fibers

Article
Effect of Silane Coupling Treatment on the Adhesion
between Polyamide and Epoxy Based Composites
Reinforced with Carbon Fibers
Vincenzo Fiore * , Vincenzo Orlando, Carmelo Sanfilippo, Dionisio Badagliacco
and Antonino Valenza
Department of Engineering, University of Palermo, Viale delle Scienze, Edificio 6, 90128 Palermo, Italy;
vincenzorlando22@gmail.com (V.O.); carmelo.sanfilippo01@unipa.it (C.S.); dionisio.badagliacco@unipa.it (D.B.);
antonino.valenza@unipa.it (A.V.)
* Correspondence: vincenzo.fiore@unipa.it; Tel.: +39-091-238-63721




Received: 29 June 2020; Accepted: 25 July 2020; Published: 28 July 2020


Abstract: The increasing efforts aimed to design structures with reduced weight and better mechanical
performances has led in recent years to a growing use of fiber reinforced polymer materials in several
fields such as marine. However, these materials can be composed of chemically very different
elements and, hence, may be difficult to joint. This research aims to improve the adhesion between a
thermoplastic matrix of polyamide reinforced with short carbon fibers (PA12-CR) and a carbon fiber
reinforced epoxy matrix (CFRP). Two different silane coupling agents, (3-Aminopropyl)trimethoxysilane
(AM) and (3-Glycidyloxypropyl)trimethoxysilane (EP), were applied, through the spray deposition
method, on the PA12-CR substrate to create a reactive layer between the adherents. Different
deposition methods and coupling agents curing conditions were also investigated. The wettability
of the PA12-CR surface as well as the chemical modifications induced by silane treatments were
investigated through contact angle and Fourier Transform Infrared spectroscopy (FTIR) analyses.
Furthermore, the interfacial adhesion between PA12-CR and CFRP substrates was evaluated through
Mode I delamination tests (DCB). The effectiveness of the most promising treatment was finally
verified on sandwich structures, having PA12-CR printed as internal core and CFRP laminates as
external skins, through quasi-static three-point bending mechanical tests. Overall, the epoxy-based
silane (EP) allowed significantly better resistance to the delamination up until the tensile failure of
the CFRP substrate.

Keywords: adhesion; Silane coupling agent; DCB test; epoxy; Polyamide 12; carbon fibers

1. Introduction
The current use of carbon fiber-reinforced composite is mostly limited to the production of low
volume components, both in automotive, nautical and aircraft fields, due to the high material costs
and long production times. Nonetheless, the demand for light components with better performances
is growing, driven by the need to produce multi-material structural components that are capable of
increasing functionality, performance and recyclability [1]. Hence, structural joints are often required
in several engineering structures in order to join composite to metal substrates or different composite
components such as fiber-reinforced thermoset and thermoplastic composites [2].
In such a context, the joining technologies most commonly used for composite structures include
mechanical fixing [3,4] casting (welding) [5,6] and adhesive bonding [7–9]. In particular, adhesive
joints are widely used due to their several advantages in comparison to their mechanical counterparts
such as lower structural weight, lower manufacturing cost, better damage tolerance, no damages

Fibers 2020, 8, 48; doi:10.3390/fib8080048 www.mdpi.com/journal/fibers

Fibers 2020, 8, 48 2 of 14

on the composite structure and avoiding of stress concentrations [10]. In this context, it is worth
emphasizing that the preparation of the surface of substrates represents an essential key point to
improve their adhesion strength, thus increasing the overall mechanical response of the joint. Surface
pre-treatment can have three functions aimed to improve bond strength using chemical or physical
interactions [11], that is, increasing surface tension, increasing surface roughness and changing surface
chemistry. However, thermoplastic based materials may not be easily glued with thermosetting
adhesives due to their intrinsically low reactivity, surface energy and polarity [12] and require changes
in surface chemistry and topography before bonding to ensure a reliable and durable joint [10]. Typical
surface treatment methods for thermoplastic composites include the use of coupling agents [2], plasma
treatment [13], etching [14] and oxidizing treatment [15].
Among these different approaches, silane agents have been extensively used in several industrial
fields as efficient coupling agents due to their easy applicability, durability and versatility as well
as low costs [16–18] in order to increase the fiber-matrix adhesion strength. Moreover, they can be
used as adhesion promoters in many adhesive formulations or as substrate primers, giving stronger
adhesion [19].
One of the most widely used thermoplastic polymers is the polyamide (PA), often used in the
form of a fiber [20] or even a matrix reinforced with other types of fibers to obtain a composite
structure [21]. PA based composites are both inexpensive and highly resistant to wear, as well as they
show high mechanical strength, stiffness and dimensional stability. Nevertheless, problems arise at the
time of gluing with thermosetting-based adhesives such as epoxy ones. The weak adhesive strength
between polyamides and epoxy polymers is mainly due to the very slow diffusion of the epoxy in the
thermoplastic, with consequent limited intermolecular diffusion [12]. This issue is more pronounced
for high viscosity epoxy adhesives. The lack of penetration into the polyamide composite leads to a
low concentration of epoxy groups able to react with the polyamide at the bonding interface leading to
a weak adhesion. The deposition of a reactive layer of silane agent can create a covalent “bridge” layer
between the functional groups of the polyamide and the reactive groups of the epoxy resin.
The present work focuses on the improvement of the interfacial adhesion between thermoset (i.e.,
epoxy) and thermoplastic (i.e., nylon 12) based composites by means of two silane coupling agents. In
particular, a 3D printed substrate made by polyamide 12 reinforced with carbon microfibers (PA12-CR)
was joined with a bidirectional carbon fabric reinforced epoxy laminate (CFRP). Both silane coupling
agents were applied over the surface of the PA12-CR substrate through the spray deposition method,
before the joints manufacturing.
Besides evaluating the most suitable silane, two different application methods and coupling
agents curing conditions were also investigated. Delamination tests were carried out in Mode I (i.e.,
DCB tests) for the evaluation of the interfacial adhesion. Furthermore, contact angle analysis and
Fourier Transform Infrared Spectroscopy (FTIR) were also performed on the PA12-CR surface to
evaluate the effectiveness of the chemical treatments. Finally, the effect of treatment on the adhesion
between thermoset to thermoplastic-based composites was evaluated by performing three-point
bending quasi-static tests on sandwich structures having PA12-CR printed as internal core and CFRP
laminates as external skins.

2. Experimental

2.1. Materials
The 3D printed panels are made of a PA12 based composite reinforced with 30% by weight of
short carbon fibers (average length and diameter equal to 100 µm and 10 µm, respectively). This
composite (PA12-CR), was manufactured through Fused Deposition Modeling technique by OCORE
s.r.l. (in the next OCORE). The filament (3F PATH CF 9742 BK) used for 3D printing of PA12-CR
substrate was supplied by LEHVOSS Group Company. Table 1 shows the main mechanical properties
of the PA12-CR.
Fibers 2020, 8, 48 3 of 14

Table 1. Main mechanical properties of polyamide 12 reinforced with carbon microfibers (PA12-CR).

Mechanical Properties at 23
◦ C/50% RH Normative Value
Tensile Strength ISO 527 170 MPa
Elongation at break ISO 527 2%
Modulus of Elasticity ISO 527 15 GPa
Charpy Impact Strength ISO 179 47 KJ/m2

The CFRP substrate was produced by using bidirectional twill carbon fabrics having 200 g/m2
areal weight and a DEGBA epoxy resin (SX-8 EVO), supplied by Mates Italiana, as reinforcement and
matrix, respectively. The epoxy resin was mixed in the ratio 100:30 by weight with its amine-based
hardener. Two silane coupling agents were used—that is, (3-Glycidyloxypropyl)trimethoxysilane (EP),
an epoxy bifunctional silane produced by Sigma Aldrich and the (3-Aminopropyl)trimethoxysilane
(AM), an amino bifunctional silane produced by Gelest. These two coupling agents were chosen
because, in the epoxy-based silane the epoxy ring can bind with the amine groups of the epoxy resin,
while in the amino-based silane the amine groups react with the epoxy resin.
The chemical formula and main properties of the coupling agents are reported in Table 2:

Table 2. Details of the silane coupling agents.

(3-Aminopropyl)trimethoxysilane (AM) (3-Glycidyloxypropyl)trimethoxysilane (EP)
Empirical Formula C9 H23 NO3 SI C9 H20 O5 Si
Molecular Weight 179.29 236.34
Assay 97% ≥98%
Reactive Groups Amine/Methoxy Epoxy/Methoxy
Density 1.027 g/mL at 25 ◦ C 1.07 g/mL at 25 ◦ C
Refractive Index 1.424 1.429

2.2. Surface Pre-Treatment Process

The manufacturing of components with high specific mechanical properties represent an essential
key point in several industrial fields such as marine field. It is worth noting that a mechanical abrasion
of the surface of the printed PA12-CR components is usually carried out by OCORE company, because
it leads to a 20% weight reduction as well as a 10% thickness reduction of the resulting composites.
For this reason, all the PA12-CR substrates used in the present paper were smoothed, following the
procedure suggested by OCORE (Table 3):

Table 3. Description of surface pre-treatment.

Type of Pre-Treatment Description of Pre-Treatment
Roughing Performed by a belt sander equipped with 40, 80 and 120 grit
Finishing Performed by a vibrating sander equipped with 150 grit
Cleaning and removing dust Performed by a compressed air jet and absorbent paper

2.3. PA12-CR Surface Treatment Methods

For both silane coupling agents, the solution was prepared according to the method proposed by
Calabrese et al. [22]:

1. Composition of the solution—90% v/v of ethanol, 5% v/v of distilled water, 5% v/v of silane,
2. The obtained solution was magnetically stirred for 10 min at room temperature in a fume hood;
3. Then, acetic acid was added to modify the pH of the solution from 11.4 to 4.2;
4. Finally, the solution was left to rest in the fume hood in a stirrer for 24 h.

For each silane agent, the solution was applied over the surface of the PA12-CR substrate through
the spray deposition method with the aid of an airbrush. In particular, some samples were covered
with a single layer of silane agent while other samples were treated by depositing a second layer
of silane agent over the first one. Following this procedure, a comparison between two deposition
Fibers 2020, 8, 48 4 of 14

methods (in the next named “1 Layer” and “2 Layers”) was carried out to evaluate the effect of the
number of coupling agent layers on the adhesion between the composite substrates (i.e., PA12-CR and
CFRP). Two different curing process were also performed (in the next “Total Cure” and “Partial Cure”)
to investigate the possibility of reducing the treatment time thus the components production time.
A detailed description of the different types of treatments investigated is shown in Table 4:

Table 4. Different coupling agents curing conditions, deposition and relative PA12-CR
treatment description.
Type of Cure Type of Deposition Pa12-Cr Treatment Description
1. Layer (1)Spray deposition of the layer
(2)Cure for 3 h in oven at 80 ◦ C
(3)Hand lay-up lamination
(4)Cure for 24 h in vacuum at room temperature
2 Layers (1)Spray deposition of the 1st layer
Total Cure
(2)Cure for 10 min in oven at 80 ◦ C
(3)Spray deposition of the 2nd layer
(4)Cure for 3 h in oven at 80 ◦ C
(5)Hand lay-up lamination
(6)Cure for 24 h in vacuum at room temperature
1 Layer (1)Spray deposition of the layer
(2)Cure for 10 min in oven at 80 ◦ C
(3)Hand lay-up lamination
(4)Cure for 24 h in vacuum at room temperature
(5)Post-cure for 3 h in oven at 80 ◦ C
2 Layers (1)Spray deposition of the 1st layer
Partial Cure
(2)Cure for 10 min in oven at 80 ◦ C
(3)Spray deposition of the 2nd layer
(4)Cure for 10 min in oven at 80 ◦ C
(5)Hand lay-up lamination
(6)Cure for 24 h in vacuum at room temperature
(7)Post-cure for 3 h in oven at 80 ◦ C

2.4. Analysis of the Treated Surfaces

The wettability of both untreated and treated surfaces of PA12-CR substrate were evaluated
through contact angle measurements. Furthermore, these surfaces were analyzed by means of Fourier
transform infrared (FTIR) spectroscopy, in order to evaluate the effectiveness of the silane coupling
agents. To obtain statistically significant results, five tests for each type of joint were carried out. For
the contact angle analysis, the drop image was processed by means of ImageJ software. The FTIR
analysis was performed through a PerkinElmer infrared spectrometer model Spectrum II (PerkinElmer,
Waltham, MA, USA). The analysis was carried out in transmission mode between 450 and 4000 cm−1
and the resolution was set at 4 cm−1 .

2.5. Manufacturing Process of the Joints

The number of carbon layers used as reinforcement of CFRP laminate (i.e., four) was chosen in
order to achieve a flexural stiffness as comparable as possible between PA12-CR and CFRP substrates.
All the joints were manufactured through vacuum bagging technique [23]. The curing conditions for
each treatment investigated are reported in Table 4. The codes and the relative treatment conditions of
the joints analyzed in this study are reported in Table 5:
Fibers 2020, 8, x FOR PEER REVIEW 5 of 14

each treatment investigated are reported in Table 4. The codes and the relative treatment conditions
of the joints analyzed in this study are reported in Table 5:
Fibers 2020, 8, 48 5 of 14
Table 5. Nomenclature and description of samples.

Code Description
Table 5. Nomenclature and description of samples.
UT Untreated
Code
AM_T_1L Amino-based silane—Total Cure—1 Description
Layer
UT Untreated
AM_T_2L Amino-based silane—Total Cure—2 Layers
AM_T_1L Amino-based silane—Total Cure—1 Layer
AM_P_1L Amino-based silane—Partial
AM_T_2L Cure—1
Amino-based Layer Cure—2 Layers
silane—Total
AM_P_2L Amino-based silane—Partial
AM_P_1L Cure—2
Amino-based Layers Cure—1 Layer
silane—Partial
AM_P_2L
EP_T_1L Amino-based
Epoxy-based silane—Total silane—Partial
Cure—1 Layer Cure—2 Layers
EP_T_1L
EP_T_2L Epoxy-based silane—Total
Epoxy-based silane—Total Cure—2 Layers Cure—1 Layer
EP_T_2L Epoxy-based silane—Total Cure—2 Layers
EP_P_1L
EP_P_1L Epoxy-based silane—Partial Cure—1
Epoxy-based Layer Cure—1 Layer
silane—Partial
EP_P_2L
EP_P_2L Epoxy-based silane—Partial Cure—2
Epoxy-based Layers Cure—2 Layers
silane—Partial

2.6. Samples
2.6. Samples Preparation
Preparation for
for the Double Cantilever
the Double Cantilever Beam
Beam Test
Test
For the
For the evaluation
evaluation of
of the
the delamination behavior in
delamination behavior in Mode
Mode I,I, DCB
DCB tests
tests were
were performed
performed according
according
to ASTM
to ASTM D D 5528-01
5528-01 standard
standard [24].
[24]. The
The preparation
preparation ofof the
the specimens
specimens was
was carried
carried out according to
out according to the
the
relative specifications of the hinged DCB specimens. In accordance with the standard,
relative specifications of the hinged DCB specimens. In accordance with the standard, the nominal the nominal
dimensions are—width
dimensions are—width B B in the range
in the range 20–23
20–23 mm;
mm; length
length LL≥≥ 125
125 mm;
mm; laminate
laminate thickness
thickness 22 hh in
in the
the
range 2–3
range 2–3 mm.
mm. The
The initial
initial length
length of
of the
the artificial delamination aa00 was
artificial delamination was set
set to
to 36
36 mm
mm (Figure
(Figure 1).
1).

Figure 1.
Figure Typical dimensions
1. Typical dimensions and
and set-up
set-up of
of aa Mode
Mode II delamination
delamination test
test (DCB)
(DCB) specimen
specimen [24].
[24].

The artificial delamination was created using a 13 µm thick film of a non-stick polymer layer of
The artificial delamination was created using a 13 μm thick film of a non-stick polymer layer of
FEP (Fluorinated Ethylene Propylene) during the lamination phase. Since the width of the hinges is
FEP (Fluorinated Ethylene Propylene) during the lamination phase. Since the width of the hinges is
18 mm and the initial length of the artificial crack a0 is 36 mm, the samples have been shortened in
18 mm and the initial length of the artificial crack a0 is 36 mm, the samples have been shortened in
correspondence with the delaminated area.
correspondence with the delaminated area.
Before gluing the hinges, white spray paint was applied on the edge of the specimens to monitor
Before gluing the hinges, white spray paint was applied on the edge of the specimens to monitor
the crack propagation more easily and accurately during the delamination.
the crack propagation more easily and accurately during the delamination.
After roughening the surfaces of the hinges with sandpaper, the hinges were glued on the upper
After roughening the surfaces of the hinges with sandpaper, the hinges were glued on the upper
and lower faces of the specimen with a commercial cyanoacrylate based adhesive. The positioning of
and lower faces of the specimen with a commercial cyanoacrylate based adhesive. The positioning of
the hinges must be done with special care to make sure that the axis of the hinge aligns perpendicular
the hinges must be done with special care to make sure that the axis of the hinge aligns perpendicular
to the longitudinal direction of the specimen thus avoiding torsional stresses during the test.
to the longitudinal direction of the specimen thus avoiding torsional stresses during the test.
Finally, a rule bar was glued on the whitewashed edge with double-sided tape to monitor the
Finally, a rule bar was glued on the whitewashed edge with double-sided tape to monitor the
advancement of the crack through images acquired by a digital camera.
advancement of the crack through images acquired by a digital camera.
The Modified Beam Theory (MBT) was used for the calculation of GIC init , GIC prop and the R-curve
The Modified Beam Theory (MBT) was used for the calculation of GIC init, GIC prop and the R-curve
(Equation
(Equation (1)). GIC
(1)). G ICinit is is
init thethe value
value ofof
thethe Energy
Energy Release
Release Rate
Rate correspondent
correspondent to to
thethe first
first propagation
propagation of
of the crack, while the GIC prop is the plateau value of the Energy Release Rate achieved during the
the crack, while the GIC prop is the plateau value of the Energy Release Rate achieved during the
delamination
delamination process.
process.
3Pδ
GIC = . (1)
2B(a + |∆|)
The visual observation of the first advancement of the crack (VIS) [24] was used for the evaluation
of the critical load, Figure 2.
 3𝑃𝛿
𝐺𝐼𝐶 = . (1)
2𝐵(𝑎+||)
Fibers The visual
2020, 8, observation of the first advancement of the crack (VIS) [24] was used for6 ofthe
48 14
evaluation of the critical load, Figure 2.

Figure 2. Visual
Visual analysis of the crack propagation.

coefficient∆ 𝛥is aiscorrective

The coefficient coefficient
a corrective obtained
coefficient by linearly
obtained approximating
by linearly the values
approximating theassumed
values
by the cubic
assumed root
by the of the
cubic rootyield (C1/3
of the ) as(C
yield a 1/3
function of the total
) as a function of thelength of theof
total length delamination a. The
the delamination a.
distance between the intersection of the linear regression line with the abscissa axis and
The distance between the intersection of the linear regression line with the abscissa axis and the originthe origin is
equal
is equal ∆ [24].
toto 𝛥 [24].
The values
The values ofofthe loadPPand
theload displacementδδwere
anddisplacement werestored
stored by
by the TextExpert control
software of the Zwick/Roell Z005 material testing machine (Zwick-Roell, Ulm, Germany), while the
propagation of crack a was monitored by a Nikon digital camera controlled by the remote-control
software digiCamControl (v2.1.2), setting a time-lapse of 5 s. The experimental tests were carried out
in displacement control with a crosshead speed of 2 mm/min. mm/min.

2.7. Mechanical
2.7. Mechanical Analysis
Analysis of
of Sandwich
Sandwich Structures
Structures
The effectiveness
The effectiveness ofof the
the most promising treatment
most promising treatment was was finally
finally verified
verified on
on aa sandwich structure
sandwich structure
through three-point bending mechanical tests. This sandwich structure, which can
through three-point bending mechanical tests. This sandwich structure, which can be used to produce be used to produce
both structural
both structuralandandnon-structural
non-structuralcomponents,
components, is is formed
formed by by
a 3D a 3D printed
printed architecture
architecture consisting
consisting of a
of a PA12 matrix reinforced with short carbon fibers, as core material. The printed structure
PA12 matrix reinforced with short carbon fibers, as core material. The printed structure is then covered is then
covered
on on both
both sides withsides with aoflamina
a lamina of bidirectional
bidirectional carbon fabriccarbon fabric reinforced
reinforced epoxy
epoxy resin resinas
(CFRP) (CFRP)
skin. Toas
skin. To confirm
confirm the effectiveness
the effectiveness of the
of the best best chemical
chemical treatment treatment
on theon the PA12-CR
PA12-CR to CFRP
to CFRP adhesion,
adhesion, two
two sandwich structures were mechanically compared—that is, the first one
sandwich structures were mechanically compared—that is, the first one with untreated PA12-CR with untreated PA12-CR
core
core (UT)
(UT) and andthe the second
second oneone
withwith PA12-CR
PA12-CR coretreated
core treatedwith
withepoxy-based
epoxy-basedsilane
silane coupling
coupling agent
agent
(EP_P_1L). The architecture of the sandwich section is shown
(EP_P_1L). The architecture of the sandwich section is shown in Figure 3. in Figure 3.
Fibers 2020, 8, 48 7 of 14
Fibers 2020, 8, x FOR PEER REVIEW 7 of 14

Figure 3.
Figure Sandwich specimen
3. Sandwich specimen for
for three-point
three-point bending
bending test.
test.

Sandwich specimens were

Sandwich specimens were subjected to quasi-static
subjected to quasi-static three-point
three-point bending tests using
bending tests using aa universal
universal
testing machine (U.T.M.) model Z005 by Zwick/Roell, equipped with a 5 kN load cell. All the tests
testing machine (U.T.M.) model Z005 by Zwick/Roell, equipped with a 5 kN load cell. All the tests
were
were carried
carried out
out according
according to
to the
the ASTM
ASTM C393
C393 standard
standard [25],
[25], in
in displacement
displacement control.
control. The
The support
support
span and the crosshead speed were set to 95 mm and 2 mm/min, respectively. The length and width of
span and the crosshead speed were set to 95 mm and 2 mm/min, respectively. The length and width
the specimens
of the specimenswere
wereequal
equaltoto
165165mm
mmandand3030mm,
mm,respectively.
respectively.Before
Beforecarrying
carryingout
out the
the tests,
tests, white
white
spray paint was applied to each specimen to better monitor the failure mechanism
spray paint was applied to each specimen to better monitor the failure mechanism of the structure.of the structure.
The
The flexural
flexural stress
stress and
and strain
strain were
were calculated
calculated by
by the
the following
following Equations
Equations (2)
(2) and
and (3):
(3):
𝑃∙𝐿
P·L
𝜎σ ==2t(d + c)b , , (2)
(2)
2𝑡(𝑑+𝑐)𝑏

6·δ·d
6∙𝛿∙𝑑,
𝜖 =
=L𝐿22 ,
(3)
(3)
where P is the load applied in the midsection of the specimen, L is the support span length, b the width,
where P is the load applied in the midsection of the specimen, L is the support span length, b the
c the core thickness, d the total sandwich thickness, t the skins thickness and δ the displacement of
width, c the core thickness, d the total sandwich thickness, t the skins thickness and δ the displacement
the midsection of the specimen. In particular, the sandwich structures were compared in term of the
of the midsection of the specimen. In particular, the sandwich structures were compared in term of
maximum flexural strength σmax (i.e., calculated by the Equation (2) when P reaches the maximum
the maximum flexural strength σmax (i.e., calculated by the Equation (2) when P reaches the maximum
value Pmax ) and the equivalent flexural modulus Ef (i.e., evaluated by the slope of the stress-strain curve
value Pmax) and the equivalent flexural modulus Ef (i.e., evaluated by the slope of the stress-strain
in the linear elastic range taking into account the isotropic structure, equivalent to the composite [26]).
curve in the linear elastic range taking into account the isotropic structure, equivalent to the
composite
3. [26]).Discussion
Results and

3. Results
3.1. andSurface
PA12-CR Discussion
Treatments
FTIR analysis
3.1. PA12-CR was
Surface carried out on PA12-CR substrate surfaces in order to verify the effectiveness
Treatments
of silane treatments. Amino-based silane, similarly to epoxy-based silane, has CH2 and CH3 bonds
FTIR by
identified analysis
peaks was carried outbetween
of wavelength on PA12-CR substrate
2850 and 2920 cmsurfaces in order
−1 , which to present,
are also verify the effectiveness
however, in the
of silane treatments. Amino-based silane, similarly to epoxy-based silane, has CH 2 and CH3 bonds
thermoplastic substrate. For this reason, it is possible to verify the presence of the silane through the
identified
Si-O bond,by peaks of wavelength
characterized between
by the peaks between2850
1000and
and2920 cm
1100 cm,−1
−1 which are also present, however, in
. In Figures 4 and 5, it is possible to
the thermoplastic
observe substrate.
the difference betweenForthe
thisspectra
reason,ofitthe
is possible to verify
treated and the presence
untreated PA12-CRofsubstrates.
the silane through
the Si-O bond, characterized by the peaks between 1000 and 1100 cm−1. In Figure 4 and Figure 5, it is
possible to observe the difference between the spectra of the treated and untreated PA12-CR
substrates.
 Fibers 2020, 8, x FOR PEER REVIEW 8 of 14

Fibers2020,
Fibers 2020,8,8,48
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14

Figure 4. Fourier transform infrared (FTIR) on untreated and (3-Aminopropyl)trimetoxysilane (AM)

treated4.PA12-CR
Figure substrates.infrared (FTIR) on untreated and (3-Aminopropyl)trimetoxysilane (AM)
Fourier transform
treated PA12-CR substrates. infrared (FTIR) on untreated and (3-Aminopropyl)trimetoxysilane (AM)
Figure 4. Fourier transform
treated PA12-CR substrates.

Figure 5. FTIR on untreated and (3-Glycidyloxypropyl)trimethoxysilane (EP) treated

Figure 5. FTIR
PA12-CR substrates. on untreated and (3-Glycidyloxypropyl)trimethoxysilane (EP) treated PA12-CR
substrates.
For both5.silanes,
Figure theuntreated
FTIR on presence and
of the(3-Glycidyloxypropyl)trimethoxysilane
Si-O bond in comparison to the reference is noted.
(EP) treated Moreover,
PA12-CR
For both silanes,
for thesubstrates.
amino-based the presence
silane, of the
a variation Si-Ocurvature
of the bond in comparison
of the rangetobetween
the reference is noted.
2300 and cm−1 can
3700 Moreover,
forobserved,
be the amino-based silane, athe
which identifies variation
vibrationofof
the thecurvature of the
amino group ofrange between
the silane. 2300
For the and 3700 cm
epoxy-based −1 can
silane,
For
is a both
peak silanes,
be observed,
there which the presence
identifies
at the wavelength the of the
cmSi-O
vibration
1740 bond
of theinamino
comparison
−1 , characteristic ofgroup to
of the
the double reference
thebond
silane. is representative
For
C=O, noted. Moreover,
the epoxy-based of
for the
silane,
the epoxyamino-based
there silane, a variation of the curvature of the range
ring.is a peak at the wavelength 1740 cm , characteristic of the double bond
−1 between 2300 and 3700 cm−1C=O,can
be observed,
The effectwhich
representative theidentifies
ofthe
of the vibration
epoxycoupling
silane ring. agents is offurther
the amino group by
evidenced of the
the silane.
results For
of thethecontact
epoxy-based
angle
silane, there
measurements is
The effect(Figurea peak
of the silane at
6) whichthe wavelength
coupling
show agents 1740
that theissurface cm −1, characteristic of the double bond C=O,
furthertreated
evidencedwithbyepoxy-based
the results of the contact
silane angle
has a better
representative
measurements
wettability (i.e.,of thelowest
(Figure
the epoxy ring. show
6) which
contact thatthan
angle) the surface treated
the surfaces ofwith
bothepoxy-based
untreated and silane has a better
amino-treated
The effect
wettability
substrates. (i.e.,ofthe
Moreover, thethe
silane
lowest
lower coupling
contact agents
angle)
standard is further
than
deviation the evidenced
surfaces
evidenced by treated
forofboth
both the results
untreated ofand
surfacestheshows
contact
thatangle
amino-treatedthe
measurements
substrates.
silane (Figure
Moreover,
treatment 6) which
the lowerby
is characterized show that
standard the surface treated with epoxy-based silane
deviation evidenced for both treated surfaces shows
high repeatability. has a better
that
wettability (i.e., the is
the silane treatment lowest contact angle)
characterized by highthan the surfaces of both untreated and amino-treated
repeatability.
substrates. Moreover, the lower standard deviation evidenced for both treated surfaces shows that
the silane treatment is characterized by high repeatability.
Fibers 2020, 8, x FOR PEER REVIEW 9 of 14
Fibers2020,
Fibers 2020,8,8,x48
FOR PEER REVIEW 99ofof14
14

45
40
45
35
40

[°] [°]
30
35

angle
25
30
angle
Contact
20
25
15
20
Contact

10
15
5
10
05
UT EP AM
0
UT EP AM
Figure 6. Contact angle between epoxy resin and PA12-CR substrates.
Figure 6. Contact angle between epoxy resin and PA12-CR substrates.
Figure 6. Contact angle between epoxy resin and PA12-CR substrates.
3.2.
3.2.Analysis
Analysisof of
thethe
Double Cantilever
Double Beam
Cantilever Test
Beam Test
3.2. Analysis
The of the
Theresults
resultsofofDouble
the
theDCBCantilever
DCBtests
testsare
areBeam
shownTest
shownininFigure
Figure7.7.
The results of the DCB tests are shown in Figure 7.
250
(a)
250
171
(a) 200
171
200
2]

133
IC init [KJ/m

150 114
2]

133
GIC initG[KJ/m

150 114 81
100
65
81
100 44
65
50
22 25
44 16
50
22 25
0 16

250
(b)
250
(b) 200
146
2]

200 132
prop [KJ/m

150 105 146

2]

132
GIC[KJ/m

150 105
100 64
49 58
GIC prop

100 64
50 49 58 21
20
10
50 21
0 20
10
0

Figure 7. (a) GIC init and (b) GIC prop values obtained from DCB tests.
Figure 7. (a) GIC init and (b) GIC prop values obtained from DCB tests.
The use of silane coupling agents evidenced that the ammine-based silane (AM) treatment provides
a slight improvement Figure 7. (a)
in the GICof
case init and (b) GIC prop values obtained from DCB tests.
1 layer and Total Cure (47.7% on GIC init and 18.4% on GIC prop ),
Fibers 2020, 8, x FOR PEER REVIEW 10 of 14

The use of silane coupling agents evidenced that the ammine-based silane (AM) treatment
Fibers 2020, 8, 48 10 of 14
provides a slight improvement in the case of 1 layer and Total Cure (47.7% on GIC init and 18.4% on
GIC prop), while in all the other cases it leads a significant decrease of the adhesion. This behavior can
be dueintoallthe
while theinsufficient
other casesconditions for reaction
it leads a significant between
decrease ofAM silane andThis
the adhesion. epoxy in the case
behavior can beof partial
due to
cureinsufficient
the (i.e., 80 °C conditions
for 10 min before the hand
for reaction lay-up
between AM phase
silaneof CFRP substrate)
and epoxy in the case of partial cure (i.e.,
80 ◦ COnforthe contrary,
10 min beforethethetreatment
hand lay-up withphaseepoxy-based
of CFRPsilane (EP) leads to significantly better results.
substrate)
In particular, the highest
On the contrary, increase was
the treatment withrecorded
epoxy-basedfor EP_P_1L
silane (EP)treatment,
leads towhich allows better
significantly to achieve an
results.
increase
In of 288.6%
particular, and 202.2%
the highest increaseon G was and GIC prop
IC initrecorded for, respectively.
EP_P_1L treatment, These results
whichcan be due
allows to the high
to achieve an
reactivityofbetween
increase 288.6% and the epoxy
202.2%groupson GICof initthe
andEP coupling
GIC agent and These
prop , respectively. the amine groups
results can beof due
the epoxy
to the
resinreactivity
high [27]. between the epoxy groups of the EP coupling agent and the amine groups of the epoxy
resin The
[27].results also show that in the case of “2 Layers” deposition method, an adhesion reduction
for both
The the silane
results coupling
also show that agents
in thewascase found.
of “2 This
Layers”maydeposition
be due to method,
the fact that, by applying
an adhesion a second
reduction for
layer,the
both the totalcoupling
silane thickness of the
agents was silane
found. coating
This mayincreases,
be due to which leads
the fact that,tobya applying
worsening of the layer,
a second joint
mechanical
the properties
total thickness of thecaused
silane by the cohesive
coating increases,breakage
which leads between the two layers
to a worsening of theof silane.
joint Similar
mechanical
results were
properties obtained
caused by the bycohesive
Hoikkanen breakage et al. between
[28] whothe evidenced
two layers that in thermoplastic
of silane. urethane–
Similar results were
stainless by
obtained steel hybrids etstructures
Hoikkanen al. [28] who theevidenced
thicknessthat of in
thethermoplastic
silane coating leads to a decrease
urethane–stainless in the
steel hybrids
mechanicalthe
structures strength dueoftothe
thickness thesilane
failure withinleads
coating the silane layer. Hence,
to a decrease in theitmechanical
is reasonable to assert
strength duethat
to the
deposition
failure withinof athe
single
silanelayer
layer.is adequate
Hence, it to is create a homogeneous
reasonable to assert that coating layer.
the deposition of a single layer is
The optical
adequate to createmicroscope
a homogeneous observations
coating of the fracture surfaces of untreated specimen (Figure 8)
layer.
evidence that themicroscope
The optical resin is almost entirely on
observations of the CFRP
fracture surface
surfaceswith ofonly small traces
untreated specimen visible on the
(Figure 8)
PA12-CR that
evidence surface. Thisis experimental
the resin almost entirelyresult on theevidences
CFRP surface that with
this only
specimen failed visible
small traces by adhesive
on the
mechanism,
PA12-CR due to
surface. theexperimental
This low compatibility result between
evidencesthe thatthermoplastic
this specimenbased failedcomposite
by adhesive and the epoxy
mechanism,
resin.
due to On
the the
lowcontrary,
compatibilityFigure 9 shows
between thethat the treatment
thermoplastic basedwith epoxy-based
composite and thesilane
epoxyagent leads
resin. Onto thea
partial cohesive failure mode of the EP_P_1L specimen—that is, presence
contrary, Figure 9 shows that the treatment with epoxy-based silane agent leads to a partial cohesive of a greater amount of resin
on themode
failure PA12-CRof thesubstrate. This confirms the
EP_P_1L specimen—that improved
is, presence of acompatibility
greater amount between
of resinepoxy
on theresin
PA12-CR and
thermoplastic
substrate. Thissubstrate
confirms that determines
the improved the significant
compatibility increment
between epoxy ofresin
the adhesion between CFRP
and thermoplastic and
substrate
PA12-CR substrates.
that determines the significant increment of the adhesion between CFRP and PA12-CR substrates.

Figure 8. Optical microscope observations of the fracture surfaces of (A) carbon fabric reinforced epoxy
Figure 8. Optical microscope observations of the fracture surfaces of (A) carbon fabric reinforced epoxy
resin (CFRP) and (B) PA12-CR of untreated (UT) specimen after DCB test.
resin (CFRP) and (B) PA12-CR of untreated (UT) specimen after DCB test.
Fibers 2020, 8, x FOR PEER REVIEW 11 of 14
Fibers 2020, 8, 48 11 of 14
Fibers 2020, 8, x FOR PEER REVIEW 11 of 14

Figure 9. Optical microscope observations of the fracture surfaces of (A) CFRP and (B) PA12-CR of
EP_P_1L
Figure 9.specimen
Figure 9. Optical after DCB test.
Optical microscope
microscope observations of the
observations of the fracture
fracture surfaces
surfaces of
of (A)
(A) CFRP
CFRP and
and (B)
(B) PA12-CR
PA12-CR of
of
EP_P_1L specimen after DCB test.
EP_P_1L specimen after DCB test.
3.3. Mechanical Analysis of the Sandwich Structure
3.3. Mechanical Analysis of the Sandwich Structure
3.3. Mechanical
As alreadyAnalysis
stated, of the Sandwich
from the experimentStructure results it was noticed that the treatment with epoxy-
As
basedAs already
silane stated,
coupling from
agent the experiment
showed results
the best results it was
effect on noticed
the that the
adhesion treatment
between with epoxy-based
PA12-CR and epoxy-
CFRP
already
silane coupling stated,
agent showed from the experiment
the best effectevidence, it
on the adhesionwas noticed that
between PA12-CR the treatment
and CFRP with
substrates.
substrates.
based silaneTo confirm this experimental the quasi-static flexural response of typical
To confirm
sandwich thiscoupling
experimental
structures,
agentevidence,
usedthis
showed the
by OCORE
the quasi-static
best effect on
company as bearing
the adhesion
flexural response
structure
between
of of typical
aflexural
boat, was
PA12-CR
sandwich
evaluated.
and CFRP
structures,
substrates.
usedAs bycan
OCORETo confirm
company experimental
asstress-strain
bearing structure evidence, the quasi-static response of typical
sandwich be seen
structures, from
used the
bystress-strain
OCORE company trendsofshown
a boat,inwas
as bearing Figureevaluated.
10, the
structure of atreatment
boat, waswith epoxy-based
evaluated.
As
silaneAs can
couplingbe seen
agent from the
(EP_P_1L) led to an trends
increase shown
of bothin Figure
the 10, the
flexural treatment
strength σ with epoxy-based
max (i.e., 5%) and the
can be seen from the stress-strain trends shown in Figure 10, the treatment with epoxy-based
silane coupling
equivalent agent
flexural (EP_P_1L)
modulus led
Ef (i.e., to an increase of both the flexural strength σ max (i.e., 5%) and the
silane coupling agent (EP_P_1L) led19.2%)
to an of the sandwich
increase of both structure,
the flexural compared
strengthto untreated
σmax (i.e., 5%)samples
and the
equivalent
(UT). In flexuralthe
addition, modulus
treated Efstructure
(i.e., 19.2%) of the sandwich
evidences a partial structure,
recovery compared
of its load to untreated
capacity, duesamples
to the
equivalent flexural modulus Ef (i.e., 19.2%) of the sandwich structure, compared to untreated samples
(UT). In
better addition,
adhesion the treated
between CFRP structure
skin and evidences
printed a partial core,
PA12-CR recovery
up toof15itsMPa.
load These
capacity, due to the
experimental
(UT). In addition, the treated structure evidences a partial recovery of its load capacity, due to the
better adhesion
evidences confirm between CFRP skin
the beneficial effectand printed
of this PA12-CR
treatment on thecore, up to 15between
adhesion MPa. These
PA12-CR experimental
core and
better adhesion between CFRP skin and printed PA12-CR core, up to 15 MPa. These experimental
evidences
CFRP skin confirm
of the the beneficial
sandwich effectThe
structure. of this treatment
results are on the adhesion
summarized in Table between
6. PA12-CR core and
evidences confirm the beneficial effect of this treatment on the adhesion between PA12-CR core and
CFRP skin of the sandwich structure. The results are summarized in Table 6.
CFRP skin of the sandwich structure. The results are summarized in Table 6.

Figure 10.
Figure Typical stress-strain
10. Typical stress-strain flexural
flexural curves
curves of
of UT
UT and
and EP_P_1L
EP_P_1L sandwich
sandwich structures.
structures.

Figure Table 6. Comparison

10. Typical between
stress-strain treated
flexural and
curves untreated
of UT sandwich
and EP_P_1L structures.
sandwich structures.
Table 6. Comparison between treated and untreated sandwich structures.
σmax [MPa] Ef [MPa]
Table 6. Comparison
Average between treated
σmax [MPa]and untreated sandwich
Dev.St. f [MPa]structures.
EAverage Dev.St.
UT 39.8 Averag 3.7 Aver 1198 222.8
σmax [MPa]
Dev.St. Ef [MPa]
Dev.St.
EP_P_1L 41.8 2.3 1428 146.6
e
Averag age
Aver
UT 39.8 Dev.St.
3.7 1198 Dev.St.
222.8
e age
UT 39.8 3.7 1198 222.8
 EP_P_1L 41.8 2.3 1428 146.6

Figure 11 shows that epoxy-based silane treatment leads to a modification of the failure
mechanism.
Fibers 2020, 8, 48 12 of 14
The untreated sample, due to the poor adhesion between CFRP and PA12-CR substrates,
experienced skin-core delamination immediately after the fracture of the printed substrate (Figure
11a). On the
Figure contrary,
11 shows thatEP_P_1L treated
epoxy-based samples,
silane having
treatment antoimproved
leads skin-core
a modification of theadhesion, experienced
failure mechanism.
a pure CFRP skin tensile failure (Figure 11b).

Figure Failure
11. 11.
Figure modes
Failure of sandwiches:
modes (a) delamination
of sandwiches: failure failure
(a) delamination of UT specimen and (b) tensile
of UT specimen and (b)failure
tensile
of EP_P_1L
failure of specimen.
EP_P_1L specimen.

The untreated sample, due to the poor adhesion between CFRP and PA12-CR substrates,
4. Conclusions
experienced skin-core delamination immediately after the fracture of the printed substrate (Figure 11a).
The present paper aims to present one of the possibilities of how the adhesive properties
On the contrary, EP_P_1L treated samples, having an improved skin-core adhesion, experienced a
between
pure thermoplastic
CFRP skin tensile failure(i.e.,(Figure
Polyamide
11b). 12) and thermoset (i.e., epoxy) based composites, both
reinforced with carbon fibers, can be improved. To this scope, two different silane coupling agents,
(3-Aminopropyl)trimethoxysilane (AM) and (3-Glycidyloxypropyl)trimethoxysilane (EP), were applied,
4. Conclusions
through the spray deposition method, on the polyamide 12 based substrate to create a reactive layer
The present paper aims to present one of the possibilities of how the adhesive properties
between the adherents. Furthermore, two different deposition methods that is, 1 Layer and 2 Layers
between thermoplastic (i.e., Polyamide 12) and thermoset (i.e., epoxy) based composites, both
as well as two coupling agents curing conditions namely Total and Partial Cure were also performed.
reinforced with carbon fibers, can be improved. To this scope, two different silane coupling agents,
Through tests of Contact Angle, Fourier Transform Infrared spectroscopy (FTIR), Mode I
(3-Aminopropyl)trimethoxysilane (AM) and (3-Glycidyloxypropyl)trimethoxysilane (EP), were applied,
delamination tests (DCB) and three-point bending tests has been verified that:
through the spray deposition method, on the polyamide 12 based substrate to create a reactive layer

between The
theepoxy-based silane (EP) two
adherents. Furthermore, allows to obtain
different better adhesion
deposition improvement
methods that in comparison
is, 1 Layer and 2 Layers as to
amine-based silane (AM). In particular, (3-Glycidyloxypropyl)trimethoxysilane
well as two coupling agents curing conditions namely Total and Partial Cure were also performed. (EP) leads to
Through improvements,
tests of ContactinAngle,
comparison
FouriertoTransform
the reference sample,
Infrared of about(FTIR),
spectroscopy 288% and
Mode197% for the GIC init
I delamination
and G IC prop , respectively;
tests (DCB) and three-point bending tests has been verified that:
 The application of the second layer of silane coupling agent is not effective for improving the
• The epoxy-based
adhesion. silane (EP)ofallows
The deposition a singletolayer
obtain bettertoadhesion
allows improvementcoating
create a homogeneous in comparison
layer; to
amine-based silane (AM). In particular, (3-Glycidyloxypropyl)trimethoxysilane (EP) leads to
improvements, in comparison to the reference sample, of about 288% and 197% for the GIC init
and GIC prop , respectively;
• The application of the second layer of silane coupling agent is not effective for improving the
adhesion. The deposition of a single layer allows to create a homogeneous coating layer;
Fibers 2020, 8, 48 13 of 14

• The Partial Cure has beneficial effect on the adhesion only in the case of epoxy-based silane,
whereas it is not useful for amine-based silane, due to the insufficient conditions for reaction
between AM silane and epoxy in this curing conditions (i.e., 80 ◦ C for 10 min before the hand
lay-up phase of CFRP substrate);
• The application of the epoxy-based silane treatment led to an improvement of the adhesion
between CFRP skin and printed PA12-CR core, thus leading to the improvement of the overall
flexural response of the sandwich structures (i.e., +5% and +20% in the flexural strength and in
the equivalent flexural modulus, respectively);
• The enhanced adhesive properties lead to an improvement of the skin-core adhesion, thus resulting
in the change of the failure mode from delamination between PA12-CR substrate and CFRP to
tensile failure of the CFRP skin.

Author Contributions: Conceptualization, V.F. and A.V.; methodology, V.F. and A.V.; validation, V.F.; formal
analysis, A.V.; investigation, V.O., C.S. and D.B.; data curation, V.O., C.S. and D.B.; writing—original draft
preparation, V.O.; writing—review and editing, C.S., D.B. and V.F.; supervision, A.V. All authors have read and
agreed to the published version of the manuscript.
Funding: This research received no external funding.
Acknowledgments: Authors would thank OCORE s.r.l., for providing thermoplastic based reinforced composites
and carbon fabrics.
Conflicts of Interest: The authors declare no conflict of interest.

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