Methods for Improving the Integration of Functionalized Carbon ...

CHAPTER 8

Methods for Improving the Integration of Functionalized Carbon Nanotubes in Polymers L. VALENTINI*, D. PUGLIA AND J. M. KENNY University of Perugia, Dipartimento di Ingegneria Civile e Ambientale, Strada di Pentima 4, Terni, 05100, Italy *E-mail: [email protected]

8.1 Introduction Due to their exceptional mechanical, thermal and electrical properties, in addition to the low density with respect to the class of organic and inorganic tubes, carbon nanotubes (CNTs) are extremely promising for the development of high-performance nanostructured materials. Since their discovery in 1993, the research in this exciting field has been in continuous evolution, with most of the research focused on the assessment of the CNT properties and the development of advanced structural composites based on CNTs.1,2 However, the incorporation of nanotubes is not a trivial task, particularly as a good dispersion for a chemical grafting to the polymer matrix is mandatory to maximize the advantage of nanotube reinforcement. In fact, the affinity to adhere to each other renders asgrown CNTs intractable and indispersable in common solvents.3 On the other hand, it has been demonstrated that CNTs can interact with different classes of compounds.4–20 The formation of supramolecular complexes allows a better processing of CNTs for the fabrication of innovative nanodevices. In addition, CNTs can undergo chemical reactions that make them more soluble for their integration into organic systems. Two of the key RSC Nanoscience & Nanotechnology No. 27 Carbon Nanotube-Polymer Composites Edited by Dimitrios Tasis # The Royal Society of Chemistry 2013 Published by the Royal Society of Chemistry, www.rsc.org

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Methods for Improving the Integration of Functionalized Carbon Nanotubes in Polymers 235

challenges that are preventing the realization of composites made out of CNTs are securing a reliable control over their surface chemistry through either covalent or non-covalent modification and achieving dispersion. In this Chapter, we report on some examples of nanocomposites with CNTs, highlighting a meshwork of interactions between the mechanical, electrical and optical properties of CNTs and the interface with the polymer matrix. CNTs are considered ideal materials for reinforcing fibers due to their exceptional mechanical properties. Functionalization of CNTs seems to be the most effective way to incorporate these nanofibers into the polymer matrix. It is generally accepted that the fabrication of high-performance nanotube–polymer composite depends on the efficient load transfer from the host matrix to the tubes. If the percentage of nano-reinforcements is very low or if it is well-dispersed, there are more strong interfaces that slow down the progress of a crack.21,22 To address these issues, several strategies for the preparation of such composites have been reported. Here we report some of these strategies involving physical mixing in solution, infiltration of monomers in the presence of nanotube sheets and chemical functionalization of CNTs by plasma treatment.

8.2 In Situ Polymerization Methods 8.2.1

Poly(methyl methacrylate) (PMMA)-based Nanocomposites

It is known how the selective localization of nanoparticles [i.e. carbon black (CB)] at the interface of a polymer blend23,24 represents an alternative route to obtain conductive materials. Following this concept, it was recently proposed25 that the localization of the nanotubes at an interface instead of a homogeneous dispersion within the whole composite volume enhances the conductivity of the material with a low nanotube content. A compromise between the nanotube dispersion and their localization at the interface can be obtained by preparing thin films of CNTs containing polymers. In this regard, more recently, a novel approach was proposed in which pre-aligned arrays of multi-walled carbon nanotubes (MWNTs) were grown on a substrate by chemical vapour deposition,26 then a monomer (i.e. methyl methacrylate) was infiltrated and polymerized into these arrays. The resulting composite films showed good dispersion of nanotubes in the polymer matrix with an enhanced thermal stability. Similar synthesis approaches have been used to develop composite architectures consisting of intercalated networks of nanotubes and polymers.27–29 Zhang et al.30 obtained a CNT–polymer composite by infiltration of a monomer liquid into aligned CNT aerogel fibers with subsequent in situ polymerization. PMMA/MWNT composite fibers showed that the PMMA filled the spaces of the nanotube fibers and bound the nanotubes together. PMMA in the composite fibers exhibited local order. The resultant composite fibers with 15 wt% nanotube loading exhibited a 16-fold and a 49-fold increase in tensile strength and Young’s modulus, respectively, compared with the control PMMA.

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Figure 8.1

Chapter 8

(a) Image showing semi-transparent carboxy-SWNT after methyl methacrylate (MMA) infiltration and polymerization. (b) Image of the PMMA (left image) and carboxy-SWNT/PMMA (right image) samples after the polymerization and subsequent peeling off from the fluorine tin oxide surface. (c) Field emission SEM (FESEM) top view image of nanotube after PMMA polymerization. (d) A back-side view of the nanotubes/PMMA composite after the peeling off from the substrate. Reproduced with permission from Valentini et al.33

Carboxylated single-walled carbon nanotubes (SWNTs) suspended in acetonitrile were elecrophoretically deposited between two electrodes under the influence of a DC electric field.31,32 This process enabled the anchoring of the tubes in the form of bundles on the positive electrode, thus providing an easy route to obtain functional nanostructures by infiltrating and polymerizing a methyl methacrylate-based monomer solution. The nanotube/PMMA system obtained with this procedure demonstrated outstanding mechanical properties functioning as semi-transparent conductive thin films.33 Optical images (Figure 1a) of the composite film prepared by methylmethacrylate infiltration and subsequent polymerization, show that the films

Methods for Improving the Integration of Functionalized Carbon Nanotubes in Polymers 237

detached from the substrate are flexible and can be deformed easily (Figure 1b). The sample retains the nanotube original shape and size inside the resulting composite matrix (Figure 1c), even after the polymerization process and the subsequent peeling off from the substrate (Figure 1d). The resulting PMMA is found to coat the CNTs as observed from a high-resolution scanning electron microscopy (SEM) image of composites shown in Figure 1(d).

8.2.2

Hybrid Conducting Polymers

The development of transparent conductive electrodes based on SWNT thin films represented an outstanding scientific breakthrough for applications in the area of optoelectronics.34 However, to build integrated CNT–polymer-based systems it is necessary to engineer the interfaces between the two constituents through organized nanotube architectures. More generally for the manufacturing sector ‘flexible’ is synonymous of ‘rollable’, thus the development of deposition techniques fully compatible with plastic substrates, low temperature processes and solution processable materials, and suitable for flexible substrates for roll-to-roll manufacturing technologies is mandatory. One-step electropolymerization deposition processes are envisaged as the most interesting deposition methods in view of potential technological applications. For this reason, there is a growing interest in the integration of materials obtained in such way to obtain multifunctional nanostructured composites and hybrid materials. The selective localization through electrophoretic deposition of nanotubes at the interface of polymers to obtain flexible, transparent and conductive materials could represent a novel approach. Fluorene polymers and copolymers (either obtained by electrochemical35,36 or chemical processes37–39) are proven to be among the most promising materials in the field of organic light-emitting devices (OLEDs). The properties of supramolecular structures of polyfluorene–CNT hybrids have been recently reported.40–42 The use of SWNT films as electrodes for electropolymerization of the fluorene units has been investigated. The unique structural and electronic properties of CNTs render them an ideal candidate to function as a model carbon nanoelectrode for electrodeposition. This represents a direct and effective method for fabricating CNT–polymer composites by incorporating CNTs into a polymer matrix without considering organized nanotube architectures in selected polymer matrixes as well as engineering the interfaces between the two constituents. The enhanced conductivity of fluorene polymer chains43 can be attributed to the entrapped nanotubes and nanotube bridging (Figure 8.2). The one-dimensional structure of CNTs may also induce and promote oriented polymerization, hence yielding an enhanced supramolecular order and higher conductivity.43

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Figure 8.2

FESEM image of the polyfluorene deposited on the carboxy-SWNTs/ fluorine–tin-oxide electrode. Reproduced with permission from Valentini et al.43

8.3 Melt Blending and Solvent Dispersion 8.3.1

Thermoplastic Polymers

In general, the mechanical properties and glass transition temperature are reported to be enhanced in the presence of CNTs. A practical method of producing CNT–polymer composites is by melt mixing. For this purpose, the goal of this study was to prepare SWNT–polymer composites by melt mixing using a shear mixer. Here an isotactic polypropylene matrix (iPP) was selected as an example because thermoplastics are materials with a higher consumption due to their well-balanced physical and mechanical properties and their easy processability at a relatively low cost that makes them a versatile material.44 The objectives of this study included: (1) to study the non-isothermal crystallization behaviour of SWNT-reinforced iPP in detail and to compare the results to those of neat iPP, and (2) to describe the effect of SWNTs on the mechanical properties of neat iPP. The results were then compared with those obtained for nanocomposites containing CB as a filler. The thermal parameters of the crystallization temperature (Tc), melting temperature (Tm), crystallization enthalpy (DHc), heat of fusion (DHf), supercooling temperature (DT 5 Tm – Tc) and percentage of crystallinity (Xc) were obtained and reported in Table 8.1. The supercooling temperatures reported in Table 8.1 are significantly shorter for reinforced iPP. This result indicates that the induction time for PP crystallization is reduced by the addition of low percentage SWNT fractions. In addition, the obtained results show that the crystallization peak temperature, Tc, increases when both nanotubes and CB fillers are

Methods for Improving the Integration of Functionalized Carbon Nanotubes in Polymers 239

Table 8.1

Thermal parameters of the prepared samples. Reproduced with permission from Lo`pez Manchado et al.44

Material

Tc (uC)

DHc (J g21)

xc (%)

Tm (uC)

DT (uC)

PP PP–SWNTs (0.25%) PP–SWNTs (0.5%) PP–SWNTs (0.75%) PP–SWNTs (1%) PP–CB (0.25%) PP–CB (0.5%) PP–CB (0.75%) PP–CB (1%)

115.22 117.62

297.63 295.33

51.38 50.17

162.06 161.47

46.84 43.85

118.39

294.89

49.94

160.37

41.98

119.85

296.12

50.59

161.12

41.27

120.38 115.80 116.46 116.57 117.14

296.39 295.06 293.68 295.22 297.65

50.73 50.03 49.30 50.11 51.39

162.16 162.21 161.06 162.97 161.28

41.78 46.41 44.60 46.40 44.10

incorporated in the polymer matrix, this effect being more evident in the presence of SWNTs. As the filler concentration was increased, the Tc continued to increase. It is assumed that an increase in Tc is associated with an increased number of heterogeneous nuclei for crystallization. These results lead us to the conclusion that SWNTs behave as effective nucleating agents for PP crystals in the composite, even at very low percentages. Analogous results have been recently obtained by other research groups.45–48 The effect of -COOH- and phenol-functionalized CNTs on mechanical, dynamic mechanical and thermal properties of polypropylene (PP) nanocomposites were considered, and the results confirmed in both cases that the percentage crystallinity was found to increase on phenol and carboxylic functionalization of MWNTs.

8.3.2

Confinement of CNTs in Block Copolymer Matrix

The fabrication of a solution of CNTs with good dispersion and stability has been of great interest because most of the potential applications of SWNTs are based on solution processes such as spin coating and dip coating.49–51 The physical adsorption on to the nanotube surface of surfactants and/or macromolecules has been shown as a possible way to stabilize SWNTs in both aqueous and organic media.52–57 Block copolymers have attracted significant attention as nanostructured materials, as they self-assemble to form well-defined, ordered, periodic nanoscale morphologies.58–63 The versatility of this unique class of polymers offers tremendous potential for their use as templates and scaffolds for applications in microelectronics, separation devices, optics and optoelectronics.64–67 More generally to separate and solubilize as-synthesized nanotubes, they have to be functionalized. It was demonstrated that the nanotube treatment with octadecylamine (ODA) and other amines, such as nonylamine,

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dodecylamine, pentacosylamine, tetracontylamine, pentacontylamine and alkylaryl amine as well as aromatic amines, aid the tube solubilization in several solvents (e.g. toluene, chlorobenzene, dichlorobenzene, dimethylformamide, tetrahydrofuran, hexamethylphosphoramide and dimethylsulfoxide).68 Along with the utilization of block copolymers as CNT dispersants, the role of an organic surfactant for the confinement of the nanotubes inside the selfassembled block copolymer matrix was reported. More generally a surfactant consists of two parts, one hydrophilic and the other one hydrophobic, and due to this architecture it is used as a bridge between nanofillers and polymeric matrices.69 In particular, when a block copolymer matrix is used, an adequate surfactant can be used to selectively disperse nanofillers in one of the blocks of the block copolymer matrix. This selectivity is important in designing the properties of block copolymer-based composites. Starting from the approach reported elsewhere for metallic nanoparticles we focused our attention on a hybrid system consisting of a poly(styrene-bisoprene-b-styrene) (SIS) block copolymer and soluble nanotubes.70 The nanotubes have been modified with a surfactant that interacts with only one block of the self-assembling block copolymer matrix. In particular, we have investigated the possibility of modifying ODA-functionalized CNTs (ODASWNTs) with dodecanethiol as a surfactant and to use this mixture as nanofiller for the production of composites based on SIS block copolymer. When the surfactant is used, the nanotubes are aligned along the block copolymer domains and appear to be embedded in the styrene phase, as shown in Figure 8.3 in which the interlamellar periodicity of approximately 20 nm is regular along the sample.

Figure 8.3

Tapping mode atomic force microscopy (TM-AFM) height image of dodecanethiol (DT)–ODA-SWNTs/SIS composite film. The arrow serves to indicate the nanotube location. Scale bar, 500 nm. Reproduced with permission from Peponi et al.70

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8.3.3

Solvent Dispersion

Production processes for CNTs often produce mixtures of solid morphologies that are mechanically entangled or that self-associate into aggregates. Entangled or aggregated nanoparticles often need to be dispersed into fluid suspensions in order to develop materials that have unique mechanical characteristics or transport properties. While mechanical dispersion methods, such as ultrasonication, separate nanotubes from each other, but can also fragment the nanotubes, decreasing their aspect ratio during processing, chemical methods use surfactants or functionalization to change the surface energy of the nanotubes, improving their wetting or adhesion characteristics and reducing their tendency to agglomerate in the continuous phase solvent. The solubility of CNTs may be necessary for their chemical and physical examination, as it allows easy characterization and facilitates their manipulation. Exhaustive research was addressed to overcome the poor solubility of CNTs in either water or organic solvents. With the aid of surfactants,71,72 organic molecules73,74 or small biomolecules,75,76 SWNTs can be dispersed in aqueous solution. Conjugated polymers and small molecules can also be employed in organic solvents.77,78 Covalent sidewall functionalization is another effective method to improve the solubility and stability of SWNTs in solution.79 However, the introduction of a third component and the modification of the sidewall would affect the pristine properties of the tubes which should be avoided. Over the years, constant effort has been devoted to finding appropriate media to solubilize pristine nanotubes. Various solvents have been investigated in order to solubilize and disperse SWNT aggregates. Non-hydrogen-bonding Lewis bases, such as dimethylformamide (DMF) and N-methylpyrrolidone (NMP), have demonstrated the ability to readily form stable dispersions of SWNTs produced by different techniques.80–82 Availability of stable CNT suspensions is a prerequisite for production of polymer composites using a liquid phase compounding strategy. In a recent work, nanocomposite films based on SWNTs and poly(DL-lactide-coglycolide) copolymer (50:50 PLGA) were processed and analyzed.83 Specifically, using a solvent casting process, dispersion of pristine and COOH-functionalized CNTs were considered, with the aim of investigating the effect of different functionalization systems on the physical stability and morphology of the obtained PLGA films. Both covalent and non-covalent functionalization of CNTs were considered in order to control the interactions between PLGA and SWNTs and to understand the role of the filler in the biodegradation properties. It has been observed that both the system composition and SWNT functionalization may play a crucial role on the autocatalytic effect of the degradation process. These studies suggest that the degradation kinetics of the films can be engineered by varying the CNT content and functionalization. Analogous conclusions were reported in a study by Armentano et al.,84 in which poly(L-lactide) (PLLA)/SWNTs

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nanocomposite films were produced using the solvent casting method, and morphological, thermal and mechanical properties were investigated. The role of SWNT incorporation and functionalization on PLLA bio-polymers was investigated. Pristine SWNTs and carboxy-SWNTs were considered in order to control the interaction between PLLA and the nanotubes. Biological investigations showed osteoblasts cultured on PLLA/carboxy-SWNTs nanocomposites had higher cell adhesion and proliferation than osteoblasts cultured on PLLA and PLLA/SWNTs nanocomposites. Recent results on the introduction of functionalized CNTs in biodegradable matrices using solvent dispersion can be found in the studies by Yang et al.85 and Lin et al.,86 in which electrospinning of the biodegradable polylactide (PLA) and its composites containing CNTs was studied in terms of solution concentrations and solvents effects, as well as CNT loadings. The results revealed that the PLA fibers obtained from the solutions using the mixed solvents of chloroform/assistant solvent showed better morphologies than those from the solutions using chloroform as the single solvent. This is due to the synergistic effect of the improved conductivity and altered viscosity with addition of the assistant solvent. The combination of SWNTs and silver (Ag) nanoparticles with a biodegradable polymer matrix was also considered.87 Different SWNT amounts were mixed with Ag nanoparticles and introduced in the poly(ecaprolactone) (PCL) polymer matrix by a solvent casting process. Results showed a good dispersion of nanostructures in the PCL matrix and an increase of the Young’s modulus with Ag content in the binary systems. The PCL/Ag composites exhibited poor electrical properties, whereas in the PCL/Ag/ SWNTs ternary films higher values of conductivity were measured compared with both of the binary composites (Figure 8.4). Results obtained in this research indicate that the addition of a small percentage of SWNTs significantly promoted the electrical properties of PCL/Ag nanohybrid films. Biocompatibility of binary and ternary composites, evaluated by bone marrow-derived human mesenchymal stem cells (hBM-MSCs), suggested that the combination of Ag nanoparticles and SWNTs with a biodegradable polymer opens new perspectives for biomedical applications.

8.4 Chemical and Physical Methods of CNT Dispersion 8.4.1

Epoxy Nanocomposites

The direct fluorination of SWNTs and their subsequent derivatization provide a versatile tool for the preparation and manipulation of nanotubes with variable sidewall functionalities.88–93 Recent studies have shown that covalently attached fluorine moieties in SWNTs can be efficiently displaced by alkylamino functionalities.93 The nucleophilic substitution offers an opportunity for SWNTs to be integrated into the structure of the epoxy systems through the sidewall amino functional groups.

Methods for Improving the Integration of Functionalized Carbon Nanotubes in Polymers 243

Figure 8.4

DC electrical resistivity of binary PCL/SWNTs, PCL/Ag and ternary PCL/Ag/SWNTs composites. Reproduced with permission from Fortunati et al.87 PCL (neat matrix); PCL/15Ag (PCL + 15% wt. Ag nanoparticles); PCL/0.5SWCNTs (PCL + 0.5% wt. SWNTs); PCL/1SWCNTs (PCL + 1% wt. SWNTs); PCL/15Ag/0.5SWCNTs (PCL + 15% wt. Ag nanoparticles + 0.5% wt. SWNTs); PCL/15Ag/1SWCNTs (PCL + 15% wt. Ag nanoparticles + 1% wt. SWNTs).

The functionalization of CNTs through plasma treatment represents a novel and easy approach to scale up towards industrial applications. In more recent works, there were many attempts to fluorinate CNT sidewalls in such manner.94–97 The CF4 plasma treatment of SWNT sidewalls was demonstrated to enhance the reactivity of tubes with aliphatic amines.96 The cure reaction of diglycidyl ether of bisphenol A-based epoxy resin (DGEBA), when reacted with butylamine molecules (BAMs) anchored on to the plasma treated fluorinated SWNTs, was reported. The advantage of this method was that the functionalization could be achieved through a simple approach, which is widely used in thin film technologies. As covalently modified CNTs with fluorine groups offer the opportunity for chemical interactions with the amine systems, it was recently demonstrated that this

244

Figure 8.5

Chapter 8

Comparison between experimental data and the chemorheological model for (top) DGEBA/MDEA and (bottom) DGEBA/MDEA/C-DWNTs systems, respectively. Reproduced with permission from Terenzi et al.98

reaction proceeds through the intermolecular elimination of HF and the formation of C–N bond.93–95 Another example of how the functionalization of CNTs represents an open issue for the preparation and manipulation of CNT-based nanocomposites with multifunctional properties was reported by Terenzi et al.98 It was shown that CNT dispersion affected the rheological properties of

Methods for Improving the Integration of Functionalized Carbon Nanotubes in Polymers 245

double-walled CNT (DWNT)-based polymer nanocomposites appreciably. Grafted N-methyldiethanolamine (MDEA) on carboxy-functionalized DWNTs were used and the chemorheology of the amino-functionalized DWNTs during the cure reaction of an epoxy system was studied. Calorimetric and rheological tests (Figure 8.5) revealed how the presence of MDEA functionality on DWNTs has a strong influence on the maximum degree of cure and on the gel time of the epoxy system. The use of kinetic and chemorheological models showed an excellent agreement with the experimental data. Recent results from our group on the modeling of SWNT alignment in an epoxy liquid monomer by the application of a DC electric field was also reported;99 experimental tests, performed to verify the effectiveness of the model, are based on the application of an electric field to a liquid epoxy–SWNT colloid (0.025 wt%), while measuring the current and observing the system by optical microscopy. A good agreement was found between the model results and the experimental measurements. According to these results, a few minutes were sufficient to obtain a highly oriented SWNT suspension in the epoxy resin.

8.4.2

Assembly of CNTs

The main available approaches for the alignment of CNTs can be grouped into two main categories: (a) the post synthesis assembly approaches, which involve dispersing CNTs in solutions, followed by aligning them using spincoating, Langmuir–Blodgett assembly,100 mechanical shearing101 or blown bubble102 films technique, and then fixed the aligned CNT structures/patterns by solvent evaporation or resin solidification; and (b) the in situ growth approaches by direct growing aligned CNTs by controlled chemical vapor deposition (CVD) and arc discharge techniques. Several reviews have summarized the studies focused on CNT assemble and characterization,102 as well as direct growth of aligned CNTs by the CVD method.103,104 One important issue remains the selective positioning with predetermined orientations at a large scale on a substrate. Several attempts have been based on the chemical patterning of the substrate,105,106 electrophoretic deposition107 or dielectrophoresis.108 More recently, Shimoda et al.109 reported that CNTs were aligned on hydrophilic glass parallel to solution surface, whereas Russell et al.110 demonstrated that different alignments were obtained by the evaporation method and dip-coating on to indium-tin-oxide-coated glass. The flow-directed alignment has been also reported by Lieber and co-workers.111 Another convenient method to obtain an organized assembly of CNTs consists on controlling the wettability of the conducting surfaces and their orientation by changing the pulling speed. In suggested mechanisms of nanotube orientation (Figure 8.6a), during the drying process of the liquid film on the vertical substrate under the gravitational force, the downwardly de-wetting liquid film exerts a hydrodynamic drag force

246

Figure 8.6

Chapter 8

The dip-coating deposition of C-SWCNT solutions on fluorine doped tin oxide: (a) A schematic outline of the dip-coating procedure that was used to assemble carboxy-SWNTs. (b) FESEM image of carboxy-SWNTs deposited on to neat fluorine-tin-oxide sample from acetonitrile solution by vertically dip-coating the neat fluorine-tin-oxide in carboxy-SWNT dispersion with a pulling speed of 0.05 mm min21 (the arrow indicates the pulling direction). Reproduced with permission from Valentini et al.113

defined as Fh 5 glV, where g is the liquid viscosity, l is the nanotube length and V is the velocity of the hydrodynamic flow estimated as the rate of de-wetting, V 5 ch3/6gL where h is the contact angle, c is the surface tension of the liquid and L is a constant of order 10.112 Accordingly to the data reported by Russell et al.,110 the high evaporation rate of the acetonitrile with respect to the dip-coating rate and the low hydrodynamic drag force exerted by the substrate with lower wettability induce the nanotube orientation parallel to the solution surface.113

Methods for Improving the Integration of Functionalized Carbon Nanotubes in Polymers 247

Combing the substrate oxygen plasma treatment and the nanotube dispersion in acetonitrile, it was observed that the tubes orient perpendicular to the flow direction, favoring their assembly in networks perpendicular to pulling direction (Figure 8.6b). The control of the wettability of a surface and as well as the dipcoating speed makes possible the realization of highly organized CNT-based architectures.

8.5 Conclusions The primary objective of this report is a ‘‘mix and match’’ approach towards innovative classes of multifunctional nanostructured composites and hybrid materials. Such materials are expected to stimulate evolutionary advances and revolutionary breakthroughs in emerging key technology areas. Polymers hold great promises for a widely applicable design and fabrication of structural and functional material. A new paradigm of ordering polymeric materials at the mesoscale is required. Importantly, a novel approach must assist in bridging the gap between intrinsic properties of organic/inorganic materials and the final hybrid material. In this report we propose a few concepts for interfacing polymers and nanotubes—which possess highly specific and widely variable functions, yielding nanostructured composites. Hereby, the surface of the nanofillers will serve as a template for assembling, pattering and ordering the organic materials. One of the major benefits of this approach is that it strictly involves the high aspect ratio of the nanofillers with organic compounds, which is foreseen to enhance the incorporation of organic and inorganic constituents markedly. The approach is also modular, as all components are fully exchangeable (i.e. ‘‘mix and match’’) to meet specific requirements. In terms of perspective, the scientific focal points will be based on: 1. Demonstrate ‘‘proof of concept’’, that is, to achieve interfacing electronically active nanofillers with polymers. More generally for the manufacturing sector, polymer is synonymous of flexible, thus the development of deposition techniques fully compatible with plastic substrates, low temperature processes and solution processable materials, and suitable for flexible substrates for roll-to-roll manufacturing technologies is mandatory. 2. Demonstrate the fabrication of nanostructured surfaces and the mutual adhesion of components through either covalent chemical or non-covalent supramolecular means. The challenge in this field is to reduce the manufacturing steps for the assembly of nanocomposites trying to preserve, where possible, the efficiency with respect to the conventional architectures and to improve their stability. 3. Demonstrate that the surfaces of these hybrid nano-objects are ‘‘responsive’’ to external stimuli, such as light or their chemical environment, by grafting polymeric structures on to surfaces.

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