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With this New Year message, I greet the entire B-MRS community in Brazil and abroad.
The year of 2019 was once again a major challenge for science, technology and innovation in Brazil, as well as for public universities. B-MRS concern with the scenario in the country was expressed in public notes and in the manifestation entitled Carta de Camboriú, which once again highlighted the fundamental role that knowledge generation and transfer plays in society. In 2020 we need to remain attentive to the actions and policies implemented by governments at different levels, as Brazil’s sustainable development cannot be expected without this generation of knowledge, today essentially done by universities and public organizations. There will be no development if the diligent work of researchers from Brazil is not accompanied by continued funding. No country in the world has developed or develops without public resources to build a technological base.
Despite the difficulties mentioned, the resilience of the Brazilian scientific community, and that of materials research in particular, made major contributions in 2019. Many of them were recorded in B-MRS monthly newsletters and our other communication channels. Our annual meeting in Balneário Camboriú had a record number of registrations and one of the largest audiences of all time. The enthusiasm of students and researchers was in stark contrast to the justified pessimism since the beginning of the year. This gives us reason for optimism in 2020, and B-MRS will continue its efforts to provide a space for debate and dissemination of the scientific-technological contributions of researchers from Brazil and abroad.
After two terms, ending in February 2020, at the head of B-MRS, this is my last message as president. I would like to thank very much my Board and Council colleagues, and I wish the whole materials research community health and success in 2020, looking forward to meeting many of you in Foz do Iguaçu (PR), from August 30 to 3 September, for our next meeting.
Professor Osvaldo Novais de Oliveira Junior
Professor Luciana Reyes Pires Kassab (Faculdade de Tecnologia de São Paulo / CEETEPS) and Professor Sidney José Lima Ribeiro (UNESP – Araraquara Campus), both B-MRS members, are co-authors of the book “Nanocomposites for Photonic and Electronic Applications”. Also participating in the edition was Professor Raúl Rangel-Rojo, from Universidad Autónoma Metropolitana (Mexico). The work of editing the book was motivated by an invitation from Elsevier.
Recently published by Elsevier, the book addresses the applications of nanocomposites in photonics, electronics, optics, biophotonics and renewable energies, as well as their properties and preparation and characterization techniques. More information about the book: https://www.elsevier.com/books/nanocomposites-for-photonics-and-electronics-applications/pires-kassab/978-0-12-818396-0
B-MRS member Miguel Henrique Boratto won the prize to the best doctoral thesis in Materials Science defended in Brazilian institutions in 2018. The prize was awarded by Capes, the Brazilian federal government agency under the Ministry of Education, responsible for quality assurance in undergraduate and postgraduate institutions in Brazil.
Boratto´s doctoral dissertation, entitled “Semiconducting and insulating oxides applied to electronic devices “, was defended in 2018 in the Graduate Program in Materials Science and Technology of Unesp-Bauru, and conducted under the guidance of Professor Luis Vicente de Andrade Scalvi.
Boratto received the award in Brasilia on December 12th.
Seven scientific articles on topics in the area of materials are part of the latest volume of the Annals of the Brazilian Academy of Sciences (AABC). This is the result of the AABC call for articles in 2018, made in partnership with B-MRS, with the theme “Materials Sciences for a Better Future”. “This was a great opportunity to celebrate the success of materials research in Brazil,” says Professor Frank Crespilho, associate editor of AABC. To participate in the call, the authors submitted their work through the journal’s website at SciELO (an electronic library covering a selected collection of Brazilian scientific journals).
AABC publishes scientific articles from all fields of knowledge, and Materials Science and Technology works are welcome in all editions. AABC publications are free of cost to authors and open access. More information for authors can be found at http://www.scielo.br/revistas/aabc/iinstruc.htm.
According to the president of B-MRS, Professor Osvaldo Novais de Oliveira Junior, the growing importance of materials research has been revealed in major technological advances in all areas. In this context, B-MRS has played the role of bringing together students and researchers from Brazil, and their collaborators from other countries. “The partnership with the Brazilian Academy of Sciences is an important milestone of this performance of B-MRS, consolidated with this series of articles published in the Annals of the Brazilian Academy of Sciences,” says the president of B-MRS. “The quality of the articles and variety of topics in this edition of the Annals are representative of the strength of the materials research community in Brazil,” he adds.
Published articles can be accessed free of charge (open access) in volume 91, number 4 of the Annals of the Brazilian Academy of Sciences. Following is the list of articles on topics in the area of Materials published in this issue of the magazine:
- “Metallic Phthalocyanines: impact of the film deposition method on its supramolecular arrangement and sensor performance” http://www.scielo.br/pdf/aabc/v91n4/0001-3765-aabc-91-04-e20181201.pdf
- “Materials from renewable resources: new properties and functions” http://www.scielo.br/pdf/aabc/v91n4/0001-3765-aabc-91-04-e20181160.pdf
- “Proteins and Peptides at the Interfaces of Nanostructures” http://www.scielo.br/pdf/aabc/v91n4/0001-3765-aabc-91-04-e20181236.pdf
- “Weathering Resistance of Waterborne Polyurethane Coatings Reinforced with Silica from Rice Husk Ash” http://www.scielo.br/pdf/aabc/v91n4/0001-3765-aabc-91-04-e20181190.pdf
- “Hydrogen production from aqueous glycerol using titanate nanotubes decorated with Au nanoparticles as photocatalysts” http://www.scielo.br/pdf/aabc/v91n4/0001-3765-aabc-91-04-e20190082.pdf
- “Dendritic Gold Nanoparticles Towards Transparent and Electroactive Electrodes” http://www.scielo.br/pdf/aabc/v91n4/0001-3765-aabc-91-04-e20180817.pdf
- “Size and shape-controlled nanomaterials based on modified polyol and thermal decomposition approaches. A brief review” http://www.scielo.br/pdf/aabc/v91n4/0001-3765-aabc-91-04-e20181180.pdf
Prof. Carlos Alejandro Figueroa (UCS) has been selected by the Royal Society, one of the oldest and most renowned scientific societies in the world, based in London, to receive a Newton Advanced Fellowship, with which he will develop research over two years on ultra-low friction materials in collaboration with a group from the University of Southampton (UK).
Figueroa is a member of B-MRS and was elected member of the Deliberative Council of the Society for 2020-2024.
Graphene-based products are already being used by manufacturers, from heat-dissipating helmets to antistatic packaging. However, this wonderful material, as it is often called, still has much to deliver to society. As it is two-dimensional, flexible and excellent conductor of electricity, among other properties, graphene can be the basis of a series of high-performance miniaturized electronic and optoelectronic devices. However, this requires producing, at an industrial scale, a graphene whose network of atoms is free of unwanted impurities, but which contains, besides the carbon inherent in the graphene, small amounts of other elements (doping) in order to control its electronic properties.
In a work totally carried out in Brazil, a scientific team has proposed a process that can help produce large-scale graphene that is suitable for electronic devices. “The process developed in our group allows us to improve and adjust the graphene properties, as well as the removal of contaminants from its surface,” said Professor Claudio Radtke (UFRGS), corresponding author of an article reporting the study, recently published in The Journal of Physical Chemistry C.
The team acquired graphene samples produced by chemical vapor deposition (CVD) and transferred to silicon substrates. This technique is currently one of the most suitable for large-scale production of relatively large area graphene sheets, but it leaves residual impurities and generates defects in the graphene. To remove impurities, it is common to apply a heat treatment in an atmosphere of carbon dioxide (CO2), which is efficient in removing contaminants, but ends up generating new defects in the graphene sheet. The good news is that these defects can be neutralized (passivated).
While looking for strategies to passivate these defects, then PhD student Guilherme Koszeniewski Rolim found a scientific paper from 2011, which pointed to, through theoretical calculations, the possibility of using nitric oxide (NO) to passivate graphene defects with nitrogen atoms, while doping it to modulate its electronic properties (mainly transforming it into a semiconductor material, an essential condition for using graphene in electronic devices).
The team then decided to experimentally verify the theoretical prediction and, after performing the traditional treatment with CO2 at 500 °C, they applied a second heat treatment to the samples, this one in nitric oxide atmosphere and at different temperatures, from room temperature to 600 °C.
After the process, the researchers used various characterization techniques to check the results and gladly confirmed that nitrogen doping had taken place and that it had passivated the defects, thus improving the material’s electronic properties. However, the researchers also noted an unwanted effect of nitric oxide treatment: etching of graphene sheets at some points. After much scientific work, the team was able to determine the cause. During heating, there was a conversion of NO to NO2, which, as it is a much more reactive compound than the former, eventually oxidized the graphene.
However, the Brazilian team found a solution to this problem. The “eureka” moment occurred as the researchers were trying to determine the amount of nitrogen atoms that had been incorporated into graphene using a technique based on the analysis of nuclear reactions triggered by the effect of an ion beam on the graphene samples. In order to apply this technique, the team had to use an isotopically enriched nitric oxide in the heat treatment, which has a purity of 99.9999% instead of 99.9% of the gas previously used.
The analysis did not yield the expected results as it failed to quantify nitrogen, which was below the detection limit. However, the use of the enriched gas eventually brought great satisfaction to the team. Indeed, when the researchers compared the electronic properties of both sample types, they found that graphene treated with enriched gas always had superior properties. “Initially, such a result created much confusion in the interpretation of the results,” says Professor Radtke. “But after a few more experiments, it became one of the most important points of the article, highlighting the importance of gas purity during processing,” he adds. Specifically, the conclusion was that by properly controlling the temperature and purity of the gas during the treatment one can eliminate the problem of oxidative graphene degradation.
Thus, based on solid knowledge and scientific method, as well as some serendipity, the UFRGS team was able to develop a process of waste removal, defect neutralization and graphene doping, which improved the electronic properties of the material without producing deleterious side effects. Because it is a heat treatment in a gas atmosphere, a step that is now part of the industrial production of graphene, the process proposed by the Brazilian team could be easily applied in the production of graphene sheets for devices.
“The insertion of heteroatoms (such as nitrogen) into the graphene network without the degradation of its properties is especially important in the production of optoelectronic devices, high speed transistors, low power electronics and photovoltaic cells,” says Radtke, noting that manufacturing these graphene-based devices may be a reality in years to come. “The Graphene Flagship (European consortium of industries, universities and institutes) has announced the implementation of a pilot plant to integrate graphene at different production stages of devices as early as 2020,” comments the professor from UFRGS.
The study, which was funded by the Brazilian agencies CNPQ (mainly through INCTsNamitec and INES), Capes and Fapergs, was developed within the PhD in Microelectronics by Guilherme Koszeniewski Rolim, held at the UFRGS Graduate Program in Microelectronics and defended in 2018. The experimental work was carried out at the UFRGS Solid Surface and Interfaces Laboratory and the Brazilian National Synchrotron Light Laboratory.
[Paper: Chemical Doping and Etching of Graphene: Tuning the Effects of NO Annealing. G. K. Rolim, G. V. Soares, H. I. Boudinov, and C. Radtke. J. Phys. Chem. C, 2019, 123, 43, 26577-26582. https://doi.org/10.1021/acs.jpcc.9b02214.]
In 2004, three young chemistry graduates from the Brazilian Federal University of São Carlos (UFSCar) created a nanotechnology-based materials company. Today, Nanox has about 30 products developed, a technological platform consisting of seven patents (three worldwide, one in Europe, one in the United States) and over 200 clients, not only in Brazil, but also in 13 other countries.
Nanox’s business is to develop, produce and market nanotechnology-based materials whose properties (bactericidal, fungicidal, repellent, anti-sweat, antiallergic…) add value to a particular product (packaging, flooring, carpet, t-shirt…). Thus, Nanox provides its customers (companies in various segments) nanomaterials that can be easily incorporated into their products, which bring tangible benefits to end consumers.
Today Nanox’s flagship products are silver-based antimicrobial additives. The company has developed a series of such products within three broad lines: solution additives (liquid), powder additives (solid), and additives already mixed with polymeric materials.
As shown by the ratio between the number of products launched and the company’s years of existence (about 30 innovations in 15 years), innovation is part of everyday life at Nanox. Generally, the process is as follows. In its contacts with the market, the Nanox team identifies latent demands that can be met by applying the technologies that the company has mastered. The team then validates their innovation ideas with potential customers and begins to work on product development.
At its 500 m2 headquarters, located in the city of São Carlos (state of São Paulo, Brazil), Nanox has about 150 m2 of internal laboratories for research and development and quality control. There are three physicochemical laboratories, one for materials engineering and one for microbiology, in which the team performs bactericidal and fungicidal efficiency tests. The company has two researchers (one master’s and one doctor) dedicated to R&D activities, but, depending on the project and the development phase, the team may include up to five people. In addition, Nanox partners with external research laboratories to perform activities where there is no internal expertise and for those requiring expensive equipment such as electron microscopy or X-ray characterization of materials.
History and cases
It all started at a UFSCar research center supported by the São Paulo Research Foundation (Fapesp), the Multidisciplinary Center for the Development of Ceramic Materials (CMDMC), today the Center for the Development of Functional Materials (CDMF). There, under the guidance of Professor Elson Longo, friends André Luiz de Araujo (who worked at the company until 2011 and to date remains a shareholder), Daniel Tamassia Minozzi (current COO) and Luiz Gustavo Pagotto Simões (current CEO) were doing their undergraduate and master´s research.
In 2004, at the behest by the Brazilian home appliance company Multibrás to CMDMC, the trio saw an opportunity for entrepreneurship in the nanotechnology-based materials segment, which at that time had few products and very few companies in Brazil.
The project consisted of developing nanostructured films to protect metallic surfaces. To make it possible, Nanox obtained funding from Fapesp’s Pipe program, dedicated to supporting innovation research in small companies. This would be the first of seven fundings for Nanox from the Pipe program to support various phases of technology and product development, among other Brazilian public federal fundings.
In 2005, Nanox sold a product for the first time. It was a titanium dioxide nanoparticle film applied in the filters of hair dryer used in beauty salons, manufactured by the Brazilian company Taiff. The bactericidal and fungicidal effect of the nanomaterial guaranteed more salon hygiene and consumer health. The product earned Nanox a Brazilian award (Finep Innovation Award) in 2007, as well as widespread publicity and visibility.
In 2006, realizing that there was plenty of room for Nanox innovations in plastic products, the partners decided to start developing nanomaterials in the form of additives that could be incorporated into various polymers. Through partnerships with companies (Nanox customers), these innovations have reached end-consumers. An example is PVC films (those used in the home environment to pack cut fruits and other foods) with antibacterial shield. In 2014, the Brazilian company AlpFilm launched a line of films with additives from Nanox, whose antibacterial and antifungal effect allows conserving packaged foods longer by avoiding their degradation. Another Nanox case is a packaging that doubles the validity of fresh milk thanks to the antibacterial effect of the additive. The world’s first bactericidal milk bottle began to be used by the Brazilian agro-industry Agrindus in 2015, and was the headline for food and packaging industry websites and magazines in several countries.
In 2009 there was another milestone in the history of Nanox. A presentation the company prepared for a General Electric team in Brazil ended up at the company’s Mexican branch and generated so much interest that, 15 days later, Nanox was undertaking its first export, which consisted of plastic additives to make refrigerator boxes in Mexico. From that moment on, Nanox began to look towards the foreign market, starting a strategy that includes investments in international fairs, representatives in several countries and training the team to deal with bureaucratic issues inherent to the export process and the introduction of products in different countries. This journey is currently reflected in exports that represent 12% of the company’s revenues, with recurring sales to Argentina, Chile, Colombia and Mexico; halfway toward the US market, and distributors in countries from Latin America, Eastern Europe and Asia. In addition, this year Nanox participated in a business acceleration program for Plug and Play Tech Center, a Silicon Valley-based innovation platform that has hosted companies such as Dropbox and PayPal. Nanox was one of 15 companies selected from 1,000 companies worldwide.
See our interview with Luiz Gustavo Pagotto Simões, PhD (2009) in Chemistry from UNESP, co-founder and current CEO of Nanox.
B-MRS Newsletter: What were the most important factors that allowed Nanox to develop in its various phases?
Gustavo Simões: It was a sum of factors. Financial resources, both public and venture capital – the latter from 2006 on, when the company became a Ltd., as well as the work of entrepreneurs and the team to validate products and bring them to market. We always use the resources of Fapesp and Finep to lower capital acquisition costs for development, especially at some crucial moments of the company. For example, at a time when we had a technology but its scale was too small, we got a Pipe phase 3 that allowed us to scale up production. The investor was also important; it improved the administrative and commercial structure of the company. The most important thing was to validate everything we thought could be a Nanox product, and you can’t do it without money or personnel. In addition, we must thank Professor Elson Longo, who accompanied Nanox in all its phases as a supporter, scientific advisor, partner, promoter…
B-MRS Newsletter: What were the main difficulties Nanox has faced thus far?
Gustavo Simões: In fact, trading nanotechnology in Brazil is not easy. At that time, many people said they wanted to have nanotechnology, but very few took a chance on this. We were very lucky to have some key partners like Taiff and IBBL. These companies decided, in a market as competitive as Brazil, to differentiate themselves and add a product like ours into their product. So the difficulty of getting customers has always been among the greatest issues. And also to survive this madness that is Brazil for entrepreneurship. The exchange rate variations, for example, have a direct impact on the company, and we have to get around such situations, this requires creativity and flexibility. It is rare to plan and get out what you have planned.
B-MRS Newsletter: Nanox is recognized worldwide and exports its products to various countries. Tell us a little about Nanox’s internationalization and what it is like for this Brazilian company to compete in foreign markets.
Gustavo Simões: Latin American markets are similar to Brazil’s market. They are less regulated, which increases the possibility of competition because there may always be a local player that competes with you. On the other hand, these markets are easier to access than the more regulated markets, such as the US, where you need multiple regulatory agency registrations and licenses, which require a number of expensive studies and tests. Not everyone is willing to do this. So, higher regulation creates a barrier to enter the market which decreases the number of competitors. We’re in the process of getting licenses to be able to sell our products in the United States, and we’ve already obtained some. In some products, we will only have three competitors in the United States.
In addition to this regulatory issue, other factors that hinder export are cultural issues, such as language. In Latin America, Brazil is the only Portuguese-speaking country. In Brazil there are also some bureaucracies, for example in banks, which hinder exports and may also make a business line not worth it. This has to change.
So, internationalization is quite expensive. You have to attend fairs abroad and have a team trained in the export bureaucracy and regulation of the markets you want to reach. However, I believe that in products like ours, more technology intensive and less labor intensive, Brazil is very competitive. We even have incentives to export. If you export, you do not pay some taxes and the product has a more competitive price abroad. Exports account for approximately 12% of Nanox’s revenues, but this percentage is expected to grow. After the last international fair in which we participated (in the plastics segment) we received orders from Iran, India, Pakistan…
B-MRS Newsletter: What do you think is Nanox’s main contribution to society?
Gustavo Simões: A contribution is the training of human resources, always with very good interaction here. A lot of people have worked here and today they are doing really well working in multinational companies. Moreover, I believe it’s important to share through media, lectures, etc. our experience from the point of view of entrepreneurship, to show that there is a different way of working, besides working in a private company or as a Professor. It is important to show that there is a possibility and that there are incentives and support in the country, perhaps not as many as we would like, but much more than in other places. In addition, the other contribution we make is our products for food safety and better quality of life. But, as Elson [Longo] says, if I can leave a line in the literature, that’s a lot; now, if I can motivate a person to undertake and run a project, this is very important.
B-MRS Newsletter: What is your goal/dream for Nanox?
Gustavo Simões: We want to consolidate internationalization, and we want to place ourselves as global players. We are making a very strong move, even though the dollar is crushing us because we are earning in reais [Brazilian currency] and spending in dollars. Over the next 5 years, we expect to have a larger international market share in revenues, so much that we have opened an office in the United States and are talking to investors to get funds over there.
B-MRS Newsletter: Leave a message for people who are considering entrepreneurship.
Gustavo Simões: I would say that entrepreneurship is worthwhile and necessary. I believe that the technical knowledge we receive in Brazil in our undergraduate courses, for example in Materials, leaves nothing to be desired elsewhere in the world. We have to convert knowledge into wealth, and there is only one way to do that – which is through entrepreneurship.
I think this issue of university-business interaction and spin-offs is the future for us to create a differentiated value-added economy in a country where we have a huge consumer market. If we can use all these financial and human resources, these extremely well-trained people, and generate products and services for the economy, I think it will be a very promising future.