Nanocomposites: mixing CNTs into polymers

1.Introduction 2. Composites of multiwalled carbon nanotubes (MWNT) with polycarbonate (PC) produced by masterbatch dilution technique ‡Electrical resistivity ‡Dispersion and alignment ‡Influence of processing parameters on electrical resistivity 3. Composites of MWNT and SWNT with PC produced by direct incorporation ‡Percolation of different commercial MWNT in PC ‡Percolation of SWNT in PC ‡Stress-strain behaviour 4. Summary

Benefits of CNTs to polymers
± Electrical conductivity ± Improvement of mechanical properties, especially strength ± Enhancement of thermal stability ± Enhancement of thermal conductivity ± Improvement of fire retardancy ± Enhancement of oxidation stability ± Effects at low CNT contents because of the very high aspect ratio

How to introduce CNTs into polymers .

Melt mixing of CNT with thermoplastic polymers .

Inc. Cambridge. PC Lexan 121 (PC2) or PC as used for the masterbatch (PC3) ± Haakeco-rotating.5 cm3capacity) ± Brabender PL-19 single screw extruder . intermeshing twin screw extruder with one kilogramm mixtures ± DACA Micro Compounder. conical twin screw extruder (4.Preparation of the PC-MWNT composites ‡ Masterbatch technology: polycarbonate(PC) + PC based masterbatch (15 wt% MWNT) ± masterbatch (Hyperion Catalysis International. USA) diluted with PC Iupilon E2000 (PC1).

Characterization of the masterbatch (PC + 15 wt% MWNT) .

Dispersion in PC-MWNT composites .

Alignment in PC-MWNT composites .

Comparison for different set of PC masterbatch dilution .

Detection of percolation and influence of processing conditions investigated by dielectric spectroscopy .

Direct incorporation of different kinds of commercial MWNT into PC .

masterbatch dilution. and CB addition .Comparison of direct incorporation of CNT.

Direct incorporationof SWNT1 into PC .

Direct incorporation of SWNT1 into PC .

Direct incorporation of SWNT1 into PC .

Direct incorporationof SWNT2 into PC .

Direct incorporation of SWNT2 into PC .

elongation at break reduced especially above percolation concentration ‡ . production method (resulting in different sizes.0 and 3.Summary ‡ ‡ Melt mixing is a powerful method to disperse CNT into polymers Masterbatch dilution technique (based on a PC masterbatch) ± percolation in the range of 1.35 wt% ± stress-strain behavior of the composites: modulus and stress are enhanced. and the purifying/modification steps ± for commercial MWNT percolation occurs between 1.30 and 0. purity and defect levels).5wt%) ± effects of mixing equipment and PC viscosity on percolation are small Direct incorporation method ± percolation strongly depends on the kind of CNT.0 wt% MWNT ± suitable processing conditions can shift percolation to lower values (0.0 wt% and is lower at lower MWNT diameters and higher purity ± HipCO-SWNT (CNI) percolation between 0.

treated with phenyl isocyanate (2 mmol. Upon completion. washed with methanol (200 ml). 1 h) in DMF (1 mg ml-1). Dow-Grubbs solvent system). and dried for a week over phosphorus pentoxide in a vacuum desiccator. right) was carried out with dimethylhydrazine (0. approximate Mw = 280 kD. anti-solvent.0) was added to these dispersions and dissolved with stirring (Fig. Sigma-Aldrich) at 80 °C for 24 h. crushed into a fine powder with a mortar and pestle. and moisture. 150 W. dried at 130 °C under vacuum for 10 h to remove residual solvent. 1d. 1f) in a hydraulic hot press (Model 0230C-X1. left). Dried graphite oxide (50 mg) was suspended in anhydrous DMF (5 ml. and then pressed (Fig. Reduction of the dispersed material (Fig. 1d. The coagulated composite powder (Fig. PHI-Tulip) at 18 kN with a temperature of 210 °C.Graphene±polymer composite ‡ Graphite oxide was prepared by the Hummers method from SP-1 graphite (Bay Carbon). 1e) was isolated via filtration. PDI = 3. and recovered by filtration through a sintered glass funnel (50 ml. Polystyrene (Scientific Polymer Products. the coagulation of the polymer composites was accomplished by adding the DMF solutions dropwise into a large volume of vigorously stirred methanol (10:1 with respect to the volume of DMF used). .1 ml in 10 ml of DMF. Sigma-Aldrich) for 24 h. medium porosity). Stable dispersions of the resulting phenyl isocyanate-treated graphite oxide materials were prepared by ultrasonic exfoliation (Fisher Scientific FS60.


. g.48 vol. c.% (left) and 2.4-mm thickness and processed in the same way. AFM image of phenyl isocyanate-treated graphite oxide sheets on mica and profile plot showing the 1 nm thickness. e.4 vol.12 vol. Hotpressed composite (0. Suspension of phenyl isocyanatetreated graphite oxide (1 mg ml-1) and dissolved polystyrene in DMF before (left) and after (right) reduction by N. A typical AFM non-contact-mode image of graphite oxide sheets deposited onto a mica substrate from an aqueous dispersion (inset) with superimposed cross-section measurements taken along the red line indicating a sheet thickness of 1 nm. b. d. Composite powder as obtained after coagulation in methanol.N-dimethylhydrazine. f. SEM and digital image (inset) of natural graphite.% (right) graphene in polystyrene. Low (top row) and high (bottom row) magnification SEM images obtained from a fracture surface of composite samples of 0.% of graphene) and pure polystyrene of the same 0.Process flow of graphene± polymer composite fabrication ‡ a.

Advantages of Nanosized Additions The Nanocomposites 2000 conference has revealed clearly the property advantages that nanomaterial additives can provide in comparison to both their conventional filler counterparts and base polymer. strength. Properties which have been shown to undergo substantial improvements include: ‡ Mechanical properties e. water and hydrocarbons Thermal stability and heat distortion temperature Flame retardancy and reduced smoke emissions Chemical resistance Surface appearance Electrical conductivity Optical clarity in comparison to conventionally filled polymers . modulus and dimensional stability Decreased permeability to gases.g.

develop a better understanding of formulation/structure/property relationships. further research will be necessary to. could reduce impact performance. for example. . better routes to platelet exfoliation and dispersion etc. Some of the data presented has suggested that nanoclay modification of polymers such as polyamides. Clearly this is an issue which would require consideration for applications where impact loading events are likely.Disadvantages of Nanosized Additions ‡ To date one of the few disadvantages associated with nanoparticle incorporation has concerned toughness and impact performance. In addition.

. Similar mechanical property improvements were presented for polymethyl methacrylate ± clay hybrids. the further benefits of short/long glass fibre incorporation. all the above being achieved with just a 5% loading of montmorillonite clay. together with nanoclay incorporation. ‡ Further data provided by Akkepeddi of Honeywell relating to polyamide-6 polymers confirms these property trends.Examples of Mechanical Property gains due to Nanoparticle Additions ‡ Data provided by Hartmut Fischer of TNO in the Netherlands relating to polyamide ± montmorillonite nanocomposites indicates tensile strength improvements of approximately 40 and 20% at temperatures of 23ºC and 120ºC respectively and modulus improvements of 70% and a very impressive 220% at the same temperatures. In addition. are clearly revealed. In addition Heat Distortion Temperature was shown to increase from 65ºC for the unmodified polyamide to 152ºC for the nanoclay-modified material.

These include potential for utilization as mirror housings on various vehicle types. mower hoods and covers for portable electronic equipment such as mobile phones. . door handles. pagers etc. engine covers and intake manifolds and timing belt covers.Area of Applications ‡ Such mechanical property improvements have resulted in major interest in nanocomposite materials in numerous automotive and general/industrial applications. More general applications currently being considered include usage as impellers and blades for vacuum cleaners. power tool housings.

cereals and boil-in-the-bag foods. Further data reveals the extent to which both the amount of clay incorporated in the polymer. Specific examples include packaging for processed meats. confectionery. Such excellent barrier characteristics have resulted in considerable interest in nanoclay composites in food packaging applications. also extrusioncoating applications in association with paperboard for fruit juice and dairy products. . aspect ratio is shown to have a major effect. and the aspect ratio of the filler contributes to overall barrier performance. with high ratios (and hence tendencies towards filler incorporation at the nano-level) quite dramatically enhancing gaseous barrier properties. both flexible and rigid. cheese. In particular. together with co-extrusion processes for the manufacture of beer and carbonated drinks bottles. The use of nanocomposite formulations would be expected to enhance considerably the shelf life of many types of food. Data provided from various sources indicates oxygen transmission rates for polyamide-organoclay composites which are usually less than half that of the unmodified polymer.Gas Barrier ‡ The gaseous barrier property improvement that can result from incorporation of relatively small quantities of nanoclay materials is shown to be substantial.

Fuel Tanks ‡ The ability of nanoclay incorporation to reduce solvent transmission through polymers such as polyamides has been demonstrated. As a result. . the reduced fuel transmission characteristics are accompanied by significant material cost reductions. Data provided by De Bievre and Nakamura of UBE Industries reveals significant reductions in fuel transmission through polyamide±6/66 polymers by incorporation of a nanoclay filler. Of further interest for this type of application. considerable interest is now being shown in these materials as both fuel tank and fuel line components for cars.

. to enhance both toughness and hardness of these materials without interfering with light transmission characteristics. With polyamide based composites. Similarly. nano-modified polymers have been shown. spherilitic domain dimensions being considerably smaller. when employed to coat polymeric transparency materials. An ability to resist high velocity impact combined with substantially improved abrasion resistance was demonstrated by Haghighat of Triton Systems. this effect has been shown to be due to modifications in the crystallisation behaviour brought about by the nanoclay particles. nanoclay incorporation has been shown to significantly enhance transparency and reduce haze. In comparison to conventionally filled polymers.Films ‡ The presence of filler incorporation at nano-levels has also been shown to have significant effects on the transparency and haze characteristics of films.

Thus. Data provided by Beall from Missouri Baptist College indicates the significant extent to which nanoclay incorporation can reduce the extent of water absorption in a polymer. Similar effects have been observed by van Es of DSM with polyamide based nanocomposites. Specifically. Hydrophobic enhancement would clearly promote both improved nanocomposite properties and diminish the extent to which water would be transmitted through to an underlying substrate. Thus an ability to minimize the extent to which water is absorbed can be a major advantage. thus indicating the beneficial effects likely from nanoparticle incorporation in comparison to conventional microparticle loading. van Es noted a significant effect of nanoclay aspect ratio on water diffusion characteristics in a polyimide nanocomposite. applications in which contact with water or moist environments is likely could clearly benefit from materials incorporating nanoclay particles. . increasing aspect ratio was found to diminish substantially the amount of water absorbed. In addition.Environmental Protection ‡ Water laden atmospheres have long been regarded as one of the most damaging environments which polymeric materials can encounter.

‡ Type I: Organic polymer embedded in an inorganic matrix without covalent bonding between the components. . ‡ Type II: Organic polymer embedded in an inorganic matrix with sites of covalent bonding between the components.Preparation and Characterization of Novel Polymer/Silicate Nanocomposites ‡ Five categories cover the majority of composites synthesized with more recent techniques being modifications or combinations from this list.

‡ Type IV: Co-formed interpenetrating networks of inorganic and organic polymers with covalent bonds between phases.Preparation and Characterization of Novel Polymer/Silicate Nanocomposites ‡ Type III: Co-formed interpenetrating networks of inorganic and organic polymers without covalent bonds between phases. ‡ Type V: Non-shrinking simultaneous polymerization of inorganic and organic polymers. .

Preparation and Characterization of Novel Polymer/Silicate Nanocomposites ‡ The great majority of nanocomposites incorporate silica from tetraethoxysilane (TEOS). hydrolysis and condensation as seen in Scheme 1. The formation of the inorganic component involves two steps. .


PVA. polyethylene oxide (PEO). which typically lasts up to 24 hours. PAN. or salt catalyzed polyphosphazene. PVAc (300 mg) is dissolved into an 50/50 by volume acetic acid/methanol (10 mL) mixed solvent in a capped vial. and polyethylene oxide/polypropylene oxide (PPO/PEO) block nanocomposite is as follows: 300 mg of polymer is dissolved into 10 mL of a 50/50 by volume tetrahydrofuran (THF)/ethanol mixed solvent in a capped vial. ‡ . To this solution is added TEOS (336 mg). To this solution is added TEOS (373 mg). The nanocomposite self assembles during the curing process. The synthesis of polyvinyl acetate (PVAc)/silicate nanocomposites requires a different approach from the other nanocomposites. A catalyst is then introduced as an aqueous solution (150 l) and the mixture is capped and sonicated at 50oC for 30 minutes. acid. The solution is then sonicated for 5 minutes in a sealed vial at room temperature and poured into a Teflon mould and loosely covered at room temperature. Additional heating at 100 °C for 30 minutes aids in removing lingering acetic acid from the nanocomposite. The nanocomposite self assembles as the volatile solvent slowly escapes during the condensation process. PEO/PPO. The solution is aged from hours to days depending upon the catalyst used in a sealed vial and poured into a Teflon mold and loosely covered at room temperature. MEEP ‡ A general synthesis for a base.Polymers considered: PEO. PVAc.

Since the nanocomposites formed by the ceramic condensation process do not form bonds to the polymer component. However. (Type I nanocomposites) mechanical stabilization is achieved without a great loss of ionic conductivity (13). Traditional stabilization methods. however this crosslinking lowers ionic conductivity ± tests performed in our laboratory revealed this to be a factor of 30-45 for MEEP-like phosphazene polymers. however it lacks the mechanical stability to be used in a practical device (12). yet they were also found to be glassy and brittle. . The polyphosphazene MEEP is a well-known SPE with very high room temperature conductivity.Applications ‡ One of the most interesting of these applications is as solid polymer electrolytes (SPE) for lithium batteries. these nanocomposites have the highest tensile strength of any of the catalyst types studied. such as deep UV or electron beam crosslinking methods do improve the physical stability of SPEs. This reduction is due to the additional covalent linkages formed during the crosslinking process that inhibit chain segmental motion and ion transfer.

Homogeneous nanocomposites with good IPNs are often stronger. more resilient. whereas heterogeneous composites are often mechanically weaker and opaque.Goal for Type I Nanocomposites ‡ The goal in the process is to form a completely interpenetrating network (IPN) of both inorganic and organic phases. . and optically transparent.

Among these strategies. due to the strong inter-particle hydrogen bonds between hydroxyl groups. silica has greater reinforcing power. abrasion resistance. to reduce the rolling resistance.Novel Rubber Nanocomposites with Adaptable Mechanical Properties ‡ Silica particles have become more important in tire applications since the introduction of the Green Tire® by Michelin. in turn. such as improving tear strength. age resistance and adhesion properties than carbon black [6-8]. chemical modifications of rubbers by attaching functional groups interacting with silica [9-22] and surface treatments of silica by reducing surface polarity with different silane coupling agents [22-36] are the most popular techniques. ‡ . However. the agglomeration nature of silica is generally believed to be responsible for the significant Payne effect which brings about considerable rolling resistance for tire applications. In order to reduce the filler-filler interaction and/or to enhance the mechanical properties of silica filled composites. As a filler. researchers have been working for many years on different strategies to improve silica-rubber interaction and.

Additionally. meaning that the final silica composite was unsatisfactory in terms of reducing silica agglomeration. For the latter. the chemical modification was limited to rubber chain ends [12.18.22]. In summary.Novel Rubber Nanocomposites with Adaptable Mechanical Properties ‡ However. due to these flaws none of the methods mentioned above could simultaneously ensure both the ability in reducing the silica agglomeration and improving the material performance.11.14. the chemical modification reaction of rubber was usually not applicable to commercial production and its degree of modification was usually very low [9. For the former technique. the used coupling agents are expensive and it could possibly lower the crosslinking density by reacting with the chemical ingredients for vulcanization. .35]. these techniques admittedly have quite a few drawbacks. and at the same time it degraded the mechanical performance of such silica filled material for tire applications.20].17. This technique would lead to lower overall cure rates [34.

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