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CARBON NANOTUBES/EPOXY MATRIX CARBON NANOTUBES/EPOXY MATRIX NANOCOMPOSITE SYSTEMS NANOCOMPOSITE SYSTEMS METE 715 POLYMER NANOCOMPOSITES METE 715 POLYMER NANOCOMPOSITES M.S. Ümit TAYFUN M.S. Ümit TAYFUN POLYMER SCIENCE & TECHNOLOGY POLYMER SCIENCE & TECHNOLOGY

Epoxy/CNT nanocomposites

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CARBON NANOTUBES/EPOXY MATRIX NANOCOMPOSITE SYSTEMS

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Page 1: Epoxy/CNT nanocomposites

CARBON NANOTUBES/EPOXY CARBON NANOTUBES/EPOXY MATRIX NANOCOMPOSITE MATRIX NANOCOMPOSITE

SYSTEMSSYSTEMS

METE 715 POLYMER NANOCOMPOSITES METE 715 POLYMER NANOCOMPOSITES

M.S. Ümit TAYFUNM.S. Ümit TAYFUN

POLYMER SCIENCE & TECHNOLOGYPOLYMER SCIENCE & TECHNOLOGY

Page 2: Epoxy/CNT nanocomposites

The idea of combining CNTs with thermosets is very appealing from several perspectives.

In general, the mechanical and physical properties such as electrical conductivity were found to depend on the degree of dispersion of the CNTs.

Control of the nanotube dispersion can be facilitated by manipulating the polymer-CNT interface.

This can be accomplished via either primary or secondary interactions between the CNT and resin. Secondary interactions can occur between certain functional groups attached to the CNT surface and the resin, wrapping a polymer around the nanotube or by using surfactants.

While some of these approaches have resulted in enhanced CNT dispersion, it is presumed that covalent interactions will yield the best dispersion and the best properties.

Page 3: Epoxy/CNT nanocomposites

It is crucial to disperse them homogeneously in the matrix to exploit the potential of CNT.

This is difficult to achieve since CNT tend to aggregate because of attractive van der Waals interactions.

To improve dispersion of CNT in an epoxy matrix, Surfactants, for example polyoxyethylene-8-lauryl, have been used to disperse CNT before their introduction into a polymer matrix.

The extraordinary mechanical (and electronic) properties of CNT depend on their specific chemical structure, and covalent functionalisation ntroduces defects and degrades the nanotube properties.

This leads people to search for alternative ways to disperse CNT and to improve their bonding into polymer matrices.

Page 4: Epoxy/CNT nanocomposites

Comparision Comparision of micro- and nano-scale fillers

The distribution of micro-scale fillers is homogeneous throughout the matrix, and the differentiation of individual particles in a matrix can be done easily.

However, when GNPs and CNTs are filled into the same volume of matrix,it is hard to disperse individual particles uniformly, considering the particle agglomeration due to the electrostatic interaction and van der Waals force, the real distribution of nano-scale fillers should be more complicated.

P.-C. Ma et al. / Composites: Part A 41 (2010) 1345–1367

Page 5: Epoxy/CNT nanocomposites

DispersionDispersion

In addition to the size effect of fillers, the physical nature of particles also plays an important role in dispersing them into polymer matrix.

It has been proved that these bundles and agglomerates result in diminished mechanical and electrical properties of composites as compared with theoretical predictions related to individual CNTs.

P.-C. Ma et al. / Composites: Part A 41 (2010) 1345–1367

Page 6: Epoxy/CNT nanocomposites

Ultrasonication: shock waves promotes the ‘‘peeling off” of individual nanoparticles located at the outer part of the nanoparticle bundles, or agglomerates, and thus results in the separation of individualized nanoparticles from the bundles

Calendering process: the gap width between the rollers can be mechanically adjusted, thus it is easy to get a controllable and narrow size distribution of particles in viscous materials to achieve the desired level of particle dispersion

Dispersion TechniquesDispersion Techniques

Page 7: Epoxy/CNT nanocomposites

Calendering may not be applied for dispersing CNTs into thermoplastic matrices, such as polyethylene, polypropylene and polystyrene. In contrast, CNTs can be conveniently dispersed into the liquid monomer or oligomer of thermosetting matrices, and nanocomposites can be obtainedvia the in situ polymerization.

The minimum gap between the rollersis about 1–5 lm, which is comparable to the length of CNTs, but ismuch larger than the diameter of individual CNTs.

These dimensional disparities between the roller gap and the CNT dimensions may suggest that calendaring can better disperse the large agglomerated CNTs into small ones at sub-micron level, although some individual CNTs may be disentangled out from the agglomerates

P.-C. Ma et al. / Composites: Part A 41 (2010) 1345–1367

Page 8: Epoxy/CNT nanocomposites

Ball milling: grinding method used to grind materials into extremely fine powder for use in paints

Stir and extrusion: MWCNTs can be dispersed more easily than SWCNTs by employing stir. Extrusion is particularly useful to produce CNT/polymer nanocomposites with a high filler content

Dispersion TechniquesDispersion Techniques

Page 9: Epoxy/CNT nanocomposites

Epoxy/CNT NanocompositesEpoxy/CNT Nanocomposites

Page 10: Epoxy/CNT nanocomposites

DispersionDispersion

Carbon nanotubes are bended andtwisted together, aggregating to a bulk

structure in micro-scale.

In Fig.2, it can be seen that the CNTs arein a very good dispersion state, and the

degree of aggregation between CNTs decreases greatly. It is easy to

distinguish the single nanotube.

Therefore, the ultrasonic dispersion of carbon nanotubes can decrease the degree of aggregation, helping to make full use of the outstanding characteristics of the CNTs.

Mechanical and electrical properties of carbon nanotube reinforcedepoxide resin composites, LIANG Shu-quan, et al/Trans. Nonferrous Met. Soc. China 17(2007)

Page 11: Epoxy/CNT nanocomposites

DispersionDispersion

The fracture surface of pure epoxide resin in Fig. 5(a) is very smooth, which is a typical brittle fracture. This indicates that the epoxide resin is very brittle.

The appearance of tensile fracture surface has changed greatly after adding carbon nanotubes in Figs.5(b)−(d).

When the content of carbon nanotubes is 0.25%, the appearance of tensile fracture surface of composites becomes rougher and ragged like clouds.

With further increase of carbon nanotubes, the tensile fracture surface is much rougher and their crack becomes more random.

Mechanical and electrical properties of carbon nanotube reinforcedepoxide resin composites, LIANG Shu-quan, et al/Trans. Nonferrous Met. Soc. China 17(2007)

Page 12: Epoxy/CNT nanocomposites

DispersionDispersion Characterisation of the nanocomposites macroscopic morphology was conducted by light microscopy.In the S.T. Buschhorn’s work, multiwall carbon nanotube particles were dispersed into the highly viscous Epoxy resin

using the three roll millElectrically conductive mixture contained 0.1 wt. % MWCNTs

‘’Direction sensitive deformation measurement with epoxy/CNT nanocomposites’’ S.T. Buschhorn*, M.H.G. Wichmann, J. Gehrmann, L. Böger, K. Schulte, 2008 Nanotechnology 19, 475-503

Page 13: Epoxy/CNT nanocomposites

Adding a small quantity of a commercial block copolymer considerably enhances the mechanical properties of CNT–epoxy (CE) composites compared to the pure epoxy resin

Q. Li et al.: Carbon nanotube/epoxy resin composites using a block copolymer as a dispersing agent, phys. stat. sol. (a) 201, No. 13, R89– R91 (2004)

Page 14: Epoxy/CNT nanocomposites

Functionalization of CNTs

Page 15: Epoxy/CNT nanocomposites

Functionalization of CNTs

M. Abdalla et al. / Polymer 48 (2007) 5662e5670

the increase in the relative intensity of the D-band can be taken as a crude measure of the degree of functionalization.

Carboxylic acid functional groups were identified on the surface of the oxidized MWCNTs by FT-IR Spectroscopy.

Page 16: Epoxy/CNT nanocomposites

Functionalization of CNTs

Effects of Silane Functionalization on the Properties of CNT/Epoxy Nanocomposites, Peng Cheng MA at Al, Adv. Funct. Mater, 2008

The presence of CNT in the epoxy matrix increased the Tg of The presence of CNT in the epoxy matrix increased the Tg of nanocomposite due to the difference in the extent of cross-nanocomposite due to the difference in the extent of cross-

linking reactions of epoxy.linking reactions of epoxy.

Page 17: Epoxy/CNT nanocomposites

Pristine, carboxylic and ester functionalized (MWCNT)/poly(vinylidene fluoride)(PVDF)composites

Functionalization of CNTs

Large dielectric constant of the chemically functionalized carbon nanotube/polymer composites, Q. Li et al. / Composites Science and Technology 68 (2008) 2290–2296

In Fig. a and d, the length of the carboxylic functionalized MWCNTs is obviously shorter than that of pristine MWCNTs.

The Fig. b and e shows that the amorphous carbon materials in carboxylic functionalizedMWCNTs are less than that in pristine MWCNTs.

In Fig. c and f, the catalysts embedded in the tip of MWCNTs had been removed. The closed tube tip was opened and the wall structure of the tubes was not damaged by acid treatment.

Page 18: Epoxy/CNT nanocomposites

Electrical Conductivity of Epoxy/CNT NanocompositesElectrical Conductivity of Epoxy/CNT Nanocomposites

Mechanical and electrical properties of carbon nanotube reinforcedepoxide resin composites, LIANG Shu-quan, et al/Trans. Nonferrous Met. Soc. China 17(2007)

With increasing addition of carbon nanotubes, the resistivity of the composite decreases dramatically. This means the conductivity of the composite increase greatly.According to the percolation theory, when the content of carbon nanotubes is low, the carbon nanotubes distribute randomly in the matrix, and do not form a conductive network.

With increasing content of carbon nanotubes, they begin to connect and interact with each other to form a network.

The above percolation threshold values, the continuous conductive channel is developed in the frame of the network, the resistivity will decrease greatly.

The matrix will change from insulator to semiconductor.

The percolation thresholdvalues for electrical characteristic transformation are0.3% and 1.1%, respectively.

Page 19: Epoxy/CNT nanocomposites

Effects of Silane Functionalization on the Properties of CNT/Epoxy Nanocomposites, Peng Cheng MA at Al, Adv. Funct. Mater, 2008

The electrical conductivity of nanocomposites containing silane-CNT decreased due to the wrapping of non-conductive silane onto CNT surface and well-dispersed CNTs.

Electrical Conductivity of Epoxy/CNT NanocompositesElectrical Conductivity of Epoxy/CNT Nanocomposites

Page 20: Epoxy/CNT nanocomposites

Improvement in electrical, thermal and mechanical properties of epoxy by filling carbon nanotube, Zhou et al. – eXPRESS Polymer Letters Vol.2, No.1 (2008) 40–48

Generally, the percolation threshold is considered to be lowerfor fiber-shaped fillers (high aspect ratio) than for spherical particles.

The percolation thresholdhas been determined to be below 0.1 wt%. However, once CNT loading is higher that 0.2%, resistivity decreased with CNT content slowly.

Electrical Conductivity of Epoxy/CNT NanocompositesElectrical Conductivity of Epoxy/CNT Nanocomposites

Page 21: Epoxy/CNT nanocomposites

Improvement in electrical, thermal and mechanical properties of epoxy by filling carbon nanotube, Zhou et al. – eXPRESS Polymer Letters Vol.2, No.1 (2008) 40–48

Impedance of the sample decreases significantly with frequency at frequencies higher than 100 kHz, indicating that at high frequency the impedance of the sample is dominated by the capacitance of the epoxy matrix.

Therefore, it is possible to determinethe connectivity between the CNT and polymer matrix by using the complex resistivity of the sample at different frequencies over a broad frequencyrange.

Electrical Conductivity of Epoxy/CNT NanocompositesElectrical Conductivity of Epoxy/CNT Nanocomposites

Effect of frequency on resistivity of nanophased epoxy

Page 22: Epoxy/CNT nanocomposites

ReferencesReferences The effect of interfacial chemistry on molecular mobility and morphology of

multiwalled carbon nanotubes epoxy nanocomposite, M. Abdalla et al./Polymer 48, 2007

Dispersion and functionalization of carbon nanotubes for polymer-based nanocomposites, P.-C. Ma et al. / Composites: Part A 41 (2010) 1345–1367

Carbon nanotube/epoxy resin composites using a block copolymer as a dispersing agent, Q. Li et al. phys. stat. sol. (a) 201, No. 13, R89– R91 (2004)

Effects of Silane Functionalization on the Properties of CNT/Epoxy Nanocomposites, Peng Cheng MA et al./ Adv. Funct. Mater, 2008

Direction sensitive deformation measurement with epoxy/CNT nanocomposites, S.T. Buschhorn et al./ 2008 Nanotechnology 19, 475-503

Large dielectric constant of the chemically functionalized carbon nanotube/polymer composites, Q. Li et al. / Composites Science and Technology 68 (2008) 2290–2296

Mechanical and electrical properties of carbon nanotube reinforced epoxide resin composites, LIANG Shu-quan, et al/Trans. Nonferrous Met. Soc. China 17(2007)

Improvement in electrical, thermal and mechanical properties of epoxy by filling carbon nanotube, Zhou et al. – eXPRESS Polymer Letters Vol.2, No.1 (2008) 40–48