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Materials Engineering

Small-scale Revolution

Nanotechnology begins to interest private enterprise in Brazil after the good results in the academic world

Take a strand of hair. Look at it and try to imagine a thickness 10,000 times smaller than the insignificant thing in your hand. Right, this is what we are going to deal with. Or rather, how science deals with objects of this size, these tiny surfaces obtained in the universe of nanometers, the scale that measures atoms and molecules by dividing the meter billions of times. It is therefore impossible to see with the naked eye or to handle a nanometric object without an arsenal of equipment, headed by the most advanced electron microscopes, which make it possible to access a world hitherto untouched and now capable of generating comfort, business and wealth. Discoveries about nanomaterials are thus inaugurating a new stage on an industrial scale.

This time, Brazil has the conditions for correcting a route that was scorned in the past, when microelectronics introduced the chip, setting the course for today’s modernity. There is a consensus that the country has good infrastructure and qualified personnel to carry out nanoscience. A serious challenge now has to be overcome in order to be competitive: competencies have to be added up. One of the ways to achieve this objective and to attract the attention of investors to transform this knowledge into products is a joint action prepared by a group of researchers supported by FAPESP and by executives from the Federation of Industries of the State of São Paulo (Fiesp).

The idea is to promote talks and to display the programs and projects already existing and supported by the Foundation. The encounter, still without a date defined for it, should make it possible, on the one hand, to identify the needs of the private sector for the application of directed research. On the other, the intention is to stimulate and to expand the participation of scientists and researchers and their entrepreneurial potential. To do so, a selection of works on nanotechnology will be at a display open to the public on Fiesp’s premises, so as to make the theme more concrete for an audience that knows nothing about the subject or has seen little reference to it, besides showing Brazil’s capacity to qualify for entering the race, running parallel to the major powers.

The coordination of this work lies with physicist and professor at the State University of Campinas (Unicamp) Cylon Gonçalves da Silva, who led the implantation of the National Laboratory of Synchrotron Light, of the Ministry of Science and Technology, in Campinas. He was also responsible for the proposal for a National Nanotechnology Program in the last government and the coordinator of the project for a National Reference Center in Nanotechnology. “These proposals aimed at putting the debate on technology outside the academic walls in Brazil”, Cylon comments.

Self-cleaning glass
The revolution engendered by the arrival of nanostructures is creating innovations in the area of materials engineering that, though still limited by the high operational costs, are beginning to take on an industrial scale. An obvious case is self-cleaning glass, launched in Europe in 2002. A film 40 nanometers thick is applied to the glass, with incrustations of titanium oxide (TiO2) particles. When the ultraviolet light present in sunlight hits the glass, a change takes place in the state of oxidation, stealing the electrons from bacteria, funguses and other microorganisms and killing them. The film also causes a high surface tension, preventing water from sticking to the glass. It is transformed into drops and falls to the ground, taking the dirt with it. Dust and other substances that stick to the glass together with the water are also eliminated. Without any microorganisms or any water, it becomes much easier for the glass to remain clean.

The price of this new product is between 30% and 40% above the conventional lines in use. In the long term, the self-cleaning option saves on expenses with cleaning. A situation that should shortly be repeated in the textile industry, with the arrival of stainproof cloth, which has already been developed and is currently at the experimental stage in the United States. A company called Nanotex has the proposition of working with molecular engineering on a nanometric and submicrometric level of fibers to produce this cloth. Due to a process similar to the one applied to glass, treatment with nanoparticles gives cloth the property of repelling liquids. You can spill hot coffee or ice-cold Coca-Cola on it, and nothing sticks. It will be heaven for housewives and for the clumsy in general.

The advances in the practical applications are reinforcing the forecasts for growing investments in the area of nanotechnology. In the last year alone, world-wide funds have more than doubled. Countries like the United States, Japan, China, Canada, South Korea, Taiwan, Australia and the European Union are investing something around US$ 5 billion a year in the industry, between private capital and state sector capital. National Science Foundation (NSF), the American foundation that fosters science, in turn, estimates a global market for products and processes based on nanotechnology as capable of hitting the US$ 1 trillion mark in ten or, at the most, 15 years.

In Brazil, preliminary calculations by the Ministry of Science and Technology (MCT), which is drawing up a National Nanotechnology Program, forecast R$ 1.2 billion in investments for the next four years, 30% of this total coming from the private sector by means of incentives sponsored by the government. The intention is to direct investments towards areas previously defined as a priority, like farming and cattle raising, petrochemicals, communication, health, and the aeronautical industry.

Given the importance that nanotechnology is beginning to take on in the world scenario, Professor Cylon believes that the measurement of success for the implantation of any program aimed at the area in Brazil ought to take into consideration the winning over of a fraction of the world market in nanotechnology, carried on in the country by Brazilian companies and research centers. Enthusiastic about the topic and its prospects, particularly in the state of São Paulo, where a major part of the research into nanoscience is concentrated, over the last two years he has devoted himself to kindling an awakening of businesspersons to the issue, through talks and presentations.

At the beginning of July, Cylon was in Santa Catarina, at the headquarters of Embraco, a Brazilian company that is a world leader in the manufacture of compressors used in refrigerators and the like, to talk about this nanometric future. “There, they are already concerned with what may happen in the refrigeration industry as a result of the advances in this area”, says the professor. “The new technologies may make compressors, their main product, obsolete, just as transistors did away with electronic valves”, is the example he gives. “This horizon will reproduce itself in many other segments of the economy.”

To assure that companies with the stature and importance of an Embraco will continue to exist and to provide employment inside Brazil, instead of running the risk of other countries taking over the leadership by qualifying themselves in new technologies, the support of scientific research directed towards meeting the needs of the private sector is fundamental. Obviously, the counterbalance expected from the business world calls for greater involvement in financing these studies, as an incentive for the formation of small companies of a highly technological nature.

Molecular sieves
In the universe of nanotechnology, the country is not all that far behind, compared with the others. The knowledge that has been built up in this field is still very incipient in the four corners of the globe. One example of the promising situation in Brazil lies in the zeal of researcher Aparecido dos Reis Coutinho, a lecturer from the Physics Area Group of the Methodist University of Piracicaba (Unimep), in setting up a business aimed at practical applications for his discoveries, which resulted in the company called Multivácuo. With a proposal for research directed towards the synthesizing of molecular sieves using carbon-based materials, Coutinho received funding from FAPESP’s Small Business Innovation Research Program (PIPE).

At the moment, he is finishing setting up a pilot plant, to produce one kilo a day of carbon molecular sieve (CMS). CMS’s are materials with a porous structure in which nanopores predominate, classified as a result of their size and shape. The family of advanced carbon materials is made up of products with a low weight and high resistance, and they are applied in special processes of absorption, such as the control and purification of the air in the atmosphere, processes for separating gases, industrial systems using vacuum or compressed air, separating organic impurities and recovering solvents, and in gas chromatography, amongst other possibilities.

The researcher reveals that he is to sign a commercial contract with Petrobras to supply these carbon molecular sieves, which will be used in natural gas storage systems, to be used in the tanks of automobiles (see the article on page 72). The intention is to lower the pressure in the storage of natural gas and to make it possible to reduce the steel walls, as well as to adopt other tank formats. The use of CMS inside this container will bring about the adsorption of natural gas through the nanopores with a carbonous structure (called, in this case, adsorbed natural gas ANG), which will make it possible to reduce the volume of the tank and to decrease the pressure at which the fuel is stored.

“Putting the supply contract with Petrobras into effect will make it possible to expand production to 10 kilos a day in a short space of time and, in future, to implement an industrial CMS unit.” The initial importance lies in supplying these sieves for researches carried out by several groups that are importing these products. Aside from the applications of carbonous materials in segments of industry, another with a potential market is health, for incorporating this technology into the hemodialysis treatment of patients suffering from renal insufficiency. At the moment, Brazil imports practically all the material for this kind of filtering from the United States and Europe.

Coutinho’s most recent cause for pride was forwarding to the National Institute of Industrial Property (INPI) the patent registration for the process for producing carbon molecular sieves in cold plasma reactors, by means of ionized gases obtained by electric current and at room temperature. The use of this reactor was the great innovation in this process, which enjoyed the fundamental and decisive participation of researchers from the Plasmas and Processes Laboratory of the Technological Institute of Aeronautics (ITA), in the guise of technical assistance. Compared with the conventional process, the use of cold plasma technology shows the advantages of getting CMS with a more orderly nanoporous structure and a reduction in the time for activating the materials, besides being a clean process from the environmental point of view.

In an area similar to Coutinho’s, where a partnership with Petrobras has also resulted, chemist and professor Jairton Dupont, from the Federal University of Rio Grande do Sul (UFRGS) tried to remove compounds from oil that pollute the environment, using the resources of nanotechnology. He developed nanocatalysts. Catalysts are substances that speed up or modify chemical reactions that make it possible to lower the concentration of aromatic compounds during the stages of oil refining when gasoline and benzene appear. Combustion in gasoline engines thus becomes more complete, for example, without leaving waste in the air that may be carcinogenic and contribute towards the formation of acid rain.

Patented in conjunction with Petrobras, the catalyst also brings the advantage of being reusable, and the reactions can be brought about under mild conditions of pressure and temperature (60° C and only 2 atmospheres). The ones that are usually employed in this kind of reaction work at a high temperature and pressure (300° C and 150 to 200 atmospheres). Up until February, Dupont enjoyed financial support from the National Petroleum Fund (CTPetro). Now, he receives finance straight from Petrobras’s Research Center (Cenpes).

Always bearing in mind cost and ease of production in developing methods of synthesis that make the processing of nanometric materials possible, Professor Edson Roberto Leite, from the Multidisciplinary Center for the Development of Ceramic Materials (CMDMC), one of the ten of FAPESP’s Research, Innovation and Diffusion Centers (Cepids), is developing a series of technologies that should make it to the market shortly. In his laboratory at the Federal University of São Carlos (UFSCar), he has been working with nanostructured materials since 1999.

The main lines of activity are around nanocrystals of ceramic oxides and thin nanostructured films. “The most advanced works that allow one to think of putting them onto the market are those related to the development of nanocomposite catalysts. These products have applications in high temperature catalytic reactions, such as reforming methane and oxidating methanol, processes used for generating hydrogen”, Professor Leite explains. “We are also working on the development of molecular precursors for generating nanoparticles of metallic oxides, with finance from a Brazilian company that does not yet allow this to be made public”, he adds.

Electronic paper
Many of the investigations under way involve being committed to strategies that it is not advisable for disclosure, given the competitive environment. In these cases, reservation and caution tend to be the rule. Edson Leite ponders that amongst the projects that he is coordinating, there are those that have a propensity toward practical application before the end of this year, depending on investments of private capital, and others at a stage of development that means an average of from three to six years for implementation.” Nanocomposites should revolutionize catalyzing materials, making a series of advances possible, particularly in the generation of clean energy and controlling pollution and the environment.

“In the area of electronics, for example, we are working on a project developing thin transparent films and conductors for deposition on flexible substrates that are going to make it possible to create malleable liquid crystal displays (LCDs) and to spawn a kind of electronic paper that is being considered for replacing, in the future, the pages of books, magazines and newspapers. This can only be viable by getting nanoparticles. Another project in this area is the development of thin superparamagnetic films with a potential application in magnetic memories.”

Electronic tongue
A story that endorses the country’s encouraging future in the nano area comes from the arduous, but very tasty, work carried out by researchers from the Brazilian Agricultural Research Corporation (Embrapa), in São Carlos, over a period of eight years. Coordinated by materials engineer Luiz Henrique Capparelli Mattoso, in partnership with the University of São Paulo (USP), they created the first “electronic tongue”, based on nanostructured polymer conductors, using ultrathin films made up of molecules “designed” to react to the substances. This was how they built a device that is more sensitive than the human tongue, for tasting and analyzing drinks. Fitted with a set of sensors that perform a role similar to that of the taste buds, the equipment manages to attain the efficiency of an enologist.

It has the capacity, for example, for identifying precisely a red wines produced with Cabernet Sauvignon or Chardonnay grapes, just as it can handle the detection of differences that are almost imperceptible to the human palate, which there are between the various brands of mineral water or kinds of coffee: it goes so far as to be up to 10,000 times more sensitive than a human being for detecting standard flavors, like the presence of sugar or salt in water.Created with funding from FAPESP, the invention has been patented in several countries and has prospects for industrial use.

It has already been adopted by the Brazilian Association of the Coffee Industry (Abic) and may help in environmental control, monitoring the levels of contamination by heavy metals and pesticides in rivers and springs, as well as controlling the controlling the quality of the water at the treatment stations. In the food industry, the tongue will have the role of increasing the strictness of quality control in making beverages. For the time being, the equipment is fit to work with wines, coffee and mineral water, and the researchers are now developing sensors to analyze milk, grape juice and orange juice. In the pharmaceutical industry, the electronic tongue can be used to test drugs and improve the taste of bitter medicines.

Researcher José Maciel Rodrigues Júnior has been more time on the nanoworld highway, with his ten years of work carried out on nanostructured systems, first at the Federal University of Minas Gerais (UFMG) and nowadays at USP?s School of Medicine in Ribeirão Preto. “Now in August we are incubating Nanocore Biotecnologia, on the university campus”, he says. “I believe that it is the first Brazilian company with a platform in micro- and nanotechnology.” They have started to produce biodegradable nanoparticles, in the format of nanocapsules that wrap up the active ingredient of medicines and even vaccines capable of interacting only when they hit the target, much used in chemotherapy treatment and also in the cosmetics industry. “The investment now is in an industrial plant for producing microspheres, to make the clinical study of medicines feasible”, he explains.

Instruments of light
The conquests that can be mobilized for larger projects, on a scale of economic importance, and which express the country in the ambit of nanotechnology, have already clocked up considerable experience. There are also potent instruments available, like the synchrotron light source and the most powerful electron microscope to do nanoscience in South America, installed in the National Synchrotron Light Laboratory (LNLS), in Campinas, maintained with funds from the MCT. It is open to professionals both from public and private sector institutions and for companies.The expansion of the frontiers of knowledge and the evolution of humanity have been marked by mastery over materials and new sources of energy, as Cylon likes to explain: “Nanotechnology is the harbinger of a new waves of innovations, such as have been happening since the Industrial Revolution, when the manipulation of few natural fibers (cotton, wool) was mastered on a large scale, and the textile industry came into being. It is the last possible wave of technology, because it manipulates the basic element of matter, which is the atom”.

The Project
1. Molecular Sieve System Using Carbon Precursors (nº 00/13406-5); Modality Small Business Innovation Research Program (PIPE); Coordinator Aparecido dos Reis Coutinho – Multivácuo; Investment
R$ 307,112.00 and US$ 4,538.00
2. Nanocomposite Catalyst and its Processing (nº 02/04725-5); Modality
Industrial Property Support Program (PAPI); Coordinator Edson Roberto Leite – UFSCar; Investment R$ 6,000.00
3. Characterization of Polymer Sensors of Interest to Agroindustry (nº 00/11177-9); Modality Regular line of grants for research; Coordinator
Luiz Henrique Capparelli Mattoso – Embrapa; Investment R$ 32,470.12 and US$ 31,794.55