polymers

Article
Crystal Structure and Mechanical Properties of
Uniaxially Stretched PA612/SiO2 Films
Yichao Wu 1 , Anmin Huang 2 , Shuhong Fan 1 , Yuejun Liu 1, * and Xiaochao Liu 1, *
1 Key Laboratory of Advanced Packaging Materials and Technology of Hunan Province,
Hunan University of Technology, Zhuzhou, Hunan 412008, China; cliffwuther@163.com (Y.W.);
f1s1h1@163.com (S.F.)
2 Zhuzhou Times New Material Technology Co. Ltd., Hunan Zhuzhou 412008, China;
huanganmin@csrzic.com
* Correspondence: yjliu_2005@126.com (Y.L.); xcliu_2014@163.com (X.L.)




Received: 4 February 2020; Accepted: 18 March 2020; Published: 23 March 2020


Abstract: Stretching has a significant effect on the microstructure and ultimate performance of
semi-crystalline polymers. To investigate the effect of stretching on structure and mechanical properties
of uniaxial stretched PA612/SiO2 , PA612 and PA612/SiO2 films were prepared at four temperatures
close to the glass transition temperature at various strain. The samples were characterized by a
transmission electron microscope (TEM), wide-angle X-ray diffractometer (WAXD), Two-dimensional
wide-angle X-ray Scattering (2D-WAXS), differential scanning calorimeter (DSC), dynamic mechanical
analyzer (DMA), and stretching tests. The results showed that the α phase was the dominant phase
in PA612 casting film, no obvious γ phase was observed, while both stretching and the presence of
SiO2 can induce the generation of α phase and improve the crystallinity of PA612. Crystals were
oriented along the stretching direction and the b axis was parallel to the equatorial direction after
stretching. The interplanar spacing of (010/110) decreased with the increasing stretching temperature
and expanded with the increasing strain, while stretching temperature and strain present negligible
effect on the interplanar spacing of (100). The grain size increased with the stretching temperature
while decreased with strain. The presence of SiO2 led to reduce the yield stress and the stress drop
beyond yielding of the composite. Uniaxial stretching gave rise to a significant improvement in the
fracture stress and the glass transition temperature.

Keywords: crystal structure; mechanical properties; uniaxial stretching; polyamide 612

1. Introduction
Due to the exploitation of petroleum, the development and application of biobased or
semi-biobased polymers which are ideal substitutes of petroleum-based polymers have been a
hot research topic. Nylon 612 (PA612) is a semi-biobased material with excellent comprehensive
performance. Its raw material, dodecanedioic acid, can be obtained from vegetable oil derivatives and
the biobased content in Nylon 612 can reach up to 66% [1]. Meanwhile, PA612 exhibits advantages in
low moisture sensitivity, high flexibility, and ductility over short-chain nylons (e.g., PA6, PA46) and
superior mechanical strength compared with long-chain nylons (e.g., PA1012, PA1212). Therefore,
PA612 can be applied in various fields, including automobile manufacturing, aerospace engineering
and electronic appliances [2,3]. PA612 films exhibits great potential as a packaging material in virtue of
its low moisture absorption, good dimensional stability, and high mechanical strength.
The ultimate properties of polymers is governed by the microstructure such as crystal structure,
crystal orientation and crystallinity, which is significantly affected by external conditions, such as
low-intensity γ radiation, temperature gradient, and stretching field. During γ radiation, a part of

Polymers 2020, 12, 711; doi:10.3390/polym12030711 www.mdpi.com/journal/polymers

Polymers 2020, 12, 711 2 of 13

molecular chains was broken which impassion that low molecular weight polymers were generated
resulting in reorientation of molecular chains in the amorphous zone and increased crystallinity [4–6].
Temperature slope crystallization is another way of inducing the orientation of the molecular chain,
in which the melt is induced to crystallize in the lower temperature direction by the temperature
difference between both sides of the sample [7]. The crystal orientation and conditions for positive
and negative spherulites in PA612 during temperature slope crystallization had been investigated by
Yoshida [8]. To apply a stress field is an effective approach to induce crystal orientation and crystal
transition during stretching. Wang reported a thorough study of the crystal structure of PA612/PA1012
composite and its crystal transition during stretching [9–11]. The Brill transition of α crystal of PA1012
in composite to γ crystal was observed during heating, while stretching was mainly responsible for the
induction of γ crystal of PA1012. However, the crystal transition of PA612 was not observed during
heating due to the Brill transition temperature of PA612 is close to its melting temperature [12].
Stretching not only affects crystallization and crystal orientation of nylons, but also their
macroscopic properties [13–15]. Liu prepared uniaxial and biaxial stretched PA6-66/MMT composite
films [16]. After stretching, the crystallinity of composite films was enhanced and the transition of β
phase to α phase was observed. The mechanical strength of composite films is highly improved and it
is mainly affected by the stretching ratio. Uniaxial and biaxial stretching led to decreased transmittance
and increased haze in the PA6-66/MMT films and the thermal shrinkage of the films increased with
increasing stretching ratio.
Stretching is commonly observed in film fabrication process (e.g., blowing, casting, and biaxial
stretching). During stretching process the molecular chains of semi-crystalline polymers prefer to
orient along the stretching direction and the transition of spherulites to highly oriented shish-kebab
structure was observed [10]. In this case, the crystallinity of semi-crystalline polymers increases, and
the stretching-induced crystal orientation [17] and crystal transition [18,19], which are two key factors
that remarkably affect the mechanical performance of materials [20]. Hitherto, the reports regarding
the crystallization behavior of PA612 is rather limited. Moreover, to the best of our knowledge, the
stretching-induced crystallization, and the structure-property relationships of PA612 films has not been
systematically reported, which could be a sever hindrance for the application of PA612 films.
The modification with nanoparticle is an effective approach to improve the ultimate properties
of polymers. In virtue of their small sizes and high specific areas, nanoparticles can be used as
nucleators to induce crystallization of polymers and enhancing their performance. For instance, the
amino-modified Al2 O3 flakes have been convinced to effectively improve the strength, abrasion, and
toughness of PA612. The high content nano-TiO2 can induce the formation of γ crystals and increase
the melting point of PA612 [21]. Nanoscale SiO2 is also an important particle to significantly enhance
the tensile strength and impact strength of polymers. Serving as a nucleator, SiO2 can enhance the
stretching strength and storage modulus, and increase decomposition temperature and glass transition
temperature [22]. The recent reports demonstrated that SiO2 induced the generation of γ crystals, thus
enhancing the crystallinity of PA6 and reducing the grain size. It was also observed that by addition of
less than 3 wt.% SiO2 , the impact and bending strength of PA6 can be simultaneously improved [23,24].
To date, the incorporation of SiO2 into PA612 matrix has not been investigated, which is yet significant
for the enhancement of macro-properties of PA612.
In this work, nano-SiO2 was incorporated into PA612 by melt blending to fabricate nanocomposites,
and the PA612 nanocomposites were melt casted into films, followed by uniaxial stretching at various
parameters. The effects of SiO2 and the stretching process on the morphology, crystallization behavior,
the crystal orientation of PA612 films were investigated in detail, and furthermore the mechanical
properties of the stretched films were studied to shed light on the processing-structure-property
relationships of the PA612 nanocomposites.
Polymers 2020, 12, 711 3 of 13

2. Materials and Methods

2.1. Materials
PA612 (Zytel 151L NC010) was purchased from Dupont Co. (DE, USA). Nano-SiO2 modified by
KH550 with the particle size of 30 nm was supplied by HongSheng Co. (Zhejiang, China).

2.2. Preparation of the PA612/SiO2 Composite and Film

SiO2 and PA612 were dried in a vacuum oven at 80 ◦ C for 4 h, after which the composite were
pre-mixed using a high-speed mixer for 5 min. The PA612/SiO2 composites were prepared via melting
compounding using a twin-screw extruder with a screw speed of 165 rpm. The temperature profile
ranges from 210 ◦ C to 240 ◦ C. The neat PA612 experienced the same extrusion procedure for comparison.
Then the films were prepared by a casting extruder with the temperature profile ranges from 240 ◦ C to
260 ◦ C, and the thickness of the film was controlled to be ca. 0.12 mm. Composite films with different
SiO2 content (0 wt.%, 3 wt.%) are assigned as S0 and S3, respectively.

2.3. Preparation of Uniaxially Stretched Films

According to ISO 527, the casting films were cut into dumbbell-shaped samples with the length
of 120 mm and width of 6 mm using a punching machine. The films were then uniaxially stretched
by a universal testing machine equipped with a heater. During the experiment, different stretching
ratios were selected to perform the stretching process at four temperatures of 30 ◦ C, 80 ◦ C, 120 ◦ C,
and 160 ◦ C. The films were stretched at a speed of 50 mm/min after preheated for 5 min in stretching
temperature and then quenched to room temperature.

2.4. Transmission Electron Microscopy (TEM)

PA612/SiO2 composite films were sliced with an ultra-thin microtome after embedded with epoxy
resin. The sheet was placed on a copper grid for observing on JEOL 1230 (SANYO, Osaka, Japan) with
a voltage of 90 KV.

2.5. Differential Scanning Calorimetry (DSC)

Q20 instrument (TA Instruments Co, Delaware, USA) was employed to carry out the thermal
analysis. The sample was heated from 25 ◦ C to 250 ◦ C under a nitrogen atmosphere with the heating
rate of 10 ◦ C/min. The crystallinity (Xc) of the sample is calculated by the following formula:
h i
Xc = ∆Hf / (1 − ϕ)·∆H0f (1)

where Xc is the crystallinity, ϕ is the content of SiO2 , ∆Hf is the melting enthalpy, ∆H0f is the melting
enthalpy when PA612 is completely crystallized, ∆H0f of PA612 is 258 J/g according to the report [21].

2.6. Wide-Angle X-Ray Diffraction (WAXD)

WAXD measurements were carried on the Rigaku Ultimate IV X-ray diffractometer (Rigaku,
Tokyo, Japan) with Cu Kα radiation (λ = 0.154 nm). The tests were under reflection mode with a range
of 5◦ –40◦ and a scanning rate of 4◦ /min. The interplanar spacing d and the grain size Lhlk are calculated
by Equations (2) and (3), respectively:
d = λ/2sinθ (2)

Lhlk = (Kα ·λ)/(β·cosθ) (3)

where d is the interplanar spacing, λ is the wavelength of the Cu Kα radiation (0.154 nm), θ is half of
the diffraction angle, Lhlk is the average grain size perpendicular to the hlk crystal plane, Kα is the
grain size constant (0.89), β is the full width at half maximum.
Polymers 2020, 12, 711 4 of 13

2.7. Two-Dimensional Wide-Angle X-Ray Scattering (2D-WAXS)

2D-WAXS measurements were carried out on a Xeuss 2.0 system (Xenocs SA, Sassenage, France)
with Cu Kα radiation. The detector was set perpendicular to the film surface with a distance of
183.71 mm and an exposure time of 5 min. All 2D WAXS patterns were corrected by the Fraser method
to compensate the detection of a flat-plat detector.
Polymers 2020, 12, x FOR PEER REVIEW 4 of 13
2.8. Dynamic Mechanical Thermal Analysis (DMA)
The dynamic
The mechanical
dynamicmechanical analysis
analysis waswas conducted
conducted usingusing a DMA242C
a DMA242C dynamicdynamic
mechanicalmechanical
analyzer
analyzer
(TA (TA Instruments
Instruments Co, Delaware,
Co, Delaware, USA) at USA) at a frequency
a frequency of 2 Hzof 2 Hza with
with heatinga heating
rate ofrate of 3 °C/min
3 ◦ C/min from
from◦ C
−20 −20
to°C120to◦120
C in°Ctheintensile
the tensile
mode.mode.
The The
glassglass transition
transition temperature
temperature (Tg ) (T g) was determined from
was determined from the
the peak
peak of loss
of loss factor
factor (tanδ)(tanδ) vs. temperature
vs. temperature curves.
curves.

2.9. Tensile
2.9. Testing
Tensile Testing
The uniaxially
The uniaxially stretched
stretched films
films were
were tested
tested by
by an
an electromechanical
electromechanical universal
universal testing
testing machine
machine
(Wance testing machine Co, Shenzhen, China) in the tensile direction at room temperature
(Wance testing machine Co, Shenzhen, China) in the tensile direction at room temperature of of 25
25 ◦°C
C
with aa tensile
with tensile rate
rate of
of 50
50 mm/min.
mm/min.

3. Results

3.1. Morphology of
3.1. Morphology of SiO
SiO22 in
in Films
Films
The
The TEMTEM graphs
graphs of
of PA612/SiO composite films
PA612/SiO2 composite films with
with different
different stretching
stretching ratios are shown
ratios are shown inin
Figure 1. It can be clearly observed that the SiO particles are liable to agglomerate in the
Figure 1. It can be clearly observed that the 2SiO2 particles are liable to agglomerate in the PA612 PA612 matrix.
Notably, compared
matrix. Notably, with the unstretched
compared films (ε = films
with the unstretched 0), the(εagglomerated SiO2 particles
= 0), the agglomerated SiO2inparticles
the filmsinwith
the
strain of 2 begin
films with straintoof
move alongtothe
2 begin stretching
move along direction due todirection
the stretching the stretching-induced orientation of the
due to the stretching-induced
molecular
orientationchains.
of the As a result,chains.
molecular the SiOAs
2 particles
a result,slip
theand
SiOtransform
2 particles into
slip aand
beaded morphology.
transform into a

Figure 1.
Figure 1. TEM
TEM graphs
graphs of
of the
the PA612/SiO
PA612/SiO22 films
films at
at the
the strain
strain of
of (a)
(a) εε == 00 and
and (b)
(b) εε =
= 2.
2.

3.2. Crystallization Behavior

3.2. Crystallization Behavior of
of Uniaxial
Uniaxial Stretched
Stretched PA612
PA612 and
and PA612/SiO
PA612/SiO22Films
Films
Figure 2 illustrates the primary heating DSC curve of PA612 before and after stretching, and the
corresponding data are collected in Table 1. 1. As shown in Figure 2a, a wide broad broad recrystallization
recrystallization
peak in 190–210 ◦°C C was found for each unstretched
unstretched films, which could be attributed to the incomplete
crystallization
crystallization ofofnylon
nyloncrystals
crystalsdue due to the
to the films
films quenching
quenching on the oncold
the chill
coldroll
chill roll during
during film
film casting
casting
process.process. In addition,
In addition, this peak thisis peak
moreisintense
more intense
for thefor theannealed
film film annealed at high
at high temperature.
temperature. The
The crystallization of nylon films was facilitated and the crystal lamellae were thickened
crystallization of nylon films was facilitated and the crystal lamellae were thickened during high during
high temperature
temperature annealing
annealing [25]. [25]. However,
However, thisthis
peakpeak is absent
is absent forfor thestretched
the stretchedfilms.
films. This
This could
could be
attributed to the strain-induced crystallization
crystallization of the films. Additionally,
Additionally, the crystallinity
crystallinity of PA612
was reduced after heat treatment at different temperatures, which is consistent with PA66, it may be
attributed to the rupture of ordered structures caused by the recombination of molecular molecular chains
chains [26].
[26].
As shown in Figure 2b, the melting point of PA612 raises as the increasing of stretching temperatures.
This may be attributed to the fact that high temperatures favor the movements of molecular chains.
As a result, crystal growth rate and crystallization degree are higher than those in the lower
temperature.
Polymers 2020, 12, 711 5 of 13

As shown in Figure 2b, the melting point of PA612 raises as the increasing of stretching temperatures.
This may be attributed to the fact that high temperatures favor the movements of molecular chains. As a
result, crystal growth rate and crystallization degree are higher than those in the lower temperature.
Polymers 2020, 12, x FOR PEER REVIEW 5 of 13

Figure 2. The DSC curves of PA612

PA612 films
films at
at the
the strain
strain of (a) εε == 0 and (b) ε =
of (a) = 1.5.
1.5.

Table 1. The crystallinity for uniaxially stretched PA612 film.

Table 1. The crystallinity for uniaxially stretched PA612 film.
Stretching
Stretching Temperature Melting
Melting Temperature Melting Enthalpy
Melting enthalpyCrystallinity
Crystallinity
Strain Strain Temperature (◦ C) Temperature (◦ C) (J/g)
(%)
(℃ ( (℃ ( (J/g( (%(
0 0 30 30 218.2
218.2 68.4768.47 26.5 26.5
0 0 80 80 218.6
218.6 62.2562.25 24.1224.12
0 0 120 120 219.1
219.1 63.6963.69 24.6924.69
0 160 218.6 62.79 24.34
0 160 218.6 62.79 24.34
1.5 30 216.8 65.12 25.24
1.5 30 216.8 65.12 25.24
1.5 80 217.5 67.97 26.34
1.5 1.5 80 120 217.5
218.3 70.5467.97 27.3426.34
1.5 1.5 120 160 218.3
216.5 71.0170.54 27.5227.34
1.5 160 216.5 71.01 27.52
The DSC curves of uniaxially stretched PA612 and PA612/SiO2 films at the stretching
The DSC curves of uniaxially stretched PA612 and PA612/SiO2 films at the stretching temperature
temperature of 120 °C under varied strain are shown in Figure 3, and the corresponding data are
of 120 ◦ C under varied strain are shown in Figure 3, and the corresponding data are listed in Table 2.
listed in Table 2. Two melting temperatures (ca. 205 °C and 218 °C) are found for the films stretched
Two melting temperatures (ca. 205 ◦ C and 218 ◦ C) are found for the films stretched at the strain
at the strain ε = 2 and ε = 2.5, regardless of the addition of SiO2 particles. In addition, the melting
ε = 2 and ε = 2.5, regardless of the addition of SiO2 particles. In addition, the melting enthalpy of
enthalpy of neat PA612◦films at 205 °C is lower than their PA612/SiO2 counterparts. Zhang et al.
neat PA612 films at 205 C is lower than their PA612/SiO2 counterparts. Zhang et al. demonstrated
demonstrated that the crystals with deficient regularity are feasible to melt in the lower temperature,
that the crystals with deficient regularity are feasible to melt in the lower temperature, and the high
and the high melting temperature is attributed to the melting of perfectly crystallized spherulites [27].
melting temperature is attributed to the melting of perfectly crystallized spherulites [27]. In the DSC
In the DSC curves of the films stretched at high strain, the presence of low temperature melting peaks
curves of the films stretched at high strain, the presence of low temperature melting peaks suggests the
suggests the generation of imperfect crystal fragments, which should be originated from the
generation of imperfect crystal fragments, which should be originated from the stretching-induced
stretching-induced extraction of lamellae from spherulites [28]. For PA612 films, the low temperature
extraction of lamellae from spherulites [28]. For PA612 films, the low temperature melting enthalpy
melting enthalpy increased from 1.02 J/g at ε = 2 to 6.71 J/g at ε = 2.5, indicating that the amount of
increased from 1.02 J/g at ε = 2 to 6.71 J/g at ε = 2.5, indicating that the amount of crystal fragments
crystal fragments is positively related to the strain. This phenomenon is more significant for
is positively related to the strain. This phenomenon is more significant for PA612/SiO2 composite
PA612/SiO2 composite films, in which the low temperature melting enthalpy of PA612/SiO2
films, in which the low temperature melting enthalpy of PA612/SiO composite increases to 17.29 J/g at
composite increases to 17.29 J/g at ε = 2.5. It revealed that the SiO22particles increase the crystallinity
ε = 2.5. It revealed that the SiO2 particles increase the crystallinity of the composite films and affect the
of the composite films and affect the movement of crystal lamellae during stretching.
movement of crystal lamellae during stretching.
It can also be found from Table 2 that the crystallinity ascends with the strain regardless of the
It can also be found from Table 2 that the crystallinity ascends with the strain regardless of the
incorporation of the SiO2. It indicates that the presence of strain-induced crystallization of molecular
incorporation of the SiO2 . It indicates that the presence of strain-induced crystallization of molecular
chains for the stretched films. It should be noted the addition of SiO2 is capable of improving the
chains for the stretched films. It should be noted the addition of SiO is capable of improving the
crystallinity for both unstretched and stretched films. Specifically, the2 crystallinity of PA612 films
crystallinity for both unstretched and stretched films. Specifically, the crystallinity of PA612 films
enhance with the increasing of strain, and the maximum value appears at ε = 2 (34%). However, as
enhance with the increasing of strain, and the maximum value appears at ε = 2 (34%). However, as the
the strain is higher than 2, the crystallinity decreases. A similar tendency can be found for PA612/SiO2
strain is higher than 2, the crystallinity decreases. A similar tendency can be found for PA612/SiO
films at low strain, whereas the crystallinity of PA612/SiO2 films increased at ε = 2.5 dramatically. The2
films at low strain, whereas the crystallinity of PA612/SiO films increased at ε = 2.5 dramatically.
reduction of the crystallinity of PA612 films at ε = 2.5 may 2be attributed to the over-high stretching
ratio, giving rise to the rupture of the crystal spherulites [29,30].
Polymers 2020, 12, 711 6 of 13

The reduction of the crystallinity of PA612 films at ε = 2.5 may be attributed to the over-high stretching
ratio, giving rise to the rupture of the crystal spherulites [29,30].
Polymers 2020, 12, x FOR PEER REVIEW 6 of 13

Figure 3. The
3. The DSC
DSC curves
curves of uniaxially
of uniaxially stretched
stretched (a) PA612
(a) PA612 films
films and (b)and (b) SiO
PA612/ PA612/SiO
2 films at films at
2 different
different
strain. strain.

Table 2. The crystallinity of uniaxially stretched PA612 and PA612/SiO films.

Table 2. The crystallinity of uniaxially stretched PA612 and PA612/SiO22 films.
Melting
Melting Melting Low Temperature
Melting Low Temperature
Melting Crystallinity
Crystallinity
Sample Strain
Sample Strain Temperature (◦ C) Enthalpy (J/g) Melting Enthalpy (J/g) (%)
Temperature (℃( enthalpy (J/g( enthalpy (J/g( (%(
S0S0 0 0 219.1219.1 63.6963.69 _ _ 24.69
24.69
S0S0 1 1 217.3217.3 66.6466.64 _ _ 25.8
25.8
S0 1.5 219.8 70.54 _ 27.34
S0 1.5 219.8 70.54 _ 27.34
S0 2 217.3 87.88 1.02 34.06
S0 2 217.3 87.88 1.02 34.06
S0 2.5 217.3 72.48 6.71 28.09
S0S3 2.5 0 217.3218.3 72.4864.31 6.71_ 28.09
25.60
S3S3 0 1 218.3217.7 64.3166.36 _ _ 25.60
26.52
S3S3 1 1.5 217.7218.3 66.3675.34 _ _ 26.52
30.10
S3S3 1.5 2 218.3217.7 75.3483.18 _3.68 30.10
33.2
S3S3 2 2.5 217.7218.1 83.1890.11 17.29
3.68 36.01
33.2
S3 2.5 218.1 90.11 17.29 36.01

To further investigate the variation of crystal structure during stretching, the films were
To furtherbyinvestigate
characterized WAXD, asthe shownvariation of crystal
in Figures 4 andstructure
5. Two during diffractionstretching,
peaks are the observed
films were at
characterized by WAXD,
◦ ◦as shown in Figure 4 and Figure 5. Two diffraction
approximately 20 and 23 in each curve, corresponding to the (100) and (010/110) plane of α crystals peaks are observed at
approximately 20° and 23° in each curve, corresponding to the (100) and
respectively. It indicates that only α phase crystals exist in the PA612 or PA612/SiO2 films after (010/110) plane of α crystals
respectively.
stretching, It indicates
since that only diffraction
the characteristic α phase crystals
peak ofexist in the
γ phase PA612
occurs at or
21◦PA612/SiO 2 films after
[31]. It indicates that
the α phase is the dominant phase in PA612, which is different from the casted PA6 and that
stretching, since the characteristic diffraction peak of γ phase occurs at 21° [31]. It indicates PA1012the
α phase is the dominant phase in PA612, which is different from the casted
films that mainly contain γ phase crystals [9,32]. As shown in Figure 5b, the diffraction peak of (100) PA6 and PA1012 films
that mainly
planes contain γ phase
of unstretched PA612crystals [9,32].intense
film is more As shownthanin theFigure
(010/110)5b, the diffraction
planes, peak that
suggesting of (100)
the planes
PA612
of unstretched PA612 film is more intense than the (010/110) planes,
crystals prefer to grow along the direction perpendicular to (100) planes during quenching in the suggesting that the PA612
film
crystals prefer to grow along the direction perpendicular to (100) planes
casting procedure [33]. The (100) planes of PA612 are perpendicular to the hydrogen bond planes, theduring quenching in the film
casting procedure
molecular chains move [33]. rapidly
The (100) planes
along the of PA612
film castingaredirection
perpendicularwith low to the hydrogen
activation bond
energy andplanes,
high
the molecular chains move rapidly along the film casting direction with
steady nucleation free energy, which favors crystal growth [8]. Notably, the intensity of diffraction low activation energy and
high of
peak steady
(100) nucleation
planes in the free energy, which
unstretched films (ε favors
= 1) iscrystal
much growth
lower than [8]. the
Notably,
stretched thecounterparts.
intensity of
diffraction peak of (100) planes in the unstretched films (ε = 1) is
This should be ascribe to the twisting and rotation of crystal lamellae caused by the stretchingmuch lower than the stretched
[34].
counterparts. This should be ascribe to the twisting and rotation of crystal
As shown in Figure 6, the c axes of α phase, which is parallel to the direction of molecular chains, show lamellae caused by the
stretching orientation
preference [34]. As shown alongin theFigure
MD after6, the c axes of
stretching. The α (010)
phase, which
planes is parallel
present to theofdirection
the priority orientationof
molecular chains, show preference orientation along the MD after stretching.
during stretching, resulting in a rapid increment of diffraction peak intensity after drawing [35]. The (010) planes present
the priority of orientation during stretching, resulting in a rapid increment of diffraction peak
intensity after drawing [35].
Polymers 2020, 12, 711 7 of 13
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Figure 4. The WAXD curves of (a) PA612 and (b) PA612/SiO2 films uniaxially stretched at different
temperature.

Figure 4.
Figure 4.4.The
The WAXD
WAXD
The WAXD curves
curves of (a)
of
curves (a)ofPA612
PA612 and (b)
and
(a) PA612(b)
andPA612/SiO
PA612/SiO films 2uniaxially
22 films
(b) PA612/SiO uniaxially stretchedstretched
stretched
films uniaxially at different
at different
at
temperature.
different temperature.
temperature.

Figure 5. The WAXD curves of uniaxially stretched (a) PA612 and (b) PA612/SiO2 films at different
strain.

The 2D-WAXS patterns (Figure 6) illustrate the crystal orientation of the PA612/SiO2 films. In
the 2D-WAXS patterns of unstretched samples, the two homogeneous Debye-Scherrer diffraction
rings are observed at ca. 20° and 23°, corresponding to (100) and (010/110) planes of α crystals,
respectively [25,33]. The diffraction signals of the two diffraction rings along the meridian
disappeared and concentrate along the equator after stretching, which indicates the orientation of the
crystal because of the increased strain. Moreover, the films with higher strain present reduced the
arcs more, and the (010/110) planes show more concentrated intensity than (100) planes. It shows that
the orientation
Figure 5. Thedegree ofcurves
WAXDcurvesthe crystal
of planes
uniaxially along
(a)the
stretched meridian
(a) PA612
PA612 and direction increased
(b) PA612/SiO
PA612/SiO films with
at the strain
different
Figure 5. The
The WAXD
WAXD curvesofof
uniaxially stretched
uniaxially stretched PA612
(a) and and
(b) PA612/SiO
(b) 2 films at different
22 films at strain.
different
and strain.
strain.

The 2D-WAXS
The 2D-WAXS patterns
patterns (Figure
(Figure 6)
6) illustrate
illustrate the
the crystal
crystal orientation
orientation ofof the
the PA612/SiO
PA612/SiO22 films.
films. In
In
the 2D-WAXS patterns of unstretched samples, the two homogeneous Debye-Scherrer
the 2D-WAXS patterns of unstretched samples, the two homogeneous Debye-Scherrer diffraction diffraction
rings are
rings are observed
observed atat ca.
ca. 20°
20° and
and 23°,
23°, corresponding
corresponding to to (100)
(100) and
and (010/110)
(010/110) planes
planes ofof αα crystals,
crystals,
respectively [25,33]. The diffraction signals of the two diffraction rings
respectively [25,33]. The diffraction signals of the two diffraction rings along the meridianalong the meridian
disappeared and
disappeared and concentrate
concentrate along
along the
the equator
equator after
after stretching,
stretching, which
which indicates
indicates the
the orientation
orientation ofof the
the
crystal because
crystal because of
of the
the increased
increased strain.
strain. Moreover,
Moreover, the the films
films with
with higher
higher strain
strain present
present reduced
reduced thethe
arcs more, and the (010/110) planes show more concentrated intensity than (100) planes.
arcs more, and the (010/110) planes show more concentrated intensity than (100) planes. It shows that It shows that
the orientation
the orientation degree
degree of
of the
the crystal
crystal planes
planes along
along the
the meridian
meridian direction
direction increased
increased with
with the
the strain
strain and
and
the orientation
the orientation rate
rate of
of (010/110)
(010/110) planes
planes is
is higher
higher than
than that
that of
of (100)
(100) planes.
planes.
Figure 6.
Figure 6. The
The 2D-WAXS
2D-WAXS of of uniaxially
uniaxially stretched
stretchedPA612/SiO
PA612/SiO22films
filmsatatthe
thestrain
strainofof(a)
(a)ε ε= =
0, 0,
(b)(b)
ε =ε1,= (c)
1,
ε =ε1.5,
(c) (d)(d)
= 1.5, ε =ε2,=(e) ε = ε2.5.
2, (e) = 2.5.

The 2D-WAXS
The interplanarpatternsspacing(Figure
(d-spacing) and grain
6) illustrate the size
crystal of the stretched
orientation of films as a function
the PA612/SiO of
2 films.
stretching
In the 2D-WAXStemperature
patterns andof stress are illustrated
unstretched samples, intheFigure
two7homogeneous
and Figure 8, respectively.
Debye-Scherrer Thediffraction
d-spacing
of (010/110)
rings are observed ca. 20◦ and
plane inatstretched PA612 23◦and PA612/SiO2 films
, corresponding to (100)decreases with increasing
and (010/110) planes ofofαstretching
crystals,
temperature.
respectively This can
[25,33]. Thebe accredited
diffraction to the
signals slip,two
of the deflection,
diffraction and recombination
rings along the meridian of crystal lamellae
disappeared
during
and stretching
concentrate at high
along temperature
the equator [36,37]. Aswhich
after stretching, shown in Figure
indicates the8,orientation
comparedof withthe the neatbecause
crystal PA612
of the increased strain. Moreover, the films with higher strain present reduced the arcs more, and the
(010/110) planes show more concentrated intensity than (100) planes. It shows that the orientation
degree of the
Figure crystal
6. The
The planesof
2D-WAXS along the meridian
uniaxially stretcheddirection
PA612/SiO increased
films at with
at the
the the of
strain strain
(a) εε =and
= 0, theε orientation
0, (b)
(b)
Figure 6. 2D-WAXS of uniaxially stretched PA612/SiO 22 films strain of (a) ε == 1,
1, (c)
(c)
rate of
ε =(010/110)
1.5, (d) ε =planes
2, (e) ε is
=
ε = 1.5, (d) ε = 2, (e) ε = 2.5.
higher
2.5. than that of (100) planes.
The interplanar spacing (d-spacing) and grain size of the stretched films as a function of stretching
The interplanar
temperature
The interplanar spacing
and stressspacing (d-spacing)
are illustrated and 7grain
in Figures
(d-spacing) and grain size
and 8,size of the
the stretched
respectively.
of stretched films of
The d-spacing
films as (010/110)
as aa function
function of
plane
of
stretching
in stretched temperature
PA612 and and stress
PA612/SiO are illustrated
films decreasesin Figure
with 7 and
increasing Figure
of 8, respectively.
stretching
stretching temperature and stress 2are illustrated in Figure 7 and Figure 8, respectively. The d-spacing temperature.The d-spacing
This can
of
of (010/110)
be (010/110)
accredited plane
to the
plane inslip,
in stretched PA612
deflection,
stretched PA612 andand
and PA612/SiO22 films
recombination
PA612/SiO films decreases
of crystal lamellae
decreases withduring
with increasing
increasing of stretching
stretching
of stretching
at high
temperature. This
temperature. This cancan be be accredited
accredited to to the
the slip,
slip, deflection,
deflection, and and recombination
recombination of of crystal
crystal lamellae
lamellae
during stretching at high temperature [36,37]. As shown in Figure 8,
during stretching at high temperature [36,37]. As shown in Figure 8, compared with the neat PA612 compared with the neat PA612
Polymers 2020, 12, 711 8 of 13

temperature
Polymers
Polymers 2020, [36,37].
2020, 12,
12, xx FOR As shown
FOR PEER
PEER REVIEW
REVIEWin Figure 8, compared with the neat PA612 films, the PA612/SiO2 88films of
of 13
13
exhibit an analogous tendency in the d-spacing of the two diffraction planes and the grain size of the
films,
films, the
the PA612/SiO
spherulites. 2 films
It implies
PA612/SiO exhibit
that the
2 films
an
an analogous
addition
exhibit of SiO2 plays
analogous tendency in
in the
the d-spacing
an insignificant
tendency role in of
d-spacing thethe
of two
two diffraction
crystal
the phase and
diffraction
planes
structure
planes and
and the
the grain
transition size
grainof of
of the
PA612
size spherulites.
during
the It
It implies
stretching.
spherulites. that
that the
The grain
implies sizeaddition
the of PA612
addition of SiO
ofwas plays
plays an
an insignificant
SiO22apparently affected by
insignificant
role in
in the
stretching
role crystal
crystal phase
the temperature
phaseandand structure
andstrain, and transition
structure it is climbing
transition of
of PA612 during
with the
PA612 stretching.
stretching
during The
The grain
temperature
stretching. size
size of
increases.
grain of PA612
Hence,
PA612
was apparently
highapparently
was affected
stretching temperatures by stretching temperature
conduce temperature
affected by stretching to complete the and strain,
andgrains and
strain,during it is climbing
and itstretching. with
is climbingAfter the stretching
with stretching, the
the stretching
temperature
grain size increases.
declined Hence,
drastically high
and stretching
remained temperatures
constant after conduce
ε = 1.5. to
temperature increases. Hence, high stretching temperatures conduce to complete the grains complete
The addition the
ofgrains
SiO during
led to
2 during a
minished the grain size, indicating the grain refining effects of SiO2 .

Figure
Figure 7.7. The
The(a)
The (a)d-spacing
(a) d-spacingand
d-spacing and(b)
and (b)grain
(b) grainsize
grain sizeof
size uniaxially
ofof
uniaxially stretched
stretched
uniaxially PA612
PA612
stretched and
and
PA612 PA612/SiO
PA612/SiO
and 2 films (ε
2 films
PA612/SiO (ε
2 films
=(ε1.5)
= 1.5) at
= 1.5) different stretching
at different
at different temperature.
stretching
stretching temperature.
temperature.

Figure 8.
Figure
Figure The (a)
8. The
The (a) d-spacing
(a) d-spacing and
d-spacing and (b)
and (b) grain
(b) grain size
grain size of
size of uniaxially
of uniaxially stretched
uniaxially stretched PA612
stretched PA612 and
PA612 and
and PA612/SiO films at
PA612/SiO222 films
films at
at
different strain.
different
different strain.
3.3. Mechanical Properties of Uniaxial Stretched PA612/SiO2 Films
3.3.
3.3. Mechanical
Mechanical Properties
Properties of of Uniaxial
Uniaxial Stretched
Stretched PA612/SiO
PA612/SiO22 Films Films
Figure 9 demonstrates the stress-strain curves of S0 and S3 at different temperatures. It can be
Figure
Figure 99 demonstrates
demonstrates the
the stress-strain
stress-strain curves
curves of
of S0
S0ofand
and S3 atat different
different temperatures.
temperatures. It It can
can be
found that the stretching temperature and the presence SiOS32 both affect the yield behavior of the
be
found
found that
that the
the stretching
stretching temperature
temperature and
and the
the presence
presence of
of SiO
SiO 2 both affect the yield behavior of the
2 both affect the yield behavior of the
films. As increasing of stretching temperature, the yield stress gradually decreases and the yield point
films.
films. As
As increasing
increasing of
of stretching
stretching temperature, the the◦ yield stress gradually decreases andand the
the yield
yield point
disappears as the temperature istemperature,
higher than 80 yield
C. Thestress gradually
presence of SiOdecreases
2 leads to the diminution in
point
disappears
disappears as
as the
the temperature
temperature is
is higher
higher than
than 80
80 °C.
°C. The
The presence
presence of
of SiO
SiO 2 leads to the diminution in
2 leads to the diminution◦in
the yield stress, as well as reduces the stress drop (Figure 9b) at the stretching temperature of 30 C.
the
the yield
yield stress,
stress, as
as well
well as reduces the
theofstress drop
drop (Figure 9b)
9b) atat the stretching temperature of of 30
30 °C.
Yalcin et al. revealed thatasthe
reduces
necking stress
the samples (Figure
is proportional thetostretching
the stresstemperature
drop [33]. Hence, °C.
the
Yalcin
Yalcin et al. revealed
et al. revealed that the necking of the samples is proportional to the stress drop [33]. Hence,
incorporation of SiO2 that the necking
can alleviate filmof the samples
necking duringisstretching.
proportional to the stress
Meanwhile, drop [33].
the samples Hence,
stretched
the
the incorporation
incorporation
◦
of
of SiO
SiO 2 can alleviate film necking during stretching. Meanwhile, the samples
2 can alleviate film necking during stretching. Meanwhile, the samples
at 30 C exhibit a typical stress-strain behavior of typical semi-crystalline polymers. It consists of
stretched
stretched at
at 30 °C
°C exhibit
30yielding,exhibit aa typical
typical stress-strain
stress-strain behavior
behavior of
of typical
typical semi-crystalline
semi-crystalline polymers.
polymers. as It
It
elastic region, strain-softening, necking, and orientation hardening stages. Nevertheless,
consists
consists of elastic
of elastic region, yielding,
region, exceeded strain-softening,
yielding,80strain-softening, necking,
◦ C, the yielding necking,
and orientation
and orientation hardening stages.
the stretching temperature and strain-softening regionhardening
disappear andstages.
the
Nevertheless,
Nevertheless, as the stretching temperature exceeded 80 °C, the yielding and strain-softening region
curve transform from the elastic region to the orientation hardening directly without neckingregion
as the stretching temperature exceeded 80 °C, the yielding and strain-softening stage.
disappear
disappear and the
the curve
andnonreactivecurve SiO transform
transform from
from the
the elastic
elastic region
region to the
the orientation hardening directly
Generally, the 2 serves as a plasticizer within thetomatrix, orientation hardening
while the reactive SiO2 directly
present
without
without necking stage.
necking effect
stage. or Generally,
Generally, the nonreactive
the nonreactive SiO 2 serves as a plasticizer within the matrix, while
a reinforcement a plasticizing effect due SiO 2 serves as a plasticizer within the matrix, while
to its processing method and the reactivity of the
the
the reactive
reactive SiO
SiOon2 present a reinforcement effect or a plasticizing effect due to its processing method
2 present a reinforcement effect or a plasticizing effect due to its processing method
grafted groups SiO2 surface [22,23,38]. As shown in Figure 9, the yielding point of Sample S3 was
and
and the
the reactivity
reactivity of
of the
the grafted
grafted groups
groups on
on SiO
SiO2to surface [22,23,38]. As shown in Figure 9, the yielding
2 surface [22,23,38]. As shown in Figure 9, the yielding
lower than that of Sample S0, and it is difficult explain why the yield stress of S3 samples are lower
point
point of Sample S3 was lower than that of Sample S0,
of Sample S3 was lower than that of Sample S0, and
and itit is
is difficult
difficult to to explain
explain whywhy the
the yield
yield stress
stress
of
of S3
S3 samples
samples are are lower
lower thanthan S0 S0 samples.
samples. On On the the one
one hand,
hand, it it couldn’t
couldn’t attribute
attribute toto the
the plasticizing
plasticizing
effect
effect under
under these
these conditions,
conditions, because
because the the peak
peak of of loss
loss factor
factor of of S0S0 is
is higher
higher than
than S3
S3 and
and the
the glass
glass
transition
transition temperature of S0 is lower than S3 (Figure 11 and Figure 12). On the other hand, it
temperature of S0 is lower than S3 (Figure 11 and Figure 12). On the other hand, it is
is not
not
Polymers 2020, 12, 711 9 of 13

than S0 samples. On the one hand, it couldn’t attribute to the plasticizing effect under these conditions,
because the peak of loss factor of S0 is higher than S3 and the glass transition temperature of9S0
Polymers 2020, 12, x FOR PEER REVIEW
is
of 13
lower than S3 (Figures 11 and 12). On the other hand, it is not the reason for the changing of crystal
structure;
the reason the
for SiO particlesof
the 2changing diminished the grain
crystal structure; thesize
SiO(Figure 8), diminished
2 particles and the yield thestress
grainof S3 (Figure
size should
be higher than S0. This phenomenon should be investigated further. As the stretching
8), and the yield stress of S3 should be higher than S0. This phenomenon should be investigated temperature
increased,
further. Asthe
thestress-strain curves of S0increased,
stretching temperature and S3 tendthetostress-strain
overlap each other,ofindicating
curves S0 and S3that
tendthe
to effect
overlapof
SiO2 on the matrix is negatively related to the mechanical properties at high stretching temperature.

Figure 9.
Figure (a)the
9. (a) thestress-strain
stress-straincurves
curvesof
ofPA612
PA612 (solid
(solid line)
line) and
and PA612/SO
PA612/SO2 (dotted
(dotted line)
line) films
films at
at different
different
temperature and (b) the zoom-in view of the curves at 30 ◦ C.
temperature and (b) the zoom-in view of the curves at 30 °C.

The stress-strain
The stress-strain curves
curves of of the
the stretched
stretched PA612
PA612 and and PA612/SiO
PA612/SiO22 films films with
with different
different strains
strains are
are
shown in in Figure
Figure 10.10. Herein,
Herein, all all samples
samples were were stretched
stretched at at room
room temperature ◦
(25 °C).C). The
The stretched
shown temperature (25 stretched
PA612 films still show yielding and strain-softening at the ε = 0 and
PA612 films still show yielding and strain-softening at the ε = 0 and ε = 1, but disappeared when ε = 1, but disappeared when
the
the films were stretched to high strain and the stretched PA612/SiO
films were stretched to high strain and the stretched PA612/SiO2 2samples exhibit no significant samples exhibit no significant
yielding or
yielding or strain-softening
strain-softeningregion. region.Combined
Combinedwith withFigure
Figures 6 and
6 and 10, it10,
Figure canit be
canconcluded
be concluded thatthat
the
fracture strength of the films after stretching are positively correlated
the fracture strength of the films after stretching are positively correlated with the orientation of thewith the orientation of the
crystal. Moreover,
crystal. Moreover, as as the
the stretching
stretching strain
strain increasing,
increasing, thethe crystal
crystal orientation
orientation turn turn more
more obvious,
obvious, the
the
elongation at break decreases and the fracturing strength increases dramatically,
elongation at break decreases and the fracturing strength increases dramatically, and this is related and this is related to
the orientation degree of crystal and the reorientation of polymer chains.
to the orientation degree of crystal and the reorientation of polymer chains. This could be due to the This could be due to the
development of
development of fibrous
fibrous crystals
crystals at at high
high strain
strain after
after the
the dislocation,
dislocation, deflection,
deflection, andand orientation
orientation ofof the
the
crystals [39]. The movement of the fibrous crystals and the amorphous
crystals [39]. The movement of the fibrous crystals and the amorphous region is strongly hindered region is strongly hindered
after sufficient
after sufficientstretching
stretchingwith with high
high strain.
strain. TheThe molecular
molecular chains chains
in thein the amorphous
amorphous region region were
were highly
highly oriented.
oriented. The followed
The followed forcedforced stretching
stretching wouldwouldbringbring
aboutabout thethe extractionand
extraction andstraightening
straightening ofof
molecular chains, and the completed crystals are damaged into smaller
molecular chains, and the completed crystals are damaged into smaller crystallization units under crystallization units under
stress [36].
stress [36]. A A part
part of
of the
the molecular
molecular chainschains werewere extremely
extremely stretched
stretched before
before fracturing
fracturing [40,41]. As aa
[40,41]. As
result, for the PA612 samples, the fracture strength increases and the elongation
result, for the PA612 samples, the fracture strength increases and the elongation at break decreases at break decreases as
increasing of stretching strain, where the maximum fracture stress of
as increasing of stretching strain, where the maximum fracture stress of stretched films was three stretched films was three times
than that
times thanofthatunstretched films and
of unstretched filmstheand
elongation at breakatisbreak
the elongation reduced from 160%
is reduced fromto 160%
35%. These
to 35%. changes
These
can be attributed to the hindered movement of molecular chains in
changes can be attributed to the hindered movement of molecular chains in the amorphous regions the amorphous regions and highly
oriented
and highly fibrous
orientedcrystals
fibrous[35]. The PA612/SiO
crystals samples exhibit
[35]. The 2PA612/SiO similar trends of fracture stress and
2 samples exhibit similar trends of fracture
elongation
stress at break, butatthey
and elongation break,have buthigher
they fracture
have higherstressfracture
and lower elongation
stress and lower at break. This isatbecause
elongation break.
the SiO hinders
This is because
2 the movement of molecular chains when the films were
the SiO2 hinders the movement of molecular chains when the films were stretched. stretched.

Figure 10. The stress-strain curves of the stretched (a) PA612 and (b) PA612/SiO2 films. (The curves
were recorded at room temperature).
result, for the PA612 samples, the fracture strength increases and the elongation at break decreases
as increasing of stretching strain, where the maximum fracture stress of stretched films was three
times than that of unstretched films and the elongation at break is reduced from 160% to 35%. These
changes can be attributed to the hindered movement of molecular chains in the amorphous regions
and highly
Polymers 2020, oriented
12, 711 fibrous crystals [35]. The PA612/SiO2 samples exhibit similar trends of fracture
10 of 13

The stress-strain
Figure 10. The
Figure stress-strain curves
curves of
of the
the stretched
stretched (a)
(a) PA612 and (b) PA612/SiO
PA612/SiO22 films. (The
(The curves
curves
were recorded at room temperature).
Polymers 2020, 12, x FOR PEER REVIEW 10 of 13
The storage modulus and tanδ as a function of temperature curves of uniaxially stretched PA612
and PA612/SiO2 films are shown in Figures 11 and 12, respectively, from which we can obtain the
The storage modulus and tanδ as a function of temperature curves of uniaxially stretched PA612
glass transition temperature (Table 3) and investigate the toughness-rigidity transition of the films.
and PA612/SiO22 films are shown in Figure 11 and Figure 12, respectively, from which we can obtain
Indeed, thetransition
the glass glass transition
temperaturetemperatures
(Table 3)were highly improved.
and investigate As increasing of
the toughness-rigidity stretching
transition strain,
of the films.the
storage modulus increases accompany with the decreases of the loss factor peak and
Indeed, the glass transition temperatures were highly improved. As increasing of stretching strain, the monotonically
elevated glassmodulus
the storage transitionincreases
temperature. It indicates
accompany with that
the the increased
decreases strain
of the losswould
factorlead peakto and
enhanced
the
rigidity and reduced
monotonically toughness.
elevated Moreover,
glass transition the glass It
temperature. transition
indicatestemperature and storage
that the increased modulus
strain would lead of
PA612/SiO
to enhanced2 films wereand
rigidity higher than toughness.
reduced that of PA612 films regardless
Moreover, of the stretched
the glass transition or unstretched
temperature and storage films
and this is consistent
modulus of PA612/SiO with22 films
PA6/SiO 2 composites
were higher than where thePA612
that of SiO2 particles improved
films regardless ofthe
theglass transition
stretched or
temperature
unstretchedand storage
films and this modulus of PA6
is consistent [38].
with In the 22PA612
PA6/SiO samples,
composites thethe
where tanδ vs.
SiO temperature
22 particles curves
improved
show two peaks
the glass when
transition the ε = 2 and storage
temperature ε = 2.5 modulus
from Figure 11b,[38].
of PA6 which would
In the PA612 help to confirm
samples, thatvs.the
the tanδ
molecular
temperature chains were
curves extracted
show fromwhen
two peaks the stretching-induced
the ε = 2 and ε = 2.5lamellae fragments
from Figure 11b, whichfromwould
spherulites.
help
to
However, this phenomenon was not shown in stretched PA612/SiO2 films.

Figure11.
Figure 11.The
The(a)
(a)storage
storagemodulus
modulus vs.
vs. temperature
temperature and
and(b)
(b)tanδ
tanδvs.
vs.temperature
temperaturecurves ofof
curves uniaxially
uniaxially
stretched PA612 films.
stretched PA612 films.

Figure12.
Figure 12.The
The(a)
(a)storage
storagemodulus
modulus vs.
vs. temperature
temperature and
and(b)
(b)tanδ
tanδvs.
vs.temperature
temperaturecurves ofof
curves uniaxially
uniaxially
stretchedPA612/SiO
stretched PA612/SiO 2 films.
22films.

Table 3. The glass transition temperature of uniaxially stretched PA612/SiO22 films.

Strain ε=0 ε=1 ε = 1.5 ε=2 ε = 2.5

S0 (Tgg/°C) 45.2 50.5 58.6 62.1/79.35 50.2/81.4
S3 (Tgg/°C) 74.0 79.0 81.0 82.9 84.2
Polymers 2020, 12, 711 11 of 13

Table 3. The glass transition temperature of uniaxially stretched PA612/SiO2 films.

Strain ε=0 ε=1 ε = 1.5 ε=2 ε = 2.5

S0 (Tg /◦ C) 45.2 50.5 58.6 62.1/79.35 50.2/81.4
S3 (Tg /◦ C) 74.0 79.0 81.0 82.9 84.2

4. Conclusions
In this study, uniaxially stretched PA612 and PA612/SiO2 films were prepared with the
electromechanical universal testing machine; the crystal structure and mechanical properties were
investigated in detail. The PA612 casting films were dominated by the α phase and this was not affected
by stretching temperature or strain. The crystal was oriented in the stretching direction and the b axis
was paralleled with equatorial direction. The stretching temperature and strain had a positive and
negative effect on the interplanar spacing of (010), respectively. Strain induced the generation of α
crystals and effectively improved the crystallinity of PA612. Additionally, the addition of SiO2 did not
affect crystal form and crystal structure of PA612, but led to refined grain size and affects the extraction
of crystal lamellar. The addition of SiO2 led to reduced yield stress and the strain-softening beyond
yielding of the composite, necking was relieved during stretching. After stretching, the loss factor
peak of films decreased and the glass transition temperature increased from 45.2 ◦ C to 81.4 ◦ C for the
S0 samples and 74.0 to 84.2 for the S3 samples. The maximum fracture stress of stretched film was
three times of that of unstretched films, the elongation at break of stretched films dropped to 35% for
S0 samples, and the PA612/SiO2 samples exhibit similar trends.

Author Contributions: Y.W. conceived and carried out all the experiments, as well as analyzed the data; Y.W.,
A.H. and S.F. designed the experiments together, A.H. and S.F. contributed equally to this work; Y.W. wrote the
paper. Y.L. and X.L. designed the project and revised the manuscript, and they also contributed equally to this
work as corresponding authors. All authors have read and agreed to the published version of the manuscript.
Acknowledgments: This work was financially supported by the National Natural Science Foundation of China
(contract grant number 11872179), the Natural Science Foundation of Hunan Province (contract grant number
2018JJ4072), and the Scientific Research Project of Education Department of Hunan Province (contract grant
number 19B152, 19A138, and 18K079).
Conflicts of Interest: The authors declare no conflict of interest.

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