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Composites: Part A
journal homepage: www.elsevier.com/locate/compositesa
a r t i c l e i n f o a b s t r a c t
Article history: A series of polyamide 6/multi-walled carbon nanotubes (PA6/CNT) nanocomposites were prepared using
Received 12 July 2017 a masterbatch dilution process, followed by microinjection molding of a part with a three-step decrease
Received in revised form 19 September in thickness along the flow direction. Morphology observations revealed that there was a preferential
2017
orientation of CNT in the flow direction, which is attributed to the prevailing high shear rates in mIM.
Accepted 23 September 2017
Available online 25 September 2017
The distribution of CNT after melt processing was evaluated by dissolving experiments. Additionally,
the correlation between electrical resistivity and development of microstructure for each section of the
microparts was considered. The thermal behavior of PA6/CNT nanocomposites and corresponding micro-
Keywords:
A. Polymer-matrix composites (PMCs)
parts was evaluated using differential scanning calorimetry. Results indicated that the addition of CNT
B. Microstructures had little effect on the melting behavior of PA6/CNT nanocomposites and corresponding microparts.
D. Thermal analysis However, the crystallization behavior was changed significantly and a double crystallization peak was
E. Injection molding observed for samples incorporating CNT.
2017 Elsevier Ltd. All rights reserved.
https://doi.org/10.1016/j.compositesa.2017.09.016
1359-835X/ 2017 Elsevier Ltd. All rights reserved.
S. Zhou et al. / Composites: Part A 103 (2017) 8495 85
Fig. 1. (a) Images of the mold insert and a micropart; (b) three-step configurations of the microparts, red arrows indicate the boundary of each section; (c) sampling positions
of each section for morphology observations.
fractured surfaces were coated with a thin layer of platinum prior where DHm is the melting enthalpy of PA6 and DHcalc represents the
to observations. expected melting enthalpy of PA6 based on the measured melting
enthalpy for pure polymer and the mass fraction of it in the blend-
2.3.3. Dissolving experiments and transmission electron microscopy ing composite. The melting enthalpy of 100% crystalline PA6 is
It has been reported that the dissolving experiments, that show 230 J/g [47].
the state of nanotubes dispersion in a good solvent for the polymer
matrix, are helpful to reflect the state of dispersion that was
achieved in the solid state [51]. Thus, in order to obtain a qualita- 3. Results and discussion
tive evaluation of the CNT dispersion within corresponding sam-
ples, the original masterbatch, CNT5 extrudate and different 3.1. Morphology
sections taken from CNT5 microparts were dissolved in formic acid
for 1 h at 40 C. Small pieces of PA6/CNT masterbatch, CNT5 extru- The morphology of extrudates obtained from the masterbatch
date and cut sections from CNT5 microparts were immersed in dilution process was examined using SEM and the results are given
about 50 mL formic acid with external stirring. These solutions in Fig. 2. The bright dots (the end of CNT) and the fibril-like struc-
were formulated to acquire an equivalent amount of CNT in each ture underneath the polymer surface, which are pointed out by red
vial. The state of dispersion of CNT in PA6/formic acid solution arrows, indicate the presence of CNT. In addition, the mean dis-
was recorded in digital photos by a Canon camera (Japan). Further- tance between the individually dispersed CNT decreases with an
more, the PA6/CNT/formic acid solution was diluted with distilled increase of CNT loading concentration, which is favorable for the
water. Afterward, the solution was sonicated (Branson B-220, USA) formation of 3D conductive pathways. In general, CNTs were uni-
for 3 min at 125 W. A drop of the above-mentioned solution was formly dispersed within the extrudates, regardless of CNT concen-
placed on a copper grid (400-mesh, Formvar Carbon Film, Electron tration, which further confirmed that the masterbatch dilution
Microscopy Sciences). To observe the nanostructure of CNT, the process is an effective method to fabricate polymeric composites
sample was examined by transmission electron microscopy containing CNT.
(TEM, Philips CM 10) at an acceleration voltage of 80 kV, after com- The development of internal microstructure within each section
plete evaporation of the liquid phase. The diameter and length of of PA6/CNT microparts, and the effect of CNT concentration on the
CNT were measured manually with the help of an image analysis morphology of subsequent microparts were evaluated using SEM.
software (Image J). All samples for PA6/CNT microparts were fractured in liquid nitro-
gen along the TD, i.e. perpendicular to flow direction. Fig. 3 shows
2.3.4. Differential scanning calorimetry the microstructure of the thick section obtained from CNT5 micro-
The melting and crystallization behavior of pure PA6 and parts. Fig. 3a and b were taken from the core layer of the thick sec-
diluted PA6/CNT samples as well as each section of corresponding tion whereas Fig. 3c and d were taken from the shear layer, which
microparts were determined using a differential scanning is close to the mold wall (Fig. 1c). Fig. 3a and c suggest that CNTs
calorimeter (DSC, Q2000, TA Instruments) under nitrogen atmo- are relatively uniformly distributed within the matrix since no
sphere at a constant gas flow rate of 50 mL/min. Thin slices taken obvious CNT aggregates were observed in either the core layer or
from the middle of each section were cut along the TD. The mea- shear layer. Interestingly, more bright dots could be observed in
surement which consists of a heating phase followed by a cooling Fig. 3d (shear layer) when compared with Fig. 3b (core layer), sug-
phase was carried out between 40 and 240 C at a ramp rate of gesting that CNTs are preferentially aligned in the flow direction,
10 C/min. The melting and crystallization temperatures were which could be attributed to the influence of higher shearing effect
detected from the heating and cooling graphs, respectively. The that prevails in the shear layer [40,41]. This is consistent with our
crystallinity (vc) of each sample was calculated with Eq. (2): previous observations for PS/CNT microparts [40]. Consequently,
this would increase the probability of CNT-CNT contact along the
DH m
vc 2 flow direction, thereby leading to a reduction of electrical resistiv-
DHcalc ity in the FD when compared with that in the TD.
S. Zhou et al. / Composites: Part A 103 (2017) 8495 87
Fig. 2. The morphology of cryo-fractured surface of diluted extrudates: (A1A3) 2 wt%, (B1B3) 5 wt%, and (C1C3) 10 wt%, respectively.
Fig. 3. The morphology of thick section of CNT5 microparts from: (a, b) core layer; (c, d) shear layer.
Similarly, it could be deduced from Figs. 4 and 5 that CNT had a detectable bright dots in corresponding layer of the middle
relatively uniform distribution in the middle section and thin sec- (Fig. 4d) and thin (Fig. 5d) sections seemed to be smaller than that
tion of CNT5 microparts, respectively. However, the number of observed for the thick section (Fig. 3d). As a result, it could be
88 S. Zhou et al. / Composites: Part A 103 (2017) 8495
Fig. 4. The morphology of middle section of CNT5 microparts from: (a, b) core layer; (c, d) shear layer.
Fig. 5. The morphology of thin section of CNT5 microparts from: (a, b) core layer; (c, d) shear layer.
expected that this would lead to a higher electrical resistivity for vated shearing conditions. Chen et al. [53] reported similar findings
both the middle and thin sections, indicating the shearing condi- in CNT filled poly(vinylidene fluoride) (PVDF) composites. However,
tions that exsited in different sections of the microparts play a piv- Pegel et al. [19] pointed out that although higher shear rates could
otal role in determing the microstructure. Studies [40,41] have provide suitable CNT dispersion in a host polymer matrix, secondary
shown that there is a significant increase of maximum shear rates agglomeration of CNT was also prevented which is thought to be
with a simultaneous reduction of the thickness of mold cavities. detrimental to the enhancement of electrical conductivity of corre-
Therefore, it seems to be resonable to attribute the development sponding composites. Moreover, the length reduction of CNT during
of microstructure in each section to the variation of shearing condi- the melt processing, especially under severe shearing conditions,
tions. Li and Shimizu [52] found that the CNT could achieve a better could be another concern which would significantly devalue the
dispersion in a polymer matrix when they were processed at ele- electrical conductivity of subsequent products [54].
S. Zhou et al. / Composites: Part A 103 (2017) 8495 89
Fig. 6. The morphology of thick section of CNT2 microparts from: (a, b) core layer; (c, d) shear layer.
Fig. 6 displays the internal microstructure of the thick section of each other, which is advantageous to the enhancement of overall
CNT2 microparts. The CNTs were uniformly dispersed in each layer, electrical conductivity.
as no obvious CNT agglomeration could be observed. Moreover, it
is hard for CNT to form intact 3D conductive pathways within 3.2. Electrical resistivity
PA6 due to their lower loading fraction. In addition, Fig. 7 illus-
trates the morphology of the thick section of CNT10 microparts. The electrical resistivity (q) of compression molded PA6/CNT
As shown in Fig. 7b and d, there is no significant difference in samples and each section of corresponding microparts is reported
the quality of dispersion of CNT in each layer of thick section at in Fig. 8. No q could be measured for the thin section of CNT2
such a high filler concentration. Furthermore, a conductive net- microparts due to a lack of conductive pathways, as displayed in
work could be easily observed with CNT particles entangled with Fig. 8b. However, the q in the TD for both the thick and middle
Fig. 7. The morphology of thick section of CNT10 microparts from: (a, b) core layer; (c, d) shear layer.
90 S. Zhou et al. / Composites: Part A 103 (2017) 8495
Fig. 8. Electrical resistivity of (a) compression molded PA6/CNT samples and sections of (b) CNT2 microparts, (c) CNT5 microparts and (d) CNT10 microparts.
sections is almost two orders of magnitude higher than that mea- pointed out that the percolation threshold for PA6/CNT composites
sured in the FD, indicating a preferential orientation of CNT in the in lIM is 46 wt%. In the case of CNT5, the values of electrical con-
flow direction. In addition, there was a reduction of q in the middle ductivity would be dominated by the formation of conductive net-
section when compared with that of the thick section with respect work through physical interconnection amid the dispersed CNTs
to the measurement directions. It was illustrated in Section 3.1 that and small CNT aggregates. Thus, the improved dispersion of CNTs
high shear rates would improve the dispersion of CNT in a polymer or disentanglement of CNT aggregates in the middle section of
matrix. Thus, there would be a better dispersion of CNT in the mid- resulting microparts might be detrimental to the formation of
dle section when compared with the thick section. Although the intact conductive network [19,58], thereby lowering the electrical
formation of a conductive network seemed to be unlikely at such conductivity in according section [58].
a lower CNT loading concentration (2 wt%), the improvement of The q measured in the TD for each section of CNT10 microparts
electrical conductivity in the middle section could be explained exhibited a similar trend as reported for their CNT5 counterparts.
by a hopping or tunneling mechanism [55]. In this case, a phys- However, the q measured in the FD for the middle section was
ical contact between the incorporated fillers is unnecessary as long lower than that for the thick section. It was observed in Fig. 7 that
as they are close enough to allow the passage of electrons [56,57]. sufficient conductive pathways were formed within PA6 matrix at
As the orientation and dispersion of CNT are favored in PA6 with an a CNT loading fraction of 10 wt%. The favored orientation of CNT in
increase of shear rates, the average distance between individually the FD tends to increase the probability of CNT-CNT contact, lead-
dispersed CNT decreases in the middle section and the transport ing to an enhanced electrical conductivity in the middle section
of electrons is therefore facilitated through tunneling between when compared with that obtained for thick section. Furthermore,
adjacent CNTs [53,55]. it is clear from Fig. 8c and d that the presence of very high shearing
Fig. 8c shows that there was an increase of q measured in the effect is unfavorable for the construction of conductive pathways
TD and FD for CNT5 microparts from the thick to thin sections. within subsequent microparts since the thin section showed the
However, similar to CNT2 microparts, the q measured in the FD highest q, regardless of CNT loading concentrations.
was invariably lower than the value obtained from the compres-
sion molded samples (Fig. 8a), which further confirmed a preferen- 3.3. Dissolving experiments and transmission electron microscopy
tial alignment of CNT in the flow direction. The increase of q in the
middle section was consistent with the morphology observations To qualitatively observe the dispersion of CNT in PA6/CNT mas-
discussed in Section 3.1, which could be attributed to the improved terbatch, diluted composites and corresponding microparts, the
dispersion of CNT and the disentanglement of CNT aggregates aris- dissolving experiments were carried out with respect to each
ing from the increasing shear rates. For example, Ferreira et al. [38] sample. The observation of dissolved samples in formic acid for
S. Zhou et al. / Composites: Part A 103 (2017) 8495 91
Fig. 11a and b show the DSC heating and cooling behavior,
Fig. 9. Digital photos of PA6/CNT/formic acid solutions after 2 months: 1. PA6/CNT
masterbatch; 2. CNT5 extrudate; from 3 to 5 are the thick, middle and thin sections
respectively, of pure PA6 and diluted PA6/CNT extrudates with var-
of CNT5 microparts, respectively. ious CNT concentrations. It could be deduced from Fig. 11 that the
incorporation of CNT had little effect on the melting behavior of
PA6 matrix. However, the crystallization process was greatly
PA6/CNT samples is presented in Fig. 9. The solutions of extruded affected with the presence of CNT. For pure PA6, only a single crys-
CNT5 and sections taken from corresponding microparts appear tallization peak (Tc1) was detected in the vicinity of 192 C. For
as homogeneous black solutions, indicating relatively homoge- PA6/CNT extrudates, as indicated in Fig. 11b and Table 1, Tc1
neous distribution of individual nanotubes or very small CNT shifted to higher values when compared with that obtained from
aggregates [51]. However, a black sediment coupling with nearly pure PA6. Moreover, the onset crystallization temperature (Tonset)
transparent solution is visible for PA6/CNT masterbatch (sample increased significantly upon the addition of CNT, indicating that
1), corresponding to the existence or remnants of CNT agglomer- CNT played a role of nucleation agent. In addition, a second crystal-
ates. Therefore, the dispersion of CNT is improved after melt dilu- lization temperature (Tc2) was observed at higher temperatures for
tion and subsequent mIM processes. CNT-containing PA6 composites, and its position gradually shifted
Characterization of the nanostructure of CNT in respective sam- to higher temperatures with an incremental loading fraction of
ple was carried out by TEM. The CNTs have a hollow structure, CNT, which suggested that the appearance of the second crystal-
which could be clearly observed in Fig. 10c, d and f. The measured lization peak in PA6 could be related to the presence of CNT. Sim-
diameter of CNT ranges from 5 to 10 nm, which is consistent with ilar observations have been reported by Logakis et al. [46] and
the technical data provided by manufacturer. However, Fig. 10f Krause et al. [59]. The appearance of the double crystallization
indicated that the length of CNT is significantly reduced when peak in PA6/CNT composites could be explained by the formation
compared with their original length (over 10 mm) [46], suggesting of two different types of crystal morphologies or the two-step crys-
that melt processing has a significant effect on the length reduction tallization due to the presence of one-dimensional filler, i.e. CNT,
of CNT. Although the CNT5 extrudate has a homogeneous disper- which has been detailed by Logakis et al. [46]. In the first case,
sion in formic acid (Fig. 9, sample 2), Fig. 10a and b indicate the the CNT surface may induce the crystallite growth in a manner that
Fig. 10. TEM graphs of (a, b) extruded CNT5, (c, d) CNT5 thick section and (e, f) CNT5 middle section.
92 S. Zhou et al. / Composites: Part A 103 (2017) 8495
Fig. 11. DSC (a) heating and (b) cooling curves obtained from pure PA6 and PA6/CNT extrudates with various filler concentrations.
Table 1
Melting temperature (Tm), crystallinity (vc), crystallization temperatures (Tc1, Tc2) and onset crystallization temperature (Tonset) of pure PA6, PA6/CNT extrudates and different
sections of corresponding microparts.
is perpendicular to the nanotube axis, which leads to the develop- allowed for polymer chains to form well-developed crystals during
ment of trans-crystalline structure [38]. However, the polymer mIM due to the fast filling rate, high thermal gradients and short
chains tend to form the spherulites in the regions where are far cycle times. Therefore, a slight downshift of Tm observed in sec-
away from the nanotubes [46]. Thus, the co-existence of two differ- tions of pure PA6 microparts (Table 1) indicates the existence of
ent types of crystals could possibly contribute to the appearance of imperfections in resulting crystalline structures. However, a sec-
the double crystallization peak. In the other case, it was proposed ond melting peak (ca. 222.65 C) is noticeable for the middle sec-
that the presence of double crystallization peak could be related to tion, suggesting that the prevailing shearing conditions in the
the two-step crystallization of polymer chains. The incorporation middle section [41] might partially promote the formation of
of fillers in a polymer matrix would greatly accelerate the crystal- well-aligned structures. Table 1 reveals that although the Tm of dif-
lization process of polymer chains [47]. Phang et al. [60] proposed ferent sections of PA6 microparts decreased when compared with
that both the high aspect ratio of CNT and the higher crystallization that of pure PA6, a remarkable increase of crystallinity (vc) was
temperature are favorable for the formation of thermodynamically achieved for these sections. This could thus be attributed to the
stable a-phase crystals. Both mechanisms suggest that the appear- variation of shearing conditions in different sections of microparts,
ance and the intensity of the second crystallization peak could be as given in Ref [40,41]. The higher shear rates facilitated the orien-
related to the number of the incorporated CNTs. tation of polymer chains in flow direction, leading to a higher vc for
The thermal behavior of pure PA6 and sections taken from cor- sections that experienced relatively high shearing conditions.
responding microparts is given in Fig. 12. As shown in Fig. 12 and Moreover, the cooling effect would be accentuated in different sec-
Table 1, the melting temperature (Tm), Tc1 and Tonset for each sec- tions of PA6 microparts [63]. Under such circumstances, however,
tion of pure PA6 microparts decreased as compared with these val- a relatively stable crystalline structure was hardly formed by poly-
ues obtained from pure PA6. This could be attributed to the mer chains, which in turn resulted in a reduction of Tm. Interest-
influence of thermo-mechanical history experienced by polymer ingly, the vc of thin section was comparable to that of thick
melts in mIM which determines the microstructure during the section. However, the Tm in the thin section was at least 2 C lower
molding process [61]. For example, Kamal et al. [62] found that a than that of the thick section. Therefore, it appears that a combina-
five-layer crystalline structure is observed in a POM micropart in tion of extremely high shear rates and fast cooling rates in the thin
comparison with commonly observed three-layer structure in section is unfavorable for the formation of perfect crystallites,
CIM macroparts. Moreover, there would not be sufficient time which contributes to a reduction of Tm.
S. Zhou et al. / Composites: Part A 103 (2017) 8495 93
Fig. 12. DSC (a) heating and (b) cooling curves obtained from pure PA6 and sections of pure PA6 microparts.
Fig. 13. DSC (a) heating and (b) cooling curves obtained from pure PA6 and sections of CNT5 microparts.
Fig. 13 displays the thermal behavior of pure PA6 and different from the original PA6 in the masterbatch. Thus, the existence of
sections taken from CNT5 microparts. As shown in Fig. 13a, only a two different types of PA6 polymer chains might be reflected in
marginal difference of the Tm was recorded, suggesting that the the crystallization process, thereby leading to a relatively lower
mIM process had little effect on the melting behavior of these vc for the diluted samples such as PA6/CNT extrudates and sections
microparts. Similar to PA6/CNT extrudates (Fig. 11b), the presence of corresponding microparts, as given in Table 1.
of CNT in each section of corresponding microparts had a signifi- The effect of CNT loading concentrations on the thermal behav-
cant effect on the crystallization behavior and a double crystalliza- ior of the middle section of microparts as compared with pure PA6
tion peak was also observed. Compared with the CNT5 extrudate, a is shown in Fig. 14. Except for the middle section of pure PA6
slightly higher Tc2 (Table 1) for each section of corresponding microparts, Fig. 14a and Table 1 reveal that there was an approxi-
microparts might suggest a shear induced crystallization effect in mately 4 C reduction of Tm for the middle section of all microparts,
mIM samples. However, the achieved vc for each section of CNT5 regardless of CNT loading concentrations. This behavior may be
microparts was lower than that of corresponding sections of pure explained by the consideration that the decrease of Tm is associ-
PA6 counterparts, indicating that the presence of CNT might hinder ated with the formation of imperfect crystals. Moreover, there
the formation of ordered crystalline structure or domains, which was a reduction of vc with an incremental loading fraction of
resulted from the limited space and confinement effect that CNT, indicating a steric hindrance effect. Additionally, aside from
imposed on the polymer chains by CNT, irrespective of the hetero- CNT10 micropart, the vc for the microparts is invariably higher
geneous nucleation effect induced by the incorporated fillers. The than that observed in corresponding extrudates, which further
other possible explanation could be associated with the fact that supports the shear-induced crystallization effect in mIM. Therefore,
the pure PA6 which was used to dilute the masterbatch is different it could be concluded that the crystallization process is strongly
94 S. Zhou et al. / Composites: Part A 103 (2017) 8495
Fig. 14. DSC (a) heating and (b) cooling curves obtained from pure PA6 and middle section of PA6/CNT microparts with various filler concentrations.
influenced by the presence of CNT, while the employed molding Microscopy (The University of Western Ontario) for providing TEM
conditions or thermo-mechanical history determines the analysis.
microstructure of products.
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