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Nanotechnology

Reinforced rubber

Company creates nanostructured material from polymer and clay for application in various industrial segments

Miguel BoyayanTennis balls made from the new material take longer to go softMiguel Boyayan

Expectations are high in the laboratories of Orbys, a small company founded four years ago and currently housed in the Technology Company Incubator Center (Cietec), located on the University City campus in São Paulo. If all goes well, Imbrik, a material made from natural rubber and clay for use in products of various industrial segments, will begin being manufactured on a commercial scale next year. In industry it is common to add clay to rubber in the formula, mainly to reduce the cost of the compound. What is new is the Orbys technology that allows the clay to be finely divided down to a nanometric thickness, which is 100,000 times less than the thickness of a hair. The nanometric clay and rubber mixture, called a nanocomposite, provides the product with some advantages. Called Imbrik, according to the company it has several levels of resistance and malleability and occupies a position between raw and vulcanized rubber, like the rubber used in tires. It can be used to manufacture a series of items that use rubber as their raw material, like footwear, sporting articles, toys, tires and automobile parts. The first batches of the new material will come on to the market in 2009 and should be used to manufacture tennis balls and shoe soles. “Negotiations with the manufactures of these materials are well advanced. We’re confident that the two products will be available for consumers next year”, expects naval engineer, Eduardo Figueiredo, owner of Orbys. The price of Imbrik, according to the entrepreneur, will be the same as, or in some cases, lower than competing types of industrial rubber.

The story of Imbrik started in the laboratories of the Chemistry Institute at the State University of Campinas (Unicamp). It was there that Professor Fernando Galembeck and his team began developing a new substance by mixing natural rubber and clay. “The first experimental result that led to this product was obtained by researcher, Márcia Rippel, during work for her PhD (that she finished in 2005). The partnership with Orbys allowed us to see some application possibilities for the nanocomposite and at the same time it helped us understand what was necessary to arrive at the final product”, Galembeck underlines.

The researcher also highlights another positive research aspect in this work, which was the discovery that Imbrik can be stabilized by electrostatic adhesion, a physical phenomenon in which the negative particles of natural rubber and clay form a sandwich with a “filling” of positive ions (atoms that have lost an electron) from the liquid in which these two materials are immersed. “Electrostatic adhesion is a mechanism that had already been discussed in literature for decades but had been somewhat discredited. We showed that it’s fundamental for stabilizing the product. The curious thing is that it was discovered before we noticed that its formation was largely due to this adhesion mechanism. In this case, as in many others, the technology came before the theory and the scientific models”, Galembeck points out. This discovery generated articles that were published in scientific journals, like the Journal of Physical Chemistry, Chemistry of Materials and Polymer.

Granulated Imbrik...

Miguel BoyayanGranulated Imbrik…Miguel Boyayan

The research was very successful and resulted in two patents being deposited relative to the process for producing polymer nanocomposites with exfoliated clay, the name given to the process used for separating slices of the mineral. In December 2004, Orbys acquired the exclusive right to commercially use the technology. The contract signed with Unicamp’s Innovation Agency (Inova) provided for the payment of amounts relating to the right to use the patent and to royalties (the numbers have been kept secret by the parties). The royalties relative to a percentage of sales of the product were forecast to begin being paid two years after licensing, but as there was a delay in finalizing the technology payment was postponed. In July this year, confident of the success of their product, Orbys requested an extension of the patent to other countries.

In the licensing process, the company signed a Technical Cooperation Agreement with Unicamp, with the aim of improving the production process and developing industrial applications for nanocomposites. “We took two and a half years to come up with Imbrik and make the process industrially viable. We took six months to arrive at the prototype for the tennis ball, which was ready in January this year”, says Figueiredo. In 2005, the company started a development program for polymeric nanocomposite-based materials for the footwear industry, with support from the Brazilian Institute of Leather, Footwear and Artifacts Technology (IBTeC) and Unicamp. Since the license was granted R$ 2.5 million has already been invested in developing Imbrik, with the major part of the funds (R$ 1.8 million) being put up by the owner of Orbys. The rest corresponds to new funding obtained from development agencies, like FAPESP, the National Council for Scientific and Technological Development (CNPq), the Studies and Projects Funding Agency (Finep) and the Brazilian Support Service for Micro and Small Companies (Sebrae).

At FAPESP, Orbys obtained approval for four projects from the Innovative Research Program in Micro and Small Companies (Pipe). One of them is more advanced, is in the second phase of execution and is aimed at the development of nanocomposites from synthetic rubbers, similar to Imbrik. The project provides for funds of around R$ 300,000 that will be used in laboratory trials and to buy equipment that will make the pilot plant viable, with capacity to produce 1,300 kg of nanocomposites a month. Help from Sebrae was used to fund trials of the new material at the Technological Research Institute of the State of São Paulo (IPT), while the CNPq gave two scholarships for developing nanocomposite blends formulated from a mixture of two or more polymers or rubbers with clay. The funds from FINEP were used to develop research for the application of nanotechnology in the production of inputs for the footwear sector and for the manufacture of adhesives from the polymer nanocomposite. This latter research did not give the hoped-for results in the adhesives segment, although it was important for the development of soles and other applications.

...for molding shoe soles...

Miguel Boyayan…for molding shoe soles…Miguel Boyayan

Clay in slivers
Polymer nanocomposites, like Imbrik, are materials formed by combining a polymer (plastic or rubber) and a synthetic or natural inorganic compound, like clay. It can be prepared by mixing, through adding clay to natural or synthetic latex. The secret of the new non-toxic material, manufactured from natural inputs, lies in improvements in its physical and chemical characteristics. “The clay grains are structured in the form of overlapping sheets that are similar to a pile of playing cards. These sheets, also called lamellas, are separated nanometrically (equal to a millimeter divided by 1,000,000) and mixed with the latex. When these lamellas adhere strongly to the polymer they give it superior mechanical properties”, says chemist, Arlete Tavares Almeida, R & D Manager for Orbys.

Imbrik is a transparent material, with a color that varies from light beige to brown. The input is presented in various ways, such as an emulsion (liquid), sheets, bales and in granules. Its mechanical properties vary according to the polymer-clay composition used in the manufacture. According to Orbys, among the various advantages of the polymer nanocomposite it is worth highlighting its greater breaking point, greater thermal stability (which means that it can support higher temperatures without being degraded) and its greater resistance to bending and force without becoming deformed. It is also more chemically resistant to oils and solvents and forms more perfect and less porous films. Finally it has high barrier properties, which means a reduction in gas permeability by up to 90%. These latter qualities drew the attention of a national manufacturer of tennis balls, who is interested in increasing the durability and resistance of his product, which is sold in bulk without the pressurized packaging that protects the balls. “Imbrik retains the gas in the balls and increases their useful life”, explains chemist, Adriana De Donato, who is responsible for the industrial production area at Orbys. Gas loss in the ball is what makes it soft and unsuitable for playing with. An Argentinian company has also already shown an interest in the nanocomposite and is testing prototypes of balls made from the material.

According to Figueiredo, the Orbys polymer nanocomposite is being evaluated by some 30 industries in 8 different market segments, among which are five large footwear manufacturers. “Our partner in the footwear sector is the IBTeC, from Novo Hamburgo, in Rio Grande do Sul. We’ve already made sole prototypes from Imbrik and now the footwear industries are carrying out tests”, says the owner of Orbys. A strong appeal of the sole is that it is environmentally correct. “Because it’s vulcanized and therefore has no sulfur, like much of the rubber used in shoes, it can be considered recyclable and reprocessable. In fact these are the characteristics of Imbrik, generally”, explains Arlete. In addition to natural rubber Orbys is developing a line of products that includes nanocomposites obtained from synthetic rubber.

... and a ring for industrial springs

Miguel Boyayan… and a ring for industrial springsMiguel Boyayan

The large scale production of Imbrik will not be done by Orbys, but by a partner industry. “The sensitive part of the project that consists in the exfoliation of the clay or separation into sheets and preparation of the suspension will be done by us. The rest of the process is going to be outsourced. We already have a memorandum of intention with a rubber supply company in São Paulo state”, says the owner of Orbys, emphasizing that he prefers not to divulge the name of the company because the contract has not yet been signed. Initial production is estimated at 25 tons a month. Although it has not yet closed any supply contracts future plans are bold. “In 2014 we expect to reach 1800 tons a year, which will represent revenues of more than R$ 25 million”, says Figueiredo, who before setting up Orbys, worked for 20 years in telecommunications, the oil industry, defense and the export of agricultural commodities.

The projects
1.
Development of a new series of synthetic polymer and montmorillonite-type clay nanocomposites from lattices of nitrylic rubber, nitrylic carboxyamide and styrene-butadiene (nº 05/59845-3); Modality Innovative Research Program in Micro and Small Companies (Pipe); Coordinator Arlete Tavares Almeida – Orbys; Investment R$ 350,678.00 (FAPESP)
2. Development of applications for polymer/clay nanocomposites and their production process on an industrial scale; Modality Program for the Development of Human Resources for Strategic Activities in Support of Technological Innovation (RHAE-Inovação); Coordinator Eduardo Figueiredo – Orbys; Investment R$ 96,000.00 (CNPq)

Scientific articles
VALADARES, L. F.; Linares, E. M.; Bragança, F. C.; Galembeck, F. Electrostatic Adhesion of Nanosized Particles: The Cohesive Role of Water. The Journal of Physical Chemistry C. v.112, (23): 8534-8544. 2008.
BRAGANÇA, F.C.; Valadares, L.F.; Leite, C.A.P.; Galembeck, F. Counterion Effect on the Morphological and Mechanical Properties of Polymer-Clay Nanocomposites Prepared in an Aqueous Medium. Chemistry of Materials. v. 19, (13): 3334-3342. 2007.

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