Composites: Part B 35 (2004) 173178 www.elsevier.

com/locate/compositesb

Processing and properties of poly(methyl methacrylate)/carbon nano ber composites

Jijun Zenga, Bethany Saltysiakb, W.S. Johnsonb, David A. Schiraldic, Satish Kumara,*
a

School of Textile and Fiber Engineering, Georgia Institute of Technology, 801 Ferst Drive, Atlanta, GA 30332-0295, USA b School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta GA 30332-0245, USA c Department of Macromolecular Science and Engineering, Case Western Reserve University, Cleveland, OH 44106, USA

Abstract Single wall carbon nanotubes, multi-wall carbon nanotubes, as well as carbon nano bers (CNF) are being used for reinforcing polymer matrices. In this study, poly(methyl methacrylate) (PMMA) nanocomposites have been processed by melt blending, containing two different grades (PR-21-PS and PR-24-PS) of CNF manufactured by Applied Sciences Inc. The amount of nano bers used was 5 and 10 wt%, respectively. The PMMA/CNF composites were processed into 4 mm diameter rods and 60 mm diameter bers using small-scale melt spinning equipment. At 5 wt% CNF, composite rods as well as bers show over 50% improvement in axial tensile modulus as compared to the control PMMA rod and bers, respectively. The reinforcement efciency decreased at 10 wt% CNF. The PMMA/CNF nanocomposite bers also show enhanced thermal stability, signicantly reduced shrinkage and enhanced modulus retention with temperature, as well as improved compressive strength. The CNF reinforcement efciency has been analyzed using the modied Cox model. q 2003 Elsevier Ltd. All rights reserved.
Keywords: Carbon nano ber; Poly(methyl methacrylate); Nanocomposite

1. Introduction Single wall carbon nanotubes (SWNT) [1 5], multi-wall carbon nanotubes (MWNT) [6 11], as well as carbon nano bers (CNF) [12 16] are being used for reinforcing polymer matrices for improved mechanical, thermal, and electrical properties [17]. The typical diameters of SWNTs are in 0.7 1.5 nm range, of MWNTs in the 10 50 nm range, and that for CNF in the 60 200 nm range. In SWNT and MWNT, graphitic planes are parallel to the tube axis, while in carbon nano bers, graphitic planes make a small angle to the CNF axis [18]. Modication of poly(methyl methacrylate), PMMA, with SWNT and MWNT can result in nanocomposites with enhanced mechanical and electrical properties. SWNT/PMMA composites have been processed using combination of solvent casting and melt mixing [19]. The elastic modulus and yield strength of SWNT/PMMA composite bers increased with nanotube loading and draw ratio; at 8 wt% SWNT loading, the elastic modulus of PMMA increased from 3.1 to 6 GPa. Polarized resonant Raman spectroscopy indicated that the nanotubes in
* Corresponding author. Tel.: 1-404-894-2490; fax: 1-404-894-8780. E-mail address: satish.kumar@tfe.gatech.edu (S. Kumar). 1359-8368/03/$ - see front matter q 2003 Elsevier Ltd. All rights reserved. doi:10.1016/S1359-8368(03)00051-9

the bers were well aligned, leading to the observed anisotropic properties. Jia et al. incorporated MWNT into PMMA by an in situ polymerization process [20]. The mechanical properties and the heat deection temperatures of composites produced using this in situ process were found to increase with increasing levels of MWNT. MWNT/PMMA composites were also processed by melt blending [21]. The nanotubes were found to be well dispersed in the polymer matrix with no apparent damage or breakage. Incorporation of 26 wt% MWNTs increased the threshold temperature for thermal degradation by 30 8C over that of unlled PMMA. The storage modulus of the compounded polymer was signicantly increased by the incorporation of nanotubes, especially at elevated test temperatures. PMMA/SWNT composite thin lms with varying nanotube concentration have also been processed using spin coating [22]. In this paper, we report melt processing of PMMA/CNF composites as well as their structure and properties.

2. Experimental PMMA used in this study was obtained from Cyro Incorporated and has a melt ow index of 1.8 g/l0 min

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(measured at 230 8C/3.8 kg). Two CNFs, PR-21-PS and PR24-PS of Pyrograf-IIIe were obtained from Applied Sciences Inc., of Cedarville, OH. Both CNFs are pyrolytically stripped CNF and polyaromatic hydrocarbons are removed from surface. PR-21-PS is a larger diameter ber than that of PR-24-PS. A detailed listing of properties as well as other characterization of these CNFs is given elsewhere [18,23]. Before blending, PMMA pellets were dried under vacuum at 80 8C for at least 12 h. CNFs were dried under vacuum at 150 8C for the same time period. A Rheomixw TW100 counter rotating twin-screw extruder controlled by a Haake Rheocordw 90 system was used for blending. In a typical experiment, 95 g of PMMA pellets and 5 g of CNF were rst dry mixed by hand for 10 min, then fed to the extruder, to make a 5 wt% composite. The temperatures from the feed to die zone were set as 180, 200, 220, and 240 8C, respectively, and a screw speed of 50 rpm was used. The extrudate was quenched in a room temperature water bath and then pelletized. Unlled PMMA pellets were also processed using the same procedure, to produce a control sample. The PMMA control and PMMA/CNF composite samples were vacuum dried at 80 8C for over 12 h. After drying, these pellets were extruded using a lab-scale piston driven spinning system (manufactured by Bradford Research Ltd) at 260 8C through a 6 cm long, 4 mm diameter cylindrical orice. No spinneret was used. Extruded rods of 4 mm diameter were collected free fall without any drawing. For ber spinning, the extruded material from the same set up was collected at 150 m/min to result in an approximate ber diameter of 60 mm. The morphology of the composites and composite bers were examined using Leo 1530 scanning electron microscope. For SEM observation, samples were fractured in liquid nitrogen and coated with gold using a Sputter Coater (from Edwards High Vacuum International). The 4 mm diameter extruded rods were mounted using copper tubing as the tabs and an epoxy adhesive. For tensile testing, 60 mm diameter bers were mounted on paper tabs. Both the rods and bers were tested tension using an Instron tensile tester. For accurate strain measurement on the 4 mm diameter rods, an extensometer was used. Single lament tensile tests were carried out at a 2.54 cm gauge length using a universal tester (Instron, model 5567) operating at a 100% strain rate. Fiber compressive strength was measured using the loop test [24,25]. Thermogravimetric analysis was carried out with a TA Instruments TGA 2950 thermogravimetric analyzer at a heating rate of 10 8C/min from room temperature to 1000 8C under a continuous air purge. The dynamic storage modulus E0 ; and loss factor, tan d; of PMMA and composite bers were determined in tension mode using RSA III Solids Analyzer (manufactured by Rheometric Scientic, Inc.). Dynamic strain was set at 0.3% and frequency at 1 Hz. The measurements were carried out

from 25 to 130 8C in a temperature step mode with setting the temperature step at 1 8C and soak time 15 s. The initial static stress was set at 2 MPa and the static force was set to be 50% larger than the previously measured dynamic force during the test. Fiber shrinkage was determined using TA instruments thermo-mechanical analyzer (TMA 2940) at a heating rate of 5 8C/min from room temperature to 120 8C under a continuous nitrogen purge. The applied stress was set at 0.2 MPa.

3. Results and discussion Scanning electron microscopy was used to observe the dispersion and distribution of nano bers within the extruded rod as well as in the bers. All specimens are mounted such that the plane viewed under the microscope is a cross-sectional cut perpendicular to the extrusion direction. Micrographs in Fig. 1 show that the nano bers are well dispersed. Fig. 2 gives the facture surface of the composite ber. Good nano ber dispersion is also clearly seen in the PMMA/CNF composite ber.

Fig. 1. Scanning electron micrographs of PMMA/CNF composite rod: (a) PMMA/PR-24-PS 5 wt%; (b) PMMA/PR-21-PS 5 wt%.

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model estimates stress transfer to nano bers of length l; diameter d; axial tensile modulus Ef and volume fraction V (3.0% for this study, presuming densities are 2.0 and 1.20 g/cm3 for CNF and PMMA, respectively) in a matrix of modulus Em (4.7 GPa in Table 1) and Poissons ratio n (0.32 for PMMA [28]) with the factor s l Em 1 b d 1 nEf lnp=4V Combining this with the rule of mixture yields a composite modulus Ec of   tanh b 2 VEf Ec 1 2 VEm q 1 2 b
Fig. 2. Scanning electron micrograph of PMMA/CNF composite ber containing 5 wt% PR-21-PS carbon nano ber. Table 1 Mechanical properties of PMMA/CNF composite rods Sample PMMA control PMMA/PR-21-PS 5 wt% PMMA/PR-21-PS 10 wt% PMMA/PR-24-PS 5 wt% PMMA/PR-24-PS 5 wt% Tensile modulus (GPa) 2.0 3.1 2.3 3.2 3.6

The tensile properties for the extrudates are given in Table 1. It is clear that the PMMA/CNF composite offers an improved tensile modulus. Fiber spinning of PMMA and of PMMA/CNF nanocomposites was accomplished without difculty at 260 8C, at a take up speed of 150 m/min. Tensile properties of the composite bers are given in Table 2. While tensile strength and elongation were slightly reduced by the presence of CNFs in the PMMA matrix, ber tensile modulus increased by more than 50%, and ber compressive strength was more than doubled by the addition of 5 wt% CNF. However, the modulus increase with 10 wt% CNF was less signicant. The observed tensile properties of PMMA control bers are comparable to the previously reported literature [19]. Increase in ber compressive strength which result from CNF incorporation have also been observed in nanocomposite bers produced using smectic clays and silsesquioxane ller materials [12,18,26]. A modied Coxs [27] model can be used to calculate the Youngs modulus of the polymer/CNF composite. This
Table 2 Mechanical properties of PMMA/CNF composite bers Sample PMMA control PMMA/PR-21-PS 5 wt% PMMA/PR-21-PS 10 wt% PMMA/PR-24-PS 5 wt% PMMA/PR-24-PS 10 wt% Diameter (mm) 60 ^ 4 61 ^ 12 63 ^ 10 62 ^ 5 63 ^ 5 Tensile modulus (GPa) 4.7 ^ 1.5 8.0 ^ 1.2 7.7 ^ 1.0 7.5 ^ 1.3 7.6 ^ 0.9

Where q is the orientation factor. Assuming the orientation factor q to be 1, and CNF modulus to be in the range of 100 600 GPa [23,28,29], the modulus for the composite ber is predicted to be in the range of 7 19 GPa at 5 wt% (or 3 vol%) CNF. Since the value of 7 GPa is very close to the measured modulus reported in Table 2, at this weight fraction nano carbon ber, it is tempting to conclude that the modulus of nano carbon bers is about 100 GPa. However, this assumes that the CNF orientation is ideal in the composite ber. However, the previous work on PET/CNF [18] showed that even in highly drawn bers, orientation of CNFs was relatively low. Another point is that the orientation of single crystal graphite decreases rapidly with the graphitic plane misorientation [30,31]. For example, at 108 misorientation, the graphite modulus decreases from 1020 GPa to around 120 GPa. Carbon ber misorientation coupled with the sharp angular dependence of the graphite modulus accounts for the relatively low modulus for the PMMA/CNF composite ber and the axial modulus of the CNFs would be higher than 100 GPa. Thermogravimetric analysis (Fig. 3) shows that the CNFs onset of decomposition is approximately 550 8C, while PMMA begins to degrade at about 300 8C. PMMA/ CNF composite exhibits an onset degradation temperature, higher than that of pure PMMA. The peak degradation rate in PMMA/CNF composite is at about 60 8C higher than in the control PMMA. Incorporation of high temperature nanoparticles, such as smectic clays and silsesquioxanes, have also shown to increase thermal decomposition temperatures [32,33]. The dynamic mechanical properties of PMMA and PMMA/CNF nanocomposite bers are given in Fig. 4.

Tensile strength (GPa) 0.20 ^ 0.04 0.17 ^ 0.04 0.16 ^ 0.04 0.16 ^ 0.03 0.15 ^ 0.01

Elongation at break (%) 16 ^ 3 10 ^ 6 10 ^ 6 10 ^ 5 9^4

Compressive strength 28 ^ 2 73 ^ 11 66 ^ 20

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Fig. 3. Weight loss in PMMA, PMMA/Carbon nano ber composites, and in carbon nano bers when heated in air at 10 8C/min.

Fig. 4. Dynamic mechanical properties of PMMA and PMMA/CNF composite bers. (a) Dynamic storage modulus E0 ; (b) tan d:

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Fig. 5. Thermal shrinkage in PMMA and PMMA/CNF composite bers.

Both grades of CNFs were found to increase the high temperature modulus of the matrix polymer. Both the modulus and modulus retention at high temperature were also observed in increase in polyacrylonitrile (PAN)/SWNT composites [34]. The dynamic mechanical data show that the glass transition temperature of the PMMA/CNF composite ber is about 5 8C higher than that of the control PMMA. The composite bers also show tan d peak of higher magnitude than the control PMMA. Similar tan d peak behavior has also been reported for PMMA/MWNT system [21]. When molecular mobility is restricted due to the presence of nano reinforcement, it results in not only enhanced glass transition temperature, but also in decreased tan d peak magnitude. For example, in PAN/SWNT at 10 wt% carbon nanotube loading, the glass transition temperature increased by 40 8C and tan d magnitude decreased signicantly [34]. The increase in tan d peak magnitude and a narrower tan d peak in the composite ber may be a result of more uniform heat distribution in the PMMA/CNF due to its higher expected thermal conductivity, as compared to the control PMMA. The thermal shrinkage data for both the control and the composite PMMA/CNF bers is given in Fig. 5. Since PMMA is a glassy polymer, it is expected that considerable shrinkage would result when oriented bers are allowed to relax at elevated temperatures. This behavior is different from that observed when traditional, semicrystalline polymer bers, such as polyester and polypropylene are exposed to elevated temperatures. The absence of strain-induced crystallinity in PMMA ber leads to the large dimensional change as shown in Fig. 5. The presence of CNFs decreased the magnitude of PMMA ber shrinkage considerably. At a temperature of approximately 110 8C, unlled PMMA is found to shrink by 30%; the PMMA/CNF (95/5) composite bers exhibits only 5% shrinkage under the same conditions. One might also expect that the effect of reinforcement in glassy polymers, such as PMMA, would be more

profound than would be observed in more rigid, semicrystalline polymer nanocomposites. Although the two grades of CNFs used in this study have different diameters [23], they show no difference in mechanical and thermal reinforcement effects of PMMA matrix. This suggested that these two CNFs have similar mechanical and surface properties, and differ mainly in diameter.

4. Conclusions The glassy polymer, poly(methyl methacrylate), PMMA, can be reinforced by incorporation of CNF via melt mixing. While at 5 wt% CNF loading, the modulus of the composite ber increased substantially, similar improvements were not observed at 10 wt% nano ber loading. This suggests that the optimum CNF reinforcement is perhaps below 10 wt%. Of course, optimum reinforcement concentration would also be a function of CNF diameter and its dispersion level. The nanocomposite bers also exhibit increased compressive strength and reduced thermal shrinkage as compared to the control PMMA.

Acknowledgements The nancial support provided by Applied Sciences Incorporated and National Science Foundation is gratefully acknowledged. The authors would also like to acknowledge the help of Dr Ron Jacobson of Applied Sciences Incorporated for providing useful information.

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