polymers

Article
Enhancing the Mechanical and Thermal Properties of
Epoxy Resin via Blending with
Thermoplastic Polysulfone
Zeyu Sun 1,2,3 , Lei Xu 1,2 , Zhengguo Chen 1,2 , Yuhao Wang 1,2 , Rogers Tusiime 1,2 ,
Chao Cheng 1,2 , Shuai Zhou 1,2 , Yong Liu 1,2 , Muhuo Yu 1,2,3 and Hui Zhang 1,2,3, *
1 State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials
Science and Engineering, Donghua University, Shanghai 201620, China; [email protected] (Z.S.);
[email protected] (L.X.); [email protected] (Z.C.); [email protected] (Y.W.);
[email protected] (R.T.); [email protected] (C.C.); [email protected] (S.Z.);
[email protected] (Y.L.); [email protected] (M.Y.)
2 Shanghai Key Laboratory of Lightweight Structural Composites, Shanghai 201620, China
3 Center for Civil Aviation Composites, Shanghai 201620, China
* Correspondence: [email protected]; Tel.: +86-1368-179-2738




Received: 13 February 2019; Accepted: 5 March 2019; Published: 11 March 2019


Abstract: Efficient enhancement of the toughness of epoxy resins has been a bottleneck for expanding
their suitability for advanced applications. Here, polysulfone (PSF) was adopted to toughen and
modify the epoxy. The influences of PSF on the mechanical and thermal properties of the epoxy resin
were systematically studied by optical microscopy, Fourier transform infrared spectrometer (FT-IR),
differential scanning calorimetry (DSC), thermogravimetric analyzer (TG), dynamic mechanical
thermal analyzer (DMA), mechanical tests and scanning electron microscope (SEM). The dissolution
experimental results showed that PSF presents a good compatibility with the epoxy resin and could
be well dissolved under controlled conditions. The introduction of PSF was found to promote the
curing reaction of the epoxy resin without participating in the curing reaction and changing the curing
mechanism as revealed by the FT-IR and DSC studies. The mechanical properties of PSF/epoxy
resin blends showed that the fracture toughness and impact strength were significantly improved,
which could be attributed to the bicontinuous phase structure of PSF/epoxy blends. Representative
phase structures resulted from the reaction induced phase separation process were clearly observed in
the PSF/epoxy blends during the curing process of epoxy resin, which presented dispersed particles,
bicontinuous and phase inverted structures with the increase of the PSF content. Our work further
confirmed that the thermal stability of the PSF/epoxy blends was slightly increased compared to that
of the pure epoxy resin, mainly due to the good heat resistance of the PSF component.

Keywords: polysulfone; epoxy resin; toughness; reaction induced phase separation

1. Introduction
Epoxy resins (EP) have been widely used in construction, machinery, aerospace and other
related fields due to their low cost, excellent bonding performance, outstanding mechanical
properties, easy processability, dimensional stability, superior thermal and chemical resistance [1–3].
Unfortunately, the high crosslinking density, large internal stress, poor brittleness and poor impact
resistance of the epoxy resins after curing has greatly limited their application in some high-tech fields.
Therefore, improving the toughness of epoxy resins has been recognized as a crucial way to expand
their applications and has attracted much attention in recent years [3–5].

Polymers 2019, 11, 461; doi:10.3390/polym11030461 www.mdpi.com/journal/polymers

Polymers 2019, 11, 461 2 of 17

Toughness modification of epoxy resins by rubber elastomer [6,7] is very effective but it reduces
the mechanical properties and thermal stability of the epoxy resin. Toughening of the epoxy resin
with a small amount of liquid crystal polymer [8,9] achieves a worthy toughness effect and makes the
composite material have both the high orientation of the liquid crystal and the 3-dimensional network
structure of the epoxy resin. However, thermotropic liquid crystal polymers have a relatively high
melting point, thus difficult to process and have poor compatibility with epoxy. When nanoparticles are
employed to modify the toughness of epoxy resins [10–12], the nanoparticles transfer the external force
to the surroundings and induce microcracks in the EP matrix hence achieving purposeful toughening.
Nonetheless, the price of nanoparticle materials is generally expensive, and many nanoparticles are
prone to agglomeration during the modification process. Thermoplastic materials do not only have
good toughness but also possess high modulus and good heat resistance. They therefore would
significantly improve the toughness of the epoxy resin when applied as toughening agents. Compared
to other methods, involving thermoplastic resins would improve the toughness of the EP without
reducing its modulus and heat resistance [12]. Meanwhile, this can also give the epoxy some new
properties, such as low water absorption and high thermomechanical performances [13], an area that
has become a research hotspot in recent years.
The frequently-used thermoplastics consist of poly(ether-sulfone) (PES) [14–17], poly(ether-ether-
ketone) (PEEK) [18,19], polyetherimide (PEI) [20–22], polysulfone (PSF) [23–27] and so forth. Due to a
similar molecular structure, PSF has good compatibility with bisphenol A type epoxy resin. Moreover,
many studies have shown that PSF modified epoxy resin can achieve a good toughness effect without
reduction in the thermal stability. Chen et al. [23] found that addition of 5%wt PSF into epoxy could
improve the impact strength while the flexural strength and flexural modulus do not change much.
Hu et al. [24] reported that adding PSF into epoxy could significantly improve fracture toughness
but might reduce the flexural strength. Other studies have carried out in-depth analyses on the
morphology and mechanical properties of PSF/epoxy blends [24,25]. When toughening epoxy resin,
different content of PSF form different phase structures which is associated with the toughening
effect. Oyanguren et al. [25] studied the phase structure of PSF/epoxy resin materials and found the
fracture toughness reached its maximum value of 1.10 MPam1/2 , which was an improvement of nearly
69.23% when the phase structure of the PSF/DGEBA composites with PSF content of 10 wt% was
bi-continuous. Tanaka et al. [26] synthesized polysulphones with cross-linkable pendant vinyl benzyl
groups (PSF-VB) as a toughening agent for epoxy resin. Their results indicated that when 10 wt%
PSF-VB was added, the fracture toughness of the PSF/epoxy resin composites was increased by 65%
while the mechanical properties of composites were not lost. The epoxy resin and PSF-VB were found
to be entangled in the presence of dicumyl peroxide (DCP), whereas the phase structure appeared
double continuous. However, much effort has been put on the relationship between phase structures
and mechanical properties of the cured epoxy resin. Rather, fewer reports stress the influence of PSF
on the curing behavior of the epoxy resin, consequently on the change of the phase structure and the
mechanical properties after curing.
In this work, PSF resin was used as a toughening agent in the modification of bisphenol A
epoxy resin. The effect of PSF on the curing behavior of the epoxy resin at different heating rates
was systematically studied and the curing mechanism of the epoxy resin in the presence of PSF was
analyzed. The results indicated that the addition of PSF promoted the curing reaction of epoxy resin
but does not change its curing mechanism. The toughening of the resultant resin by PSF and the
effective improvement in the mechanical properties can be ascribed to the absorption of external energy
by different phase separation structures formed by curing induction of the epoxy resin. Relatedly,
our studies also revealed that the addition of PSF also improved the heat resistance of the epoxy resin.
Polymers 2019, 11, 461 3 of 17

2. Materials and Methods

2.1. Materials
Bisphenol A epoxy resin (E51) with epoxy equivalent 182–192 g/mol, was obtained from Baling
Petrochemical Co. Ltd. (Yueyang, China). Polysulfone (PSF) (Udel P1700), with a particle size of
ca. 80 µm, from the Acomo Co., Ltd. (Chicago, IL, USA). The curing agent was Dietheyltoluene
diamine(DETDA) (Ethacure 100), supplied by the Albemarle Corporation (Carolina, NC, USA). 1,
4-epoxy-butane (THF) was purchased from Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China)
and used as solvent.

2.2. Preparation of the PSF/Epoxy Composites

The PSF powder was first dissolved in the epoxy resin at 130 ◦ C until the mixed system was
completely clarified. Then an appropriate amount of curing agent was added into the mixed system,
after which the solution was cooled to 80 ◦ C, followed by mechanical stirring until a uniform mix
was obtained. Finally, the mixed system was vacuum defoamed in an oven at 80 ◦ C until there were
no more visible bubbles. The mixed system was transferred to a mold coated with release agent
and placed in an oven at 120 ◦ C for 4 h. After cooling and demolding, cured product of PSF/epoxy
composite were obtained. According to the different weight ratios of PSF to epoxy resin, the samples
were recorded as 0, 5, 10, 15 and 20 phr, respectively.

2.3. Characterizations
Compared to other methods, involving thermoplastic resins would improve the toughness of the
EP without reducing its modulus and heat resistance [12]. Meanwhile, this can also give the epoxy
some new properties such as low water absorption and high thermomechanical performances [13],
an area that has become a research hotspot in recent years. Rectangular specimens of 36 mm × 13 mm
× 3 mm were prepared for DMA analysis, on a single cantilever mode at a frequency of 1 Hz heating
from 40 to 250 ◦ C.
The tensile strength and flexural strength/modulus tests were performed following ASTM
D638-10 and ASTM D5045-14 Standards. For a typical Flexural strength and modulus test, specimen
dimensions were 127 mm × 12.7 mm × 3.2 mm. The fracture toughness of the PSF/epoxy blends
was determined by a single-edge notched 3-point flexural test (SENB) according to ASTM D5045-14.
Rectangular specimens of 44 mm × 10 mm × 5 mm with a 5 mm length notch were prepared for
measurement. A WANCE 203 B-TS micro computer controlled electromechanical universal testing
system was applied to perform these measurements. Izod pendulum impact tests were performed
based on ASTM D256-10 standard under impact speed and impact energy of 3.5 m/s and 5.5 J,
respectively. The sample sizes was 63.5 × 12.7 × 6.35 mm and each sample possessed a constant notch.
The fractured surfaces of the cured PSF/epoxy blends with and without etching were analyzed in
detail with a Hitachi SU8010 Scanning Electron Microscope (SEM, Tokyo, Japan) system. The surfaces
were etched with 1,4-epoxybutane (THF) for 24 h at room temperature to remove the thermoplastic
phase. Following that the specimens were dried in vacuum overnight at 100 ◦ C.
The curing kinetics of epoxy resin and epoxy/PSF blends were measured using a NETZSCH
204F1 Differential Scanning Calorimetry (DSC, NETZSCH, Bavarian, Germany). The specimens were
heated under a flow of nitrogen (50 mL/min−1 ) from 20 to 350 ◦ C at a heating rate of 5, 10, 15 and 20
◦ C/min, respectively. The glass transition temperatures (Tg) of the PSF/epoxy blends were explored

by a TA Q20 differential scanning calorimetry (DSC) instruments from 40 to 250 ◦ C at a heating rate
of 10 ◦ C/min under a nitrogen flow (50 mL/min−1 ). Thermogravimetric analyzer (TGA, NETZSCH,
Bavarian, Germany) was used to determine the thermal stability of PSF/epoxy. The samples were
carried out at 20 ◦ C/min from room temperature up to 900 ◦ C in nitrogen atmosphere.
Polymers 2019, 11, 461 4 of 17

3. Results and Discussion

3.1. The Solubility of PSF in Epoxy Resin

In order to study the compatibility of epoxy resin and PSF, we observed the dissolution process
of PSF powder in epoxy resin and the results are shown in Figure 1. It was found that the PSF was
completely dissolved in 15 min at 120 ◦ C. Furthermore, the solution was transparent in general with
no visual heterogeneity. These phenomena suggest that PSF has a good solubility in epoxy resin even
within
Polymers a relatively
2019, 11, x FORshort
PEERtime.
REVIEW 4 of 15

Figure 1.
Figure The dissolution
1. The dissolution process
process ofof polysulfone
polysulfone (PSF)
(PSF) powder
powder in in epoxy
epoxy resin
resin at 120 ◦°C,
at 120 C, followed
followed by
by
optical microscopy
optical microscopy (a)
(a) 00 min,
min, (b)
(b) 33 min,
min, (c)
(c) 66 min,
min, (d)
(d) 99 min,
min, (e)
(e) 12
12 min,
min, (f)
(f) 15
15 min.
min.

3.2. Curing Kinetics of PSF/Epoxy Resin Blends

3.2. Curing Kinetics of PSF/Epoxy Resin Blends
It is well known that the curing behaviors of epoxy resin are essentially related to the properties of
It is well known that the curing behaviors of epoxy resin are essentially related to the properties
the cured materials. Thus, the effect of PSF on the curing behaviors of epoxy resin was analyzed by DSC
of the cured materials. Thus, the effect of PSF on the curing behaviors of epoxy resin was analyzed
as shown in Figure 2. It is clearly evident that the curing of the epoxy resin is an exothermic process no
by DSC as shown in Figure 2. It is clearly evident that the curing of the epoxy resin is an exothermic
matter with or without the existence of PSF. As the heating rate in a PSF/epoxy resin system increased,
process no matter with or without the existence of PSF. As the heating rate in a PSF/epoxy resin
the value of the initial curing temperatures (Ti ), the final curing temperature(Tf ) and the highest curing
system increased, the value of the initial curing temperatures (Ti), the final curing temperature(Tf)
temperature rate (Tp ) gradually increased. Moreover, the shape of the exothermic peak gradually
and the highest curing temperature rate (Tp) gradually increased. Moreover, the shape of the
became sharp. A similar trend was observed for PSF/epoxy systems with different PSF content,
exothermic peak gradually became sharp. A similar trend was observed for PSF/epoxy systems with
which can be ascribed to the steady improvement of thermal inertia, with an increase in the heating
different PSF content, which can be ascribed to the steady improvement of thermal inertia, with an
rate. In addition, the values of Ti , Tf and Tp reduced with the increase in PSF content, which suggests
increase in the heating rate. In addition, the values of Ti, Tf and Tp reduced with the increase in PSF
that adding PSF into epoxy resin promotes the curing reaction by reducing the activation energy. This
content, which suggests that adding PSF into epoxy resin promotes the curing reaction by reducing
result can be traced to the gradual enhancement of the exothermic lag of the curing reaction on the
the activation energy. This result can be traced to the gradual enhancement of the exothermic lag of
addition of PSF.
the curing reaction on the addition of PSF.
Apparently, the activation energy (∆E) and reaction order (n) are crucial kinetic parameters in
the curing process and thus the theoretical basis to control the curing process of epoxy resin. ∆E
directly reflects the degree of difficulty of the curing reaction, which can be calculated according to
the Kissinger method [28] as shown in Equation (2). The reaction order (n) corresponding to the
complexity of the reaction can be used to estimate the curing reaction mechanism. It is quantified
according to the Crane equation [29], disclosed in Equation (3).

d(ln(1) β /Tp2 ∆E

=− (1)
d(1 /Tp R
(a) (b) (c)
Polymers 2019, 11, 461 5 of 17

d(ln β) ∆E

= −( +2T p ) (2)
d(1 /Tp nR
where β is the heating rate(◦ C/min), Tp is the peak temperature, R is the ideal gas constant which is
8.314 J/(mol·K), E is the activation energy (kJ/mol) and n is the reaction order.

Polymers 2019, 11, x FOR PEER REVIEW 5 of 15

Figure 2. Differential scanning calorimetry (DSC) curves of PSF/epoxy systems at different heating
rates of the sample (a) 0 phr, (b) 5 phr, (c) 10 phr, (d) 15 phr and (e) 20 phr.
(a) (b) (c)
Apparently, the activation energy (ΔE) and reaction order (n) are crucial kinetic parameters in
the curing process and thus the theoretical basis to control the curing process of epoxy resin. ΔE
directly reflects the degree of difficulty of the curing reaction, which can be calculated according to
the Kissinger method [28] as shown in Equation (2). The reaction order (n) corresponding to the
complexity of the reaction can be used to estimate the curing reaction mechanism. It is quantified
according to the Crane equation [29], disclosed in Equation (3).
d( ln(1) β⁄T2p ) ΔE
=- (1)
d( 1⁄Tp ) R
(d) (e)
d( ln β ) ΔE
= -( +2T ) (2)
d( 1⁄T
Figure 2. Differential scanning calorimetry (DSC)
p) n R of pPSF/epoxy systems at different heating
curves
rates of the sample (a) 0 phr, (b) 5 phr, (c) 10 phr, (d) 15 phr and (e) 20 phr.
Where β is the heating rate(°C/min), Tp is the peak temperature, R is the ideal gas constant which is
8.314According
J/(mol·K), to E isthe
theKissinger
activationandenergy (kJ/mol)
the Crane and n is
equations, the
the reaction
peak order. (Tp ) of the PSF/epoxy
temperature
According to the Kissinger and the Crane equations, the peak
system with different PSF content at different heating rates β was substituted temperature (Tpinto
) of the
the PSF/epoxy
Equations
system
(2) andwith(3). different PSFthe
content 2
ln(β/Tatp different heating
were rates β was
as asubstituted
function ofinto the Equations
After that, ) and lnβ plotted 1000/T p , shown(2)
in
and
Figure(3).3a,b,
Afterrespectively.
that, the ln(β/T p2) slope
The and lnβof were
each plotted as awas
fitted line function of 1000/T
obtained p, shown
by linear in Figure
regression 3a,b,
method.
respectively.
The complex The correlation each fittedR2line
slope ofcoefficients wastwo
of the obtained by linear
linear fittings all regression method.
reached 0.99 or higher,Theindicating
complex
correlation
an excellentcoefficients
fitting. R of the two linear fittings all reached 0.99 or higher, indicating an excellent
2

fitting.

(a) (b)
Figure
Figure 3.3. Plots
Plotsfor
fordetermining
determiningthe theactivation energy
activation of of
energy thethe
curing reaction
curing by by
reaction Kissinger equation
Kissinger (a)
equation
ln(β/T p2) vs.
(a) ln(β/T 21000/T
) vs. , (b)
1000/T
p lnβ
, vs.
(b) 1000/T
lnβ vs. .
1000/T
p .
p p p

Based on the Equations (2) and (3), the calculated values of ΔE and n are summarized in Table 1.
It was found that the value of ΔE decreased first and then increased with the growing PSF content,
nonetheless, always smaller than that of a pure epoxy resin. Thus, one might speculate that the added
PSF promoted the curing reaction of epoxy resin and the promoting effect increased first and then
Polymers 2019, 11, 461 6 of 17

Based on the Equations (2) and (3), the calculated values of ∆E and n are summarized in Table 1.
It was found that the value of ∆E decreased first and then increased with the growing PSF content,
nonetheless, always smaller than that of a pure epoxy resin. Thus, one might speculate that the added
PSF promoted the curing reaction of epoxy resin and the promoting effect increased first and then
decreased with the increase in PSF content. This might be assocaited with the molecuar structure of
polysulfone (both ends have hydroxyl groups) [30], which might have played a catalytic role in the
curing reaction of the epoxy resin. At relatively lower PSF content, the amount of hydroxyl groups in
the blend system increases with increasing PSF content, thus promoting the curing reaction of epoxy
resin. This is respective with the decrease of the apparent activation energy. However, when the
PSF content exceeded 15 phr, the viscosity of the whole system increased significantly. Consequently,
the steric effects of the PSF macromolecules increase the difficulties of the epoxy resin contacting with
the curing agent, to some extent hindering their curing reaction. Moreover, as evident from Table 1,
the reaction order (n) of each system was stable between 0.87 and 0.88, demonstrating that the addition
of PSF does not change the curing reaction mechanism of epoxy resin.

Table 1. Cure kinetic parameters and R2 of PSF/epoxy systems with different PSF content.

Sample 0 phr 5 phr 10 phr 15 phr 20 phr

∆E (kJ/mol) 58.969 57.009 57.997 54.730 55.043
R1 2 0.995 0.998 0.998 0.998 0.999
n 0.871 0.878 0.88 0.874 0.875
R2 2 0.996 0.999 0.999 0.998 0.999

3.3. The Chemical Structures of the PSF/Epoxy Resin Blends

Various outstanding properties of epoxy resin were obtained by their fully crosslinked structures.
Here, in order to elucidate the influence of PSF on the chemical structures of the cured epoxy resin,
FT-IR analysis was conducted on the PSF, the neat epoxy resin before curing and the cured PSF/epoxy
resin blends as given in Figure 4. The peak of 915 cm−1 is the characteristic absorption of epoxy group
while the 1623 cm−1 is the N–H characteristic peak in the curing agent E100 [27]. Both 915 and 1623
cm−1 vanished totally in the PSF/epoxy blends after curing indicating the completion pf the cure
reaction. The peak at 1154 cm−1 is the stretching vibration peak of the sulfone group [27] and it could
be detected after the curing reaction of epoxy resin which means that the addition of PSF would not
actively participate the curing reaction of the epoxy resin.
epoxy resin, FT-IR analysis was conducted on the PSF, the neat epoxy resin before curing and the
cured PSF/epoxy resin blends as given in Figure 4. The peak of 915 cm−1 is the characteristic
absorption of epoxy group while the 1623 cm−1 is the N–H characteristic peak in the curing agent E100
[27]. Both 915 and 1623 cm−1 vanished totally in the PSF/epoxy blends after curing indicating the
completion pf the cure reaction. The peak at 1154 cm−1 is the stretching vibration peak of the sulfone
Polymers 2019, 11, 461 7 of 17
group [27] and it could be detected after the curing reaction of epoxy resin which means that the
addition of PSF would not actively participate the curing reaction of the epoxy resin.

Figure 4. Fourier
Figure Fouriertransform
transforminfrared (FT-IR)
infrared spectrum
(FT-IR) of epoxy
spectrum resin (E51)
of epoxy before
resin (E51)curing,
beforethecuring,
PSF/epoxy
the
blends after
PSF/epoxy curingafter
blends withcuring
different
withPSF contentPSF
different andcontent
PSF. and PSF.

3.4. Dynamic Mechanical Thermal Analysis of the PSF/Epoxy Blends

3.4. Dynamic Mechanical Thermal Analysis of the PSF/Epoxy Blends
The dynamic mechanical thermal analysis gave more insight into their viscoelastic properties
The dynamic mechanical thermal analysis gave more insight into their viscoelastic properties as
as well as the morphologies of PSF/epoxy blends. The variations of the storage modulus of the
well as the morphologies of PSF/epoxy blends. The variations of the storage modulus of the
PSF/epoxy blends after curing with temperatures is shown in Figure 5a. It is found that the growing
PSF/epoxy blends after curing with temperatures is shown in Figure 5a. It is found that the growing
content of PSF in the blends elevated the storage modulus though it always decreased below that of
content of PSF in the blends elevated the storage modulus though it always decreased below that of
pure epoxy resin. The tanδ values of the epoxy/PSF blends are plotted against the temperature in
pure epoxy resin. The tanδ values of the epoxy/PSF blends are plotted against the temperature in
Figure 5b. The results present only one peak, implying one Tg of the blends. We also notice that the
Figure 5b. The results present only one peak, implying one Tg of the blends. We also notice that the
Tg of PSF/epoxy blends is smaller than that of pure epoxy resin and it increases with the increase in
Tg of PSF/epoxy blends is smaller than that of pure epoxy resin and it increases with the increase in
PSF content. This can be explained in terms of the added PSF reducing the curing degree of the epoxy
PSF content. This can be explained in terms of the added PSF reducing the curing degree of the epoxy
resin, which results in a decrease in the storage modulus and Tg of PSF/epoxy blends [31]. Both the
resin, which results in a decrease in the storage modulus and Tg of PSF/epoxy blends [31]. Both the
storage modulus and Tg of PSF/epoxy blends increasing with the increase in the PSF content may
storage modulus and Tg of PSF/epoxy blends increasing with the increase in the PSF content may
have been caused by the higher storage modulus Tg of PSF.
have been
Polymers caused
2019, by PEER
11, x FOR the higher
REVIEWstorage modulus Tg of PSF. 7 of 15

(a) (b)
Figure 5. Curves of (a) storage
Figure 5. modulus E’
storage modulus E’ and
and (b)
(b) tan
tan δδwith
withtemperatures
temperaturesofofPSF/epoxy
PSF/epoxy cured
cured
products
products containing
containing different
differentPSF
PSF content.
content.

3.5. Mechanical Properties of PSF/Epoxy Blends

In this work, PSF was also used to improve the mechanical and themal properties of epxoy resin.
Therefore, the mechanical propeties including the tensile properties, flexural properties, fracture
toughness and impact strength of the cured cured PSF/epoxy blends were illustrated against the
varation of PSF content carefully. Figure 6 presents the tensile strength and modulus of cured
PSF/epoxy blends. Unfortuately, both the tensile strength and modulus reduced with the addtion of
 (a) (b)
Polymers 2019, 11, 461 8 of 17
Figure 5. Curves of (a) storage modulus E’ and (b) tan δ with temperatures of PSF/epoxy cured
products containing different PSF content.
3.5. Mechanical Properties of PSF/Epoxy Blends
3.5. Mechanical Properties of PSF/Epoxy Blends
In this work, PSF was also used to improve the mechanical and themal properties of epxoy
In this
resin. work, PSF
Therefore, was
the also used to
mechanical improveincluding
propeties the mechanical and themal
the tensile properties
properties, of epxoy
flexural resin.
properties,
Therefore, the mechanical propeties including the tensile properties, flexural properties,
fracture toughness and impact strength of the cured cured PSF/epoxy blends were illustrated against fracture
toughness
the varation andofimpact strength
PSF content of the cured
carefully. Figurecured PSF/epoxy
6 presents blends
the tensile were illustrated
strength and modulus against the
of cured
varation
PSF/epoxy of PSF content
blends. carefully. both
Unfortuately, Figurethe6tensile
presents the tensile
strength strengthreduced
and modulus and moduluswith the ofaddtion
cured
PSF/epoxy
of PSF. The blends.
tensileUnfortuately, both the
strength decreased tensile strength
obviously while theandtensile
modulus reduced
modulus keptwith the addtion
a little of
stable with
PSF. Thegrowth
the the tensile strength
of the PSFdecreased obviously
content. This can bewhile the tensile
ascribed modulus kept
to the insufficient a little stable
interfacial adhesionwithofthe
the
the growth ofparticles
polysulfone the PSFformed
content.byThis canseparation
phase be ascribed to the
to the insufficient
epoxy interfacial
resin matrix, which adhesion of the
results in weaker
polysulfone
load transfer particles formed
capability [32]. by phase separation to the epoxy resin matrix, which results in weaker
load transfer capability [32].

(a) (b)
Thetensile
Figure6.6.The
Figure tensilestrength
strength(a)
(a)and
andTensile
Tensilemodulus
modulus(b)
(b)ofofcured
curedPSF/epoxy
PSF/epoxyblends.
blends.

Theflexural
The flexuralstrength
strengthand andflexural
flexuralmodulus
modulusofofPSF/epoxy
PSF/epoxyblendsblendsisisshown
shownininFigure
Figure7.7.InIncontrast
contrast
to the tensile properties, the addition of PSF did not reduce but improved the flexural
to the tensile properties, the addition of PSF did not reduce but improved the flexural properties properties of of
the
epoxy
the epoxyresin. It It
resin. is isclear
clearthat
thatboth
boththe
theflexural
flexuralstrength
strengthandand modulus
modulus of of the cured PSF/epoxy
the cured PSF/epoxyblends
blends
grew slightly with increasing PSF ratio. However, the flexural modulus peaked with 15 phr ofofPSF
grew slightly with increasing PSF ratio. However, the flexural modulus peaked with 15 phr PSF
while expanding PSF content to 20 phr reduced the flexural modulus although still higher than thatof
while expanding PSF content to 20 phr reduced the flexural modulus although still higher than that
ofthe
thepure
pure
Polymers epoxy
2019,epoxy resin.
resin.
11, x FOR PEER REVIEW 8 of 15

(a) (b)
Figure
Figure7.7.The
Theflexural
flexuralstrength
strength (a)
(a) and
and modulus
modulus (b)
(b) of
of PSF/epoxy
PSF/epoxyblends
blendsas
asaafunction
functionof
ofPSF
PSF content.
content.
The critical stress intensity factor (KIC ) was adopted to inquire into the mechanical interfacial
properties or thestress
The critical fracture toughness
intensity of the
factor (KICepoxy/PSF blends.
) was adopted The value
to inquire KICmechanical
intoofthe was determined based
interfacial
on the ASTM
properties D5045-14
or the fracturestandard
toughnessas of
follows:
the epoxy/PSF blends. The value of KIC was determined based
on the ASTM D5045-14 standard as follows:  
P
K IC = 𝑃 1/2 f ( x ) (3)
𝐾𝐼𝐶 = ( Bw1⁄2 ) 𝑓(𝑥) (3)
𝐵𝑤
where P is the loading weight, B is the thickness of the specimen, W is the depth(width) of the
specimen, a is the crack length, x is the ratio of the crack length to the depth of specimen, a/W and f(x)
is the calibration factor which is represented as follows:
2
 Figure 7. The flexural strength (a) and modulus (b) of PSF/epoxy blends as a function of PSF
content.

The critical stress intensity factor (KIC) was adopted to inquire into the mechanical interfacial
properties or the fracture toughness of the epoxy/PSF blends. The value of KIC was determined based
Polymers 2019, 11, 461 9 of 17
on the ASTM D5045-14 standard as follows:
𝑃
where P is the loading weight, B is the thickness 𝐾𝐼𝐶 = of ( the1⁄specimen,
) 𝑓(𝑥) W is the depth(width) of the specimen, (3)
𝐵𝑤 2
a is the crack length, x is the ratio of the crack length to the depth of specimen, a/W and f(x) is the
where P is the loading weight, B is the thickness of the specimen, W is the depth(width) of the
calibration factor which is represented as follows:
specimen, a is the crack length, x is the ratio of the crack length to the depth of specimen, a/W and f(x)
is the calibration factor which is represented as follows: 2


1/2 1.99 − x (1 − x ) 2.15 − 3.93x + 2.7x
f ( x ) = 6x (4)
1⁄2
[1.99 − 𝑥(1 (1−−𝑥)(2.15 )3/2 + 2.7𝑥 2 )]
2x )(1 −−x3.93𝑥
𝑓(𝑥) = 6𝑥 (4)
(1 − 2𝑥)(1 − 𝑥)3⁄2
The impact of the PSF content on the fracture toughness in terms of critical stress intensity factor
(KIC ) The impact
of the of the PSF
PSF/epoxy blendscontent
wason the fracture
explored toughness
carefully in termsinofFigure
as displayed critical8.stress intensityall
Interestingly, factor
the
(K ) of the PSF/epoxy blends was explored carefully as displayed in Figure
blend samples showed up an extraodinary improvement of the fracture toughness relative to the neat
IC 8. Interestingly, all the
blend samples
epoxy showed up
resin. Increasing thean PSFextraodinary improvement
content is conducive of the fracture
to enhance toughness
the fracture relative
toughness to the
while theneat
KIC
epoxy resin. Increasing the PSF content is conducive to enhance the fracture
of the blend containing 15 phr PSF indicates a maximum fracture toughness. Still increasing the PSFtoughness while the KIC
of the blend
content to 20 containing
phr leads to15a phr PSF smaller
slightly indicates a maximum
KIC than that offracture toughness.
15 phr PES, Still increasing
nevertheless, the PSF
still displayed a
distinguished enhancement in fracture toughness in comparison with the pure epoxy resin (0 phr). a
content to 20 phr leads to a slightly smaller K IC than that of 15 phr PES, nevertheless, still displayed
distinguished enhancement in fracture toughness in comparison with the pure epoxy resin (0 phr).

Figure
Figure 8. Thefracture
8. The fracturetoughness
toughness
inin terms
terms of critical
of critical stress
stress intensity
intensity factor
factor (KIC) (K
ofIC ) of
the the PSF/epoxy
PSF/epoxy blends
blends as a function of PSF content.
as a function of PSF content.

Pursuing
Pursuing the the toughening
toughening effect
effect of
of PSF
PSF on
on epoxy
epoxy resin
resin further,
further, the
the Izod
Izod pendulum
pendulum impact
impact tests
tests
were conducted on the cured epoxy/PSF blends. As illustrated by Figure 9, a
were conducted on the cured epoxy/PSF blends. As illustrated by Figure 9, a remarkable increase inremarkable increase
in impact
impact strength
strength was
was detected
detected forthe
for theblends
blendswith
withrespect
respecttotothat
thatofof the
the pure
pure epoxy
epoxy resin.
resin. The
The best
best
impact strength was obtained at a PSF content of 15 phr with the highest value
impact strength was obtained at a PSF content of 15 phr with the highest value 38.2 J/m, which was38.2 J/m, which was
an
an improvement
Polymers of PEER
2019, 11, x FOR
improvement of ca. 65.3%
ca. 65.3%
REVIEW comparedtotothe
compared theneat
neatepoxy
epoxyresin.
resin.When
When thethe
PSF PSF content
content reached
9 of20
reached 15
20 phr, the impact strength of the PSF/epoxy blends decreased slightly compared to that of the blends
phr, the impact
containing 20 phr strength
PSF butofremained
the PSF/epoxy blends than
much higher decreased
valuesslightly compared
of the other samples.to that of the blends
containing 20 phr PSF but remained much higher than values of the other samples.

Figure 9. The
Figure 9. The Impact
Impact strength
strength of
of the
the PSF/epoxy blends as
PSF/epoxy blends as aa function
function of
of PSF
PSF content.
content.

3.6. Phase Structures of the PSF/epoxy Blends

In order to understand the relationship between the mechanical propeties and the internal
structures, the fractured surfaces of the PSF/epoxy blends obtained from the mechanical tests were
observed by SEM as shown in Figure 10. The micrograph of the 0 phr PSF/epoxy blend (Figure 10a)
present a smooth fractured surface, demonstrating the brittle property of the pure epoxy resin. In
contrast, with the introduction of PSF into the epoxy resin, the morphologies of the fractured surfaces
Polymers 2019, 11, 461 10 of 17

Figure 9. The Impact strength of the PSF/epoxy blends as a function of PSF content.
3.6. Phase Structures of the PSF/epoxy Blends
3.6. Phase Structures of the PSF/epoxy Blends
In order to understand the relationship between the mechanical propeties and the internal
In order
structures, thetofractured
understand the relationship
surfaces of the PSF/epoxybetween the obtained
blends mechanical frompropeties and thetests
the mechanical internal
were
structures,
observed by theSEM
fractured surfaces
as shown of the
in Figure 10.PSF/epoxy blends of
The micrograph obtained
the 0 phr from the mechanical
PSF/epoxy tests were
blend (Figure 10a)
observed
present aby SEM asfractured
smooth shown insurface,
Figure 10. The micrograph
demonstrating the of the 0 property
brittle phr PSF/epoxy
of theblend
pure (Figure 10a)
epoxy resin.
present a smooth
In contrast, with fractured surface,ofdemonstrating
the introduction the brittle
PSF into the epoxy property
resin, of the pure of
the morphologies epoxy resin. In
the fractured
contrast,
surfaces with
of thetheblends
introduction
changed of from
PSF into the epoxy
smooth resin,
to rather the morphologies
rough and increasing of the
thefractured surfaces
PSF content from
of the20blends
5 to changed from
phr increased smooth todegree.
the roughness rather rough and increasing
Additionally, uniform theparticle
PSF content from was
extraction 5 to 20 phr
clearly
increased the roughness
distinguishable from thedegree. Additionally,
cross sections of the uniform
fracturedparticle
surfaceextraction
as indicatedwasbyclearly distinguishable
Figure 10b. With the
from the of
increase cross
PSFsections
content,ofthe
theparticles
fractured surface
became as indicated
more and larger byasFigure 10b. With
illustrated the increase
by Figure 10c. Whenof PSF
the
content, the particles
blend consisted of 15 became
phr PSF more and larger
and more, as illustrated
crack pinning by Figure
was easily found10c. When
besides thethe blend consisted
particles extraction
of
as15 phr PSF
evident andFigure
from more, 10d,e
crack while
pinning thewas easily found
interfaces betweenbesides the particles
the particles and extraction
the matrixas evident
were well
from FigureIn10d,e
combined. whilethe
addition, thepolysulfone
interfaces between the particles
phases partially and the
contacted with matrix were and
each other welltended
combined. In
to form
addition, the polysulfone
a continuous phase whenphases the PSFpartially
contentcontacted with each
was increased to 20 other
phr. and tended to form a continuous
phase when the PSF content was increased to 20 phr.

Figure
Figure 10.
10. Scanning
Scanning electron
electron microscope
microscope (SEM)
(SEM) images
images of
of the
the fractured
fractured surfaces
surfaces of the PSF/epoxy
PSF/epoxy
blends:
blends:(a)
(a)00phr,
phr,(b)
(b) 55 phr,
phr, (c)
(c) 10
10 phr,
phr, (d)15 phr and (e) 20 phr.

PSF can be well

PSF welldissolved
dissolvedininTetrahydrofuran
Tetrahydrofuran (THF). Thus,
(THF). thethe
Thus, PSF/epoxy
PSF/epoxyblends werewere
blends etched with
etched
THF to
with THFremove the PSFthe
to remove phase
PSFgiving
phasemore insights
giving more into the phase
insights structures
into the phase of the two components.
structures of the two
The resulting morphologies were observed by SEM and displayed in Figure 11. Only
components. The resulting morphologies were observed by SEM and displayed in Figure 11. Only a smooth surfacea
appeared in the sample of pure epoxy (0 phr) demonstrating only one epoxy resin phase
smooth surface appeared in the sample of pure epoxy (0 phr) demonstrating only one epoxy resin as indicated by
Figureas
phase 11a. However,
indicated bynumerous cavities
Figure 11a. can benumerous
However, distinctly observed in the
cavities can bemicrographs of Figurein
distinctly observed 11b–d
the
which are the spaces occupied by PSF domains before etching. Furthermore, the
micrographs of Figure 11b–d which are the spaces occupied by PSF domains before etching. numbers and sizes of
the cavities also grew with the increase in the PSF content. Therefore, the cured PSF/epoxy blends
manifested a two-phased morphology in which the PSF domains were uniformly distributed in a
continuous epoxy resin matrix. However, when the PSF content was elevated to 20 phr, the cavities
were bonded to each other revealing a continuous phase of PSF. Nonetheless, both the continuous
and disconnected epoxy particles were surrounded by a continuous phase of PSF, representing a
combination of the bicontinuous phase and the phase inversion morphology as depicted by Figure 11e.
the system is no longer thermodynamically compatible. Consequently, the PSF/epoxy blends resin
systems cannot keep stable and a viscoelastic phase-separation process for PSF gradually occurs and
evolves. The evolution of the phase separation process of the PSF/epoxy blends is mainly through the
spinodal decomposition mechanism controlled by the growing molecular weight of the epoxy resin
networks [34]. Depending on the content of the PSF component in the resin system, the phase
Polymers 2019, 11, 461 11 of 17
structure of the resin system may be uniformly dispersed particles, a bicontinuous phase structure or
an oppositely rotated structure.

Figure
Figure11. SEMmicrographs
11.SEM micrographsofofthe
thefractured
fracturedsurfaces
surfacesof
ofPSF/epoxy
PSF/epoxyblends
blendsetched
etchedwith
withTHF;
THF;(a)
(a)00phr,
phr,
(b)55 phr,
(b) phr, (c)
(c) 10
10 phr,
phr, (d) 15 phr, (e) 20 phr.
phr.

The representative
Considering phase structures
the variations of the of PSF/epoxyproperties
mechanical blends could be ascribed
of the PSF/epoxy to the reaction
blends, it induced
can be
phase separation during curing process of epoxy resin which is related
contemplated that the dispersion of the thermoplastic structures within the epoxy resin formedto the content of PSF within
by
the resin
phase system plays
separation [33]. Before or at the
an important beginning
role of the curing
in the performance reaction,
of the epoxy the whole
resin. The resin scheme
decrease of theis
generally
tensile homogeneous.
strength and modulus While
withthe
thecuring reaction
introduction of proceeds, the molecular
the PSF content, arrayed in weight
Figureof6a,b
the might
epoxy
resin
be thegoes upofrapidly,
result leading
the tensile to thebeing
property formation
mainlyof influenced
the networkbystructures. With the
the interaction development
between the epoxy of
the curing reaction, the compatibility of the PSF resin in the epoxy resin gradually
networks, the crosslinking densities and the defects of the resin [35]. The addition of the PSF in fact deteriorates and
the system
reduces the is no longer thermodynamically
crosslinking densities and also draws compatible. Consequently,
some defects to the epoxythe resin
PSF/epoxy blends
no matter resin
the kind
systems
of cannot keep
phase structure, stable
thus and athe
reducing viscoelastic phase-separation process for PSF gradually occurs and
tensile properties.
evolves. The evolution of the phase separation
In contrast, the uniformly dispersed PSF particles processinofthe the PSF/epoxy
epoxy blendsasisshown
resin matrix mainlyinthrough
Figure
the spinodal decomposition mechanism controlled by the growing
10b,c exerted a corresponding improvement in the flexural strength and modulus, fracture molecular weight oftoughness
the epoxy
resin
and thenetworks [34]. Depending
impact strength on in
as depicted theFigures
content7–9.of the
ThePSF component
flexural property in is
the resin system,
critically the phase
associated with
structure of the resin system may be uniformly dispersed particles, a bicontinuous
the intensive rigidity of network chains of the resins. With the increase of the PSF content, this phase structure or
an oppositely
intensive rotated
rigidity andstructure.
internal friction of the networks increase, primarily contributed by PSF
identical particles [36]. Herein, theofflexural
Considering the variations the mechanical
strength andproperties
modulus of of
thethe
PSF/epoxy
samples was blends, it can be
also elevated.
contemplated that the dispersion of the thermoplastic structures within the
The enhancement of the impact strength and fracture toughness can be attributed to the fact that PSF epoxy resin formed by
phase separation
particles effectively plays an important
inhibit the crack rolepropagation
in the performance
in the ofepoxy
the epoxy
resin.resin.
Types Theof
decrease of the
toughening
tensile strength and modulus with the introduction of the PSF content, arrayed in Figure 6a,b might
be the result of the tensile property being mainly influenced by the interaction between the epoxy
networks, the crosslinking densities and the defects of the resin [35]. The addition of the PSF in fact
reduces the crosslinking densities and also draws some defects to the epoxy resin no matter the kind
of phase structure, thus reducing the tensile properties.
In contrast, the uniformly dispersed PSF particles in the epoxy resin matrix as shown in
Figure 10b,c exerted a corresponding improvement in the flexural strength and modulus, fracture
toughness and the impact strength as depicted in Figures 7–9. The flexural property is critically
associated with the intensive rigidity of network chains of the resins. With the increase of the PSF
content, this intensive rigidity and internal friction of the networks increase, primarily contributed
by PSF identical particles [36]. Herein, the flexural strength and modulus of the samples was also
elevated. The enhancement of the impact strength and fracture toughness can be attributed to the fact
that PSF particles effectively inhibit the crack propagation in the epoxy resin. Types of toughening
mechanisms like crack path deflection or plastic deformation of the resin matrix can also be adopted to
account for the increase of the toughness of the PSF/epoxy blends [19,37].
As illustrated by Figure 10d, with the formation of a bicontinuous structure, an optimal flexural
property, impact strength and fracture toughness can be obtained. The significant enhancement
of these mechanical properties is regarded to be associated with the bicontinuous structure of the
Polymers 2019, 11, x FOR PEER REVIEW 11 of 15

mechanisms like crack path deflection or plastic deformation of the resin matrix can also be adopted
to account for the increase of the toughness of the PSF/epoxy blends [19,37].
Polymers 2019, 11, 461 12 of 17
As illustrated by Figure 10d, with the formation of a bicontinuous structure, an optimal flexural
property, impact strength and fracture toughness can be obtained. The significant enhancement of
these mechanical
PSF/epoxy matrix properties
taking advantageis regarded
of theto be associated
excellent with
interfacial the bicontinuous
adhesion to absorb the structure of the
crack energy
PSF/epoxy matrix taking advantage of the excellent interfacial adhesion
and to shear yield against the crack [38]. Moreover, the crack cannot progress through the continuousto absorb the crack energy
and phase
PSF to shear yield against
embedded in thetheepoxy
crack matrix,
[38]. Moreover,
resulting the
incrack cannot progress
a dominant increase in through the continuous
the toughness of the
PSF phase embedded in the epoxy matrix, resulting in a dominant
blends with a bicontinuous phase structure. However, the addition of PSF meanwhile augmented increase in the toughness of the
the
blends with
viscosity a bicontinuous
of the blended resin, phase structure.
particularly whenHowever,
the PSFthe addition
content of PSF15meanwhile
exceeded augmented
phr. The matrix the
of 20 phr
viscosity of the blended resin, particularly when the PSF content exceeded
PSF corresponding to a phase inversion structure led to lower flexural properties, impact strength 15 phr. The matrix of 20
phr PSF corresponding to a phase inversion structure led to lower flexural
and toughness compared to those of the sample containing 15 phr PSF, which might be due to the properties, impact strength
and toughness
epoxy resin in thecompared to those
phase inverted of the sample
structure containing 15and
being discontinuous phrlacking
PSF, which might becrosslinked
a continuous due to the
epoxy resin
network [39]. in the phase inverted structure being discontinuous and lacking a continuous crosslinked
network [39].
3.7. Glass Transition Temperature of PSF/Epoxy Cured Product
3.7. Glass Transition Temperature of PSF/Epoxy Cured Product
In order to study the impact of the PSF on the thermal properties of the epoxy resin, DSC was
used Into order
analyze to the
studyglassthetransition
impact oftemperature
the PSF on (Tg)the thermal propertiescured
of the PSF/epoxy of theproducts
epoxy resin,
with DSC was
different
usedcontents.
PSF to analyzeAs theshown
glass transition
in Figure temperature
12, the addition (Tg) of the
PSFPSF/epoxy cured products
did not increase with different
but decreased the Tg
PSF
of thecontents. As shown
epoxy resin. ThisinmightFigurebe12,duethetoaddition of PSF did notchain
the macromolecular increase but decreased
of PSF hinderingthe theTg of the
contact
epoxy resin.
between This might
the epoxy resin be and due
thetocuring
the macromolecular
agent, thus lowering chain ofthePSF hindering
curing degreethe of contact
the epoxy between
resin.
the epoxy resin and the curing agent, thus lowering the curing degree
Meanwhile, the addition of PSF raises the viscosity of the system, which results in an incompleteof the epoxy resin. Meanwhile,
the addition
curing reactionof[31,40].
PSF raises the viscosity
Therefore, the Tgof ofthe
thesystem,
PSF/epoxy which results inwas
composites an incomplete
lower than thatcuring reaction
of the pure
[31,40].resin.
epoxy Therefore,
However, the when
Tg of the PSFPSF/epoxy
contentcomposites
increased, the was Tglower
of thethan that of the
PSF/epoxy pure epoxy
composites resin.
increased
However,
as a whole.when the PSFthis
We attribute content
to theincreased, the Tg of theinherently
fact that polysulfone PSF/epoxy composites
possesses increased
a higher as a whole.
Tg, which could
We attribute
have offset itsthis to the fact
influence on that polysulfone
the curing degreeinherently
of the epoxypossesses
resin. aThehigher Tg, of
results which could
the DSC haveare
curve offset
in
its influence
good agreement on with
the curing
those from degree
the ofDMAthe results.
epoxy resin. The results of the DSC curve are in good
agreement with those from the DMA results.

Figure 12.DSC
Figure12. DSCcurves
curvesof
ofPSF/epoxy cured products
PSF/epoxy cured products with
with different
different PSF
PSF contents.
contents.

3.8. Thermogravimetric Analysis

3.8. Thermogravimetric Analysis
The thermal stabilities of the cured PSF/epoxy blends were analysed by thermogravimetric
The thermal stabilities of the cured PSF/epoxy blends were analysed by thermogravimetric
analysis and the corresponding thermograms are presented in Figure 13. Two weight loss stage
analysis and the corresponding thermograms are presented in Figure 13. Two weight loss stage
patterns can be clearly distinguished from the TG curves of the PSF/epoxy blends in contrast to the one
patterns can be clearly distinguished from the TG curves of the PSF/epoxy blends in contrast to the
weight loss stage pattern for pure epoxy resin. The first weight loss is mainly due to the decomposition
one weight loss stage pattern for pure epoxy resin. The first weight loss is mainly due to the
of the epoxy resin. The second weight loss stage can be ascribed to the inherent high heat resistance
decomposition of the epoxy resin. The second weight loss stage can be ascribed to the inherent high
properties of the PSF component. The initial and second decomposition temperature of the PSF/epoxy
heat resistance properties of the PSF component. The initial and second decomposition temperature
resin increased slightly with the increase of polysulfone content but the change range was not large.
of the PSF/epoxy resin increased slightly with the increase of polysulfone content but the change
We concluded that the addition of PSF did not reduce but effectively enhanced the heat resistance of
the epoxy resin system.
Polymers 2019, 11, x FOR PEER REVIEW 12 of 15
Polymers
Polymers 2019,
2019, 11, 11,
461x FOR PEER REVIEW 1217
13 of of 15
range was not large. We concluded that the addition of PSF did not reduce but effectively enhanced
therange
heat resistance of the
was not large. Weepoxy resin system.
concluded that the addition of PSF did not reduce but effectively enhanced
the heat resistance of the epoxy resin system.

Figure 13. Thermogravimetric

Figure 13. Thermogravimetric curves
curves of
of PSF/epoxy cured products
PSF/epoxy cured products with
with different
different PSF
PSF contents.
contents.
Figure 13. Thermogravimetric curves of PSF/epoxy cured products with different PSF contents.
In order to quantitatively determine the influence of PSF on the thermal stability of epoxy resin,
In order to quantitatively determine the influence of PSF on the thermal stability of epoxy resin,
thermal stability parameters such as initial decomposition temperature (IDT) and integrated program
thermalInstability
order toparameters
quantitativelysuchdetermine
as initial decomposition
the influence of temperature
PSF on the (IDT)
thermal andstability
integrated program
of epoxy resin,
decomposition temperature (IPDT) are calculated on the basis of TG curve, as shown in Figure 14. The
decomposition temperature
thermal stability parameters (IPDT)
such asareinitial
calculated on the basis
decomposition of TG curve,
temperature (IDT)asand
shown in Figure
integrated 14.
program
IPDT was determined from the TG curves according to Dolye’s equation [41]:
The IPDT was determined
decomposition temperature from(IPDT)
the TGare curves according
calculated on theto Dolye’s
basis of equation
TG curve, [41]:
as shown in Figure 14.
The IPDT was determined from the TG curves according to Dolye’s equation [41]:
IPDT= =A*K*
IPDT A*K*(T(Tf −
f −TTii) + Tii (5)
(5)
IPDT = A*K* (Tf − Ti) + Ti (5)
where A* is equal to the integral area, which consists of S1 and S2, divided by the total
where A* is equal to the integral area, which consists of S1 and S2, divided by the total rectangular
rectangular plotting area. K* isthe
the ratio of the smaller integral area,ofS2S1to and
the smaller rectangular
by thearea
plottingwhere A*isisthe
area. K* equal
ratioto integral
of the smaller area,
integral which
area, S2 consists
to the smaller S2, divided
rectangular area formed total
by
formed by S2 plotting
rectangular and S3.area.Ti isK* the
is initial
the experimental
ratio of the smaller temperature
integral and
area, S2 T
to is the
f the final rectangular
smaller experimental area
S2 and S3. Ti is the initial experimental temperature and Tf is the final experimental temperature. The
temperature.
formed by The
S2 and calculated
S3. Talong values of IPDT along with A*K* and other parameters
i is the initial experimental temperature and Tf is the final experimental from
calculated values of IPDT with A*K* and other parameters from thermogravimetric analysis
thermogravimetric
temperature. Theanalysis are summarized
calculated values of IPDT in Table 2. The
along addition
with A*K* ofand PSF other
slightlyparameters
enhanced the from
are summarized in Table 2. The addition of PSF slightly enhanced the IDT, IPDT, A*K* and Tmax of
IDT, IPDT, A*K* and Tanalysis
thermogravimetric max of the blends.
are This may
summarized inbe due 2.
Table to The
the high heat of
addition resistance of theenhanced
PSF slightly PSF itself,the
the blends. This may be due to the high heat resistance of the PSF itself, which improved the heat
which
IDT,improved
IPDT, A*K* theand
heat resistance
Tmax of the This
of the blends. PSF/epoxy
may beresindue [42].
to the high heat resistance of the PSF itself,
resistance of the PSF/epoxy resin [42].
which improved the heat resistance of the PSF/epoxy resin [42].

Figure 14. Doyle’s proposition for the calculation of the integrated program decomposition
Figure 14. Doyle’s proposition for the calculation of the integrated program decomposition temperature
Figure 14. Doyle’s proposition fortemperature (IPDT).
the calculation of the integrated program decomposition
(IPDT).
temperature (IPDT).
Table 2. Thermal stability parameters of polysulfone (PSF)/epoxy blends.
Table 2. Thermal stability parameters of polysulfone (PSF)/epoxy blends.
PSF Content IDT (°C) IPDT (°C) * * AK Tmax (°C)
PSF Content
0 phr IDT (°C)
386.2 IPDT
364.6 (°C) A*K*
0.370 Tmax (°C)
412.2
5 phr
0 phr 389.2
386.2 369.3
364.6 0.376
0.370 412.5
412.2
5 phr 389.2 369.3 0.376 412.5
Polymers 2019, 11, 461 14 of 17

Table 2. Thermal stability parameters of polysulfone (PSF)/epoxy blends.

PSF Content IDT (◦ C) IPDT (◦ C) A* K * T max (◦ C)

0 phr 386.2 364.6 0.370 412.2
5 phr 389.2 369.3 0.376 412.5
10 phr 392.3 373.5 0.381 414.2
15 phr 394.1 378.1 0.386 416.2
20 phr 395.9 379.4 0.388 418.4

4. Conclusions
In summary, PSF was employed in this work to improve the mechanical and thermal properties
of the epoxy resin. Specifically, the solubility of PSF in epoxy resin and the influence of PSF on the
curing process, the chemical structures, the mechanical properties, the phase structures, viscoelastic
properties and thermal performance of PSF/epoxy blends were investigated carefully. The dissolution
experiment indicated that PSF had good compatibility with the epoxy resin and could be well dissolved
into it to prepare the PSF/epoxy blends. The DSC results revealed that the addition of PSF does not
upset the curing mechanism but promoted the curing of the epoxy resin. The addition of PSF lowered
the reaction enthalpy thus promoted the curing process of the epoxy resin. In fact, PSF did not actively
participate in the curing reaction as illustrated by the FT-IR measurements.
The systematic studies of the mechanical properties of the PSF/epoxy blends illuminated that
the addition of PSF could significantly enhance the flexural properties, the fracture toughness and
impact strength of epoxy resin although it slightly reduced the tensile properties. The improvement of
the mechanical properties could be attributed to the representative phase structures resulting from
reaction induced phase separation, presenting dispersed particles, bicontinuous and phase inverted
structures mostly depending on the PSF content within the blends. The analysis of the results further
revealed that the bicontinuous phase morphology obtained during the curing process of the epoxy
resin most optimized the mechanical properties. Meanwhile, due to the high heat resistance of PSF
components, the thermal stability of the PSF/epoxy blends was also slightly increased compared to
that of the pure epoxy resin.
These findings present an interesting benchmark for further understanding the effects,
mechanisms and phenomena that surround the phase structure and curing behavior of PSF and
epoxy resins. Also, as an example of the modification strategies of epoxy resins, this work reveals
that treatment with PSF not only enhances the overall toughness but also maximizes other important
properties and tunes the resin for more sophisticated applications.

Author Contributions: Conceptualization, L.X., Y.L., M.Y. and H.Z.; Data curation, L.X., Z.C. and Y.W.; Formal
analysis, C.C.; Funding acquisition, H.Z.; Investigation, Z.S., R.T. and S.Z.; Methodology, Z.S., Z.C., S.Z. and Y.L.;
Supervision, M.Y. and H.Z.
Funding: This work was supported by National Natural Science Foundation of China (Grant No. 51803024),
“Fundamental Research Funds for the Central Universities” (Project No. 16D110623, 18D110622, 2232018A3-02,
KF1826), and” Shanghai Science and Technology Committee” (Project No. 17511102801 and 16DZ112140). Dr.
Zhang would like to appreciate the financial support of Shanghai Science and Technology Committee (No.
18DZ1101003).
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Kadhim, N.; Mei, Y.; Wang, Y.; Li, Y.; Meng, F.B.; Jiang, M.; Zhou, Z.W. Remarkable improvement in the
mechanical properties of epoxy composites achieved by a small amount of modified helical carbon nanotubes.
Polymers 2018, 10, 1103. [CrossRef]
2. Yang, X.T.; Guo, Y.Q.; Luo, X.; Zheng, N.; Ma, T.B.; Tan, J.J.; Li, C.M.; Zhang, Q.Y.; Gu, J.W. Self-healing,
recoverable epoxy elastomers and their composites with desirable thermal conductivities by incorporating
BN fillers via in-situ polymerization. Compos. Sci. Technol. 2018, 164, 59–64. [CrossRef]
Polymers 2019, 11, 461 15 of 17

3. Sun, Z.; Xiao, J.; Tao, L.; Wei, Y.; Wang, S.; Zhang, H.; Yu, M. Preparation of High-Performance Carbon
Fiber-Reinforced Epoxy Composites by Compression Resin Transfer Molding. Materials 2019, 12, e13.
[CrossRef] [PubMed]
4. Xu, Z.G.; Song, P.G.; Zhang, J.; Guo, Q.P.; Mai, Y.W. Epoxy nanocomposites simultaneously strengthened
and toughened by hybridization with graphene oxide and block ionomer. Compos. Sci. Technol. 2018, 168,
363–370. [CrossRef]
5. Cicala, G.; Recca, G.; Carciotto, S.; Restucca, C.L. Development of epoxy/hyperbranched blends for resin
transfer molding and vacuum assisted resin transfer molding applications: Effect of a reactive diluent.
Polym. Eng. Sci. 2009, 49, 577–584. [CrossRef]
6. Vijayan, P.P.; Puglia, D.; Vijayan, P.P.; Kenny, J.M.; Thomas, S. The role of clay modifier on cure
characteristics and properties of epoxy/clay/carboxyl terminated poly(butadiene-co-acrylonitrile) (CTBN)
hybrid. Mater. Technol. 2017, 32, 171–177. [CrossRef]
7. Zhou, L.; Fu, Y.W.; Yin, T.; Luo, Z.Y. Synergetic effect of epoxy resin and carboxylated nitrile rubber on
tribological and mechanical properties of soft paper-based friction materials. Tribol. Int. 2019, 129, 314–322.
[CrossRef]
8. Huang, Z.F.; Tan, S.T.; Wang, X.Y. Modification of an o-cresol formaldehyde epoxy resin by the thermotropic
liquid crystalline polymer. J. Appl. Polym. Sci. 2005, 97, 1626–1631. [CrossRef]
9. Zhang, B.L.; Tang, G.L.; Shi, K.Y.; You, Y.C.; Du, Z.J.; Huang, J.F. A study on the properties of epoxy resin
toughened by a liquid crystal-type oligomer. J. Appl. Polym. Sci. 1999, 77, 117–184. [CrossRef]
10. Miyagawa, H.; Mohanty, A.; Drzal, L.T.; Misra, M. Effect of clay and alumina-nanowhisker reinforcements
on the mechanical properties of nanocomposites from biobased epoxy: A comparative study. Ind. Eng.
Chem. Res. 2004, 43, 7001–7009. [CrossRef]
Polymers 2019, 11, 461 16 of 17

11. Mousavi, A.; Roghani-Mamaqani, H.; Salami-Kalajahi, M.; Shahi, S.; Abdollahi, A. Modification of graphene
with silica nanoparticles for use in hybrid network formation from epoxy, novolac, and epoxidized novolac
resins by sol-gel method: Investigation of thermal properties. Expess Polym. Lett. 2018, 12, 187–202.
[CrossRef]
12. Goyat, M.S.; Ray, S.; Ghosh, P.K. Innovative application of ultrasonic mixing to produce homogeneously
mixed nanoparticulate-epoxy composite of improved physical properties. Compos. Part A 2011, 42, 1421–1431.
[CrossRef]
13. Blanco, I.; Cicala, G.; Costa, M.; Recca, A. Development of an epoxy system characterized by low water
absorption and high thermomechanical performances. J. Appl. Polym. Sci. 2006, 100, 4880–4887. [CrossRef]
14. Cheng, X.L.; Wu, Q.; Morgan, S.E.; Wiggins, J.S. Morphologies and mechanical properties of polyethersulfone
modified epoxy blends through multifunctional epoxy composition. J. Appl. Polym. Sci. 2017, 134. [CrossRef]
15. Wang, F.Z.; Drzal, L.T. Development of stiff, tough and conductive composites by the addition of graphene
nanoplatelets to polyethersulfone/epoxy composites. Materials 2018, 11, 2137. [CrossRef] [PubMed]
16. Rosetti, Y.; Alcouffe, P.; Pascault, J.P.; Gerard, J.F.; Lortie, F. Polyether sulfone-based epoxy toughening: From
micro- to nano-phase separation via PES end-chain modification and process engineering. Materials. 2018,
10, 1960. [CrossRef] [PubMed]
17. Blanco, I.; Oliveri, L.; Cicala, G.; Recca, A. Effects of novel reactive toughening agent on thermal stability of
epoxy resin. J. Therm. Anal. Calorim. 2012, 108, 685–693. [CrossRef]
18. Francis, B.; Rao, V.L.; Ramaswamy, R.; Jose, S.; Thomas, S.; Raju, K. Morphology, viscoelastic properties and
mechanical behavior of epoxy resin modified with hydroxyl-terminated poly (ether-ether-ketone) oligomer
with pendent tert-butyl groups. Polym. Eng. Sci. 2005, 45, 1645–1654. [CrossRef]
19. Francis, B.; Thomas, S.; Jose, J.; Ramaswamy, R.; Rao, V.L. Hydroxyl terminated poly(ether-ether-ketone)
with pendent methyl group toughened epoxy resin: Miscibility, morphology and mechanical properties.
Polymer 2005, 46, 12372–12385. [CrossRef]
20. Zhang, J.; Xie, X.M. Influence of addition of silica particles on reaction-induced phase separation and
properties of epoxy/PEI blends. Compos. Part B 2011, 42, 2163–2169. [CrossRef]
21. Korokhin, R.A.; Solodilov, V.I.; Gorbatkina, Y.A.; Shapagin, A.V. Rheological and physicomechanical
properties of epoxy-polyetherimide compositions. Mech. Compos. Mater. 2015, 51, 313–320. [CrossRef]
22. Bonnaud, L.; Pascalut, J.P.; Sautereau, H.; Zhao, J.Q.; Jia, D.M. Use of reactive polyetherimide to modify
epoxy thermosets. I. Synthesis of an amino-grafted polyetherimide. Eur. Polym. J. 2004, 40, 2637–2643.
[CrossRef]
23. Chen, Z.C.; Tian, J.; Guo, J.H.; Xie, Z.Q.; Chu, F.Y. Study on the properties of the layered-structure in the
epoxy/polysulfone blends. Thermosetting Resin. 2018, 33, 15–18.
24. Jin, H.; Yang, B.Q.; Jin, F.L.; Park, S.J. Fracture toughness and surface morphology of polysulfone-modified
epoxy resin. J. Ind. Eng. Chem. 2015, 25, 9–11. [CrossRef]
25. Oyanguren, P.A.; Galante, M.J.; Andromaque, K.; Frontini, P.M.; Williams, R.J.J. Development of bicontinuous
morphologies in polysulfone epoxy blends. Polymer 1999, 40, 5249–5255. [CrossRef]
26. Tanaka, N.; Iijima, T.; Fukuda, W.; Tomoi, M. Synthesis and properties of interpenetrating polymer networks
composed of epoxy resins and polysulphones with cross-linkable pendant vinylbenzyl groups. Polym. Int.
1997, 42, 95–106. [CrossRef]
27. Zheng, N.; Sun, W.F.; Liu, H.Y.; Huang, Y.D.; Gao, J.F.; Mai, Y.W. Effects of carboxylated carbon nanotubes
on the phase separation behaviour and fracture-mechanical properties of an epoxy/polysulfone blend.
Compos. Sci. Technol. 2018, 59, 180–188. [CrossRef]
28. Kissinger, H.E. Reaction Kinetics in Differential Thermal Analysis. Anal. Chem. 1957, 29, 1702–1706.
[CrossRef]
29. Han, J.L.; Hsieh, K.H.; Chiu, W.Y. Kinetics of curing reaction of epoxide catalyzed by tertiary amine. J. Appl.
Polym. Sci. 2010, 50, 1099–1106. [CrossRef]
30. Yang, L.P.; Li, P.; Xue, Z.M. Cure kinetics of a TGDDM epoxy/DDS system modifide with polysulfone
nanofiber. Fiber Reinf. Plast. Compos. 2007, 5, 7–10.
31. Huang, P.; Zheng, S.X.; Huang, J.Y.; Guo, Q.P.; Zhu, W. Miscibility and mechanical properties of epoxy
resin/polysulfone blends. Polymer 1997, 38, 5565–5571. [CrossRef]
32. Zhang, Y.; Song, P.A.; Fu, S.Y.; Chen, F.H. Morphological structure and mechanical properties of epoxy/
polysulfone/cellulose nanofiber ternary nanocomposites. Compos. Sci. Technol. 2015, 115, 66–71. [CrossRef]
Polymers 2019, 11, 461 17 of 17

33. Yu, Y.F.; Wang, M.H.; Gan, W.J.; Tao, Q.S.; Li, S.J. Polymerization-induced viscoelastic phase separation in
polyethersulfone-modified epoxy systems. J. Phys. Chem. B 2004, 108, 6208–6215. [CrossRef] [PubMed]
34. Li, G.; Huang, Z.B.; Xin, C.L.; Li, P.; Jia, X.L.; Wang, B.H.; He, Y.D.; Ryu, S.; Yang, X.P. Morphology evolution
of polysulfone nanofibrous membranes toughened epoxy resin during reaction-induced phase separation.
Mater. Chem. Phys. 2009, 118, 398–404. [CrossRef]
35. Varley, R.J.; Hodgkin, J.H.; Simon, G.P. Toughening of a trifunctional epoxy system - Part VI. Structure
property relationships of the thermoplastic toughened system. Polymer 2001, 42, 3847–3858. [CrossRef]
36. Rajasekaran, R.; Karikalchozhan, C.; Alagar, M. Preparation and characterization of 3,3’-bis
(maleimidophenyl)pheny phosphine oxide (BMI)/polysulfone modified epoxy intercrosslinked matrices.
Polym. Compos. 2008, 29, 773–781. [CrossRef]
37. Li, Y.Q.; Gao, J.; Li, X.Y.; Xu, X.; Lu, S.R. High mechanical and thermal properties of epoxy composites with
liquid crystalline polyurethane modified graphene. Polymers 2018, 10, 485. [CrossRef]
38. Mimura, K.; Ito, H.; Fujioka, H. Improvement of thermal and mechanical properties by control of
morphologies in PES-modified epoxy resins. Polymer 2000, 41, 4451–4459. [CrossRef]
39. Jiang, M.Q.; Liu, Y.; Cheng, C.; Zhou, J.L.; Liu, B.H.; Yu, M.H.; Zhang, H. Enhanced mechanical and
thermal properties of monocomponent high performance epoxy resin by blending with hydroxyl terminated
polyethersulfone. Polym. Test. 2018, 69, 302–309. [CrossRef]
40. Rajasekaran, R.; Alagar, M. Mechanical properties of bismaleimides modified polysulfone epoxy matrices.
Int. J. Polym. Mater. 2007, 56, 911–927. [CrossRef]
41. Doyle, C.D. Estimating thermal stability of experimental polymers by empirical thermogravimetric analysis.
Anal. Chem. 1961, 33, 77–79. [CrossRef]
42. Park, S.J.; Kim, H.C. Thermal stability and toughening of epoxy resin with polysulfone resin. J. Polym. Sci.
Pol. Phys. 2001, 39, 121–128. [CrossRef]

© 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).