Innovation on a small scale

Nanoparticles fight microorganisms and improve the efficiency of adhesives

RORIVALDO CAMARGO AND RICARDO TRANQUILIN / CMDMCSilver nanoparticles obtained in an electronic scanning microscope and colored artificiallyRORIVALDO CAMARGO AND RICARDO TRANQUILIN / CMDMC

Particles with nanotechnology that destroy bacteria on the surface of dental instruments or guarantee more transparent and efficient adhesives are already a fact of life in Brazil. With a size equivalent to 1 mm. divided by a million, these particles, when incorporated into materials like plastics, sprinkled in solution-form, or even used in coatings that are applied to metals, promote a series of benefits for consumers. The most significant function relates to the health of users via the reaction that silver nanoparticles cause in the cell walls of bacteria, eliminating them and avoiding possible contamination, in addition to leaving surfaces permanently clean and odorless. These are new materials from the field of nanotechnology, an interdisciplinary technological segment that reached the market in the first decade of this century. In fact, what has changed with regard to silver is its industrialization on a nanometric scale, because this metal has been used in medicine for curing wounds since ancient times.

From previous knowledge it is no wonder that silver has been one of the first components in the naonotechnological world. Several companies in the world have already been using this technology, mainly as a bactericide coating for products. In 2009, the nanocoating and nanoadhesives market was already a US$ 2 billion global business, according to the North American research company, BCC Research. According to the consultancy company, the forecast is that the market of this nanotechnological sector will reach US$ 18 billion by 2015. Brazilian company, Nanox, from São Carlos in the State of São Paulo, is already operating in this market. The company is a 2004 spin-off of two chemistry institutes, one from the Federal University of São Carlos (UFSCar) and the other from the Paulista State University (Unesp) in Araraquara, to form two research groups that collaborate and are members of the Multidisciplinary Center for the Development of Ceramic Materials (CMDMC), one of FAPESP’s Research, Innovation and Dissemination Centers (Cepid), coordinated by Professor Elson Longo.

Last year 40% of the sales of Nanox went to Mexico and the United States as raw material for incorporation into various types of plastic and metallic parts for the premium line of General Electric (GE) and Mabe refrigerators, such as water dispensers, drawers and shelves that avoid cross-contamination between food, bad smells and mold. “This technology acts against various microorganisms, like bacteria and fungi”, says Daniel Minozzi, one of the three partners of Nanox. Company sales reached R$ 2.1 million in 2010, compared with the R$ 1.3 million in 2009. Since 2010 Nanox technology (called NanoxClean) in the shape of fine film for application with metals has also been included in all dental equipment produced by Dabi Atlante, a 100% Brazilian-owned company, founded in 1945. “With Nonox we developed the technology that is called B-Safe in our equipment”, recounts Caetano Biagi, Dabi’s industrial director. Nanox licensed and coordinated the production and application of the product. “More than 15 materials are using our technology that possess antimicrobial action”, says Daniel.

Material with silver nanotechnology is used for covering all objects, like dentist’s chairs, the drilling equipment, the light and the instruments, hoses and trays. “We decided to put it in our whole product line as a way of providing greater biosafety for both dentists and patients, thereby avoiding cross-contamination”, says Biagi. So a dentist, when he places his hand in a patient’s mouth and then gets hold of the drill, or adjusts the light over the dental chair, runs no risk of transferring bacteria to the next patient. This dental equipment with nanotechnology is already being exported to Italy, Spain, Portugal, Poland, South Africa, China, Thailand and every country in Latin America. Around 20% of Dabi’s R$ 100 million sales comes from exports. “We don’t know any type of equipment with this technology in the world, even in the United States and Europe”, says Biagi.

Nanox products are also to be found as a bactericide in the stainless steel and plastic drinking fountains, made by IBBL, from Itu in São Paulo State, and also in the hair dryers and flat irons made by Taiff, a company from São Paulo. In these cases the nanoparticles eliminate microorganisms present in the air-jets or in the irons, thereby making the hair cleaner, according to the company. The next step from Nanox is the launch of a product with particles that have a bactericide effect on plastics that will serve for making packaging for wrapping food. “We managed to formulate these nanostructured particles via a Finep [Studies and Projects Funding Agency] Grant Program project. They can be incorporated into various types of plastic, like polypropylene and PET. This material is now included on the Anvisa [Brazilian Health Inspection Regulatory Agency] list for use in contact with food. This was possible after a study carried out by Ital [Food Technology Institute] and the state Department of Agriculture proved its non-toxicity and that the particles in the plastics did not migrate”, says Daniel.

Eduardo Cesar Nanosilica in film for labels, made by NovelprintEduardo Cesar

The uses of nanotechnology are unlimited and can cover everything from waste bags for the hospital area to carpets and rugs where mites are the main enemies to be defeated as allergy agents. “Particles don’t kill the mites, but they kill the bacteria and fungi, which are food for mites, so as a result they starve to death”. Daniel imagines that nanoparticles may also be used in refrigerated trucks, containers and computer keyboards. Another of the company’s product lines is aimed at civil construction. This technology is likely to be launched this year for a ceramic varnish for floors, wall cladding and sanitary ware that has a biocide action and has been under development for three years. “It’s an active biocide that can be incorporated into the composition of the item without altering the current production process for floors, tiles, sinks and sanitary ware”, Daniel states. The first impression is that the cost of these products with nanotechnology is high. “Normally companies do not add the value of the technology to the final price, but reduce the margin and gain in marketing, in greater sales’ capacity and in competitiveness. In the case of plastics the cost of adding the particles represents less than 10% per kilo of product”, explains Daniel.

With so many launches and nanotechnology application possibilities the company that competes with other foreign companies, some already operating in Brazil, like North American Microban, has close contact with Brazilian universities. “We always use universities for consultancy work and for exchanging ideas. A recurring aspect is characterization in the development and the end product, when we use the electronic microscopes at the universities”, Daniel says. The main partners are linked to the origin of the company in UFSCar and at Unesp, with professors Elson Longo and José Arana Varela, in addition to other groups from the University of São Paulo (USP) and from the Federal University of Rio de Janeiro (UFRJ). “Today there’s no point in producing high technology in Brazil if you don’t have support from universities”, says Professor Elson. “These products require characterization and sophisticated laboratories with equipment, like high resolution scanning microscopes that cost – 600,000, high resolution transmission microscopes at a cost of – 1.3 million, in addition to X-ray diffraction devices, photoluminescence and other devices that cost upwards of R$ 10 million”, he says. “All this to find out if the product really is nanometric and if it fulfills the functions for which it is intended. And companies are unable to buy these pieces of equipment”.

At Nanox, the partners (Daniel, Luiz Gustavo Simões and André Luiz de Araújo) met on the chemistry graduate course at UFSCar and the idea of the company came to maturity during their Master’s at Unesp in Araraquara. “We began because we had a Pipe [FAPESP Small Company Innovative Research Program] project approved in 2004”, says Daniel. Nanox started life as Science Solution (see Pesquisa Fapesp nº 121)  in the technology Company Incubator Center at the Parqtec Foundation in São Carlos. In 2006 it changed its name and received a financial injection from a risk capital company, the Novarum Fund of the Jardim Botânico Investimentos Group. Although the parties do not reveal how much was involved, market information indicates an investment of R$ 1 million. “The capital injection, plus the collaboration of the fund in the company management are very important from a financial viewpoint, in addition to providing a network of corporate contacts”, says Daniel. With regard to the technology, he says that since leaving university the evolution within the company has been great: “75% of our time is dedicated to developing products and new applications. There are 20 employees, with graduate degrees, Master’s and 2 with PhDs, in addition to the CEO, Luiz Gustavo”.

Another Brazilian company that incorporated nanotechnology into its products was Novelprint, from São Paulo, a medium size company that specializes in labels and self-adhesive stickers, and has been making labeling machinery for companies like Nestlé, Bayer, Indústrias Muller, Heliar, Monsanto, Texaco and Cervejaria Kaiser, since 1958. Novelprint is already supplying its customers with self-adhesive materials that contain nanomaterial, like nanosilica for glass bottles for beer and ice drink bottles, for example. These nanoparticles are translucent and allow more transparent labels to be made, guaranteeing greater resistance in the material. Nanomaterial applied to one of the layers of the labels and stickers also allows less glue to be used. “With the nanosilica reduced the amount of glue used by a third, from 20 to 30 grams per square meter (g/m2) to 10 g/m2”, says Derick Arippol, technical director at Novelprint, a company that has always tried to develop its own technologies. It currently has 95 patents in Brazil, 4 of which relate to nanomaterial, and 3 in the United States.

“My father [Jeffrey Arippol, president of the company] was already thinking about adhesives with nanotechnology back in 2004, mainly for use in automobile batteries and as containers for automotive oil, which had problems with adherence”, says Derick, a physicist who even set up a start-up business in graphic computing in the United States but preferred to come back to Brazil and work in the family firm. The realization of a nanotechnology project took place in 2005, when the company was approached by Finep. The state agency offered an opportunity within its Pro-Innovation Program and two years later Novelprint was already offering products containing nanotechnology. To implement this project the company hired two recently qualified PhDs from USP’s Chemistry Institute, who had worked with nanotechnology in the university, but not with adhesives or labels. “In the company labs and with the university’s collaboration, they identified which material should be used, made up the formulas and process until they came up with the end product”, explains Simon Bahbouth, director of Radeco, the consultancy company that helped Novelprint.

Although companies like Novelprint, Nanox and Dabi Atlante are really successful, the country still lacks a scenario that is favorable to products containing nanotechnology. “There’s a lack of information for companies, because businessmen don’t know about nanotechnology and there should be  better exchange with the universities”, says José Ricardo Roriz Coelho, director of the Department of Competitiveness and Technology at the São Paulo State Federation of Industries (Fiesp), who is also president of the Brazilian Plastics Industry Association (Abiplast) and president of Vitopel, Latin America’s biggest producer of packaging film. Another factor he indicates is regulation relating to nanotechnological products that come into contact with food and drink in packaging, for example. “At Vitopel we’ve developed plastic packaging containing silver nanoparticles that increases the shelf-life of green vegetables by up to 70%”, says José Ricardo. “But as there’s no regulation from Anvisa, we don’t have the legal assurance that these nanoparticles don’t harm a person’s health when in direct contact with food so we can’t launch the product on the market. Furthermore, there’s a shortage of local suppliers of nanoparticles”.

The projects
Application of ceramic coating on metallic surfaces (nº 2004/08778-1); Modality Innovative Research in Small Companies (Pipe); Coordinator Luiz Gustavo Simões – Nanox; Investment R$ 475,248.48 (FAPESP)
2. Transparent nanostructured coatings applied to glass (nº 2005/55876-1); Modality Innovative Research in Small Companies (Pipe); Coordinator André Luiz de Araújo – Nanox; Investment R$ 384,415.00 (FAPESP)