CALPHAD XXXVII - Fifth day June 19th 2008

The first days of CALPHAD were occupied (besides watching the technical sections, of course) with explorations of the environment at Saariselkä. Some of us went to the Urho Kekkonen nature Park, which starts just about 1Km from the hotel. The participants in this adventure are the three musketiers: André, Karin and José as the photo proves (Dartagnan here takes the picture).





The start of the trail is deceiving. What seemed to be a rather boring ladscape turned out to be a nice example of Scandinavian nature. We had even disturbed some locals, as these photos prove (including a rather daring activity by André).

















After that we proved that God is Computational thermodynamicist, since the only days with sunshine in the whole time were the days (or, better said, night) of the Midnight sun party and the excursion day in Tankavaara. The first photo shows our special guest (i.e. the sun) shining at midnight in the Kaunispää mountain, the second photo show our fellow calphadians searching for the samples of their next assessment. Next comes the banquet and the departure from Saariselkä.

CALPHAD XXXVII - Third day June 17th 2008

So much for the daily basis, but at least now I have learned how to download my photos to the computer using the memory card directly. Most of us arrived at Helsinki on saturday, 14th. The first CALPHAD "meeting" then took place at Helsinki´s airport on sunday morning, waiting for the only flight to Ivalo. Some photos from the happening:
















We arrived at Ivalo at lunch time and went to the hotel, transported by a sympathetic bus driver with excellent english skills (he received a compliment by John Cahn!). The rest of sunday was spent at looking for a place to lunch (the hotel restaurant, were I first tasted Renndeer meat) and visiting the "big" city of Saariselkä. We found what is important for a CALPHAD meeting, how the photos below proove:


Some of the highlights of the first day were:
- Tetsuo Mohri´s talk on CVM
- B. J. Lee´s talk on grain boundary energies
- John Agren´s talk on irreversible thermodynamics

CALPHAD XXXVII - First day June 15th 2008

It was a long period of silence, but I am returning back with my regular posts. I hope to contribute in a daily basis while I am attending the CALPHAD XXXVII conference, which takes place this time in Saariselkä/ Finland. For now I have to report the arrival of all people in the very strange place, where the sun never goes down (at this time of the year). Next I will post more informations and some photos, stay tuned.

Labour productivity

A recent report of the International Labour Organization (ILO) entitled "Key indicators of the Labour Market 5th edition" is being throughly discussed in Brazil today. This report publishes a ranking of countries in terms of the productivity of the labour force. The reason for the noise here under the equator is that the position of Brazil in this ranking got worse in comparison with 10 years ago. To explain this "disappointing" performance, some analysts are blaming the low level of education of the brazilian population. I would like to launch an alternative hypothesis: the low level of education of the brazilian population is not the cause, but the consequence of the "disappointing" behaviour in this list. My intuition tells that the low level of technology in the brazilian enterprises allowed the desconstruction policy applied to the education in the last 20 years: an educated population is not interesting to these low tech industries, since this would require better salaries.
Think about this...

"Applied" versus "fundamental" research

From time to time we hear, here in Brazil, some bureaucrat (sometimes even governors and presidents) talking about "applied" (meaning, technological) research as a kind of opposite to "fundamental" (meaning, academic) research. Although this kind of nonsense is also observed in other countries (particularly I remember one of the last ministers of science and technology of the Kohl government in Germany saying something like that), it seems to be more widespread here under the equator.

In my opinion there are only two kinds of researches: good ones and bad ones. Of course some misguided minds of the academy may be doing research only for the sake of the research. This is not "academic", it is simply bad! As it is bad to do technological research funded only by government money, without a (paying) link from the industrial sector of the country. Should we do "free" research to foster our industry? This should be denounced to the WTO as a hidden economic subside!

I agree that a government should be allowed to promote research in some critical areas, like it was the case of the genoma project, but the creativity of the scientist should not be hindered by allowing only "meaningful" research to be funded.

Let us prove this by absurd, suppose we decide to fund only socially relevant science. Surely a noble intent. Who will decide what is socially relevant? It is my guess that this will be done by a committee of three to four people. Suppose the wisest scientists are chosen to form this commission (not likely to happen), even so we exchange about 10000 thinking heads by three to four! As the popular wisdom tells, 10000 heads think better than three to four.

Another reason to let the researcher do science at his/her will is the impact on the new generations. Once I was lecturing materials science for the freshmen's year of the Escola Politécnica and there was this exercise about carbon nanotubes. After the class, one student asked me who has working on that in my department. I answered that no one did and that the technology behind that exercise was so weird (it was an experiment by IBM, who built a CMOS transistor using a carbon nanotube as gate, mounting it using an AFM) that it was unlikely that this would become commercial anytime soon. But who knows? Suppose that a real breakthrough in microelectronic device technology would come by some similar technique. Should our engineers need to learn after the university what is a carbon nanotube to survive in the job market? Research in those areas, which are not directly linked to the country reality, is necessary for the sake of our students. They must be well prepared to face the competition and this can be done only by lecturers who are aware of the major developments in the world, and this is done using research.

CALPHAD XXXVI

I just returned from State College-PA, where the CALPHAD XXXVI took place. As always it was a pleasant meeting, where not only the challenges and discoveries of computational thermodynamics where discussed, but also where friends could meet again. I will present here some of the highlights of the meeting , both scientific and social.

I was impressed by the large amount of presentations concerning the convenience or inconvenience of changing the description of pure elements, with the introduction of some physically based equation of state to handle the pressure/volume state variables. As mentioned by Larry Kaufman, these changes would require major changes in the thermodynamic descriptions of all systems, which surely is a huge task. In my opinion this is true, but someone will eventually start doing this. I believe that the actual descriptions will coexist with new, improved, physically-based models, until these acquire the same coverage of described systems and the same level of confidence of the existing models.

Another highlight of the last meeting was the elevated number of presentations dedicated to the use of the existing models and thermodynamic databases to modeling derivate thermodynamic properties, which are not usually experimentally determined, like viscosity of molten slags (Nicholas Grundy, using FactSage), surface tension (Risto Pajarre) and solder wettability (Zbigniew Moser).

As always Prof. John Morral´s presentation was a show! The "lecture" dealt with teaching phase diagram topology to undergraduate students. The techniques described have high learning potential for this arid topic (at least to our students).

The most impressive presentation was due to Prof. Dr. Byeong-Jo Lee, of the Pohang University in South Korea. He showed how standard thermodynamics, incorporation capillarity effects through tyhe Gibbs-Thompson equation was able to justify size-effects observed in nanotechnology. He exemplified considering two cases: the size-dependency of melting point in platinum nanoclusters and nanowires and the size-dependent composition of Si-Ge nanowires. His results clearly show that the usual thermodynamic tools are valid up to a quite small scale, which would not be accepted by most physicist as possible.

In the social side we had a pleasant meeting, as always. Most of the participants know each other from previous CALPHADs and the new participants are well received in general, so they quickly become part of the family. One anonymous (so nobody will be hurt due to the authorship, literally) quotation, which all participants agreed, clearly defines the CALPHAD meeting was "It was so much alcohol!" (referring to something that happened in last year´s CALPHAD, in Israel). Could not be perfectly realized in the present meeting due to the unusual closing time of the hotel bars (9 pm) and the long distance to the town, but even so we had our liquid amount available :-).

The conference excursion was to the Gettysburg battlefield. We were blessed with a sunny day as can be inferred from these photos. It was an unusual excursion, I had never visited a battlefield before. And sometimes it was a little bit awkward to walk literally over the grave of so many dead people. Our competent and passionate guide helped us to overcome this strange feeling and allowed to us, foreigners, to have some insight on the way that the Americans handle these historical events.

The banquett was very nice. The following photos show our table. As you can see, the motto was, "there is always one place more" ;-).

















Finally, one has to mention our trip to the Mad Mex bar in State College. Of course, only some of us still had some energy after five days of drinking (err..., I mean, of congress), but nevertheless, it was fun. My congratulations to the "Stone Arrogant Bastard Ale", which could be easily renamed "Stone Arrogant Bastard Bitter Ale". I finish this report with some of the pictures of that night.

Ethanol as automobile fuel and the brazilian PROALCOOL project: interview with Prof. Dr. Stephan Wolynec

The recent visit of President George W. Bush to Brazil brought to the world´s attention the brazilian PROALCOOL project. In fact, as far as I know, this is the only alternative automobile fuel project which achieved commercial status in the world. The interest of the american president adds some status to the matter and this, combined with the fact that Brazil and USA are the largest ethanol world producers, makes this technology fit for expansion outside the brazilian borders.


Prof. Dr. Stephan Wolynec is full professor (emeritus) at the Department of Metallurgical and Materials Engineering of the Escola Politécnica da USP. He is one of the most important brazilian researchers in the field of metallic corrosion and was deeply involved with the PROALCOOL project since the begining. I invited him for an interview and he, graciously, accepted. The content of this interview follows...


(Noted added for the help of the reader: Telex is an ancient communication medium, found today only in Technology Museums around the world - it was the poor equivalent of an e-mail twenty to thirty years ago).

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CGS: Please review the role of the university and of the research centers in the PROALCOOL project.

SW: The use of ethanol as a substitute of gasoline in cars in Brazil was motivated by the petroleum crisis started in 1973, which was aggravated in the last years of that decade. To overcome this situation, the Brazilian government launched the “Proalcool” program, through which it stimulated the car manufacturers to develop an ethanol fuel powered car.

The response of car manufacturers was positive, and their initial concern was basically directed, as expected, to optimize the parameters responsible for the engine performance. It was believed that it was sufficient to replace the engine of the gasoline powered car by the new engine to obtain the ethanol fuel powered car. However, it was soon realized that the ethanol fuel was not compatible with most of the materials used in the gasoline car due to corrosion problems, and that the undertaking of new materials selection was mandatory.

Two manufacturers (Fiat and Volkswagen), after adopting some surface treatments in some components of the gasoline car, started the production of ethanol fuel powered cars in the beginning of the 80’s. A euphoric start of a new automotive transport era was witnessed, which gradually began to fade due to the technical shortcomings of the new vehicle, which had in corrosion its implacable enemy. The complaints of bad performance of the vehicle, difficulties in starting the engine in cold days, the high fuel consumption, were growing, and the sales of these vehicles were collapsing. It seemed that the ethanol car had no chances to compete with its older brother, the gasoline car. However, in August of 1980 the government summoned a meeting between the car manufactures, universities and research institutes in order to discuss the possibilities of a collaborative work to solve the corrosion problems in ethanol fuel powered cars. The response of the participants of that meeting was highly positive, and the collaborative work started almost immediately. As a consequence, in the end of 1981 the ethanol fuel powered cars were already representing more than 50% of new cars in the automobile market. The participation of research institutes and university was decisive in the solution of corrosion problems. The new ethanol car became, in terms of performance and fuel consumption as good, or even better, than the gasoline car.

CGS: Which part did you play in this?


SW: At that time I was head of the Corrosion and Electroplating Laboratory at the Technological Research Institute of the State of São Paulo (IPT). This laboratory became heavily involved in the study of corrosion and corrosion protection against ethanol fuel. We performed decisive works initially with Ford and afterwards with Volkswagen. More than 10 papers were published and a considerable amount of technical reports were issued for different manufacturers involved in the task of solving the corrosion problems in ethanol cars.

CGS: The introduction of ethanol as an automobile fuel lead to considerable corrosion related difficulties at the time. Could you please explain this to our audience?

SW: The corrosion problems in the ethanol car were observed in many components. However, the most critical was that of the carburetor. At that time the carburetors in Brazil were essentially made of Zamak alloy (zinc-aluminum-copper alloy), and only in some few cars aluminum alloy carburetors were used. Already during the development stage it was found that Zamak and aluminum alloy were not corrosion resistant to ethanol and that some protective coating was necessary. Thus, the first attempt was to apply to Zamak carburetors a double dip chromate coating, but it was soon realized that the improvement in corrosion resistance it provided was only temporary.

In the first ethanol cars the corrosion of the carburetor, which is a vital component of a vehicle, was responsible for a considerable amount of corrosion products, which were dragged by the fuel, obstructing the calibrated orifices and interfering with the normal flux of the fuel, causing frequent problems of engine adjustment and increasing the ethanol consumption.

It can be stated that the ethanol car became viable only after the corrosion problems of the carburetor were solved. This was achieved when the Zamak carburetors became plated with electroless nickel. The idea of using this type of coating come out in a meeting at IPT that I and my colleagues from the Corrosion and Electroplating Laboratory had with the people of Ford R&D Laboratory. The Ford car manufacturer was the first to produce ethanol cars with this type of carburetor.

Coatings of other components of the car had also to be substituted for new coatings resistant to ethanol fuel. Thus, in the fuel tank the lead/tin coating (terne plate) was substituted by a tin coating with an intermediary coating of copper. All zinc coated components, chromatized or not, were substituted by cadmium chromatized components.

The ethanol car, in terms of materials used in its manufacture, became significantly different from the gasoline car. More than 300 components in the ethanol car are different from those used in gasoline car.

CGS: The recent introduction of the bi-fuel engines (the so called FLEX technologies), in my opinion, was quite smooth, in the meaning the the whole development, from the idea to the production, was made in a couple of years. Does this means that the above mentioned corrosion issues have been solved?

SW: I am not acquainted with this development. But, the development of the ethanol car had a very satisfactory effect upon the Brazilian car manufacturers. Before this development, we used to joke that their R&D laboratory was the telex. Every time they had a technical problem, they sent a telex to the parent firm in Unites States or Germany, and got the answer on how to solve it. But this did not work with the ethanol car. The development of this car forced the Brazilian car manufacturers to invest in their own R&D capabilities. Thus, I believe that presently they have highly qualified people and facilities to undertake the development of such technologies as the FLEX bi-fuel engines. Moreover, with the development of the ethanol car I am sure they learned how to solve the corrosion problems.

CGS: What are the actual research challenges in corrosion in ethanol media?

SW: Up to now the corrosion mechanism in ethanol media has not been properly established. This is a scientific challenge, but if we learn about this mechanism, new methods of corrosion protection could be discovered, both more efficient and cheaper.

CGS: Was the Proalcool project a successful example of interaction between universities, research centers and industries? Have we learned something from this experience?

SW: It certainly was. We had a big challenge to develop a new type of car, powered by ethanol fuel. In no place in the world there was a ready answer for this challenge. The Proalcool program showed that by joining efforts of industry engineers with that of university and research institutes scientists it was possible to develop, without relying on imported technology, and in a relatively short time, a Brazilian know-how. From this experience we learned that the scientific and technological expertise of our universities and research institutes can efficiently support the innovation efforts of our industries.