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For skeptics who may doubt that nanocomposites have yet proven themselves commercially viable materials, last years Nanocomposites 2005 Conference in San Francisco presented plenty of evidence that nanos are beginning to live up to their promise.
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Nanoclay in this Geoflow LLDPE drip emitter for irrigation tubing ensures timed release of herbicide from the plastic. PolyOnes Nanoblend MB nanoclay concentrate adds 20% to the cost but doubles product life.
Nanocomposites have scored early gains in automotive. A heater vent for the Audi A3 gains scratch resistance from Putsch GmbHs Elan XP compound of PP and PS, compatibilized by a Sud -Chemie nanoclay. It replaces painted ABS. Micrograph below shows finely dispersed PS domains in PP matrix.
Nano materials are moving into applications like Nexans plenum cable jacketing, the first such product in the U.S.
Nanoclays improve UL ratings in wire and cable by eliminating dripping and promoting char formation at relatively low cost. Sud-Chemies nanoclay in polyolefin cable jacket formulation at right does not drip, while unfilled sample at left drips.
PolyOnes in-situ polymerized Nanoblend nylon 6 chemically ties the resin to the nanoclay in the reactor. It uses half as much nanoclay to achieve better properties than melt blends (see table).
PolyOneS PP-based Nanoblend LST compound in this material-handling tray replaced a PPO alloy, giving better dimensional stability and cutting the cycle time by 30 sec.
For lab testing of tiny samples, DSM Xplore developed a twin-screw batch extruder that uses inserts to change batch size. For skeptics who may doubt that nanocomposites have yet proven themselves commercially viable materials, last years Nanocomposites 2005 Conference in San Francisco presented plenty of evidence that nanos are beginning to live up to their promise. Organized by Executive Conference Management, the conference included reports on a bevy of new commercial applications in Europe and North America, ranging from auto parts and precision moldings to wire and cable jacketing. These applications demonstrate that just a pinch of these tiny particles can cut weight and cost compared with higher loadings of conventional fillers. The benefits include improved mechanical properties, scratch resistance, barrier properties, fire resistance, and dimensional stability, plus faster extrusion and molding. News from the conference included new alloys that disperse nanoclays more efficiently, new synthetic nanoadditives, and a new naturally occurring nanotube. There was also word of new twin-screw lab extruder that makes test batches as tiny as 3 cc and an infrared test method to verify nanoclay exfoliation and orientation.
Arthur Fritts, president of NanoSperse LLC, a two-year-old compounder devoted exclusively to nano-materials, cautions against considering nano-materials just for cost savings. Long-term growth in nanocomposites wont come from substituting a cheaper material, he says. That has actually slowed nano developments. Growth will come from enhancing value. In fact, the market is already recognizing how nano-materials enhance performance. An irrigation emitter for landscape and agricultural pipe, developed by Geoflow in San Francisco and molded by the Toro Co. in Bloomington, Minn., uses the nanoclay platelets in PolyOnes Nanoblend MB concentrate to ensure slow release of herbicide from the plastic into the soil. Nanoblend is dry mixed with pellets of Geoflows herbicide, then added to LLDPE at the hopper of an injection press. That part costs 20% more than a part without nanoclay, but it extends the product guarantee from 10 years to 20. The most interesting potential application for nanoclays is thin -walling for lightweight parts, in the view of Suresh Shah, senior technical fellow at Delphi Corp., Troy, Mich. So far, people have used nanoclays to save money, but they havent taken full advantage of nanotechnology to reduce wall thickness. Since nanocomposites are stiffer but lighter than glass- or mineral-filled plastics and also enhance flow, you can reduce part weight and thickness. One way in which nanoclays improve material properties is through compatibilizing resin alloys. Putsch in Germany partnered with nanoclay supplier Sud-Chemie AG to develop a new alloy of normally incompatible PP and PS. Called Elan XP, it uses 1% to 2% of Sud-Chemies Nanofil to compatibilize 60-80% PP with 2040% PS. Elan XP was commercialized three years ago for an interior air vent for the Audi A4 and a Volkswagen van. The unpainted part replaces painted ABS. The hard PS component provides scratch resistance and a luxurious surface feel. Nanoclay also has proved effective as a flame retardant: It improves UL ratings by eliminating dripping and promoting formation of stable char. For example, Sud-Chemies new Nanofil SE 3000 nanoclay is used commercially in an EVA/PE compound to provide halogen-free flame retardency in wire and cable coatings. At only 3% to 5% loading, it improves flame retardency enough that ATH or magnesium hydroxide flame retardants can be cut from 65% to about 52% by weight. Mechanical and surface properties improve, and extrusion rates are higher, Sud-Chemie reports. Nano-materials have been used for about two years by three large European cable companies: Kabelwerk Eupen in Belgium, Nexans in France, and Draka Cable in the Netherlands. Nexans Berk -Tek unit in the U.S., with offices in New Holland, Pa., is believed to have the first nanocomposite cable jacketing in North America. Nexan introduced it 18 months ago for its plenum cable used in office buildings. Still another function of nanoclay is as a barrier enhancer. Early attention focused on food and beverage packaging, but automotive fuel systems are an emerging application. Ube America has developed a coex barrier fuel line with 2% nanoclay in nylon 6. Its gasoline barrier is reportedly five times greater than neat nylon.
In-situ compounding
PolyOne commercialized a new family of nylon Nanoblends made by in-situ polymerization of caprolactam with nanoclay. PolyOne calls them alloys because the caprolactam is chemically bound to the nanoclay before and after polymerization. This prevents the possibility of reagglomeration of clay particles in subsequent processing. Reagglomeration effectively negates the potential benefits of a nanocomposite. PolyOne first functionalizes the nanoclay with a surfactant and then adds caprolactam monomer. The caprolactam is polymerized into nylon 6, which leaves the nanoclay particles dispersed without the work and expense of melt blending, and the nylon is bound to the clay by its affinity for the surfactant chains. This alloy technology, licensed from Toyota Corp. of Japan, reportedly achieves better properties than melt blending and uses half as much nanoclay because the alloy doesnt reagglomerate.
The loss of properties from reagglomeration turned a lot of people off when they first tried nanoclay materials, says Roger Avakian, chief technology officer of PolyOne. They had paid a lot of money for the nanoclay and got worse properties than before. When we gave this new Nanoblend to customers, we didnt call it a nanocomposite because that had gotten such a bad reputation. We just said, These are property-enhancing. Nylon Nanoblends for injection molding are available with 2.5% and 8% nanoclay, the latter being a high level for a precompounded material. Nylon Nanoblend with 2.5% nanoclay shows better mechanical properties than a melt blend of 5% nanoclay (see table). In late 2004, PolyOne commercialized its first alloyed nylon Nanoblend in exterior trim for two car programs.
March 2005, is commercializing new cryogenically IN-SITU NANOCLAY ALLOYS Neat Melt milled metal, ceramic, and composite nano-powders. Property Nylon Blend Initial applications are in aluminum metal-matrix 0 5 composites, but DDGs relatively inexpensive batch Clay % process is also suited to plastics. DDG has sampled Flex Str., kpsi its nano-powders for two years in nylon 6 and 12
17.4 19.7 604 575 0.6
454 applications. Flex. Mod., kpsi Sud-Chemie reports that it has ground its nanoclays 435 Tens. Mod., kpsi into smaller sizes that offer better dispersability. Its Notched Izod, 0.6 newer Nanofil 2, 5, and 9 reportedly disperse better ft-lb/in.
than its older Nanofil 15 and 32. Its new Nanofil SE Source: PolyOne. grades reportedly also disperse better in polyolefins, even resins without maleic anhydride modification. Dyneon LLC is exploring block copolymers with controlled architecture to improve exfoliation of nanoclay platelets in melt compounding. Block copolymers with different levels of hydrophobicity can help disperse
hydrophilic nanoclays in hydrophobic resins. The block copolymers are functionalized with amine, epoxy, anhydride, and acid groups.
Nanoclay in PVC
Elam EL Industries of Israel, which makes electroluminescent wires, is using nano-particles of zinc oxide (from Degussa in Germany) and titanium dioxide (from Sachtleben Chemie GmbH in Germany) in acrylic masterbatches for uv protection of fluorescent dyes in PVC and PVDF compounds. Conventional uv stabilizers reduce photo-luminescence, particularly in fluoropolymers. Elams nano -additives dont actually prevent uv degradation of fluorescent dyes, but they keep the dyes from m igrating to the surface so they dont degrade. Meanwhile, the University of Belfast, Northern Ireland, reports the development of a nanocomposite plasticizer for PVC to replace DEHP plasticizer, which is banned in some markets because of concerns over chemical leaching. The nano-plasticizer is a soft EVA-carbon monoxide terpolymer blended with 0.5% to 4% of synthetic fluorohectorite nanoclay. The clay is sold as Somasif ME from Co-Op Chemical Co. in Japan. Surprisingly, the university researchers found that adding nanoclay in EVA-CO to PVC actually made flexible PVC clearer. Nanoclays are smaller than the wavelength of visible light, so they typically have no optical effect. But PVC with 2% nanoclay transmits more light than PVC without clay and more light than EVA-CO with clay by itself. Researchers found that compounding in two stages was gentler to the PVC and protects it from contact with the fluoro-clay. First they blended 60% PVC with 40% nano-filled EVA-CO, which melts at a lower temperature than PVC. The EVA-CO coats the clay, so it doesnt come in contact with the PVC. Then 20% more PVC is added a quarter of the way down the extruder barrel.