Arun Singh Babal,
Bhanu Pratap Singh*,
Jeevan Jyoti,
Sushant Sharma,
Abhishek Kumar Arya and
Sanjay R. Dhakate
Physics and Engineering of Carbon, CSIR-National Physical Laboratory, New Delhi-110012, India. E-mail: bps@nplindia.org; bpsingh2k4@yahoo.com; Fax: +91-11-45609310; Tel: +91-11-45608460
First published on 4th July 2016
Carbon fiber (CF) and multiwalled carbon nanotube (MWCNT)-reinforced hybrid micro–nanocomposites are prepared through melt mixing followed by injection moulding. The synergistic effect on both the static and dynamic mechanical properties with MWCNT/aMWCNT and CF reinforcement in a polycarbonate matrix is investigated by utilizing dynamic mechanical analysis, and flexural and tensile measurements. The enhancement in the flexural modulus and strength of the composite specimens as compared to pure PC for maximum loading of CF is 128.40% and 39.90%, respectively, which further improved to 142.94% and 42.60%, respectively, for CF-functionalized MWCNTs. Similarly, the storage modulus of the composite specimens reinforced with a maximum loading of CF and CF-functionalized MWCNTs show an increment of 176.57% and 203.33%, respectively over pure PC at 40 °C. Various types of parameter such as the coefficient C factor, degree of entanglement and adhesion factor have been calculated to analyze the interaction between fillers and the polymer matrix. Composite specimens containing 2 wt% of functionalized MWCNTs show a lower C value than the as-synthesized MWCNTs, which is indicative of a higher effectiveness of functionalized MWCNT-containing composite specimens. These results are well supported by optical microscopy and Raman spectroscopy by confirming the distribution of reinforcements and the interaction to PC, respectively.
In composite materials, stress transfer between the reinforcement and matrix polymer mainly depends upon their interface, because weak interaction between CF and the PC matrix causes weak interfacial adhesion between them. To address these kinds of problems, various researchers supported the idea of incorporation of nanostructures into the polymer matrix.9,10 They suggested that it will improve the properties of composite materials because of increased interfacial adhesion due to the high specific area of nanostructures. For nanostructures, CNTs are considered as the most promising candidate to reinforce the matrix-rich region due to their high aspect ratio, nanoscale diameter and superior mechanical and electrical properties that provide widespread applications that alone CF cannot provide. Therefore, in recent times the incorporation of CNTs along with CF reinforcement into a polymer matrix has gained much attention. The incorporation of CNTs benefits the fiber-dominating properties to some extent, but the real benefit is expected in the matrix-dominating properties. These micro–nanohybrid composite materials create the possibility of fabricating light-weight multifunctional materials with enhanced mechanical and electrical properties that fulfil the requirement of modern society.
The reason behind the preparation of hybrid composites is to alter the properties in order to compensate the shortcoming of one factor by incorporating the other and meet the desired requirements.11–14 Dispersion of CNTs into a matrix plays a key role to fully gain the unique properties of CNTs in composite materials.15 The incorporation of nano-sized CNTs along with a conventional micro-sized CF filler into the polymer matrix can be attained by two methods: (i) by direct incorporation into the polymer matrix16,17 or (ii) by carbon fiber utilizing CNTs.18–22 Altering the polymer matrix by dispersing MWCNTs via the direct incorporation method has several advantages over CF using MWCNTs such as low cost, high stability, ease of processing, and industrial viability. In the direct incorporation method, the CF/polymer composite is generally prepared by homogeneous dispersion of the filler by utilizing varied techniques, i.e. solvent casting and melt mixing.23
In recent years, because of their low density, high strength and modulus, CF-reinforced thermoplastic polymer composites have gained much attention.24–26 They offer various advantages over thermosetting polymers such as higher recyclability, environmental friendliness, and industrial viability as well as high damage tolerance.27 Polycarbonate (PC) is an engineering thermoplastic polymer with high mechanical properties and processability. Therefore, much attention has been given towards the development of high-performance thermoplastic composite materials using PC28 and polyphenyl sulfide (PPS)29 polymer matrices.
Currently, we are focusing on the former literature of experimental studies reported for various thermoplastic polymer composite materials. Only a handful of research has been done that discusses the mechanical properties of hybrid micro–nanocomposites. They reported an enhancement in the mechanical properties of composites along with the reinforcement content. Previous studies indicate that properties of composite materials largely depend upon the dispersion, surface modification, and alignment of fillers as well as their interaction with the polymer matrix.15,30–32 Ameli et al. synthesized both solid and foamed polypropylene/carbon fiber (PP–CF) composite materials using injection moulding.33 They reported that a foamed composite has better mechanical properties as compared to a solid composite. Hong et al. studied the carbon fiber-reinforced polypropylene composites in the presence of MWCNTs at different mixing speeds.34 They reported that a high mixing speed causes maximum dispersion of CF which improves the composite properties. Rahmanian et al. grew uniform CNTs on the surface of CF and glass fiber via the CVD method and prepared a composite with polypropylene polymer.35 They showed an increment in the tensile properties of these composites as compared to the neat short fiber composites because of the enhanced interaction between the fiber and matrix. Puch et al. investigated both the tensile and morphological properties of short CF-reinforced Nylon 6/MWCNT composites.36 They showed an increment in these properties with an increment in the total filler content. They reported the dominating behavior of the CF filler for a greater CNT content.
The static and dynamic mechanical properties of CNT polymer composites depend on the concentration of the CNTs, surface modification, adhesion, and processing technique. Herein, we report the effect of functionalization of CNTs on the static and dynamic mechanical properties of CF/PC composites to investigate the synergistic effect of the hybrid filler on the performance of PC. Prior to this study, no study has reported the effect of direct incorporation of carbon fiber along with functionalized (aMWCNTs) or non-functionalized (MWCNTs) carbon nanotubes into a PC polymer matrix via the melt mixing technique to the best of our knowledge. Static mechanical properties in the form of the tensile strength, Young’s modulus, stress–strain behavior, flexural strength, flexural modulus and dynamic mechanical properties in the form of the storage modulus, loss modulus, tanδ, and stiffness are studied and analyzed. The degree of entanglement, C factor and adhesion factor are evaluated to correlate the efficiency of reinforcement in the composites.
In this study, two types of moulds were used in injection moulding in order to examine the effect of different compositions of CF and MWCNT loading on the composite properties (Table 1). According to the standards the moulds used were: (i) tensile mould (ASTM D638), and (ii) flexural mould (ASTM D790). Flexural specimens were cut into dimensions of 12.5 mm × 6.3 mm × 3.3 mm (length × width × thickness) in order to analyze the dynamic mechanical properties of the composite materials. These flexural samples were cut using a diamond cutter machine. The whole process for the hybrid micro–nanocomposite fabrication is shown in Fig. 1.
Composite | Code | PC (wt%) | MWCNT/aMWCNT (wt%) | CF (wt%) |
---|---|---|---|---|
Pure PC | Pure | 100 | — | — |
2 wt% MWCNT/PC | PC2CNT | 98 | 2 | — |
2 wt% aMWCNT/PC | PC2aCNT | 98 | 2 | — |
2 wt% CF/PC | PC2CF | 98 | — | 2 |
1 wt% CF/1 wt% MWCNT/PC | PC1CF1CNT | 98 | 1 | 1 |
1 wt% CF/1 wt% aMWCNT/PC | PC1CF1aCNT | 98 | 1 | 1 |
5 wt% CF/PC | PC5CF | 95 | — | 5 |
10 wt% CF/PC | PC10CF | 90 | — | 10 |
15 wt% CF/PC | PC15CF | 85 | — | 15 |
20 wt% CF/PC | PC20CF | 80 | — | 20 |
18 wt% CF/2 wt% MWCNT/PC | PC18CF2CNT | 80 | 2 | 18 |
18 wt% CF/2 wt% aMWCNT/PC | PC18CF2aCNT | 80 | 2 | 18 |
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Fig. 1 Schematic diagram for the fabrication of hybrid micro–nanocomposite specimens using extrusion followed by injection moulding. |
Storage modulus (E′) = G′/γ | (1) |
Loss modulus (E′′) = G′′/γ | (2) |
tan![]() | (3) |
The role of fillers can be identified by comparing stress values of various composite materials. As seen from Fig. 2(c) and (d), strain values (above and below the yielding point) show higher stress values for composite materials with increased filler loading, below their elongation at break. The hybrid micro–nanocomposites show both higher stress and strain values. This type of evaluation is necessary for applications requiring the identification of a composite material with a higher stiffness that does not undergo yielding beyond a specified level along with maintaining higher strength properties.41
The role of reinforcement on both the elastic modulus and ultimate tensile strength (UTS) properties of composite materials is shown in Fig. 3. From Fig. 3(a), it is evident that the UTS of lone CF-reinforced composite samples increases along with CF incorporation and reaches up to 91.3 MPa for PC20CF, which is 37.3% higher than that of pure PC (66.5 MPa). As for the CNT/CF-reinforced hybrid nanocomposites, the UTS increases by 40.75% (93.6 MPa) for PC18CF2aCNT and 39.2% (92.6 MPa) for the PC18CF2CNT composite with respect to the pure PC (66.5 MPa) (Fig. 3(c)). The increase in the UTS with CNT amount in the CF/PC samples is indicative of the effective external load transfer between the fillers and the polymer matrix. Incorporation of both the CF and MWCNTs together causes a significant synergistic effect on the mechanical properties of the polycarbonate composite. The combined influence of reinforcements for the tensile and flexural modulus as well as strength is considerably larger as compared to their individual contribution in a composite material incorporated with lone CF and MWCNTs. During a MWCNT-related failure event, the stress transfer process done by MWCNTs is followed by void propagation, thus reducing the stress concentration on CF fillers.
Similar patterns of increment are seen in the elastic modulus for the CF/PC composite materials (Fig. 3(b)). Incorporation of MWCNT/aMWCNTs in the CF/PC composite causes further enhancement in the elastic modulus. The average increment in the elastic modulus for the PC20CF composite is 132.2% (3149 MPa), 143.7% (3304 MPa) for PC18CF2aCNT, and 137.4% (3219 MPa) for the PC18CF2CNT composite as comparison to pure PC (1356 MPa) (Fig. 3(b)).
By observing different CF/CNT/PC hybrid composites, it can be deduced that incorporation of small amounts of CNTs in various samples leads to higher filler–filler as well as filler–matrix interaction that causes further enhancement in both the UTS and elastic modulus value of the composite samples. All the tensile property parameters are stated in Table S1 (ESI†).
Beside this, an improvement in the average flexural modulus is 128.4% (4920 MPa) for PC20CF with respect to the pure PC polymer (2154 MPa). Incorporation of functionalized and non-functionalized MWCNTs in micro CF/PC composite material leads to a 142.94% and 136.70% enhancement over neat PC, respectively. All the flexural property parameters are stated in Table S1 (ESI†).
The results from three-point bending are coherent with the storage modulus results for the micro, nano and hybrid micro–nanocomposites. The effect of various CF loadings on the storage modulus of composite materials is shown in Fig. 5(a). From Fig. 5(a), it is obvious that the storage modulus continuously increases along with the increment in the CF content. In the glassy region, the composite samples show a trivial amount of alteration with respect to the temperature increment and maintain a plateau. This enhancement in E′ for the PC20CF (2904 MPa) and PC2CF (1750 MPa) samples is 176.6% and 66.7%, respectively, over the pure PC (1050 MPa) sample at 40 °C (Fig. 5(a)). As for the rubbery region (above Tg), the improvements are 1200% and 366% for PC20CF (39 MPa) and PC2CF (14 MPa), respectively, compared to the pure PC (3 MPa) sample at 180 °C. In addition to that, incorporation of a minor amount of MWCNTs and aMWCNTs causes further enhancement in the storage modulus value due to the filler–filler and filler–polymer interaction. The increment in E′ is 189.5% (3040 MPa) for the PC18CF2CNT sample and 203.3% (3185 MPa) for PC18CF2aCNT as compared to that of pure PC at 40 °C (Fig. 5(b)). Samples PC18CF2CNT and PC18CF2aCNT show a 4.7% and 9.7% improvement in E′ over the PC20CF sample. This increment in E′ is because of the even distribution of chopped CF as well as CNTs inside the PC matrix employed by applying appropriate shear stress during melt mixing that causes filler–polymer chain network formation, which acts as a reinforcement. Besides all of this, Fig. 5(a) and (b) also exhibit the disproportionate behavior between the modulus and temperature gradient which is attributed to the enhanced mobility of the polymer chains. Fig. 5(c) shows the increment in the loss modulus for a varied CF content. It is obvious that incorporation of reinforcement causes broadening as well as an increment in the loss modulus peak. One of the main reasons behind such a rise in the loss modulus is internal fraction that heightens the heat dissipation in the composite material. The decline in the loss modulus value after reaching its peak value is due to the free movement of chains present in the material.
The effectiveness of reinforcement on the matrix polymer can be evaluated by the coefficient C. It is a relative measurement of the decline in the modulus along with a temperature increment. The coefficient C parameters are calculated using the formula:42,43
![]() | (4) |
The value of the coefficient is inversely proportional to the reinforcement effectiveness. Fig. 6(a) exhibits the coefficient C values for varied composite specimens at a frequency of 1 Hz. It is apparent from the figures that incorporation of reinforcement leads to a continuous decline in the coefficient C values. For a similar content of reinforcement, composite specimens containing a small amount of functionalized MWCNTs demonstrate a lower C value than that of the as-synthesized MWCNTs, indicative of the higher effectiveness of aMWCNT-containing composite specimens.
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Fig. 6 Effect of reinforcement loading on (a) coefficient C factor, (b) degree of entanglement at 40 °C, (c) degree of entanglement at 130 °C, and (d) degree of entanglement at 180 °C. |
Alongside the effectiveness of reinforcement, the degree of entanglement also plays a key role in providing composite materials their specific properties. The degree of entanglement between the matrix and filler can be evaluated by the following equation:44
N = E′/6RT | (5) |
The damping factor, tanδ, is a ratio of loss to storage modulus, which measures the amount of deformation energy in the form of heat, dissipated per cycle. The glass transition temperature (Tg) of the composite samples was studied by evaluating both tan
δ and the storage modulus values. The maximum value of tan
δ and swift decline in E′ value in contrast to the temperature increment is considered as Tg. Fig. 7 exhibits the value of tan
δ for different wt% of the micro–nanohybrid composites. The depression in Tg calculated from tan
δ is almost 4 °C for varied composite samples. The Tg values resulting from tan
δ and E′ values varied from 160.2 to 156.2 °C and 145.3 to 134.3 °C for the pure PC polymer to PC18CF2aCNT composite sample, respectively (Fig. 7). As observed from Fig. 7, the area under the tan
δ peak decreases with the increased amount of reinforcement. This decline suggests that the fraction of polymer confined by reinforcement increases with the filler content and only a small portion of the polymer is involved with the glass transition temperature.
The interaction between the reinforcement and polymer matrix is assessed by evaluating the adhesion factor which is determined from the tanδ value of the composite and pure PC as a function of the filler volume fraction. It can be expressed as:42
![]() | (6) |
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Fig. 8 Effect of different weight% of filler loading on adhesion factor: (a) 2 weight% and (b) 20 weight%. |
The effect of reinforcement on the stiffness of the composite material is shown in Fig. 9. The stiffness of the composite samples highly depends on the type of reinforcement. From Fig. 9(b), it can be concluded that the presence of non-functionalized CNTs shows a higher degree of stiffness as compared to the functionalized CNTs. CF microcomposites show higher stiffness than hybrid micro–nanocomposites for the same amount of filler content. All of this is also evident in the fracture pattern of the tensile composite samples (Fig. 2(e) and (f)).
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Fig. 9 Effect of CF/MWCNT incorporation on hybrid composite properties over a specific temperature range: (a) stiffness and (b) at a lower range of temperature scale (zoomed in). |
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Fig. 10 Optical micrographs of flexural specimens: (a) 2 wt% CF/PC composite and (b) 20 wt% CF/PC composite, and tensile specimens: (c) 2 wt% CF/PC composite and (d) 20 wt% CF/PC composite. |
Fig. 11 shows the role of reinforcement under applied stress conditions. Nanofillers such as MWCNTs act as a suppressor for the propagation of nanovoid formation due to the stress. After a certain high stress value, the MWCNTs cannot contain the nanovoids and they start to stretch to form microvoids (Fig. 11(a)). At the point of microvoid formation, the role of CNTs as a reinforcement starts to decline and the role of CF reinforcement is realized (Fig. 11(b)). Due to the diameter and interaction of CF embedded in the polymer on both sides of the microvoid, it tries to prevent further deterioration and reinstate the polymer to its former condition.
As seen in Fig. 12(a), the diameter of the CF calculated using a microscope is 8.65 μm (marked with a dotted circle), which is much higher than the diameter of CF used in this study. This indicates the wetting effect of CF and supports the idea of the higher degree of interaction between CF and the PC polymer matrix. Fig. 12(b) shows the PC2CF specimen which was put under high stress conditions, and gives evidence to support the above conclusion. It shows the stretching of the polymer matrix and formation as well as propagation of microvoids due to the applied stress. CF, marked with a dotted circle, has both ends embedded into the polymers and acts as a reinforcement against the void propagation and tries to reinstate the polymer to its previous geometry (Fig. 12(b)). This provides evidence for the high mechanical properties obtained for the composite samples.
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Fig. 12 (a) Evaluation of CF diameter in 20 wt% CF/PC composite and (b) reinforcement effect of CF filler in the 2 wt% CF/PC tested specimen. |
By taking all of these observations into consideration, it can be proposed that the relation between shifting and interaction between the matrix and fillers is in good agreement with the results obtained from optical microscopy as well as tensile and flexural measurements.
Footnote |
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c6ra08487g |
This journal is © The Royal Society of Chemistry 2016 |