More characterization
experiments must be carried out to validate the diffusivities obtained and the developed
Materials 2021, 14, 291 15 of 17

diffusivity model. It was shown that the diffusivity was inversely proportional with the
viscosity. The resin uptake experiments were employed to understand the kinetics of UPR
diffusion into ABS at different temperatures. Accordingly, a resin uptake model was fitted
to the experimentally obtained data by taking the processing temperature and cure kinetics
of UR into account. The developed model was used to determine the volume fraction
of the resin at the ABS-UPR interphase. The diffusivity coefficient obtained here is pro-
vide substantial information for future studies on the process modelling of multi-material
composites and complex shaped hybrid structures. Microhardness tests showed that the
hardness of interphase was lower than both ABS and UPR regions due to the plasticization
effect of UPR molecules at the interphase. A correlation was created between the processing
condition, resin volume fraction and its microhardness at the interphase which can be used
for designing such a hybrid MMCs in the future.
In the current work, the effect of the normal force used in the swelling experiments
with the rheometer on the polymer interdiffusion at the ABS-UPR interface was not taken
into account which is considered as a future work. Similarly, the effect of processing
temperature on the viscosity up to the gelation is also defined as future work because the
change in viscosity might influence the interphase thickness which was assumed to be
negligible in this study.

Author Contributions: Conceptualization, J.S.M.Z. and I.B.; methodology, J.S.M.Z. and I.B.; valida-
tion, J.S.M.Z. and I.B.; investigation, J.S.M.Z. and I.B.; resources, I.B.; data curation, J.S.M.Z. and I.B.;
writing—original draft preparation, J.S.M.Z. and I.B.; writing—review and editing, J.S.M.Z. and I.B;
visualization, J.S.M.Z. and I.B.; funding acquisition, I.B. All authors have read and agreed to the
published version of the manuscript.
Funding: This research was funded by the research program Talent Scheme (Veni) with project
number 15897, which is (partly) financed by the Netherlands Organization for Scientific Research
(NWO) and TKI-Wind op Zee Topsector Energy subsidy from the Ministry of Economic Affairs, the
Netherlands with the reference number TEWZ118008.
Data Availability Statement: The data presented in this study are available on request from the
corresponding authors. The data are not publicly available due to legal and privacy issues.
Acknowledgments: Authors gratefully acknowledge LM Wind Power for consultations during the
project and supply of polyester resin.
Conflicts of Interest: The authors declare no conflict of interest.

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