Sciences : histoire orale

STENSGAARD Ivan, 2001-03-08

Sophie Jourdin — 2011-11-11T21:40:34Z

Ivan Stensgaard received a PhD in physics from the University of Aarhus, Denmark, in 1977. He subsequently spent two years at Bell Labs in Murray Hill, New Jersey. From 1979 to 1998 he was Associate Professor at the Institute of Physics and Astronomy of the University of Aarhus. From then on, he has been a Research Professor at the Center for Atomic-Scale Materials Physics (CAMP).

From the 1970s onwards, Stensgaard has investigated surfaces. His primary tool before the advent of the Scanning Tunneling Microscope was ion scattering. His first publication investigated radiation damage in reactor materials, and soon he moved on to investigate other surfaces, such as platinum, tungsten, and silicon. He used both backscattering and channeling of ions to infer the reconstructions of crystal surfaces. Most of his research employed ions in the MeV range, but he has also worked with low and high energies.

Because of his extensive knowledge of surface structures and the tools used to gain knowledge about them, he was in a good position to judge the efficacy of the scanning tunneling microscope when it came upon the scene in the mid-1980s. In collaboration with Flemming Besenbacher and Erik Lægsgaard, he built up a research project (CAMP) that relies extensively upon this new tool.

In our interview, Stensgaard outlines the history of CAMP and describes some of the many uses to which the STM can be put.

IVAN STENGSAARD (IS) : In the early the days, the way I recall it at least, in the STM field, most people worked on semiconductors, where the advantage is that the corrugation revealed by the STM is generally much larger than on metal surfaces. That means that the demands on the equipment are much more modest. So it was easier to enter the field of semiconductors - and of course also the technological implications were thought to be greater in that field. But when we entered the field, which must have been around 1987, there were few groups working on metal surfaces. So although the STM was really recognized as an excellent tool, there had been some delay in really using this as a common tool in studying metal surfaces.

ARNE HESSENBRUCH (AH) : But during the period of '82-'87 you would have known about the STM ?

IS : Yes.

AH : And it was something that you perhaps watched ? You watched the development of this instrumentation and you were critical to see whether it would prove its mettle for you to begin to use it ?

IS : Yes. Well we were not, as I recall it, completely convinced that it would add a lot to the insight into metal surfaces. But as soon as we did enter the field ourselves, placed the instrument in vacuum and seen the results, we were immediately convinced. I'd say from then on it has been fantastic : it has been quite easy to achieve good results with just about any topic of investigation. One saw new phenomena almost regardless of what one studied—new and completely unanticipated phenomena.

AH : So you're saying "we" now, this is presumably the CAMP group. When did that gel ? Was that in '87 ?

IS : Yes, I do mean the CAMP group. But we began collaborating earlier. Historically, I think it was like this : I returned from the US and received this grant for building up an ion scattering facility for studying surfaces [referring to an earlier mention that is not on the tape – this part of the interview will be repeated in the near future]. Some years later, Flemming Besenbacher and I worked together on ion scattering from surfaces. We looked at small molecules, and specialized on the examination of hydrogen on metal surfaces. Then in the 80's, probably around '85 or so, we began to discuss in more detail this question of building a scanning tunneling microscope. Flemming took the initiative in those days and contacted Erik Lægsgaard. Erik was really the key person in building the STM here. And from when he started until he had a table-top version, giving atomic resolution on graphite, lasted only a few months. Of course it took longer to make an instrument fitting into a vacuum system, and so on.

AH : Did you make it locally ?

IS : Yes, everything here has always been homemade.

AH : You've never bought instruments from the outside ?

IS : No. We tend to claim here that our instrument is better than what we can buy. It may sound like boasting, but I think our results help prove the contention. The fact that we can work with extremely rudimentary vibration isolation, proves that we have an highly stable instrument.

AH : So what were the characteristics of the design – the Aarhus design ?

IS : Well, there are two basic ingredients in the construction : one is the scanner tube scanning the tip across the surfaces, and I think that was copied simply from the Binnig and Rohrer design.

AH : The empty cylinder.

IS : Yes. So, the larger problem was how to approach this scanner tube tip to the surface in a controlled way so that you would come close enough to draw a tunnel current without actually colliding. To begin with we had many ideas about some mechanical way of doing it with micrometer screws, but soon we focused upon piezoelectric materials. And I think, again, that it was Erik's idea to make an inchworm. This is a really strange story. We had a very small inchworm made : only a few millimeters in diameter - maybe 10-12 mm long. It worked well and a company called DME in Copenhagen wanted to commercialize our setup. During the discussions and negotiations with them, they found out that the inchworm principle was already known, and what was worse, it was already patented. That was a something of a setback - not for our in-house microscopes but for the efforts to commercialize it. The commercially available inchworms were much bigger and not nearly as elegant as ours. But the principle was patented, and the patent had a few years left before expiration.

AH : Oh, so the patented inchworm was not intended for the STM ?

IS : No. The patent was about 10-15 years old and had been developed for something else. Whether it was developed for one of the topografiners and what they were called, the instruments used prior to STMs, I don't know. We can check the patent.

AH : Well, the topografiner was invented at the National Bureau Standards now NIST and I don't think they would have taken a patent.

IS : We could check it.

AH : So you designed the inchworm in '87, just when you were making your first STM ?

IS : Yes.

AH : But your first STM did not have an inchworm.

IS : Yes, it was a mechanical approach.

AH : Where did you get all the information for making an STM ? Did you look at the publications of Binnig and Rohrer, did you go and see them ? Did you go to the IBM labs ?

IS : No, the way I recall it, we had no personal contact. I think everything was done just using the publications.

AH : And it wasn't particularly difficult ?

IS : Not if you had a clever man like Erik. The short time required to make the first STM also indicates that it was fairly easy. Of course in retrospect many aspects of building an STM seem easy, because we know just how piezos work and what to pay attention to. The game nowadays is really to make them as compact as possible, to make them work even with vibrations in the surroundings and so on.

AH : Yes, you were saying you had very elementary vibration damping. This is another characteristic of this design ?

IS : Yes. Exactly. When you visit other STM labs, you're frequently told that they have to work at night when there is no traffic. They have all kinds of vibration damping, entire vacuum systems hanging in rubber — springs from the ceiling or something like that. They have the microscope damped with magnetic or eddy current damping. And people had to stay quiet and not move about in the room and so on. That remained characteristic until at least ten years ago. By contrast, from the beginning we hung our microscope on three or four springs, or viton-o rings, which are really rubber springs. That's all ; we have no further vibration damping. And people can even touch the UHV chamber without interfering with the tunneling. So that has been the main characteristics of the instrument here : its ability to scan fast and under adverse conditions.

AH : Fast and robust. You have told us about the robustness, could you tell us about the speed ?

IS : Fast scanning is interesting also because it has opened up new opportunities compared to other microscopes. There are more fast-scanning microscopes today but to begin with we scanned faster than most others. We scanned at the rate of one second per image, where many others spent one minute per image. This gives you the opportunity to follow dynamic processes on surfaces by sequentially recording images and then replaying the images at a faster rate - in the form of a movie. That gives you a very vivid impression of what happens on the surface. You might object that a movie yields no new information, but it turns out to be a very good means of attracting attention to dynamic processes. Such phenomena miss easily when just examining static pictures. The eye is well-suited to spotting change, so that even when there is a lot to keep track of, say 20 to 40 entities on a surface, your eye will immediately pick it up a movement of any one entity. So this question of scanning fast and taking movies, is not just a question of presenting results in a nice way, it also gives you a better insight into what is going on.

AH : But you weren't capable of making movies off the bat in 1987 were you ? How long did you need to scan in 1987, roughly ?

IS : I don't recall it really. I think we could record images in seconds, but the problem was probably rather that saving and replaying images requires a lot of data storage, and in those days the hard disks were not very big. It was slow process simply to get an image from the hard disk onto the screen.

AH : Was your ability to scan quickly a desideratum in 1987 ?

IS : Early on we probably didn't focus on the time you spent recording. It probably didn't matter whether it was 1 or 20 seconds or so. But I see now [checking on the computer] that taking movies and things like that, must have started in the late 80's. Because we have publications at least from '91 where we have included, not movies because that wasn't possible, but results based on these techniques.

AH : And what sort of thing did you image ? Metal surfaces with adsorbed atoms ?

IS : Yes, of course the standard sample in those days (as it still is for testing an STM in air) was graphite. Of course we used that as the test that our STM was working properly. Having done that we moved rather swiftly in the surface science direction again. We examined some gold-plated plastics, simply to investigate the micro-roughness. The purpose was to test the coating of large mirrors of an x-ray telescope to be used in a satellite. We also investigated some biological samples. But we were really implementing the STM in a vacuum.

AH : You say you were immediately convinced, when you saw the images, that this was a useful tool. It was seeing the images that convinced you almost instantly ?

IS : Yes

AH : Why ? There are many problems with the imaging process of course, with the noise and the interpreting just what the tunneling current actually is referring to. On metals this is less of a problem than semiconductors. Was that a help to you ?

IS : Yes, to some extent it was. Let me just mention the first system we examined, to maybe make references to that. Once we got the microscope into a vacuum we continued our work on small molecules on a metal surface. The first system we examined was one I had investigated earlier using ion scattering. We had absorbed oxygen on a particular copper surface, a copper (110) surface. And it was known what happened to the oxygen, how the surface reconstructed. What was not known was how the process took place, and that was revealed immediately almost with the STM, because we could look upon the surface while the reconstruction took place, and we could make a movie and watch the process.

AH : That must have been exciting.

IS : Yes, and then I was at least totally convinced at that time that here was an amazing tool.

AH : So the problems that there might be with interpretation were really secondary to you, you said that even with all those problems, "it's still exactly what I need ?"

IS : Yes, you said that in the case of semiconductors it is more difficult to relate the STM-produced image to the surface corrugation. That is correct of course, but you could say that we had a similar problem on our hands with oxygen on a copper surface : were we imaging the copper or the oxygen ? And it turned out that we were usually imaging the copper. This posed the question : why not the oxygen ? And why is it sometimes just the other way around, that we image the oxygen and not the copper. So scanning on metals was not completely free of problems, at least not when you have the adsorbates on them. But if you image one clean surface with only one element present, then the interpretation is straightforward.

AH : What I'm trying to understand is that when you use a completely new tool, you cannot know whether it works.

IS : I think the problems of instrumentation were so insignificant compared to the insight gained, that we were absolutely convinced of the amazing utility of the instrument. That's the way I recall it, really. There was a trend in those days—probably through the 90's—from static to dynamic problems. Other methods, such as low-energy electron diffraction, high-energy ion scattering, x-ray diffraction, are better suited for static problems. You can induce a reaction on the surface, and then you can take your tool and find out how the surface has changed. But with the STM you had a tool with which to see the transformation from one state to the next. Later on, you could even follow single atoms moving on the surface. That was really amazing, and almost impossible with other techniques. Field ion microscopy has been able to do it in some cases.

AH : Before the STM, you were using tools like ion-scattering, but it was not the tool that defined your research. Now it looks like the STM defines the group.

IS : I don't really think that's correct. No matter what you investigate,
you have to take both things into account. You have to find an interesting problem amenable to investigation with your background, its relevance and so on. Then you have to consider the available techniques. You have to find a topic amenable to the techniques available to you. I think that also describes what we did with the STM. It is a question of resources. The microscope does not define the activities ; a natural development has rather taken place. I mentioned before that we first investigated small molecules on surfaces, and we have continued to do that. Our research has now diversified but it is still to a large extent coupled to chemical reactions and the like. We have studied surfaces in greater detail – also clean surfaces although clean surfaces are less interesting for STM research because one can get the information by other means. But when you grow metal on metal for example, what happens ? How do these atoms of one metal, influence the properties of a surface of another metal. How does the surface restructure ? And, to come back to my initial point, how do the chemical properties change ? What happens if we now adsorb oxygen, what happens if we carry out a chemical reaction, let's say oxygen and CO reacting on the surface. In all these cases there has been a connection to the initial questions.

AH : Have you expanded the number of chemical reactions you worked with ?

IS : Over the years we have worked with a number of chemical reactions, but in the last few years we have focused more on catalysis. We have for many years collaborated with Haldor Topsøe AS, one of the leading companies in the catalytic world. We have collaborated on a number of issues, in once case a new catalyst was developed on the basis of our results. We proved scientifically that the catalytic conversion works. Whether that catalyst in the end will be commercially available now depends on other considerations, such as the cost of producing a catalyst, its lifetime and so on.

AH : But you discovered new catalysts with the STM, is that what you're saying ?

IS : We discovered a system that turned out to have possibilities in catalysis. We could talk in more detail about that, but it's a story in itself.

AH : Okay. What can you do now with the STM that you couldn't do in 1990 ?

IS : There has been constant improvement in speed : the rate at which you record and replay images. And new designs have made the microscope usable under new conditions. It now works over a large range of temperatures and pressures. To begin with experiments could only be carried out at room temperature, whereas we now can work from 20K or so and up to maybe 150ºC (500K). This increase in the temperature range is important for the investigation of dynamic processes because the rate at which they proceed is governed by temperature. And if you wish to study a certain reaction or a certain diffusion property, you have to have the events happen at a rate you can follow. That means that you shouldn't have too many events per second, preferably no more than one event every few seconds. And you can normally do that by adjusting the temperature.
We can also work at many different pressures now. Early on we had to work either at atmospheric (ambient) pressure or else in a very high vacuum. We have recently become able to work in the full range of pressures from ultra high vacuum to atmospheric pressures and could in principle make the system work at even higher pressures, if it weren't for some windows unable to withstand atmospheric pressure. And that again is advantageous for catalytic research, since all catalytic processes run at high pressure and high temperature. In the surface science community there has always been arguments that their field would help improve catalysts and understand catalytic reactions. That is to some extent true, but there has also been a lingering skepticism whether the processes taking place at atmospheric pressure remain the processes governing chemical reactions while raising the pressure from 10-10 Torr to atmospheric pressure. So that has been an important result : that at least in the one case that we have done so far, the system behaves identically at high pressure and in an ultrahigh vacuum, it's exactly the same things that govern the processes.

AH : What do you have to change in the STM to make it amenable to the range of pressure and temperature ?

IS : Actually not much was changed ; it's basically the same setup. The only major change is that it is located in a minor vessel ; it's in a minor chamber with a smaller volume, which is the volume that is brought up to high pressure. The suspension system has changed also, but the basic STM is the same. The suspension system is still based on a few springs, and looks differently, but the system as such is really the same. And of course minor things like gold coating surfaces to avoid reactions of those, but the heart of the microscope is completely unchanged.

AH : Why didn't you do these things 10 years ago ?

IS : I think in the field of ultrahigh vacuum there have been so many extremely interesting topics that there simply hasn't been the capacity to look in other directions. We should bear in mind that when CAMP was established in '93, much more funding became available than before. And the group grew much bigger. And although to begin with we also focused very much on processes at low to high vacuum, then at least during the second period of CAMP (from 1998 onwards) we have been able to diversify. High pressure is simply a natural development out of our original research. When I refer to new fields, I mean investigating organic molecules and other biology-related issues. So our research program has really developed quite naturally.

AH : So you started CAMP in 1993 - you, Besenbacher and Lægsgaard.

IS : The history of CAMP is more complicated – it is related to changes in the funding of Danish research. A large insurance company, Statens Livsforsikringsanstalt, was sold and a fund, Grundforskningsfonden, was set up with the money from there : 1 or 2 billion Danish kroners. Interest from the capital there was to be spent on basic research in all fields. In those days the interest rate was high and leading to a fair amount of interest each year. They requested and received many proposals for research centers. I don't recall exactly but it was a very large number. And in the end they funded 23 centers in all kinds of science : medicine, humanities – Søren Kierkegaard. We got a center too, a collaboration between our group here at Aarhus and Jens Nørskov's group at the Danish Technical University at Lyngby. The group there focused mainly on theory, and Nørskov was the director of the center, as he still is technically. The reason the two groups joined in this project was that we had had a prior collaboration within another program called FTU, research for technological development. In addition Flemming had collaborated with Jens Nørskov on another topic. So we knew each other. A proposal was made based on the joint resources of these two groups and after some external referring procedures it was eventually funded.

AH : And the project was focused on the STM ?

IS : I think the scope was broader : the interaction between small molecules and surfaces, to some extent chemical reactions. Our tool of investigation was STM but the center as such was not a STM center, it was a center doing research in a specific field. And our tool of research was the STM.

AH : You mentioned that you had contacts with Topsøe and other companies. Have you had contact with chemists, people in chemistry departments ?

IS : We have, but not much.

AH : Are they not interested in this ?

IS : I think they are in many cases, but we work in surface physics, as it is called in Danish. The English term, "surface science", is more neutral. Of course what we do is to some extent surface chemistry. But our background is just physics. You could say that a center like this might just as well have been placed at an institute of chemistry. It just so happens that we had this collaboration, and that we had not had the opportunity to interact much with chemists.

AH : So it's not the barriers between physics and chemistry that are particularly high, it just hasn't happened ?

IS : It just hasn't happened. It might have worked out differently, had we had a common institute instead of a separate physics and chemistry institute. Some of the activities going on here might as well have been placed in the institute of chemistry and vice versa. Nowadays it's not that natural to have this division into two institutes.

AH : How far is it from here to chemistry ?

IS : It's just across the parking lot, 100 meters. We're even connected underground to them, although it takes a specific key.

AH : But you don't go to each other's seminars ?

IS : Very infrequently.

AH : This does seem surprising and in need of an explanation. No ?

IS : I think much of what we're doing is of interest to chemistry as such, but our institute is comparatively small. Chemistry and physics are amazingly broad fields and our small institute is only able to cover certain areas. It has just so happened that we work in a field without a natural counterpart in the institute of chemistry. There are no ill feelings on the other side of the parking lot ; it's not based on that.

AH : And what about chemists in general out there in the world ? Do you get resonances ? Where do you publish, for instance ?

IS : We publish in papers with as high an impact as possible. We have published very large number of Physical Review Letters during the period of CAMP, on very few occasions in Nature and Science also. But that is not that easy, and sometimes you feel it is more difficult being European than if you had been American, but that's another story. We publish of course also in other journals ; some material will go to Surface Science. Surface Science does not have that high an impact, but it is obviously a very natural journal for people working in surface science. In my opinion the quality is rather mixed, but these are the main journals that we choose. We do not publish much in European journals, or journals that are particularly European such as European Journal of Physics and European Physics Letters.

AH : For any particular reason ?

IS : Simply because impact and visibility are low.

AH : When you say that in Physical Review Letters the visibility is high, is it not limited to the physics community ? Isn't your work broader ?

IS : It's probably correct, but we have colleagues in other places working in chemistry departments. And some of them will also publish in Physical Review Letters. I think it is recognized as some natural place for good work, also. But we have also published in Chemical Physics Letters, there are also a number of publications there, but they're not quite as prestigious as Physical Review Letters.

AH : Are you under pressure to produce results of commercial interest and if so, does this conflict with your own interest in pure science ?

IS : I don't' think so. I don't think we are under much pressure in CAMP to produce results of direct relevance to industry. I do think that we in CAMP all see an extra benefit or satisfaction in producing something of relevance to the "real world” and not just to pure science.

AH : So when you get around to renewing CAMP for another five years, the grant-giving bodies will not look to commercial applications ?

IS : It won't come to that. The funding will stop after ten years. It's the general policy that centers such as ours may reapply only once, so that they run for a maximum of two periods. After two periods, they ought to find alternative funding and in some way become a more integral part of the institute. What will happen in two to two and a half years from now, I don't know.

AH : You are not worried ?

IS : Not terribly, I think some kind of funding will come. I think that the government has set aside some funding for integrating centers into their host institutions.

AH : The reason I'm asking these things, is that Jens E. T. Andersen at the DTU was telling me about tremendous pressures. The DTU has now a patent office, and renewal of academic contracts is subject to results in terms of patents rather than scientific publications.

IS : The emphasis on patents has definitely increased here also, but in my opinion it has not yet become a pressure. There is a greater emphasis on it, and some of that emphasis originates from the government. A new law was introduced in Denmark. Up until maybe a year ago, you had the rights to exploit your own inventions, even as an employee and civil servant. That has now changed so that when you develop anything patentable or otherwise exploitable, you have to first contact the university. Your invention will be assessed. The university decides whether it wants to patent your invention and exploit it. If it declines, then you are free to do it yourself. So you could say that maybe the timing is a little bit strange, because on the one hand you remove some carrots from the researcher and on the other hand you apply the stick to encourage work resulting in patents. I think the general political perspective is that a fair amount of knowledge of interest to industries is generated at the universities, but no good forum for the transferal of that knowledge exists. Maybe the thinking was that having the knowledge documented in patents would facilitate the transferal.

AH : Is it possible to pinpoint advances made in the field of catalysis over the last ten years related to the possibilities of the STM ?

IS : I think this story about developing a catalyst from scratch based on pure research is rare, almost unique. There are no more than one or two other examples. Normally catalysis has been a highly empirical field. Developments have mostly been trial and error - of course guided by different kinds of knowledge. But in the end it came down to trying something, modifying it, changing the stoichiometry or the ratios, optimizing and so on. The understanding of the catalyst emerged gradually out of this process. By contrast, ours is a clear case of going directly from scientific insight into the working of a catalyst to its development.

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« Entretien avec Ivan Stensgaard », par Arne Hessenbruch, 8 mars 2001 Sciences : histoire orale, https://sho.spip.espci.fr/spip.php?article131.

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Entretien avec Ivan Stensgaard, par Arne Hessenbruch, 8 mars 2001

Lieu : CAMP Aarhus : The Scanning Tunneling Microscopy Group, Aarhus University, Denmark.

Support : enregistrement non précisé

Transcription : Arne Hessenbruch

Edition en ligne : Sophie Jourdin

WHELAN Michael, 2002-12-12

Sophie Jourdin — 2011-11-10T15:51:51Z

Professor Michael Whelan.

BERNADETTE BENSAUDE-VINCENT (BBV) : Could you tell a few details about your own work on the experimental discovery of dislocations in 1956 ?

MICHAEL WHELAN (MW) : In the 1930s there was no experimental evidence for dislocations but theoretical predictions were built up about the way dislocations behave. What was really missing was any direct observations of dislocations, although slip lines on the surface of metals had been observed by optical microscopy. The question was how could that occurat the sort of stresses that were observed experimentally ? If you work out the stress required to push one layer over another as a whole, it is much higher than it would be if you introduce the concept of a dislocation. A dislocation is like a wrinkle in a carpet ; Peter Hirsch used this image. When the concept of a dislocation came to the forefront with many papers about the behaviour of dislocations, there were unbelievers, among the Russians in particular. At the Cavendish Laboratory in Cambridge in the group of W.L. Bragg they had suggested simple X-ray experiments to detect the small subgrains that were hypothetically formed in the plastic deformation of metals.

BBV : When did you start ?

MW : I started in 1954 with Peter Hirsch. He was a post-doc in Cambridge. He had got his PhD about 1950 using X-rays to study the textures of metals. They had developed a microbeam X-ray technique under the supervision of Professor W.L. Bragg and Dr W.H. Taylor. It was essentially based on X-ray equipment - a high intensity X-ray generator with a rotating anode produced a beam of about 10 microns diameter for taking back-reflections photographs from a small area of a deformed metal.

BBV : So in 1954 X-ray diffraction was still the dominant technique for studying dislocations

MW : When I started the X-ray machine was still in the lab and there was another student still using it, Chris Ball, who eventually emigrated to Australia, and I started in the same room as the microbeam X-ray machine. I remember him telling me - you don't have to worry about the scattered beams…. I tolerated it for about six months and then moved to another room. The work with X-rays had its limitations - you could not get a smallenough beam to examine certain metals, notably nickel and copper. The scattering is very weak with X-rays and typical exposures were about 24 hours. Anthony Kelly had the idea of going to one of the new electron microscopes that had been developed to do transmission electron diffraction. An electron diffraction pattern exposure time was only a few seconds. I was asked to investigate this electron microscope technique further. Some people had already worked on it. Heidenreich in particular at the Bell Telephone Labs in the USA, but not with the idea of actually seeing dislocations.

BBV : Did Heidenreich produce the first images of dislocations ?

MW : If you read my article you will see that Japanese had also produced dislocation images. The Japanese were interested primarily inmoire fringes, but if you look at some of the pictures thatProfessor Hibi took of mica and graphite, you can see that they contained dislocation images. But they didn't really understand the concept of a dislocation. I heard that from an eminent Japanese scientist, Professor R. Uyeda. We came from the X-ray side. We were interested in crystallography whereas many electron microscopists did not know much about diffraction. It was important to have a team which was expert in diffraction to move into this field.

BBV : You mean for interpreting images ?

MW : Yes, the theory that you need to understand how the electrons interact in a crystal which contains dislocations is essentially diffraction theory. It is more or less the same theory that you have for X-rays except in the difference of scale. The theory was well known to crystallographers. It had been developed in this country by Darwin and Bragg andby Ewald and von Laue in Germany.

BBV : Where did electron microscopy come from ?

MW : Electron microcopy was developed in the 1930s by the team of E. Ruska, M. Knoll and B. von Borries working in Berlin, and was initially used by metallurgists mainly to look at surfaces. Their interest initially was to extend what they did with the optical microscope, namely to examine surfaces. They made thin replicas of surface structure and examined them in the electron microscope. They had to shadow the replicas with heavy metals to obtain good contrast. This was the main area that metallurgists were engaged in during the late 1940s when electron microscopy started to be used again after World War II, with the exception of Heidenreich in the USA and Raimond Castaing in France, who developed microprobe analysis techniques.

BBV : Did you know Castaing and interact with him ?

MW : Yes, I wrote to him as a research student and sent him some of my electron micrographs. I met him first at a conference in Madrid in 1956 at the end of my second year of research. I remember him taking me for a ride in his car through Madrid. He was a scary driver. There was a session at an EMSA conference in Portland Oregon in 1999 that was devoted to the memory of Castaing.

BBV : Did you take your Ph D in physics or in crystallography ?

MW : In the physics department in Cambridge, known as the Cavendish Laboratory.

BBV : Did you consider yourself as a physicist or as a crystallographer ?

MW : A bit of both actually. I was interested in crystallography but Cambridge had traditionally a broad natural sciences undergraduate course. You studied for three years. In the first and second years you had to study a number of subjects, for example in my case physics, mathematics, chemistry and crystallography. In the third year I specialized in physics, but in the crystallography course during the first two years I got interested in X-ray diffraction. Therefore, when I started in the Cavendish Laboratory I decided that I would join the group working on X-ray diffraction.

BBV : When did you shift from X-ray to electron microscopy ?

MW : When I started. As I have said, Kelly had initiated the work, but he left the Cavendish to work in the USA. He had taken some transmission electron micrographs with Peter Hirsch and Jim Menter, who worked in the Laboratory of Physics and Chemistry of Rubbing Solids, a subdepartment of the Physical Chemistry Department at Cambridge. He had an electron microscope with which you could do selected area electron diffraction. Selected area diffraction was a relatively new technique at that time. It enabled you not only to take an image of the specimen, but also to insert an aperture into the microscope column, selecting an area down to about a micron or half a micron in size to obtain a transmission electron diffraction pattern. You had to have a thin specimen, about 1000 Angströms thick. The simplest thin specimen you could easily obtain at that time was beaten gold foil. It could be beaten down to about 1000 Angströms thickness. It would transmit electrons at that thickness but it was heavily deformed. They saw things in the images that they could not interpret. Peter Hirsch had the idea that they could be stacking faults on inclined planes. If you can see a stacking fault it ought be possible, he thought, to see a dislocation because the dislocation in a face centric cubic metal can dissociate in two partial dislocations, like a little ribbon with the space in between them being a stacking fault. So if you could see the fault you might be able to see the dislocation by virtue of the ribbon. That was the initial suggestion that Peter Hirsch made. It was simply a hunch. Experiments had to be carried out and interpreted. That was my job.

BBV : What kind of microscope did you use in 1954 ? Was it easy to get electron microscopes in research laboratories ?

MW : At that time the Cavendish Laboratory had two electron microscopes in the Electron Microscope group headed by Dr V.E. Cosslett. One was a pre-war instrument manufactured by the Siemens Company of Berlin in 1938. You could not do electron diffraction with it. It had been picked up in Germany by the British Army as a war reparation. Ernst Ruska developed the first electron microscopes in the early 1930s based on work done in the 1920s. The first commercial firm to produce a microscope was Siemens, who engineered a microscope that Ruska had basically designed. It was a two-stage magnification instrument with a single condenser lens. You could not do selected area electron diffraction with it. You need three stages of magnification for that.

I took some electron micrographs using this instrument. The resolution was not good, but some of the micrographs of beaten aluminium showed images of dislocations. This was not realised at the time. It was only much later, with hindsight, when the micrographs were re-examined, that dislocation images were recognised.

In early 1956 I was able to use the new Siemens Elmiskop in Dr Cosslett's group. This had much better resolution, and dislocation images were recognised in the summer of 1956.

BBV : What do we see on these pictures ? Picture 1 plate 404 and Picture 2 plate 1833.

MW : Plate 404 : This relatively low magnification micrograph shows the subgrain structure of beaten aluminium foil. Subgrain boundary walls are visible. These are made up of dislocation arrays. The subgrains are about 1μm in size. Inside the subgrains there are many extinction contours. These arise from dynamical electron diffraction effects due to buckling and thickness variations in the foil.

Plate 1833 : Here at higher magnification we see subgrains of size 1 or 2 μm in diameter. In the centre we see a cross-grid network of screw dislocations constituting a low angle twist boundary, on or close to the (100) crystallographic plane. In the next subgrain we see a slip trace (the contrast feature with a 90o bend). A dislocation has moved across the grain, first on one 111 plane and has then cross-slipped to another 111 plane, leaving behind the trace of its path. In imaging dislocations by so-called « diffraction contrast », we do not attempt to resolve the atomic arrangement. There is a strain caused by the displacement of atoms near a dislocation, and it is the region of strain that is made visible as a dark line by diffraction contrast.

Only one beam is used to form the image - here the directly transmitted beam. Other diffracted beams are removed by an aperture in the objective lens of the microscope. The dislocation images reflect the fact that electrons are scattered outside this aperture. This is diffraction contrast.

BBV : What does it tell you about the material ?

MW : You don't aim at resolving the atomic structure. Metal physicists think in terms of a sort of quasi-particle. They are not usually interested in details about the atomic positions. They are interested in the concept of a dislocation as a line defect with properties such as energy, line tension, inter-line forces. What you want to see is a line.

BBV : How can you sort out the line defects that are dislocations from other spots or lines ?

MW : With some experience you can easily identify dislocation lines. Other contrast features arise from artefacts. The instrumental resolution required to observe dislocation lines is not high.

It is of the order of 100 Angströms. To see atoms you need a resolution of about 1 or 2 Angströms. Modern instruments have this resolution. To image the crystal lattice, you need to include more than the directly transmitted beam. You include a number of diffracted beams and resynthesize the atomic image by using several beams. You can use modern electron microscopes to actually see the atomic arrangement with a very thin specimen. You can gain a sort of projection of the atomic lattice structure. But then again, you have an interpretation problem. The question remains - what does the image mean ?

BBV : On which metal did you first observe dislocations ?

MW : We first observed dislocations in aluminium foil.

BBV : Following your first observation and publications I guess that there was a great excitement among physicists that increased the demand for commercial microscopes

MW : In post-war years, the Siemens company improved on the design of their pre-war instrument and manufactured the Elmiskop 1. It was presented at the London International Electron Microscope Conference in the summer of 1954. The first to be delivered from the factory was acquired by the Electron Microscope Group at the Cavendish with a grant from Nuffield foundation. It was designed mainly for biologists. Although you could do selected area diffraction with it, there was an inconvenient system for energizing the lenses which made it difficult to obtain electron diffraction patterns initially. But after a few years Siemens modified the electronics to enable fine focus illumination to be used with electron diffraction. For many years the Siemens Elmiskop had most of the world market.

BBV : Was it difficult to operate the early electron microscopes ?

MW : Most of the difficulties in those days was preparing thin enough specimens. Also adjustment of the electron beam was done mechanically, requiring some agility of the operator. Nowadays adjustments are made by magnetic deflection. Practically the only thing which is still mechanical in modern instruments is the actual movement of the specimen stage.

BBV : How long did you take to familiarize yourself with the electron microscope technique ?

MW : There was an assistant in the Electron Microscope group Bob Horne who was in charge of the Elmiskop instrument. I seem to remember that he had never studied for an undergraduate degree but he had been an electronic assistant during World War 11. He told me that he had been involved in recording ground-to-air voice communications during bombing raids on Germany using wire recordes borrowed from the BBC. The recorded voices were broadcast again during later raids to confuse the enemys defence fighter aircraft ! He acquired skills in electronics during the war. We collaborated and the first papers were co-authored by Hirsch, Horne, and myself. Horne took the pictures. He operated the instrument. The difficulty for me was to get my own hands on the instrument. But there were three viewing windows on Siemens Elmiskop. The operators window and two side windows, so it was possible for me to observe through a side window. Later when we first saw dislocations, Peter Hirsch would be observing at the other side window. To record the movement of dislocations we attached an external ciné camera, recording through the front window. We needed not only an operator but also somebody trying to tilt the specimen to give it best contrast and somebody to operate the ciné camera. So three of us, Hirsch, Horne and myself worked altogether. Another difficulty was the availability of the machine. It was the only microscope in the university. I had an afternoon session per fortnight. During the rest of the time the instrument was mainly used by biologists. (Lord Victor Rothschild was one of them. He was an eminent biologist and was Chairman of the Agricultural Research Council. He was one of the few members of the Rothschild family who did not go into the family banking business. He stayed in Cambridge doing research, and later directed research at Shell laboratories and became an advisor to Margaret Thatchers government). But when we started obtaining exciting results we got more time on the instrument. Ultimately around 1957 we got our own instrument. And we had 2 or 3 of those instruments before we left Cambridge to come here.

BBV : So it was a rapid increase. How expensive were these instruments ?

MW : In those days you could buy one for about £8000. I remember Professor Nevil Mott coming - he was the head of our department - and looking at the first Elmiskop we obtained and he said - « ah, two houses ! ». In the 1950s you could buy a professoriel style house in Cambridge for about £4000. Money was obtained from various sources. Part of the money came from the Royal Society and the rest came from the Department of Scientific and Industrial Research. The instrument was for our groups use, but it was situated as an attachment to Dr Cossletts group ; so that his technicians could advise us.

Initially we had a beam of 100 microns diameter which is quite large. The images were of poor quality, but they were not much better than Heidenreichs images because he too had not used a double condenser lens. The initial emphasis was to look at electron diffraction patterns. So we had to use the single condenser illumination. One day Bob Horne switched the lens arrangement to the system that biologists, used but with which you could not do electron diffraction. We noticed that the images obtained very clear and picturesque. After a while we saw changes taking place in the image, and the dislocations started moving around. I called Peter Hirsch to come and have a look. He said we must get a ciné camera to record the dislocation motion. One of our assistants who had worked at the National Physical Laboratory and knew something about movie cameras, advised us on who to contact at the NPL to borrow a ciné camera. We mounted the camera on the microscope, put some high speed film in it and we made a ciné film of the motion of the dislocations. We produced a silent movie. Peter Hirsch and I presented the film at various conferences and we received requests from people who wanted to obtain a copy of it for teaching students. So we started a business in the Cavendish to sell it at cost price. We still have the negatives. Recently we put it on video. I showed this movie in Japan recently on a trip to raise funds for my college at Oxford. A generation of students has grown up, who have never seen this old movie. So it is entering a second life !

BBV : How many instruments did you get when you moved in Oxford in 1966 ?

MW : We bought a new Elmiskop. With the help of research students we had converted an instrument in Cambridge to study the energy losses of the electrons when they are transmitted through the specimen. We moved it to Oxford. Then with the help of another competent research student we built another instrument based on a design of Castaing which enabled energy filtered images to be taken. There was an old EM6 electron microscope already here in John Martins lab. But we were in a Department annexe on the ground level of another building.

BBV : Did you need a special environment for using those electron microscopes ?

MW : It was not a bad building. Because it was on the ground floor vibrations were minimized. Later we bought instruments with higher resolution that required special foundations, we had concrete blocks put on the floor to minimize any vibrations coming from traffic outside the building.

BBV : How did you teach electron microscopy ?

MW : I started giving a graduate level course on the dynamical theory of scattering to research students. At the undergraduate level initially there was not much teaching of electron microscopy. There was only brief mention of it, with no experimental work. That has now changed. Undergraduates can have practical classes in electron microscopy.

BBV : Do you remember when these practical classes started ?

MW : I don't remember exactly. Probably in the late 1970s. I used to give a course on optical and electron microscopy to undergraduates. But there was no practical work ; in the practical classes they could only take X-ray pictures. Now in the practical classes they use various electron microscopes, both scanning and transmission. Compare this with the days when we started with an instrument available one afternoon a fortnight.

BBV : What is the importance of electron microscopy now in this department ?

MW : It is used as a routine technique now in the department. Anyone working in any area of materials science can get advice from the electron microscope group.

BBV : Is it also the case for the Scanning Tunnelling Microscope ?

MW : That is a different technique, a surface technique. What is interesting is that they awarded the Nobel prize to Binnig and Rohrer for inventing the STM, and at the same time they awarded it to Ernst Ruska, the German scientist who developed the electron microscope in the early 1930s, almost 60 years before. There were in fact three people involved in this work in Germany, but the other two were already dead by the time the Nobel Prize was so belatedly awarded for the invention of the electron microscope.

BBV : What is your view of Materials Science ?

MW : It is a miscellany of problems all related to the way atoms behave collectively in the solid state and even to some extent in the liquid state.

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« Entretien avec Michael Whelan », par Bernadette Bensaude-Vincent, 12 décembre 2002 Sciences : histoire orale, https://sho.spip.espci.fr/spip.php?article129.

—

Entretien avec Michael Whelan, par Bernadette Bensaude-Vincent, 12 décembre 2002

Lieu : Oxford Materials Department.

Support : enregistrement non précisé

Transcription : Bernadette Bensaude-Vincent

Edition en ligne : Sophie Jourdin

HIRSCH Peter, 2002-12-12

Sophie Jourdin — 2011-11-04T14:03:56Z

Professor Sir Peter Hirsch.

—

BERNADETTE BENSAUDE-VINCENT (BBV) : Could you tell me about how metallurgy developed in Oxford and how it grew into Materials Science ?

PETER HIRSCH (PH) : Let me first say a few words about the way I see the early developments of Materials Science in the UK. There were various trends that came together after the War. First of all there was Professor Nevill Mott in Bristol, developing Solid State Physics. His interests included inter alia defects and how they influence properties of materials. He had important activities on properties related to point defects and on the photographic effect. In the course of these studies they also developed techniques for visualizing dislocations. The group included Charles Frank, a physical chemist by training who was a material scientist par excellence. He developed a theory of crystal growth. Then there was Nabarro who worked on dislocations. So in Bristol they worked on defects, dislocations, crystal growth, the photographic effect, and also optical properties of crystals.

BBV : Where were they based ?

PH : In the Physics department at Bristol University. It was Solid State Physics. The electron theory of metals was developed there too. And Jacques Friedel was there for some time. In my opinion Solid State Physics opened the way to Materials Science. In parallel with this there was the group in the Metallurgy Department in Birmingham, lead by Alan Cottrell. He is much more of a materials scientist than I am. He was subsequently instrumental in developing Materials Science in Cambridge. His activity in Birmingham was very important because his group attempted to explain mechanical properties in terms of disclocation theory. And the third trend was what happened here in Oxford through Hume-Rothery's classic work on electron phases of alloys. He stimulated work on electron theory of metals and alloys in Physics Departments elsewhere. He was trained as a chemist.

BBV : So it came out of these three trends ?

PH : These are the main three. I may be unfair to other groups but these were the most influential groups.
There was some Metal Physics going on in the Cavendish Laboratory after the war. Bragg, who was Head of Department was of course an X-Ray crystallographer. In order to understand the intensities of diffraction spots on an X-Ray diffraction photograph, it had to be assumed that the crystals were not perfect, i.e. that crystals consisted of mosaic blocks. This was based on a theory by Darwin (1914) of the intensities of diffracted X Rays. Bragg published a note in the 1940s on the relationship between strength and particle size (mosaic blocks) in crystals. There were two groups in the Cavendish in the Metal Physics field when I came in 1946. One was Bragg's little group which developed the bubble-model, typical of Bragg's simple but brilliant ideas. Another group was Orowan's Metal Physics group which studied plasticity, fracture, creep, those sorts of topics.

BBV : It is in the Cavendish Laboratory that you started your career, isn't ?

PH : It was 1946 when I joined and there were several activities. My own work started from Bragg's interest in work hardening (when you deform a metal it becomes stronger). I actually went into the Crystallography Department of the Cavendish to work on a PhD problem that Bragg gave me. It was conceptually very simple. If you take a metal and work it, does it break up into smaller blocks ? Bragg always had very simple and brilliant ideas. If the crystal breaks up into smaller blocks (subgrains) the diffraction pattern consists of individual spots from each little subgrain. If you make the beam small enough you illuminate such a small number that you will get a few spots on the diffraction ring, whereas, with too large a beam diameter you get a continuous ring due to overlapping spots. You can count the spots (on discontinuous rings) and deduce the size of the particles. That was the project. It did actually work for heavily cold worked aluminium. We derived a particle size of 2 microns. By the time we managed to do all this by X ray diffraction, Bragg had lost interest in it. He did not actually supervise me. Bragg was interested in proteins at that point. My formal supervisor was W.H. Taylor who was head of the Crystallography Department. His interest was the structure of minerals.

BBV : When you worked in Cambridge did you consider yourself as a crystallographer ?

PH : I was a physicist working in a department of crystallography. In those days most conventional crystallographers determined crystal structures. I was one of the relatively few people not doing that.
By the time we found that cold worked aluminium breaks into subgrains, Heidenreich at the Bell Laboratories published the first pictures of metals by Transmission Electron Microscopy (TEM). He observed directly the little subgrains in heavily beaten aluminium foil. That depressed us very much because we needed exposures of many hours for our x-ray diffraction photographs, while he had a ten second exposure with his electron microscope. So we went into this field of TEM and finally we saw individual dislocations. This had a big impact because there were many metallurgists who did not believe in dislocations, who considered them as figments of the imagination of solid state physicists working out theories in tremendous detail without much supporting experimental evidence. With our technique you could see dislocations directly and see them move. And we made movies. I remember showing a movie at MIT to Bert Warren who was a well-known X Ray crystallographer. His comment was symptomatic of many metallurgists. Seing is believing. We converted people.

BBV : In terms of institutions could you describe the shift from Metallurgy to Materials departments ?

PH : There were many Metallurgy departments in this country : Sheffield, Birmingham, Imperial College, to mention a few. The activities of the groups that I mentioned gave an impetus. But an important impetus came from the United States. Bill Baker and Herbert Holloman in particular had this vision of multidisciplinary activities leading to the development of better materials, whiskers, ceramics etc.. An enormous amount of money was spent at General Electric, and Bell Telephone and the Ford Motor Company. When Alan Cottrell became Professor in Cambridge that was the real beginning of an institutional effort to develop Materials Science in this country. In my opinion that was the defining moment. Alan Cottrell left Birmingham in 1955 and went to work at the Atomic Energy Authority at Harwell where he worked on uranium and materials for nuclear reactors. Then he became Goldsmith Professor of Metallurgy in Cambridge in 1958. He started projects on ceramics and composite materials. Tony Kelly joined him to work in these areas. Alan Cottrell ‘s interest in composite materials probably stemmed partly from activities in the US but mainly from his own views on strong materials. He also supported work on superconductors. His initiative to work on different types of materials was probably the beginning of the shift from metallurgy to materials science in Universities in this country.

BBV : Could you tell something about the implementation of Materials Science here in Oxford ?

PH : The department of Metallurgy and an Honour School in Metallurgy were started by the University in 1957. Jack Christian wrote a paper on the early history (Materials World, April1997) when the department celebrated its 40th anniversary. You see from this that Hume-Rothery started as a chemist and worked in the Inorganic Chemistry Department. But he was interested in metallic phases. The idea of a separate department arose gradually. Jack Christian was appointed as demonstrator in 1951 and initially lectured on metallurgical topics to chemists. Metallography was a supplementary subject in the Chemistry Honour School. Then the Pressed Steel Company at Oxford established a readership in metallurgy named after George Kelley. Hume-Rothery became the first George Kelley reader in 1954. Jack Christian was appointed lecturer in 1955, then John Martin came from Cambridge and joined in 1957, followed by Angus Hellawell. There was a move to increase the Engineering School and to develop a Department of Metallurgy. Francis Simon who was professor of physics here was keen to establish something on the lines of the Laboratory for the Study of Metals in Chicago, which was famous in those days. Chicago was a research institute, not a teaching department, just a research institute for postgraduates. This is what Simon had in mind for Oxford. However, the industrial advisors expressed the view that we needed to educate metallurgists to go into industry. British industry wanted a teaching department. Monty Finniston, who was at the time the head of the metallurgy division at AERE Harwell and later became chairman of British Steel, made approaches to the Wolfson Foundation for financial support. The result was the establishement of the Isaac Wolfson Chair in Metallurgy which Hume-Rothery held until his retirement in 1966.
At the same time the condition that the Wolfson foundation made for giving the money for the Chair was that the University Grants Committee, an organization distributing the money from the Department of Education to the Universities, should provide the funds for the building. Funds were provided by the University Grants Committee and the building was opened in 1959. Initially the Honour School was a Joint Honour School in Chemistry and Metallurgy, which subsequently became Metallurgy. There is an interesting quote in Jack Christian's paper which indicates the University's unease with technology at that time. The Honour School should teach « no more technology than is involved in the degree courses of chemistry and physics » and it stated that « the man who has studied pure science at a university can take up technology on entering industry much more easily than one who has studied technology can later take up the pure science which may be required for his work ». It was still quite difficult to really expand engineering and to get a proper engineering metallurgy course at that time. The research that was going on here was on alloy phases (Hume-Rothery's research) ; John Martin worked on mechanical properties of alloys ; Angus Hellawell worked on solidification studies ; Jack Christian worked on phase transformations - the martensitic transformations - of metals and alloys, and also on plastic deformation of body centred cubic metals. So that was the development of metallurgy in Oxford before 1966. Clearly this department was a metallurgy department rather than a materials department. But Hume-Rothery's work was influential in encouraging solid state physicists to become interested in metals. He stimulated the understanding of the structures of metals and alloys on the basis of the fundamental electron theory of metals. He empirically developed some structure rules. He hoped that electron theory of metals would enable the prediction of the structures of metals and alloys and appointed a theoretical chemist, Simon Altmann, to work in this area.

BBV : And then you came in this Metallurgy department. Why did you move from Cambridge to Oxford ?

PH : I came in 1966. I was a physicist who had worked on electron microscopy of defects in materials. I had the opportunity to take a Cambridge chair or an Oxford chair. I decided to go to Oxford for two reasons. 1) I had been in Cambridge quite a long time (23 years) and a change opens new vistas. 2) The challenge was much greater here and my own predilection was always for building things up. The Cambridge Metallurgy department was a large and successful department built up by Alan Cottrell. In Oxford there was really a nucleus of a department (a distinguished one) and in principle one could do a job to build it up.
I had already built up a large research group in the Cavendish in Cambridge. When Bragg switched his interests to proteins (Perutz, Kendrew et al) Orowan left and went to MIT. I don't know the details but my impression is that Bragg did not work hard enough to get Orowan a senior permanent job. So the Metal Physics group in Cambridge folded up. Bragg's own little group folded up too. We made a significant effort to set up a new Metal Physics group at the Cavendish. The vision behind this was : We now had a technique to enable us to actually see with the TEM what is going on inside metals and one could see the defect distribution after deformation or irradiation of the material. One could then determine in principle what the properties of the materials were. That was the Holy Grail. There were three steps : 1) to try to understand the properties of the defects and how they interacted ; 2) to try understand how they control the macroscopic properties ; 3) if one understood the basic relation between defects and properties then one could eventually go further and predict what processing should be done to optimise properties. That was the vision but while we were successful in the first step, there was only limited success in the second step, and we never got as far as the third step.
When I came to Oxford, my aim was to get this technique of TEM - to see what goes on in the materials - transferred to a metallurgy/materials department. I wanted to get it closer to applications to « real » materials. Whereas physicists work on models, - on pure copper for instance, a metallurgy department should be looking at materials of interest technologically, such as alloys that are much closer to practical needs. My aim was to apply TEM to technologically interesting materials, real materials rather than the model materials that we looked at in Cambridge.
When I got here I did attempt to build up Materials Science. Right from the beginning my aim was to shift from metallurgy to materials science which should cover all kinds of materials and applications.

BBV : Where did this project come from ?

PH : There was no model course. We had to build this up incrementally. When I first came the University provided three new permanent posts, very generously. One was for Professor Whelan, to establish the electron microscopy group. One went to John Hunt, a solidification expert who had worked at Harwell and Bell Laboratories ; and another one was for Geoffrey Groves who worked on ceramics. Gradually we built up a Materials Department by securing more appointments. You have to realize that when I came in 1966 the number of staff was very small (4 faculty plus the Professor).The course developed gradually and changed from metallurgy to materials science. In the early years a considerable part of the teaching was carried out by research assistants or fellows supported on research grants or fellowships. The research activities were built up first, and the research groups then helped in the teaching of the Honour School.

BBV : When did you officially change the name of the department ?

PH : That was much later, 1990. The name of the Honour School was changed to Metallurgy and Science of Materials in1969 (The University would not accept "Materials Science" because Materials was not an adjective !).

BBV : Did you appoint chemists as well ?

PH : We didn't appoint chemists to teaching posts. We appointed metallurgists and physicists. But we did appoint a chemist to a research post in the department, in high resolution electron microscopy. When I retired in 1992 the department consisted mainly of metallurgists or materials scientists and physicists or ex-physicists. We appointed inter alia people who had expertise in semiconductors, superconductors, magnetic materials, materials processing, corrosion. Gradually we extended the scope of the courses in the department. The one sticking point was polymers. For a very long time we could not get a good polymer scientist. It has changed now. We now have two polymer scientists.

BBV : Did you have contacts with John Goodenough who came to the chemistry department in 1973 ?

PH : We did have contacts but we probably did not make the best of the opportunity. In this department we were more interested in the effect of microstructure on materials, metals, ceramics, semiconductors, superconductors, magnetic materials etc., rather than e.g. in the intrinsic magnetic properties of perovskites and other materials. Our interests were not sufficiently close. We became a Materials Department in that we were concerned with the effects of microstructure on properties of a wide range of materials of technological interest and with the effects of defects on devices. The work on superconductors was initially on low temperature superconductors, but later on high temperature superconductors, and the more recent studies focused on processing. There was some interaction with the Inorganic Chemistry Laboratory on electron microscopy of catalysts and superconductors.

BBV : Did you keep a close link between courses and research in the department ?

PH : Yes. We started as a metallurgy department. We built up a number of research groups, and the expertise in some of these, e.g. semiconductor and magnetic materials, enabled us to teach courses on these topics and broaden the curriculum to Materials Science. At some point we had a group working on cements, and this too led to a course in the Honour School. And there were always undergraduate and postgraduate courses on materials characterisation, where we had particular strengths. In the 1980s, I became more interested in the output end, in getting closer to the engineers.

BBV : Did you train students in engineering ?

PH : The engineers had their own faculty to teach materials to Engineers. But we did some teaching for them, and over some years they taught polymers for us. In the mid 1980s we started a joint course with the Engineers on Electronic and Structural Materials Engineering, changed to Engineering and Materials in 1992. This led to closer collaboration with the Engineers in teaching and research.

BBV : Did you also have contacts with the nuclear physics department in Oxford ?

PH : The only contact we had with the Nuclear Physics Laboratory in Oxford was on their proton microprobe, a materials characterisation tool, and fairly recently this activity was transferred to our department.

We had a lot of contacts with Harwell. From 1973 onwards I got very much involved with the study of the integrity of pressurized water reactors through the Marshall Committee. From 1982 to 1984 I became part-time chairman of the Atomic Energy Authority. This period had a strong influence on me. I felt the need to produce materials engineers, not only materials scientists. I learned during my period with the Atomic Energy Authority that the education of engineers in materials tended to be relatively poor. And this could result in inappropriate component design or manufacture. These problems sometimes led to costly mistakes. In order to develop a joint activity between engineers and metallurgists we got some support from the engineering department. To cut a long and difficult story short, we took an opportunity which presented itself around that time in the form of additional funding for engineering courses from the Government to start a course on Electronic and Structural Materials Engineering.

BBV : Was it in the 1980s ?

PH : Yes.

BBV : Did you then feel the need to add « engineering » in the name of the department on the lines of the departments in US universities that are called Materials Science and Engineering with an emphasis on the E of Engineering ?

PH : What happened here is that we developed a multiplicity of courses to provide more options for the undergraduates to increase our intake. The courses were Metallurgy and the Science of Materials, then Metallurgy, Economics and Management (1979), and finally Engineering and Materials. There is close collaboration between us and engineering through the teaching and contacts in research. This depends on individual contacts of course. In the 1980s we set up with the Engineers the Oxford Centre for Advanced Materials and Composites (OCAMAC) to foster collaborative research and contacts with industry. There is now also strong collaboration with people in chemistry and physics on a number of research programmes. We have become much more interdisciplinary, if you like. We have always considered ourselves as a bridge between the Science and Engineering Departments, with contacts with both. The fact that Physical Science and Engineering are all part of the same faculty in Oxford is advantageous to us. We did consider changing the name of the Department to Materials Science and Engineering - but that was unacceptable to the Engineers who considered Materials Engineering to be their responsibility. So we decided to change the name in 1990 to "Department of Materials".

BBV : It seems that your story is quite different from that of the US materials departments.

PH : I think that it is different ; you are quite right. Here the initiative to have Materials Departments came from academics, whereas in the US the development was led by Industry, and industrialists promoted Materials Science in Universities. (This does not mean that no materials science was going on in industry in the UK - e.g. the carbon fiber work at Farnborough.) I think it started in Cambridge first. We came along in the late 1960s. By that time there were materials science activities going on in many departments, at Imperial College and Birmingham, for instance. We could not claim to have inspired Materials science in the UK. We came along and did our own brand. There were many departments, but they were on a small scale. Concerning the definition of Materials Science I am with Merton Flemings. Structure, properties, processing, performance/application. I think it is the engineering applications that are fundamental. The philosophy of the department here was to get theoretical and practical people together. People able to develop models with people who really know what applications are important. And industrial links were fostered. It is still the philosophy today, even more so. In the last few years after my retirement the department has gone from strength to strength in that direction. There is now another site in Begbroke, five miles away from Oxford centre. It provides opportunities for collaborative research between the Department and Industry.

BBV : Where did the money come from ?

PH : The funding for work in the department came partly from the University, the Research Council and Industry. Some from charitable foundations, e.g. for building expansions. We had a large budget from the Research Council. That is another important aspect, somewhat similar to the US picture.

It is difficult to attract undergraduates to read Materials Science and Metallurgy. Enormous efforts have been spent on attracting more undergraduates, most of them not very successful. (But a recent appointment of a Schools Liaison Officer seems to be effective.) Materials Science is not a school subject, although elements are introduced into some of the school examination papers e.g. the physics curriculum. The number of courses and options that we offer in Oxford has helped a bit but it remains a problem. Some small departments in the UK were able to survive because they had a large research activity (supported on non-University funds) compared to the undergraduate activities. But in the UK as a whole some Materials Departments have closed or have been amalgamated with Engineering Departments. The change of name of department from Metallurgy to Materials does not only reflect the change in content of the courses. It is also pragmatic because metallurgy has an old-fashion ring about it and materials science is a much broader subject likely to attract more students. The image of materials for computers, aeroplanes and cars is more exciting than that of dirty blast furnaces in the steel industry.

BBV : What would you say about multidisciplinarity in the development of this department ? More specifically could you compare the situation here in Oxford with this diagram published by the National Academy of Science in 1969 with a hard core in mathematics physics and chemistry and applications around ?

PH : I would agree with this : mathematics, physics and chemistry are basic inputs in Materials Science with applications in ceramics, polymers, and so on. But in these days I would include materials for medical applications. There is somebody in this department working on biomedical materials for implants. There is also a large group in Cambridge. There is a big scope for materials in medicine, particularly for prostheses.

BBV : Finally would you consider yourself today more as a physicist or as a material scientist ?

PH : I think I am physicist who « saw the light ». True physicists would no longer consider me as a physicist. I consider myself as a materials scientist because my interest is in the effect of microstructure on the properties of materials. I am interested in quite complex materials, with potential applications e.g. high temperature intermetallics, and in modelling their complex mechanical properties. I ended up as a materials scientist. But there are materials scientists who would consider me to be a rather theoretical materials scientist. In the later years of my conversion I supported and promoted materials processing in the department although it took me rather a long time to get to this view, to appreciate the importance of this field, and to realise the need and potential for modelling.

BBV : What is your concept of materials science ?

PH : I am close to Merton Flemings's concept. To me materials science is an enabling science. We study material composition, structure, properties and processing for applications in engineering. There is now a strong group on processing here. Not only casting but various kinds of processing like spray forming, coating, making magnetic and superconductor devices etc. There are also two lecturers working on polymers now.

BBV : Does polymer synthesis now belong to Materials Science ?

PH : Polymer processing and modelling properties belong to materials science, but synthesis of new kinds of polymers - I doubt if this is a proper activity for a materials department, although it would be quite appropriate as a joint research activity with Chemistry. That would be my view for what it is worth. But composition, structure, properties, performance, Merton Fleming's picture, defines Materials Science.

BBV : What about the recent addition of end-users to this picture ?

PH : Yes end-users are important but I would consider that this links in with performance. The interaction with industry is important. Quite apart from the problem of funding it is vital for materials science, as an enabling science.

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« Entretien avec Peter Hirsch », par Bernadette Bensaude-Vincent, 12 décembre 2002 Sciences : histoire orale, https://sho.spip.espci.fr/spip.php?article126.
—

Entretien avec Peter Hirsch, par Bernadette Bensaude-Vincent, 12 décembre 2002

Lieu : Materials Department, Oxford University

Support : enregistrement non précisé

Transcription : Bernadette Bensaude-Vincent

Edition en ligne : Sophie Jourdin

HIRAO Kazuyuki, 2002-08-29

Sophie Jourdin — 2011-11-04T13:08:55Z

Kazuyuki Hirao.

—

HERVE ARRIBART (HA) : In which discipline did you take your degree and your Ph.D.?

KAZUYUKI HIRAO (KH) : I was trained in Inorganic Chemistry.

BERNADETTE BENSAUDE-VINCENT (BBV) : Why did you decide to go into Glass Science ?

KH : Well, you know, the Chemistry Department of Kyoto University is very old, 100 years old. When I had to select a laboratory, I was interested in inorganic chemistry. I belonged to the Chemistry Department but only one division of chemistry was Glass or Ceramics related to inorganic chemistry.

BBV : Did you publish books in inorganic chemistry ?

KH : Yes, I published two textbooks on Inorganic Chemistry intended for undergraduates. One of the textbooks was translated but another one I wrote myself in Japanese.

BBV : Do you have to teach inorganic chemistry ?

KH : Yes at the undergraduate level.

BBV : And do you have to teach a course in Materials Science ?

KH : Yes I have 3 courses a week : one of them is Glass Science, the second is Advanced Materials, and the 3rd one is Inorganic Chemistry. Inorganic Chemistry for undergraduate students, Glass science and Advanced Materials for graduate students.

BBV : There is no department of Materials Science at Kyoto University ?

KH : Materials Science partly belongs to chemistry. My department is called Department of Materials Chemistry. But Materials also belongs to Metallurgy. They have a department of Materials Science which is totally separated from us. We have no common class between Materials Science for chemists and Materials Science for metallurgy. We have to collaborate in the future. The Department of Materials Science also belongs to the Department of Mechanics. Chemistry and Mechanics are totally different. Polymer Chemistry is also separated. We still have to build up the new class of Materials Science. In Japanese universities, it is not usual to have interdisciplinary Materials Centers. It is usually divided. It is not good for research. Because equipment is shared.

HA : What kind of instruments ?

KH : TEM, SEM, X Ray, spectroscopy. At least in nanotechnology we ignore the boundaries between polymer science, metals, ceramics and glass. It will be possible to develop the new materials perspective.

BBV : Do you think that this traditional university system prevents you from doing Materials Science ?

KH : It is difficult to change. If you want to change anything, you will have to obtain agreements from all the professors in our departments. University professors are very conservative.

HA : Still, Professor Soga did endeavor to change the system while he was here.

KH : Yes, but in Japan if one single professor is against the change, then there will be no change at all. We don't usually have a majority decision making system.

BBV : Are the students more attracted by Materials Science in general or by Chemistry and Physics ?

KH : The entrance examination is about Industrial Chemistry. Almost 250 students are admitted. After one year, in the 2nd grade, they will be distributed into three different courses. Three classes divided mechanically. In the 4th grade they chose to enter into one the laboratories of the department. Four graduate students choose to enter in my laboratory every year. Kyoto University is a very big university. We have almost 47 chemistry professors for 250 students. 150 graduate students. Two Nobel Prizes came out from this department. It is a prestigious department.

HA : Could we come back to your PhD subject ? How did you choose it ? Was it Professor Soga who proposed it ?

KH : Yes it was about Glass Science. Thermal properties of glass.

HA : From your list of publications I can see that you have worked on many, many fieldswhile working in Professor Soga's laboratory.

KH : Yes I have been mainly interested in computer simulation of making glass structure and predicting optical properties of glass. I started computer simulation early in the 1980s. It was too early. The computer capacity was very small in the 1980s. Now we have a big project on computer simulation program and we get $5 million over five years from the government for it. Owing to the progress of computers, we can make glass structure containing 10,000 atoms.

HA : Then why did you move to non-linear optics instead of mechanical properties or low temperature behavior ?

KH : It is a good point. One major advantage of glass is transparency. Its major disadvantage is brittleness. Optical fibers are a very important because electrical wires are very limited in speed.

HA : So by the end of the 1980s you guessed that the future of glass for a large application would be optical glasses.

KH : Now we are very lucky. We are also interested in the mechanical properties of glass at the nanolevel. We are dealing with elimination of the nanobubbles. It is very important for industrial companies.

HA : So you got in to the glass making process ?

KH : Yes.

BBV : Was it industrial demand that prompted you to work on optical properties in the 1980s ? Or was it your own initiative, your choice ?

KH : In this period the optical properties were not important for glass industry. Now many glass companies are interested. So now we have a lot of industrial contacts. Before next year we intend to produce 3 commercial optical glasses called photonic glasses. For this, we need connections with venture business.

BBV : Do you mean that you conducted all these researches on optical properties without industrial support ?

KH : No, only in the beginning. Now we get a lot of industrial support. But now I get a lot of budgets from three kinds of government projects, not only from industry. We have 3 projects. One is computer simulation. One is on photoactive glass in cooperation with foreign countries. So we have a lot of post-docs in my laboratory. The third one is the nanoglass project.

HA : Could you tell us about this nanoglass project ?

KH : The government launched a nanotech program that covers a variety of projects : nanometals , nanopolymers, carbon nanotubes, nanocoatings, nanoparticles, nanosimulation and the nanoglass project. For the latter, we get $30 million for 5 years approximately.

HA : How do you spend this amount of money.

KH : Most people involved in the glass project are coming from industry, from Asahi Glass, Hoya, Nippon Electric Glass, Central Glass, Okamoto Glass, Nippon Yamamura Glass, Hitachi, ... 11 companies sent us 15 researchers whose salaries are paid by the project.

HA : How many people are working in your nanoglass project ?

KH : 100 people including the supporters. They join in Tsukuba consortium, from Osaka Institute and several university professors also support us.We have some large equipment.

HA : When did this project start ?

KH : We had a preliminary year and the project itself started in 2001.We have got a number of results. For instance CVD deposition. We also succeed in making very low optical loss glasses. We have reached 0.005dB/cm. This glass will be very useful for making waveguides. In Tsukuba we use two kinds of femtosecond lasers working at 1 kHz and 200 kHz. By using these femtosecond lasers, we not only write in waveguides but also we make crystals from glass, for example silicon crystals from amorphous silica.

HA : Last time you mentioned that you also have a laboratory in China working on crystal growth.

KH : That is right. And we have also made a lot of semiconductors, single crystals in glasses by using this material and we made photonic crystals, which can be used as optical filters.

HA : Where does the money for this nanoglass project come from ?

KH : From NEDO. It is part of METI (Ministry of Economy, Trade and Industry). No connection with AIST although METI also supports AIST. We also made a very tough glass whose strength is very high, 2 times that of standard glass. With the femtosecond laser we made very small dots, nanosize dots, that stop the cracks. We have already succeed.

HA : Was it enough to make these tiny holes on the surface ?

KH : They are under the surface. Also by using the interference technique we have made a lot of dots.

HA : I understand, it is beautiful glass but too costly for bottle makers.

KH : Of course it is not for bottle makers ! Also we have found a cheap process to make AWG (array wave-guide grating) by using the femtosecond laser. AWG are very useful for optical telecommunications. Until now, they were very expensive to make. We also managed to make a nanoglass thin film for CD. The storage medium can be a cobalt oxide-based glass, for example. When we apply a nanoglass coating on this recording material the blue beam is shrinked to ¼. This is a lens effect. We have now this optical disk standardized by Hitachi. So you know that Shuji Nakamura ; a Japanese researcher, has discovered the blue laser diode. In my case by using this blue laser diode, the recording capacity is approximately increased by a factor 4, because the beam is much smaller. And in the field of optoelectronics, we have made 3 dimensional devices including both electrical and optical circuits. We use gold containing glasses that crystallize under laser beam. Three dimensional wires can be obtained, together with optical waveguides in the same device.

HA : So this program seems to be essentially telecommunication oriented.

KH : Yes NEDO asked us to make such devices. Otherwise they would cut the financial support.

BBV : You mean that the budget is according to your practical results.

KH : Yes.

BBV : What kind of connections do you have with venture business ?

KH : For optical properties we have to make such connections. Otherwise we could not do it on university money or government money. Venture business have a lot of demands in optical properties of glasses. For instance some fibermakers make lenses inside optical fibers. With my technique of femtosecond laser we can make lense in fiber. There are many such innovations of interest for business, although optical properties are not directly related to optical devices.

BBV : Do you mean that you only do research and no development ?

KH : Optical properties are synchronized with optical devices. There is no linear sequence from optical properties to technical devices, from basic research to applied science then development. We have to work in synergy.

HA : So do you consider yourself as a materials scientist because you are dealing with devices ?

KH : Yes we have to make connections with venture business and industry. For doing this kind of research we have to build a wide network. So many venture businesses are connected with me and they are eager to be.

HA : Where does the money come from ? From big industrial companies ?

KH : So far my devices did not cost much. If one day we have to develop a costly device, the Japanese governement is able to support us immediately, at least for two or 3 years. The Japanese governement is encouraging this kind of cooperation.

HA : Do you also collaborate with foreign companies ?

KH : With Schott in Germany. They have sent a researcher here. And Corning is also willing to collaborate. In the USA glass professors are not so many in optical devices. Here we have more than 50 professors of Glass Science

BBV : Do you send students to the USA ?

KH : Not right now.

HA : Where do you locate the leading centers in your field ?

KH : I guess Osaka is the center. Glass science originated in Osaka National Center.

HA : You told me last year that you run many laboratories. How many ?

KH : I have 6 laboratories including one in China, one in Osaka, one Tsukuba ... 300 people altogether. There are autonomous and eager to make things because optical devices is a very promising field. So I don't have to be continuously behind them. There are so many things to do such as inkjet using semiconducting cadmium selenide nanoparticles. The color changes depending on particle size.

HA : This is not glass. Is it ?

KH : Yes it is, because nanoparticle CdSe particles are made in micelles and encapsuled by glass using sol-gel chemistry. The fluorescent yield increases nearly 10times using these nanoparticles. Silica sol-gel coating is necessary ; otherwise the semiconductor particles aggregate to each other. Encapsulated particles are then deposited by inkjet to make displays. We do this development by collaborating with venture business.

BBV : So you seem to work as a partner of venture business, as a manager of projects rather than as a traditional scientist supplying science for applications downstream.

KH : Yes my aim is really to make optical devices. This is what we have to do. We teach Glass Science. But in laboratory research we have to make devices. Traditional professors are not interested in devices ; I am. But you see, in Japan I don't have to move to an industrial company to make such devices.

BBV : Is it part of your obligations as a university professor to make devices ?

KH : No, teaching is the only obligation. We just have to teach and take care of the students.

BBV : Does the university system recognize your devices ?

KH : Yes now the government recognizes patents.

HA : So you feel that you are in a better position at the university because you have the freedom of choosing your topics of research and you have the money that you need for them.

KH : Yes I am very lucky.

BBV : How do you select your research projects ?

KH : The keywords are glass and optics. We have a lot of choices. One criterium is to use the femtosecond laser.

HA : You mean that you can use it to change glass composition ?

KH : If we use samarium doped glasses we can change the samarium3+ to samarium2+ with the femtosecond laser. So glass composition is very important for me. Not just to make new glasses and measure their optical properties. If we make a new glass it is to make a new device by using a new technique. We also made electrical lithography by plasma etching for nanodevices, in Osaka.

HA : On our webpage you also mention that you are working on hybrid materials.

KH : Yes usually at the macroscale, it is difficult to combine organic and inorganic components. Nanohybrids work better by using chemical reactions with micelles. Professor Tetsuo Yazawa at Himeji Institute of Technology University made a lot of nanohybrids that can be used for gas filters, for membranes, solid sensors and solid electrolytes. Conductivity is very high in the nanohybrids. Both electronic and ionic conductivities. And hybrids are also useful for glass capsules for drug delivery. So we started that kind of research on hybrids within the nanoglass project.

BBV : Do you try to compete with other materials in your nanoglass project ?

KH : No, glass offers unique advantages. We can overcome polymers. Glass is the only transparent material even at the nanoscale. I forgot ! Athermal glass is very important. We achieved athermal glass-ceramics we have to apply pressure to control the size of the nanoparticles and the growth. So nanoglass is unique and very useful.

HA : I can see that your project works very well. But do you remember any failure in your research career ? It is also instructive for our project on the history of Materials Science.

KH : For the Photoncraft project we are at the middle point so we have to submit. The nanoglass project started one year ago. We have to make an effort, otherwise budget might be cut.

HA : This morning Professor Soga told us that he considers himself as an educator rather than as a glass scientist. Is teaching and training also important for you ?

KH : You cannot separate teaching and research. Education and laboratory work together. In the field of glass, just making optical devices is a good education, a good training. Now we are training a number of students through the nanoglass project.

BBV : Do you mean that the nanoglass project is in itself a kind of training ?

KH : Yes, for graduate students. When I present the results of our nanoglass project to company presidents, they are essentially grateful for our work as educators because we train the researchers from industrial companies. Helping each other is very important.

HA : Does it mean that you are no longer interested in basic research and basic education ?

KH : No. Presently I am making devices but maybe in a few years I write a new textbook of glass science because they are so many new glasses that all conventional glasses are obsolete. This textbook should be written in English.

BBV : You want to write a textbook of Glass Science, not of Materials Science in general ? Are there any Japanese textbooks of Materials Science ?

KH : Yes and we had written one.

BBV : One final question : Do you see differences in the research styles of various countries ?

KH : In Europe originality is important. Here it is rather collaboration and harmony. We are more modest, more humble. Collaborations, mutual help and mutual learning, Interdiscipinary philosophy is my project aim.

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« Entretien avec Kazuyuki Hirao », par Bernadette Bensaude-Vincent et Hervé Arribart, 29 aout 2002 Sciences : histoire orale, https://sho.spip.espci.fr/spip.php?article125.

—

Entretien avec Kazuyuki Hirao, par Bernadette Bensaude-Vincent et Hervé Arribart, 29 aout 2002

Lieu : Department of Materials Chemistry, Kyoto University

Support : enregistrement non précisé

Transcription : Bernadette Bensaude-Vincent et Hervé Arribart

Edition en ligne : Sophie Jourdin

HAGENMULLER Paul, 2001-06-12

Sophie Jourdin — 2011-11-03T15:23:16Z

Paul Hagenmuller, born in Alsace in 1921, developed solid-state chemistry in France. He first initiated a research program at the University of Rennes (1956-60). In 1960 he set up a dynamic laboratory in Bordeaux. In 1964, Hagenmuller organized an international conference dedicated to the relations between structure and physical properties in oxides of the transition elements. The meeting gathered together chemists, crystallographers and solid-state physicists and prompted the establishment of an international community of solid-state chemists. In Bordeaux, Hagenmuller became the head of a research school working, at the interface between physics and chemistry, on the relation between atomic/electronic structure and physical properties, with a strong emphasis on industrial applications.

The Bordeaux research school has attracted scientists and students from all over the world (both developed and emerging countries) and many brilliant chemists of the next generation such as Jean Rouxel were trained in Bordeaux. Paul Hagenmuller retired in 1994. A jubilee celebration was organized at the Maison de la chimie in Paris in 1997. In 2001, his 80th birthday was celebrated in a special issue of the journal Solid State Chemistry.

HERVE ARRIBART (HA) : Pouvez vous retracer votre formation, vos débuts dans la carrière ?

PAUL HAGENMULLER (PH) : Depuis que je m'intéresse à la science je me suis préoccupé de la physique. Je me suis demandé pourquoi les matériaux avaient telle ou telle couleur, tel ou tel comportement électrique, magnétique, optique ... J'ai donc été porté vers la physique, plus tard vers la mécanique par extension, dès que j'ai entrepris mes études de science. Ces études ont eu lieu en 1940 à l'université de Strasbourg, repliée à Clermont Ferrand. Mon statut était celui d'un réfugié politique puisque j'avais quitté l'Alsace pour échapper au système politique allemand et parce que je me refusais d'être un jour mobilisé dans l'armée allemande. A Clermont, pour des raisons financières j'ai fait le choix de la chimie, séduit par la diversité des méthodes de préparation mais choqué parce que la chimie était alors très descriptive et n'était pas encore une science déductive, de réflexion.
Sur place, je suis entré en résistance, je faisais du sabotage. J'ai été arrêté en 1943 et envoyé en camp de concentration à Buchenwald. Là j'ai appris à me taire. J'ai travaillé sur les V2. J'ai appris le russe avec les prisonniers russes ; j'avais de bons contacts avec les communistes allemands. Puis j'ai été envoyé à Dora où c'était plus dur.
Après la guerre, André Chrétien m'a proposé un sujet de thèse sur la formation de nitrites complexes en solution aqueuse, puis une recherche sur la réduction de divers oxydes par des hydrures d'alcalino-terreux. J'ai accepté parce qu'il y avait un appareil mathématique. Puis au lendemain de ma thèse je me suis dit : il faut que je travaille sur des choses plus concrètes, les matériaux. J'ai voulu revenir à mes anciennes amours les matériaux. Je suis parti au Vietnam dans le cadre d'un accord avec la direction de l'enseignement supérieur et moi. Je partais pour deux ans 1954-56, au moment où la France se désengageait et voulait garder des relations culturelles. Au retour il était entendu que je pourrai choisir un poste de maître de conférences parmi ceux qui étaient disponibles en chimie. Ces deux ans de Vietnam ont été pour moi une période de décantation, de réflexion. Et quand je suis revenu j'ai voulu, d'une part, me préoccuper de physique ce qui suppose la détermination des structures atomiques - pour comprendre les propriétés physiques il faut savoir quelles sont les positions des atomes - et, d'autre part, il faut une certaine habileté à préparer des matériaux par des techniques nouvelles fort différentes.

HA : Quelles étaient alors les relations entre physique des solides et chimie des matériaux en France ?

PH : Aujourd'hui la physique s'est beaucoup rapprochée de la chimie parce que, de part et d'autre, on a compris que c'était indispensable pour faire des matériaux à propriétés spécifiques intéressantes sur le plan de la science fondamentale et intéressantes aussi sur le plan des applications. Au début des années 60, on en était à se chercher. Moi, j'avais fait un choix très clair : faire une chimie orientée vers la physique, plus tard vers la mécanique. Maintenant c'est devenu presque de routine, ne serait-ce que par ce que les chimistes pour bien connaître leurs matériaux sont obligés d'utiliser des méthodes de caractérisation physiques. La physique s'est imposée dans les perspectives de la recherche comme par les nécessités quotidiennes : savoir où sont les atomes et les électrons.
Donc au retour du Vietnam mon objectif était d'associer la physique et la chimie. J'ai eu la chance que dans mon poste à Rennes il y avait quantité d'excellents étudiants, mais en chimie personne ne voulait faire de la recherche sous prétexte qu'il n'y avait pas de moyens. J'ai décidé que j'allais lancer des thèses dans ce domaine à l'interface de la physique et de la chimie. On a d'abord tâtonné. On a travaillé sur le bore, sur les hydrures. Parmi les études réalisées à Rennes se trouvait la réduction d'oxydes par l'hydrure de lithium. On était intéressé par les hydrures de bore et d'aluminium qui comportaient des liaisons dites pont-hydrogène originales. Ceci m'a donc amené à réduire le V2O5 par l'hydrure de lithium et nous avons constaté qu'il y avait des phases intermédiaires qui devaient être les futurs bronzes de vanadium et de lithium, qu'on a appelées plus tard b et g. La phase a étant la solution solide de lithium dans V2O5. Alors j'ai pensé que ces matériaux étaient intéressants : s'il y a là un domaine d'existence, les propriétés physiques doivent varier à l'intérieur de ce domaine et si, par chance, ce domaine est suffisamment grand on peut faire ce qui est plus difficile dans les solutions solides limitées, de type oxydes non stœchiométriques. On s'est préoccupé de manière systématique des bronzes de vanadium qu'on a préparés par voie synthétique. Dans les années qui ont suivi - de 1960 à 70, j'étais alors à Bordeaux où un grand nombre de chercheurs de Rennes m'avaient suivi - on a préparé un grand nombre de phases de bronzes de vanadium par analogie avec les bronzes de tungstène qui avaient déjà été signalés. On a fait systématiquement des études magnétiques et électriques pour caractériser le mode de conductivité. Il est apparu que lorsqu'on insérait le lithium dans le réseau, on remplissait les états électroniques du vanadium, qui forment la bande de conduction. Les électrons devenaient donc de plus en plus délocalisés au fur et à mesure que leur nombre augmentait et on passait d'un état semi-conducteur à l'état métallique.

BERNADETTE BENSAUDE-VINCENT (BBV) : Quelles étaient vos relations avec le groupe de Robert Collongues ?

PH : Collongues avait été élève de Georges Chaudron, comme André Michel, Paul Lacombe, Jacques Bénard. J'avais d'excellentes relations avec Collongues. Nos domaines se recouvraient partiellement sur la non-stœchiométrie mais on avait des approches différentes. Lui enlevait des ions, nous on faisait de la chimie d'insertion. Collongues aimait bien se singulariser par rapport à moi mais dans la pratique nous avions la même politique sur des matériaux différents. Il y avait chez lui le même désir de systématique et de réflexion en profondeur. Collongues considérait que la bonne expérience était importante mais qu'elle devait illustrer une réflexion de fond. Il pensait que la science était avant tout la réflexion intellectuelle.
J'ai fait de la chimie sous pression à la manière d'un tailleur : choisir une structure cristallographique, écrire la formule d'une composition chimique, puis la stabiliser dans un degré d'oxydation élevé. Après avoir discuté la structure puis la formule, on préparait sous haute pression. C'était du design pour la conductivité électronique, les propriétés magnétiques, ou les propriétés magnéto-optiques et plus tard également pour la conductivité ionique.
Nous nous intéressions systématiquement à l'évolution de toute propriété physique originale en fonction de la composition et de la structure. Un nœud important dans cette évolution fut le colloque organisé à Bordeaux en 1964 sur les oxydes d'éléments de transition.

HA : Quelle fut la portée de ce colloque de 1964 ?

PH : Ce fut le moment où s'est constituée une communauté internationale de chimie du solide. Le colloque a rassemblé les chimistes qui nous étaient familiers, des cristallographes (Erwin-Felix Bertaut, Charles Guillaud), des physiciens (Jacques Friedel). Parmi les étrangers Mike Sienko, John Goodenough du Lincoln Laboratory au MIT qui est venu pour la première fois à Bordeaux ; des Allemands : Wilhelm Klemm, Rudolf Hoppe, Harold Schäfer ; des Hollandais, des Belges, etc. Il est apparu qu'une conjugaison des méthodes de mesure physique, des méthodes de détermination structurale et une certaine flexibilité pour les changements de composition, pouvaient permettre d'optimiser un certain nombre de propriétés physiques. D'abord le magnétisme, ensuite il y a eu la ferro-électricité - comment accroître la distortion ferro-électrique et par voie de conséquence la polarisation ; enfin, la conductivité ionique, d'abord dans des matériaux isolants au point de vue électronique et ensuite dans des matériaux dits cathodiques utilisables dans des batteries parce que conducteurs mixtes.
Je dois dire que ce qui fut déterminant pour l'avenir de la chimie du solide ce fut la venue de John Goodenough à ce congrès parce qu'il a popularisé parmi nous l'idée de l'importance de la liaison chimique. On a compris qu'on pouvait renforcer ou atténuer la liaison chimique en modifiant la composition, en particulier en jouant sur la liaison antagoniste. Par exemple si on compare le zirconate de baryum avec le titanate de baryum, la liaison baryum-oxygène est renforcée dans le zirconate par rapport au titanate. Inversement si on remplace dans le titanate de baryum, le baryum par le strontium comme la liaison strontium -oxygène est plus forte que la liaison baryum-oxygène, la liaison titane-oxygène est affaiblie, ce qui peut amener une variation très forte de la polarisation en fonction de la température, juste en dessous de la température de Curie. Et on peut avoir ainsi des matériaux aux propriétés intéressantes.

HA : Le rapprochement de la physique et de la chimie avec une orientation vers les applications constituerait-il donc l'identité de la chimie du solide à cette époque ?

PH : Oui nous avions un besoin civique de justifier les crédits que nous demandions par une application dans la vie économique. De plus, le travail avec des industriels fait naître des problèmes inattendus qui sont des challenges et qui sont nourrissants.
Une deuxième date importante dans l'institutionnalisation de la chimie du solide est 1978. Sur mon initiative la Société française de Chimie a créé en 1976 une division de chimie du solide, dont j'ai naturellement été le président. J'ai organisé la même année un premier colloque national de chimie du solide à Nantes. Sur ma proposition et sous ma présidence s'est tenu à Strasbourg en 1978 le premier congrès européen de chimie du solide, organisé par Jean-Claude Bernier (Strasbourg a été choisi pour une raison stratégique,). L'intervalle entre deux congrès consécutifs est maintenant de 3 ans ; le huitième congrès européen a lieu en juillet 2001 à Oslo.

HA : Quel était l'état des relations entre science et industrie en France à cette époque ?

PH : Il y avait une tradition de collaboration en métallurgie et en chimie : Chaudron et ses élèves, Lacombe, Bénard étaient très impliqués. Robert Collongues l'était aussi dans le domaine des monocristaux. Mais il y avait une forte hostilité syndicale au nom des grands principes : il ne faut pas mettre la science au service des grands intérêts privés. Les choses se sont atténuées à la veille de l'élection présidentielle de 1981. J'ai eu la visite de M. Kahane, longtemps doyen à Orsay, qui s'était rallié à la collaboration avec l'industrie privée. Cela a facilité cette évolution qui, de ma part, ne rencontrait aucune résistance car j'étais un scientifique et je n'avais pas à me poser des problèmes de déontologie qui me paraissaient un peu artificiels. Mais une partie de mon entourage était réticente à travailler avec l'industrie.

HA : Est-ce la crise pétrolière de 1973 qui a contribué à anoblir le rapprochement entre science et industrie ?

PH : Oui. Du fait de notre préoccupation entre propriétés physique et composition, nous avons été conduits à travailler sur des composés non-stœchiométriques d'intercalation et nous avons constaté après 1973 qu'il y avait possibilité d'intercalation ou désintercalation à basse température grâce à l'électrochimie comme on le faisait aux Etats Unis. Exxon et Bell étaient plus concernés que nous par la crise de l'énergie.
Les recherches sur la conductivité ionique ont été encouragées par la crise de l'énergie. Après la zircone déjà exploitée par Nernst, puis étudiée par la NASA et par Collongues ; il y avait eu AgI. Puis il y a eu l'alumine-b qui a suscité de nombreux travaux. CGE a dépensé beaucoup d'argent. L'alumine-b est un matériau très particulier. J'étais très sceptique. On a abaissé la température de fonctionnement, mais c'est encore trop haut pour un véhicule électrique. Et puis le soufre attaque la membrane. Finalement on a renoncé, pensant qu'avec des batteries au lithium on irait plus loin. Les derniers efforts de développement visaient plutôt le stockage d'énergie en période creuse. Les nasicons eux ne sont pas attaqués et ils présentent un avantage au plan fondamental car leur structure est plus simple. Ils ont de bonnes performances, qu'on pouvait maîtriser avec une juste proportion de sodium.

HA : Pouvez vous évoquer vos travaux sur la conduction ionique ?

PH : Avant 1973, on a publié un grand nombre de documents sur des conducteurs ioniques. On s'inspirait comme modèle de réflexion des bronzes de tungstène bien que la plupart des travaux publiés à l'époque fussent des études structurales et que les bronzes de tungstène soient métalliques. On avait également préparé une série de nouveaux bronzes de tungstène. Ce travail s'est étendu à des bronzes oxyfluorés, à des bronzes de vanadium et de molybdène contenant les deux cations vanadium et molybdène plus le sodium et le lithium. Puis au début des années 1970, on s'est attaqué aux premiers bronzes de manganèse NaxMnO2 et puis aux bronzes de cobalt KxCoO2.
Sur ces entrefaites il y a eu la grande crise pétrolière de 1973. Les pays occidentaux ont eu peur de manquer d'énergie et donc on s'est occupé de sources d'énergie non fossile et de stockage d'énergie. Un certain nombre de gens ont voulu faire des batteries. Exxon et la Bell Telephon, Whittingham et Murphy en particulier, ont travaillé sur ces matériaux non plus comme nous l'avions fait vers 500°C avec des phases en équilibre thermodynamique mais à basse température par intercalation ou désintercalation électrochimique.
Une spécialité à Bordeaux c'était les fluorures conducteurs. On remplaçait systématiquement l'oxygène par du fluor parce qu'il a la même taille et présente une liaison plus faible. On pouvait ainsi atténuer les interactions magnétiques. Comme pour la zircone, on dope les fluorures systématiquement. Watanabe avait déjà préparé les premières batteries au fluor.
Jean Rouxel s'était intéressé à l'époque où il était mon élève aux sulfures, aux sulfures à couche en particulier. Entre les couches de FeOCl et FeSCl par exemple, on pouvait intercaler beaucoup de choses, comme l'ammoniac ou les amines. Jean Rouxel a préparé NaxTiS2, un matériau qui avait été préparé par Rudorf à Fribourg, qui le considérait comme une curiosité. Mais Rouxel a très vite réalisé qu'il devait y avoir un domaine d'existence. Or il s'est avéré que Li xTiS2 avait un large domaine d'existence. Jean Rouxel a poussé dans cette voie et il a étudié un grand nombre de sulfures et sélénures à feuillets alors que nous nous intéressions plutôt aux oxydes. Il y avait une sorte d'accord empirique entre nous : Nantes les sulfures, Bordeaux, les oxydes. Nous avons étudié des matériaux sur le plan de la synthèse, dans des conditions d'équilibre thermodynamique plus que par intercalation désintercalation.
Il y a une grande variété de méthodes topologiques ou non de relative basse-température qui permettent d'obtenir des matériaux nouveaux. Mettre un mélange très fin de poudres sous hautes pression pour que se déclenche une réaction brutale qui prend fin lorsque l'un des deux constituants initiaux a disparu. Donc c'est un échauffement brutal suivi d'une trempe. Ce qui permet d'obtenir des borures ou des silicium stables seulement à haute température.
Beaucoup de ces matériaux sont métastables mais on peut les utiliser dans des dispositifs.
Jean Rouxel a apporté beaucoup dans le domaine des réactions d'intercalation-désintercalation. Les oxydes lorsqu'on les désintercale perdent des électrons cationiques. C'est une oxydation cationique. Lorsqu'on part de LixCoO2 vers CoO2 on perd des Li+, mais on perd également des électrons qui proviennent des niveaux d. Mais pour les séléniures, ce sont les niveaux anioniques qui sont les plus élevés. Et lorsqu'on oxyde, c'est l'anion qu'on oxyde. On passe de Se2- à Se- et de Se- à Se pour des raisons de stabilité de liaison. Et Jean Rouxel a montré qu'il y avait une évolution graduelle pour les éléments 3d à l'état de sulfure entre TiS2, qui a une structure à couches, et CuS2 qui a une structure avec un ion S de type pyrite. Il a fait une analyse précise dans les cas douteux où les niveaux cationiques et anioniques sont à peu près de même énergie. L'analyse très fine des distances inter-atomiques lui a montré si c'était le cation ou l'anion qui était oxydé. Il a également fait beaucoup de choses sur les bidimensionnels qui sont ici hors sujet.

HA : Qu'est-ce qui a manqué en France alors que les compétences étaient là pour donner l'impulsion sur les batteries au Lithium ?

PH : Il y a un très grand nombre de batteries réversibles au lithium pour des applications diverses depuis les montres jusqu'aux batteries de taille moyenne utilisées par les militaires pour observation spatiale avant bombardement. Mais le marché important, c'est le véhicule électrique, non polluant. Du moins en partie car on s'est résigné au véhicule hybride. Le véritable marché ce serait la voiture électrique -éventuellement hybride- ce qui suppose des batteries de grande taille. Probablement l'électrolyte sera un polymère PEO imprégné d'un sel de lithium avec un gros anion, type matériau Armand. La cathode sera probablement riche en cobalt ce sera un matériau voisin de LixCoO2, plutôt un oxyde qu'un sulfure parce que la tension est plus élevée. Mais pour l'anode ce n'est pas encore évident. Si on pouvait faire mieux que les composés d'intercalation du lithium on serait content. Mais actuellement il n'y a pas encore de solution. Il y a donc premièrement un problème de matériau qui freine cette évolution. Deuxièmement il y a un problème de prix. Ajoutez à cela qu'une batterie au lithium doit être scellée car le lithium est sensible à l'atmosphère et vous voyez que ce n'est pas évident. Une solution concurrente est la batterie hydrogène consistant à stocker l'hydrogène dans un alliage métallique et puis à libérer l'hydrogène. Ce modèle permet des puissances plus élevées que la batterie au lithium mais là aussi il y a un problème de vieillissement car après un certain nombre de cycles, l'alliage s'oxyde car l'oxyde est plus stable que l'hydrure. Ce problème n'est pas encore résolu avec un coût acceptable pour l'utilisateur. A cet égard, il y a une coupure entre le scientifique et l'utilisateur.

HA : Concernant les relations entre physique et chimie qu'est-ce qui a favorisé le rapprochement ?

PH : Les physiciens ont fait des efforts pour parler un langage plus proche de celui des chimistes. J'ai parlé déjà de John Goodenough. Nevil Mott aussi était un homme qui s'exprimait dans un langage compréhensible pour un chimiste. Par exemple, lorsqu'il a obtenu des transitions isolantes par changement de composition au sein d'un domaine d'existence, on comprenait ses préoccupations et il comprenait les nôtres bien qu'on raisonne sur des modèles un peu différents. On est ainsi arrivé à préparer dans des bronzes de tungstène oxyfluorés des matériaux qui sans changement de structure manifestaient une transition métal-isolant. Les physiciens ont fait des progrès. L'équipe de Friedel était très préoccupée de parler un langage qui nous était commun. Je pense à Denis Jérôme, Claude Berthier à Grenoble.

HA : Le travail de physiciens sur la caractérisation très fine vous a-t-il aidé ?

PH : Je me souviens de discussions à Orsay sur les hexaborures. Les physiciens voulaient des matériaux qu'on appelait thermo-ioniques - mais c'est un mot malheureux : on devrait plutôt dire thermo-électronique - c'est à dire ayant un faible potentiel d'ionisation et susceptibles de cracher un jet d'électrons relativement puissant sous tension faible. On en a fait une étude systématique et on a essayé de préparer des cristaux.

HA : Et quel était l'enjeu ?

PH : L'enjeu était d'avoir ponctuellement un faisceau d'électrons puissant, par exemple pour des soudures, des soudures localisées. Outre la collaboration avec les physiciens d'Orsay on a aussi collaboré avec ceux de Grenoble. Plus que ceux d'Orsay, les physiciens de Grenoble avaient un langage très compréhensible. Il y avait un grand homme à Grenoble, Louis Néel. Il avait publié son travail sur le ferrimagnétisme en s'appuyant sur des modèles structuraux très clairs. La répartition des cations entre les sites tétraédriques et les sites octaédriques de la structure spinelle. Donc on comprenait pourquoi on avait des interactions d'abord anti-ferromagnétiques - ce qui constitue la base du ferrimagnétisme - entre des sites tétraédriques A et des sites octaédriques B, et pourquoi l'aimantation résultante était accrue lorsque le réseau prévalent contenait des cations avec beaucoup d'électrons d célibataires. Tous ces travaux - encouragés par les recherches militaires - ont permis une collaboration très fructueuse avec Grenoble. Je pense à Bertaut en particulier. Nous avons été encouragés, par exemple, à faire des études basse-température par Pauthenay qui nous a dit : c'est aux basses- températures qu'on détecte les phénomènes peu énergétiques.
Alors c'est l'époque où nous avons manqué le prix Nobel - Je dis cela en plaisantant, bien sûr !-. Nous avons préparé les premiers oxydes purs de Cu3+ : par exemple SrLaCuO4. Nous avions une telle habitude des solutions solides qu'on pouvait imaginer de préparer une solution solide avec La2CuO4 contenant du Cu2+. Mais pour nous, les solutions solides, c'était du travail secondaire. On cherchait à préparer des oxydes purs. Si on avait été préoccupé des solutions solides on aurait pu trouver des oxydes contenant à la fois du cuivre Cu 2+ et 3++. Comme par routine on caractérisait tous nos matériaux jusqu'à la température de l'hélium liquide, on aurait trouvé la supraconductivité. On ne l'a pas fait parce qu'on voulait des phases pures et non pas des solutions solides.
Bernard Raveau l'a fait avant Alex Müller. Il avait un objectif : comprendre ce qui se passait au point de vue des corrélations. Passer d'un semi-conducteur à un métal. Müller était un très grand physicien. Il a été surpris aussi mais il a tout de suite expliqué. Raveau a fait ses solutions solides. C'est même moi qui ai transmis sa publication au M[aterials] R[esearch] B[ulletin] mais j'ai regretté à l'époque qu'il n'ait pas fait de mesure à l'hélium liquide.

HA : Après avoir évoqué vos collaborations en France, pourriez vous parler de vos liens avec l'étranger ? Vous avez été précurseur pour les relations scientifiques avec les pays en voie de développement comme la Chine, le Maroc et l'Inde. Quelles étaient vos motivations ? Comment voyez-vous la science des matériaux dans ces pays ?

PH : J'ai toujours été persuadé que la science devait être internationale. Cela me distingue de beaucoup de mes compatriotes. Je suis toujours étonné que l'on fasse des quêtes pour aider la recherche en France sur le SIDA. Toute la recherche sur le SIDA, toute recherche de pointe est internationale et ce n'est pas parce que la France dépensera un peu plus d'argent que nécessairement, il y aura des progrès significatifs. La science doit être internationale.
J'ai donc eu des liens d'abord avec les pays développés car dans ce type de relation on se fait connaître mais aussi on apprend. Je suis allé souvent aux Etats Unis, moins par enthousiasme culturel, que parce qu'on y rencontre des gens de qualité. J'ai rencontré Goodenough, Al Cotton... j'ai rencontré à Berkeley ou à Stanford des gens de grande qualité. J'ai eu des relations suivies pendant un temps avec la Grande Bretagne mais les Anglais ont un sentiment de quant à soi. J'espère qu'avec le temps la Grande Bretagne va évoluer vers une intégration dans l'Europe. Les Allemands sont très favorables à cette intégration. Dès 1961 j'avais pris l'initiative d'emmener tout mon laboratoire en Allemagne pour un voyage de 15 jours. On est allé à Stuttgart, Karlsruhe, Heidelberg, Darmstadt, Giessen, Göttingen etc.. On a été très bien reçu par Wilhelm Klemm avec qui j'ai toujours entretenu d'excellentes relations. Mais ses élèves étaient jaloux. Les Allemands se sont sentis bousculés parce qu'un peu jaloux de gens qui faisaient beaucoup de bruit. Ils avaient une bonne tradition de chimie préparative, en relation avec l'industrie. Les Allemands ont compris que pour faire des matériaux nouveaux il fallait des techniques nouvelles comme la haute pression. Mais leur but c'était la performance tandis que le nôtre c'était de stabiliser des structures électroniques peu usuelles, grâce à la synthèse. Les Allemands se sont senti un peu gênés. Les gens leur disaient : vous utilisez des équipements de haute pression mais ce que vous faites c'est de la botanique alors qu'il faudrait réfléchir. Le but d'un équipement est de faire des matériaux à façon pour répondre à des problèmes déterminés. Les collègues allemands avaient un autre point de vue et je regrette qu'il n'y ait pas eu davantage de liens.
En revanche, toujours parmi les pays développés, j'ai eu beaucoup de liens avec l'Europe de l'Est. Pour deux raisons. D'abord, il y avait des gens de qualité chez les Soviétiques, les Polonais et les Tchèques. De plus j'étais un peu agacé de cette Europe coupée en deux du fait de la guerre froide. Donc je trouvais raisonnable qu'il y ait une présence de la France là où c'était relativement facile, c'est à dire la science. C'était intéressant pour eux et pour nous car nous avons eu de ces pays des personnes remarquables. J'ai eu des relations systématiques avec des laboratoires à Prague, Cracovie, à Moscou, à Kiev, Novosibirsk, à Sofia. Avec la Roumanie, c'était impossible car Madame Ceaucescu interdisait aux scientifiques de discuter avec des étrangers.
Avec les pays en voie de développement, la situation change d'un pays à l'autre. J'ai eu des relations avec le Maroc parce que l'université de Bordeaux et l'université de Rabat avaient des liens traditionnels. Je suis allé y faire cours. Il y avait de très bons étudiants je les ai encouragés à faire une thèse. Le nombre a crû considérablement. 30 ou 35 Marocains ont fait des thèses avec moi. J'avais une politique de sélection impitoyable ; je prenais les meilleurs et je les surpayais. Je voulais qu'ils n'aient pas de souci matériel pendant leur thèse. J'ai eu des liens plus occasionnels avec la République du Congo et quelques Tunisiens mais ils préféraient Marseille.
Avec la Chine j'ai fait un choix politique. J'ai compris que la Chine était un potentiel économique et humain. La France devait être présente à un moment où la Chine était exclusivement tournée vers les Etats-Unis. Je suis allé souvent en Chine. J'ai fait venir des étudiants chinois en les choisissant bien sûr excellents. Mes espoirs ont été dépassés par le succès car ils ne sont pas retournés en Chine mais partis au Canada ou aux Etats-Unis comme professeurs ou dans l'industrie. Ils se sont bien débrouillés. Maintenant c'est différent ; une majorité d'étudiants chinois reviennent en Chine.
L'Inde est aussi un pays avec lequel j'ai eu des relations. C'est une société où le savoir est respecté, une science de caste malgré l'abolition officielle des castes. Thaïlande, Malaisie, Indonésie...j'ai privilégié les pays asiatiques par rapport aux pays africains car la culture asiatique favorise la réflexion métaphysique et par conséquent scientifique. Néanmoins j'ai eu aussi des collaborations avec le Brésil, le Chili et l'Argentine. Le but étant d'aider ces pays dans leur développement industriel. Je suis d'ailleurs membre de l'Académie des sciences brésilienne depuis 1988.
Vis à vis des étudiants du tiers monde, j'ai toujours considéré comme ma responsabilité de leur donner une thèse originale et non pas, comme on le fait souvent, de leur faire remplir des vides dans le laboratoire ou de servir de main d'œuvre. Les étudiants du tiers monde que l'on fait venir en Europe il faut bien les choisir et bien les former pour qu'ils deviennent des maîtres.

HA : Je serai curieux de connaître votre point de vue sur l'évolution de la chimie des matériaux et le rapprochement avec la biologie.

PH : Je ne me sens pas compétent dans l'interface chimie/biologie. Mais mon expérience à l'interface physique et chimie me rend plutôt sympathique cette perspective d'une ouverture de la chimie vers la biologie. Elle est défendue par Pierre Pottier, Guy Ourisson, Corriu.
Sur l'interface physique/chimie, cela s'est moins bien passé. Peut-être que je n'ai pas su convaincre. Quand on prêche, on se fait des adeptes mais aussi des ennemis. Cela est vrai au CNRS. Celui qui prêche secoue les caciques, les gens en place. Quelqu'un comme Fernand Gallais était fermement hostile à mon projet d'interface avec la physique. Par contre j'ai rencontré beaucoup de sympathies du côté de Pottier, de Jacques Livage.
Pour revenir aux oxydes supraconducteurs, il s'agit d'un cas intéressant de collaboration entre physiciens et chimistes. Très vite, j'ai compris que l'on avait plafonné et puis à un moment donné il était clair que Tc était d'autant plus élevé que la bande de conduction était plus étroite. Et plus la bande de conduction est étroite plus le matériau est instable et a tendance à se dismuter en donnant un mélange de deux phases. J'ai compris cela très vite mais beaucoup ne l'ont pas compris. Il y a donc eu un emballement. Il a rapproché les chimistes des physiciens. Il est dommage que personne n'ait proposé un modèle simple permettant aux chimistes d'innover de manière simple comme on avait innové dans le domaine de la conductivité ionique, du magnétisme, de la ferroélectricité, des magnéto-optiques ... ou même des composites thermo-structuraux. Il a manqué quelqu'un qui propose un modèle intuitif liant les propriétés à la liaison chimique. Goodenough aurait pu le faire mais il était trop vieux, trop pressé de publier des matériaux miracles. Les matériaux miracles sont difficiles à reproduire. Celui qui essaie il n'a pas le même four ... Ces matériaux sont métastables, ils ne sont jamais parfaitement purs. Ils n'ont jamais le même nombre de lacunes d'oxygène. Donc ce n'est jamais parfaitement répétitif. Cela exclut toute réplication sérieuse parce qu'un matériau n'est utilisable industriellement que s'il est relativement simple à préparer et à utiliser. Telle est la raison de l'échec de la diode Josephson sur laquelle IBM a dépensé beaucoup d'argent. A l'époque j'étais d'ailleurs conseiller d'IBM.

BBV : Est-ce qu'il y a eu des matériaux sortis de vote laboratoire qui ont été industrialisés ?

PH : Il y a d'abord eu les varistors. J'ai fait beaucoup avec la Thomson CSF dans ce domaine. Il y a eu LixCoO2 et puis il y a les céramiques composites de R. Naslain : fibres de carbone infiltrées par SiC qui permet de travailler à des hautes températures pour les matériaux de rentrée de la fusée ou du satellite dans l'atmosphère. Car lorsque l'engin revient dans l'atmosphère, il y a un risque d'oxydation. L'astuce consistait à infiltrer - non pas déposer en surface - SiC à partir d'une phase vapeur. Alors à l'air SiC s'oxyde en donnant SiO2 qui s'infiltre dans le matériau à base de carbone et permet de le prolonger.

BBV : Pourriez vous préciser quelles étaient vos relations avec l'industrie et comment elles ont évolué ?

PH : J'ai toujours eu des relations avec l'industrie. Quand j'étais à Rennes j'ai été contacté par Raymond Paul, un des responsables de la recherche à Rhône Poulenc et il m'a vivement encouragé à travailler avec Rhône Poulenc. J'ai eu plusieurs bourses de thèses payées par l'industrie - parfois il fallait publier des résultats plus tard. Rhône Poulenc a payé la thèse de Michel Pouchard sur les bronzes de vanadium au début des années 60. Ensuite il m'a paru tout naturel de travailler avec l'industrie. J'ai travaillé avec Saint-Gobain sur les verres, en particulier sur les verres conducteurs du lithium et du sodium avec Levasseur, sur les verres sulfurés à base de B2S3. Les verres sont un matériau merveilleux. Ils ont une composition qui est flexible. Vous tombez un peu à côté, cela n'a pas d'importance les propriétés ne sont guère modifiées. Vous n'avez pas le problème des matériaux cristallins où, par suite de la moindre erreur, de la moindre difficulté de préparation, une deuxième phase d'impuretés se forme à côté. Là il vous reste une phase. D'autant plus qu'on peut préparer les verres par trempe brutale donc énormément de matériaux sont vitreux alors qu'il y a 30 ou 40 ans c'était différent.
J'ai eu beaucoup de liens avec l'industrie locale : Aérospatiale et SNECMA, avec SNPA (société nationale des pétroles d'aquitaine : ancêtre d'Elf) sur comment purifier le gaz de Lacq...Ma porte était toujours ouverte, on élargissait le champ de nos recherches à la demande car l'industrie n'est pas un boulet.

BBV : Est-ce que ces liens étaient encouragés par le CNRS ?

PH : Le CNRS était informé bien sûr. Et puis quand on est devenu un laboratoire propre en 1966 Curien était très favorable aux relations avec l'industrie. On a un des contrats avec Saint-Gobain, avec Rhône Poulenc devenu Rhodia, avec Ugine Kuhlman devenu Péchiney. Nous avons même eu des liens avec General Electric aux USA pour les borures, avec BASF sur le di-oxyde de chrome pour les bandes d'enregistrement.

BBV : Quelles sont les méthodes et techniques utilisées dans votre laboratoire ? Et comment ont-elles évolué au cours de votre carrière ?

PH : Au début le B-A-BA c'était la diffraction X. Puis pour bien comprendre la structure on a eu un équipement pour des monocristaux. On a préparé des mono-cristaux pour déterminer les structures. Maintenant on a fait de gros progrès et on peut sur des spectres de poudres lorsque la poudre est de bonne qualité déterminer la structure par les méthodes Riedveld en faisant des hypothèses simples sur la structure la plus probable. La diffraction X a été fondamentale et a débouché ensuite sur la microscopie électronique en transmission qui permet de voir les défauts locaux. C'est merveilleux. La diffraction X était une méthode à grande distance. Par contre la microscopie électronique en transmission vous donne les défauts localisés et étendus. C'est une préoccupation que j'ai eu beaucoup à propos de non-stœchiométrie. Quand on passe d'une phase perovskite ABO3 à une phase brownmillérite A2B2O5, on perd de l'oxygène. Alors à haute température les lacunes d'oxygène sont désordonnées. A température plus basse, elles s'ordonnent en fonction du cation B. Quand c'est du fer ou du gallium, un cation isotrope, on a soit des tétraèdres parce qu'il y a pas de lacune, soit des octaèdres car les lacunes marchent par deux. Donc dans une structure brownmillérite on a une séquence octaèdre,-tétraèdre, octaèdre-tétraèdre, et dans la structure perovskite c'est octaèdre-octaèdre-octaèdre. Alors on peut trouver à condition de faire des recuits à température assez basse - quelques centaines de degrés - des phases intermédiaires avec 2 couches octaèdres, 1 couche tétraèdre, 3 couches octaèdres, 1 couche tétraèdre. Et bien sûr quand on chauffe le désordre s'installe à cause de l'entropie d'empilement. On a étudié de manière systématique comment on passe de défauts isolés aux défauts ordonnés, étendus. Et cela a des conséquences au point de vue de la conductivité de l'ion oxygène. Parce que maintenant on a de nouvelles préoccupations. On veut par exemple extraire l'oxygène de l'air par des membranes de perovskite lacunaire ou détruire les traces de CO en oxydant par l'eau. Dans ce cas, vous avez CO2 - qui est quand même moins toxique que CO, sauf sur le plan idéologique - et vous avez de l'hydrogène. On utilise des perovskites lacunaires qui doivent être conducteurs de l'oxygène - ce qui est normal - mais aussi conducteurs électroniques car le transfert se fait sous tension donc il faut que les ions O2- migrent à travers les lacunes de la structure. Il y a donc un aspect pratique pour les capteurs d'oxygène, la purification des gaz. Les Norvégiens utilisent ces méthodes massivement pour transformer le gaz de la Mer du Nord en un gaz exempt de CO. Norsk-Hydro dépense des sommes considérables pour cela. J'ai été invité pour parler avec les gens impliqués par ces recherches.
Donc pour résumer : nos efforts se sont situés à l'interface entre physique et chimie et se concentraient sur l'étude des relations entre composition, structure et propriétés avec la perspective d'applications industrielles.

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Pour citer l'entretien :

« Entretien avec Paul Hagenmuller », par Bernadette Bensaude-Vincent et Hervé Arribart, 12 juin 2001 Sciences : histoire orale, https://sho.spip.espci.fr/spip.php?article124.
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Entretien avec Paul Hagenmuller, par Bernadette Bensaude-Vincent et Hervé Arribart, 12 juin 2001

Lieu : Paris, France

Support : enregistrement sur cassette

Transcription : Bernadette Bensaude-Vincent et Hervé Arribart

Edition en ligne : Sophie Jourdin

COLOMBAN Philippe, 2003-02-18

Sophie Jourdin — 2011-09-19T08:07:32Z

Philippe Colomban, born in 1952, was trained as an engineer at the Ecole Nationale Supérieure de Céramiques Industrielles (at Sèvres). He started his research career in an industrial laboratory at Thomson-CSF where he prepared PLZT optically clear ceramics by sol-gel routes. Then he moved to a CNRS (Centre national de recherche scientifique) laboratory directed by Robert Collongues, where he studied proton conduction. He became an expert in the synthesis of pure monocrystals of beta-alumina. Later he moved to the ONERA (Office National d'Etudes et de Recherches Aérospatiales, The French Etablishment for Aerospace and Aeronautics).

Pour citer l'entretien :

« Entretien avec Philippe Colomban », par Bernadette Bensaude-Vincent, 18 février 2003, Sciences : histoire orale, https://sho.spip.espci.fr/spip.php?article57.

BERNADETTE BENSAUDE-VINCENT (BBV) : D'abord je voudrais vous remercier d'avoir spontanément proposé de contribuer à notre site sur l'histoire des matériaux. Ce genre de feed-back est très enrichissant. Afin de préciser votre point-de-vue, pourriez vous rappeler un peu votre parcours de chercheur ?

PHILIPPE COLOMBAN (PhC) : Enfant, je rêvais d'être géologue mais comme l'Ecole de Nancy offrait peu de débouchés dans les années 1970, j'ai opté pour l'Ecole de Céramique. La céramique est assez proche de la géologie, en effet, dans la mesure où elle traite de roches synthétiques et d'exploitation des carrières. A l'Ecole de céramique (à Sèvres) j'ai eu comme enseignant Jean-Pierre Boilot alors jeune assistant et Mme A.M. Antony qui travaillait sur la zircone en tant que céramique. Elle connaissait bien Collongues qui, lui, travaillait à l'origine sur les oxydes fer et s'était attaqué aux cristaux de zircone.

BBV : A chacun son territoire, en quelque sorte ?

PhC : Tout à fait. C'est une caractéristique de la chimie française dans les années 1950-70. Les universitaires se répartissent les domaines d'après les chapitres du PASCAL (l'encyclopédie en français de Chimie Inorganique, le pendant du GMELIN allemand) : les oxydes de fer chez Chaudron puis chez ses élèves à Vitry, les nitrures à Limoges, la zircone à Orléans, les verres et métaux de transition pour Hagenmuller à Nantes (je crois puis Bordeaux, il faudrait interroger Paul Hagenmuller). Chaque élément est pris par les maîtres d'un lieu et ses " descendants ".

BBV : Comment êtes vous arrivé au laboratoire de Collongues ?

PhC : C'est Mme A.M. Antony qui m'a envoyé chez Collongues. Il m'a confié la conduction protonique. Le choix du sujet répondait à une incitation industrielle. Il faut dire que le laboratoire Collongues avait de gros moyens pour la synthèse de cristaux. Collongues était très ouvert, très souple et savait établir des relations de confiance avec les industriels. Ce n'étaient pas toujours des liens formalisés, par écrit, plutôt des accords qui formaient un réseau de contre-parties. Ce genre de liens est possible à Paris car on circule d'un lieu à l'autre, on a une oreille partout. Alors que les laboratoires de provinces, comme celui de Hagenmuller, ont développé des liens beaucoup plus formels, avec des rivalités plus marquées entre des centres de recherche qui veulent avoir le monopole d'un sujet. A cet égard, Livage est plutôt du style Hagenmuller, à défendre son pied carré. Collongues ne faisait jamais de rétention d'information, il était vraiment un meneur d'équipe.
Pour revenir à la conduction protonique Collongues avait reçu de l'argent de l'Air Liquide à la suite de la parution d'un article par Richard Brook alors à Leeds (qui par la suite est allé dirigé le département céramique du Max Planck Institut avant de devenir directeur du département céramiques à Oxford et de l'EPSRC, l'équivalent anglais du CNRS) et J. S. Lundsgaard, un danois qui a fait son PhD chez Brook avant de travailler à Odensee puis de monter une petite société (J.S. Lundsgaard, R. Brook, J. Materials Science 9 (1976) 1061)

BBV : Quel était l'intérêt industriel de la conduction protonique en 1975 ?

PhC : Elle était alors envisagée comme une alternative énergétique. On était après le premier choc pétrolier et les énergies propres étaient désirées. C'est l'époque de la mise au point du Nafion© par Dupont pour les piles à combustibles du programme Gemini et l'on voulait des matériaux susceptibles de fonctionner à plus haute température pour éviter les catalyseurs de platine. Pour l'Air Liquide l'intérêt était de pouvoir réaliser des capteurs de teneur en hydrogène stables, rapides pouvant fonctionner à une certaine température. Avec la Thonson-CSF (G. Velasco et M. Croset) je developpais plus tard de tels capteurs " microioniques ". Ce fut les premières réalisations d'un équivalent ionique de la microélectronique (La Recherche, 148 octobre 1983, 1292-1296). En Europe nous étions deux à travailler sur la conduction protonique, moi (!) et le laboratoire d'Odensee au Danemark dirigé par Johs Jensen, le " patron " de J. S. Lundsgaard. Avec Jensen j'organisais en 1981 un colloque à l'Ecole Polytechnique où je venais d'arriver pour monter une équipe de Chimie du solide formellement avec J. P. Boilot, mais qui était encore pour quelques années surtout à Limoges où il avait été nommé professeur dans la fournée du déménagement de l'Ecole de Céramique. Ce colloque était financé par une fondation danoise et l'Ambassade de France. Il fut le premier d'une série qui après internationalisation continue encore. Johs Jensen fut vraiment la cheville ouvrière du développement des travaux sur les piles à combustibles " propres " en Europe.

BBV : En quoi consistait essentiellement votre travail dans le laboratoire Collongues ?

PhC : J'y faisais essentiellement de la synthèse et de la diffraction des RX, les analyses de diffusion diffuse de RX étaient faites à Orsay avec G. Collin et J. P. Boilot, les études Raman et IR à Thiais avec G. Lucazeau et la diffusion de neutron à l'Institut Laüe-Langevin qui venait d'ouvrir avec A. Dianoux. Faire des cristaux de zircone, c'est simple. Pour fondre l'oxyde de zirconium à 2600°C, on couple avec des copeaux de zirconium la poudre : on met l'ensemble dans un creuset, lui-même dans un suceptor qui fournit le champ électromagnétique (MHz). Les copeaux de zirconium sont portés à haute température et ils s'oxydent avec l'air et donne une bulle de liquide qui fait fondre la poudre qui se trouve autour. Pour faire des cristaux d'alumine-bêta c'est plus compliqué car l'aluminium est trop exothermique. On est obligé de chauffer avec un morceau de graphite mais le graphite se met en position de couplage minimum sous l'effet du champ électromagnétique, et il ne chauffe pas. Aussi faut-il le maintenir avec une baguette d'alumine, avec le nez à 15 cm au dessus de quelque chose qui est à 2000°C. Une fois sur deux cela explose. On portait des grands masques comme les sidérurgistes qui ouvraient les poches d'acier (Je pense que c'est un apport de Collongues qui connaissait bien le milieu en tant que responsable de la Société des Hautes Températures et Réfractaires). On arrivait à fondre pendant une heure, à stabiliser et faire croître des cristaux. Cela c'est la technique " traditionnelle " française pour faire l'alumine-bêta, celle qui a été mise au point par Y Lecars. Les américains d'Oak Ridge, de Ford disposaient de gros creusets en iridium ce qui permettait un travail plus facile.
Par rapport à Y Lecars et le thésard suivant Jacques Antoine ce que j'ai apporté c'est le flux à haute-température. La base pour obtenir la phase souhaitée c'est la température. Le diagramme de phase, pour nous, céramistes, c'est le B.A.BA. Il donne le chemin, qui permet d'optimiser la température la plus basse pour obtenir une phase donnée. On ne part pas de la composition à obtenir pour faire une synthèse, on se " promène " dans le diagramme de phase. La technique pour faire l'alumine-bêta riche et l'alumine beta '' (à 1.66) c'est faire un flux à 2000°C avec NaAlO2 qui lui peut être attaqué chimiquement (par HCl) pour récupérer les cristaux d'alumine-bêta riche ou d'alumine béta''. C'est donc un savoir de céramiste qui utilise la synthèse cristalline. C'est grâce à la formation de l'Ecole de Céramique qui était encore restée une école technique plus que scientifique jusque dans les années 1950. Je dois être un des derniers à avoir recueilli l'héritage de millénaires. On avait encore un vieux professeur C. A. Jouenne qui avait été formé avant la guerre 14 dans la tradition ancestrale. On apprenait à " manger les argiles " pour reconnaître le taux de matières humiques, les teneurs en calcium, sodium, en sable, à goûter les céramiques pour mesurer les porosités, etc. On apprenait à reconnaître les fonctions organiques au nez. La céramique, c'est l'alchimie d'autrefois. Elle se perd.
J'ai quitté la synthèse dans les années 1992-94 quand je suis revenu de l'ONERA parce qu'il n'y avait plus d'argent. La synthèse cela coûte cher et il faut deux ou trois ans pour faire un produit. Et en plus ce n'est pas très valorisé au CNRS. Au CNRS (et à l'université) les chimistes du solide ne font presque plus de synthèse, ils ne font plus vraiment leur premier métier. Ils font le travail des physiciens qui eux repassent après pour " améliorer " les modélisations des chimistes. Il est vrai que les composés d'aujourd'hui sont " compliqués " à faire et à comprendre pour ceux qui n'ont pas une triple culture générale : de chimie minérale et organique/polymères et de physique. L'ONERA jusqu'aux années 90 permettait de faire de la " belle " synthèse de matériaux ayant des finalités militaires. Ceci à pris fin vers 90-92 avec la chute puis l'effondrement des crédits -et des motivations, le bottom-up- de recherche militaire et les bouleversements des structures capitalistiques et industrielles de l'armement.

BBV : Quand et pourquoi êtes vous allé à l'ONERA ?

PhC : J'y suis allé en 1989. Il n'y avait plus d'argent à Polytechnique. La mode avait tourné : les matériaux n'étaient plus privilégiés, la biologie intéressait davantage. Moi je voulais faire des vrais matériaux, pas de la chimie en flacon. J'ai regardé un peu autour de moi. A l'ONERA, ils cherchaient quelqu'un pour redynamiser les matériaux non-métalliques, l'ancien responsable étant parti pour la Société Aérospatiale. L'ONERA fonctionnait bien : ils faisaient de la recherche amont, bien financée par l'armée et ils allaient assez loin en développement. Il y avait une grande mobilité car souvent les équipes partaient dans l'industrie avec leur projet quand il passait en phase industrielle. J'y ai développé l'usage du sol-gel et des précurseurs polymériques pour réaliser des composites à matrice céramiques thermostables (à fibres C et SiC) et aussi les premiers composites tout-oxide et à gradient de propriétés pour l'absorption micro-onde (pour rendre les missiles invisibles au radar). Avec J. C. Badot on était les premiers à développer la spectrométrie d'impédance complexe pour comprendre la mobilité des ions dans des superconducteurs ioniques en l'occurrence protoniques. On obtenait des résultats comparables à ceux que l'on pouvait extraire de la RMN ou de la diffusion neutronique. Ceci me donnait le savoir-faire et les outils conceptuels pour aider à lancer à l'ONERA l'étude des matériaux absorbants les microondes.

BBV : En quoi consistaient vos travaux sur le sol-gel ?

PhC : Le premier article sur le sol-gel " français " je l'ai écris en 1974 et il est paru en 1975. Quand j'étais à la Thomson avec Monsieur Hildebrand, un chimiste remarquable rescapé du camp de Penemund (les V2 de Von Braun !) on m'a fait travailler sur un projet de lunettes pour pilotes des Mirages de la Force de frappe nucléaire. Il s'agissait d'avoir une obturation d'une fraction de seconde pour éviter l'aveuglement par le flash de la bombe. Les Américains avaient mis cela au point aux Laboratoires Sandia (Albuquerque) et le gardaient secret ; mais des renseignements avaient été " récupérés". La publication de la première utilisation pensée, voulue, du sol-gel concerne un mélange de titano-zirconate de plomb et de lanthane le PLZT (par G.H. Haertling, C.E. Land, G.S. Snow). Les propriétés ferro-électriques permettent de faire l'obturateur : on applique un champ électrique entre deux polariseurs, la lumière qui a été polarisée ne peut pas passer et cela se ferme en moins d'une milli-seconde. Pour faire cela, il faut une céramique transparente diélectrique avec des propriétés ferro-électriques particulières. Il faut un rapport particulier de zirconium et de titane mélangés intimement avec une homogénéité à l'échelle quasi-atomique pour que la transparence soit parfaite afin de ne pas gêner la vue du pilote, déjà soumis aux fortes accélérations (plusieurs g). Sandia, un labo quasi-militaire dans le Nouveau-Mexique, a fait le mélange à partir du liquide (la fabrication a été je crois reprise par Motorola pour les mémoires optiques). Mais la voie liquide inorganique ne donnant pas satisfaction ils ont pris des précurseurs alcolates (alkoxides) qui, en plus, ne coûtaient pas cher à l'époque. C'étaient des intermédiaires pour préparer des catalyseurs pour la grande industrie des polymères ou pour fabriquer certains alcools. On les vendait par bidon d'une quinzaine de gallons pour le même prix qu'aujourd'hui la bouteille de 75cl (environ 500F) et pour une qualité souvent supérieure.
Bref, à la Thomson on a fabriqué des obturateurs pour une cinquantaine de pilotes de chasse, puis quand les crédits militaires ont chuté, la Thomson a abandonné le projet et c'est le CEA-LETI-Crismatec (je crois Laboratoire d'Etudes des Techniques Electroniques) qui l'a poursuivi.

BBV : Y-a-t-il eu des applications civiles de ces travaux ?

PhC : Des mémoires optiques, la télévision Vidicon et des DVD ont été étudiés dans les années 1980 par Thomson-CSF. On stocke presque à l'échelle atomique du dipôle ferro-électrique. A la Thomson j'avais mis au point une des techniques de Sandia qui permettait d'obtenir des céramiques PLZT transparentes sans utiliser le frittage sous charge. Cela diminuait le coût de fabrication, étape indispensable pour les applications civiles. Ce type de mémoire reste à l'étude pour ses hautes capacités et sa permanence dans le temps. L'effacement est par-contre difficile. Pour ma part, j'ai utilisé le sol-gel pour faire l'alumine-bêta au potassium, qui frittait mal (Material Research Bulletin, 15 (1980) 1817-27). Cela permet d'avoir des poudres ultrafines qu'on peut fritter à plus basse température et d'obtenir un matériau avec moins de porosité, ce qui est indispensable pour faire des mesures. J'ai ensuite développé ce thème sol-gel à Polytechnique, en particulier pour les NASICON, l'alumine, la mullite, etc. On faisait de la mesure de conductivité à impédance complexe, méthode mise au point par les électro-chimistes. Lorsque j'ai développé cela chez Collongues, puis à Polytechnique pour les NASICON, c'était très nouveau pour les solides. Il faut dire que la conductivité des superconducteurs ioniques est égale à celle des acides et donc la transposition était facile.

BBV : Comment décririez-vous la chimie des sol-gel ?

PhC : Le sol-gel existe dans la nature (tout existe dans la nature !), ma formation de géologue acquise comme hobby d'adolescent m'a beaucoup servie) ; l'argile est un matériau nanométrique que l'on met en œuvre par sol-gel. Les céramiques traditionnelles sont des sol-gel, toutes les propriétés de plasticité, de rhéologie, de réactivité,… en découlent. Et il y a une abondante littérature que les chimistes ignorent ou veulent ignorer pour présenter leurs travaux comme des nouveautés. Il s'agit d'une littérature des années 30 à 50 - Norton, Jouenne etc. -. Littérature en allemand, en français mais peu en anglais. Livage a voulu présenter le sol-gel comme quelque chose de nouveau. Ma position à moi c'est que le sol-gel est la transposition de la technologie céramique traditionnelle à de nouvelles compositions par une étape qui est la synthèse chimique d'objets nanomètriques, comme les particules d'argile, où comme la proportion d'atomes à ou près de la surface est dominante développent des propriétés analogues permettant une mise en œuvre sol-gel.
La chimie des sol-gels a démarré à l'époque où on découvrait que, à partir de précurseurs organiques, on pouvait faire de la chimie inorganique. A mon avis elle se situe au confluent de quatre courants :
La céramique traditionnelle ; Sandia, le laboratoire américain avec J. Haertling qui a aussi inventé le Rainbow©, (l'usage de la piézoélectricité marié à un métal ou un polymère pour faire des actuateurs complexes comme battre les ailes de drones ou autre) ; Rustum Roy, de Penn State qui a fait de la chimie des silicates dans les années 50 ; et enfin Joe Mazdiyasni de USAF-Base et B.E. Yoldas, un Américain qui a travaillé je crois aussi avec Larry Hench, l'inventeur des applications en biologie du sol-gel il y plus de vingt ans. Des verriers (comme Dislich et la Société Schott dans les années 40-50, les japonais S. Sakka et K. Kamiya, plus tard) avaient brevetés et étudiés l'hydrolyse de la silice, mais sans sentir de mon point de vue la richesse du procédé.

BBV : Quand et pourquoi êtes vous revenu au CNRS ?

PhC : Pour deux raisons : la première j'aime changer, travaillant avec une petite équipe j'essaye de prendre les sujets " en avance " et de glisser vers d'autres quand ils deviennent " à la mode " et que les gros labo monolithique se mettent dessus. La seconde, en 1990 l'ONERA comptait plus de 2200 personnes, aujourd'hui cela doit être 1600. Les crédits - et donc les perspectives - commençaient à chuter : plus de grands projets où l'on peut partir de l'amont pour identifier des verrous " conceptuels " ou de synthèse, les résoudre et ensuite aider au développement. Je suis revenu au laboratoire où 15 ans plutôt j'avais appris la spectroscopie de vibration pour y développer la spectroscopie Raman des matériaux et nanophases, l'Imagerie Raman de systèmes en fonctionnement. Entre 1992 et 1996 j'avais deux employeurs, le CNRS et un temps partiel à l'ONERA où je menais encore des programmes de synthèse. Maintenant je reste conseiller à l'ONERA et cela se limite à des prestations intellectuelles, à contribuer à l'encadrement de thèses, à identifier les informations, les sujets utiles pour mes collègues de l'ONERA dans les congrès où je vais ou les visites.

BBV : Etiez vous libre de publier quand vous étiez à la Thomson et à l'ONERA ?

PhC : Savoir quel est le degré de publicité à donner à des informations, c'est un art qu'on apprend sur le tas. On apprend à gérer les échanges, à juger d'une situation, à discuter avec des brouillons, etc. C'est très important car c'est une garantie de réussite.
Il faut vraiment encourager la mobilité entre industrie, centre de recherche et de développement et laboratoire académique. On connaît les gens, on connaît la configuration, on sait alors cheminer de concert pour un objectif précis, bénéfique de part et d'autre.

BBV : Et les brevets ?

PhC : Ce sont les industriels qui les prennent. Il faut qu'il y ait de la technologie pour qu'un brevet soit efficace. Plus un brevet est généraliste plus il est facile de le détourner. Ce sont les derniers brevets d'une filière, liés au produit commercialisé qui " rapportent ", les premiers servent à " tenir la filière ". Et de toute façon un brevet a la vie courte, 20 ans dans le domaine de matériaux c'est très court.

BBV : Avez vous des liens privilégiés avec des étrangers ? En particulier fréquentez-vous les meetings de la MRS ?

PhC : J'ai participé assidûment et avec plaisir au meeting annuel de Boston pendant les années 85-95. Maintenant pour des raisons familiales la date ne tombe pas très bien. Je vais assez souvent à l'E-MRS de Strasbourg en juin et régulièrement aux meetings de l'American Ceramic Society, le principal vers le 1er mai, car il y a beaucoup d'échanges et celui de Cocoa Beach en janvier, même s'il y a des sessions fermées, " secrètes ", on apprend énormément. Les e-mail permettent de travailler ensemble au quatre coins du monde.

BBV : Avez vous noté des différences de style de recherche entre les divers pays ?

PhC : Certes oui. En particulier le contraste entre la France et l'Allemagne est saisissant quand il s'agit de monter des projets communs. En Allemagne, seul le chef d'un territoire bien défini peut prendre des décisions mais il est compétent. En France, c'est plus souple mais les compétences ne suivent pas forcément. Les coopérations avec les Asiatiques (Indiens, Vietnamiens, Japonais) doivent se faire grade à grade, en respectant la hiérarchie et on doit prendre son temps. Il faut savoir être lent. Avec les Américains, c'est tout le contraire ; il faut être rapide, même si c'est une mauvaise solution. En Amérique, le temps est une donnée de la recherche, mais pas en France.

BBV : Et la différence est-elle aussi importante dans les relations avec l'industrie ?

PhC : En France, l'industrie est maintenant à la marge. Quand l'Etat était un partenaire industriel il prenait en charge la recherche sur le long terme. Il y a eu des années fastes de 79 à 83 (cela a commencé avant l'arrivée de Chevènement), où l'Etat et l'armée ont fait de gros investissements : c'est l'époque des lancements du Rafale, du porte-avion, des missiles de croisière avec les problèmes de furtivité, d'Ariane, d'Hermès, etc. Mais après le départ de Chevènement, cela a été le commencement de la fin. Maintenant le militaire ne finance plus de recherches sur le long terme : on se pose les questions quand le problème survient sur le prototype. On fait du bottom-up et on dédaigne le top-down. Toute la charge de la recherche à long terme retombe sur le CNRS voire l'université. Et les universitaires français (hors écoles d'ingénieurs) ne veulent pas faire de technologie ou n'y connaissent rien. Alors qu'aux Etats Unis et surtout au Japon, ils ont un pied dans l'industrie, un pied dans l'université et la symbiose est possible.

BBV : Que pensez-vous des initiatives du CNRS pour encourager les liens entre recherche académique et industries ?

PhC : Elles viennent plus de la direction que des commissions. Les détachements sont une formule prometteuse : on touche 15% de salaire en plus pour un détachement dans l'industrie et 30% dans le militaire. Mais la difficulté c'est le retour. Les commissions trouvent bizarre que l'on revienne ; on se retrouve sans salaire pendant 4 mois ! Enfin, maintenant le plus souvent les représentants industriels dans les commissions ne sont pas ceux qui sont dans une position de pouvoir dans leur propre milieu. Ce n'était pas le cas il y a 30 ans.

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Entretien avec Philippe Colomban, par Bernadette Bensaude-Vincent, 18 février 2003

Lieu : CNRS Laboratoire de Dynamique. Interactions et Réactivité (UMR7075 CNRS & Université Pierre et Marie Curie), 2 rue H. Dunant, 94320 THIAIS, France

Support : enregistrement sur cassette.

Transcription : Bernadette Bensaude-Vincent.

Édition en ligne : Sophie Jourdin.

ENDO Morinobu, 2002-08-26

Sacha Loeve — 2011-06-07T20:19:40Z

Morinobu Endo, né en 1946, est Professeur à la Faculté d'Ingénierie de l'Université de Shinshu à Nagano (Japon). Après un Master's degree à l'Université de Shinshu, et une Thèse en ingénierie à l'Université de Nagoya, il intègre l'université de Shinshu comme chercheur, Professeur associé puis Professeur en 1990. Il y fonde un laboratoire au sein du Department of electrical and electronic engineering. Ses recherches sont dédiées au carbone sous ses diverses formes ; elles vont du fondamental (propriétés physico-chimiques du carbone dans ses multiples formes allotropiques : graphite, nanotubes, carbone nanoporeux) à l'appliqué (fibres de carbone, composés d'insertion au graphite pour batteries et condensateurs). Morinobu Endo est notamment un pionnier des nanotubes de carbone (caractérisés en 1974 lors d'un travail effectué en collaboration avec Agnès Oberlin en France à la Faculté des sciences de l'Université d'Orléans). Ainsi en 1991, date généralement retenue pour la découverte des NTCs par Sumio Iijima, Morinobu Endo avait déjà développé et breveté un processus de fabrication donnant lieu à des usages industriels des NTCs comme composés d'insertion dans des accumulateurs lithium-ion (batteries d'usage courant pour l'électronique portable). Morinobu Endo a co-dirigé des initiatives pour la coopération université/industrie au sein de la Japan society for the promotion of science (JSPS). Depuis 2004, il préside la TANSO (Japan society of carbon). Membre du comité de rédaction de la revue Carbon, il est auteur d'une trentaine de livres sur la science du carbone et de plus de deux cent articles. Ses recherches lui ont valu de nombreuses distinctions : Carbon society of Japan Award, (1995) ; Charles E. Pettinos Award (American carbon society, 2001) ; Lee Hsun lecture series Award (Institute of metal research of China, 2002) ; ShinMai Award (Shinmai Bunka foundation, Japon, 2003) ; Ishikawa Award (Ishikawa carbon science and technology promotion foundation, 2003) ; Medal of achievement in carbon science and technology pour la découverte et la synthèse des nanotubes en 1974 (American carbon society, 2004) ; The Minister of education, culture, sports, science and technology prize for contribution to intellectual Cluster (Japon, 2005) ; Honorary citizen of Suzaka-city (2006) ; Small Times magazine best of small tech lifetime achievement Award (2006) ; JPA lectureship Award (2007).

BERNADETTE BENSAUDE-VINCENT (BBV) : In which discipline did you take your degree, and your PhD ?

MORINOBU ENDO (ME) : I started 30 years ago. I graduated from Shinshu University in 1971. Then took a Master in Electronics. I spent one year in a company, Statch. Then I came in this university in 1972 as a Research Associate.

BBV : So you spent your entire career in this University. How and when did you come into carbon science ?

ME : I became interested in carbon as a research assistant. At that time, carbon was considered as a dirty, dusty science, in comparison with the more attractive semiconductor science. But I found it promising.

BBV : Were there people already working on carbon here in the early 1970s ?

ME : Yes my professor Tsumeo Koyama was working on carbon. He was aged already but he asked me to incorporate here.

BBV : Why did you find carbon so promising ?

ME : I read a few pioneering papers by S. Mrozowski and by M. S. Dresselhaus. This encouraged me. At that time, there was an activity in carbon fibers based on Polyacrylonitrile (PAN) for aerospace industry. Industrial companies were most active in this field, especially Toray. There was a concern for new methods for preparing this promising material because PAN-based fibers were high-cost fibers. Professor Koyama asked me to prepare carbon fiber from vapor. This is a carbon fiber directly grown from the decomposition of hydrocarbons such as benzene. Vapor Grown Carbon Fibers (VGCFs) were totally different from the commercial PAN fibers. PAN Fibers are continuous while VGCFs are shorter. They have a unique structure. In the early 1970s I was able to prepare the fiber without understanding the mechanism at work, or what elements were essential.

BBV : So you had the technique but no knowledge of its structure and properties.

ME : Fortunately I had a chance to work in France with Madame Agnès Oberlin at the CNRS in Orléans.

BBV : How did you come in contact with her ?

ME : When I was a Research Associate in this university, I wrote a paper in Japanese showing that very beautiful carbon fibers can be grown by gas pyrolysis. A nice Japanese professor who was a good friend of hers, introduced my work to her. He invited her in Japan as a visiting professor and she asked to meet with me. I traveled to France with my fiber in 1974 and I worked in her laboratory for one year. In Orléans they had an electron microscope in 1973. I found that there were small opaque particles at the tip of the fibre (figure 1). In order to use the electron microscope it was necessary to use very thin fibers. For that it was convenient to stop the growth process at an early stage. I thus found that the fiber had an hollow core and later in the growth process the diameter of the fiber increased. Here on this picture you can see the particle. I found with Agnès Oberlin that this particle was iron. This result was published in France in 1976 in a paper entitled “Filamentous Growth of Carbon Through Benzene Compounds” (Journal of Crystal Growth 32 (1976) 335). In this paper we argued that VGCF had a “hollow core” which is the strongest part of the fiber. It never breaks when the fiber breaks. Sometimes you have cross-linkings of the fibers. Here just at the center of the fiber you can see the single wall nanotube (figure 2).

Figure 1. “Hollow core” in a vapor grown carbon fiber, 1976

Courtesy of Morinobu Endo.

Figure 2. Cross-linked single-wall nanotubes, 1976

Courtesy of Morinobu Endo.

BBV : Nanotubes ? You did not name it as such in 1976 ?

ME : We called it “hollow core” or “central tube”. Here you can see the fine particles at the tip (figure 3). By using bright- and dark-field image I found that they were Fe3C. This is the chemical product after cooling. At the end of the growth the particles should be iron. I suggested a growth model : the fiber first forms over this fine particles of iron then grow in the radial directions.

Figure 3. “Central tube” in the core of a vapor grown carbon fiber, 1976

According to Dr. Endo, this “central tube” is a double-layered carbon nanotube. Courtesy of Morinobu Endo.

BBV : Where this iron came from ?

ME : We were able to understand where it came from. We used a special sand-paper as a substrate. Without this sand-paper, no fiber. With this sand-paper that we used in France, we got beautiful fibers. We analyzed the electron barriers and we found that it was Fe2O3. Iron oxide coming from the sand-paper proved to be very important as a catalyst to generate the carbon fiber.

BBV : So you understood the mechanism when you came back to Japan ?

ME : I came back in 1975. I clearly described how the fiber grows, including the seeding methods, in a paper published in 1988, “Grow Carbon Fibers in the Vapor Phase” (American Chemical Society - ChemTech 18 (1988) 568-576). In a way this fiber grows in two steps : 1) this very thin fiber, the hollow core ; 2) the secondary process is the thickening of the fiber.

BBV : Do you mean that it took you about 10 years to understand the process ?

ME : No in 1988 it was already established. It is a review paper. So we put the small particle on a substrate (we used a ferrocene). Then we can grow that fiber as you can see on the screen (figure 4). As a result we got this very nice fiber. From an academic point of view, it was a full success because I was able to grow the fiber, to reproduce the product (there were many observations of such fibers but nobody could reproduce them). I clarified the growth mechanism – that the small iron particle acted as a catalyst for the decomposition of hydrocarbon, that the thin hollow tube grew then thickens to a carbon fiber. As a result we got a fiber with a diameter similar to that of the PAN fibers prepared by Toray.

Figure 4. Endo's vapor grown carbon fibers

Courtesy of Morinobu Endo.

BBV : Did you collaborate with industry in these years ?

ME : Yes we had collaborations. Showa Denko tried to develop this VGCF. But its productivity was very low. Because we put a substrate the growth rate was too slow. We tried to reduce the cost by using a continuous process. But in the same period the cost of the PAN fibers was drastically reduced so that we could not compete. Our VGCF are just beautiful fibers.

There had to be a breakthrough.

BBV : What kind of breakthrough ?

ME : I developed another method. This is the Endo-Japanese patent. I introduced the catalytic particles, which are derived from organic-metallic compounds such as ferrocene, into the reactor, in the three dimensions. The main difference is that there is no substrate. Here in this region, the particle reacts with the hydrocarbon and makes the hollow tube (figure 5). On the hollow tube then the deposition takes place. The process is in hysteresis. As a result we can get another type of fiber. It is totally different. This one is very competitve and commercialized.

I should add that at the early stage of the growth of the fiber, this is a carbon nanotube grown by a catalytic process. So it is now possible to grow carbon nanotubes by this method.

Figure 5. The Endo-Japanese patent, 1987

Courtesy of Morinobu Endo.

BBV : So you have already answered my next question : “How did you move from carbon fibers to carbon nanotubes ?” In fact, you prepared carbon nanotubes before this name came into use.

ME : We used to say “hollow core”. I get a little bit irritated about how the story is told. Here are my laboratory notebooks written in France (1974-75). Agnès Oberlin signed them. You can see a two-layered carbon nanotube. This is the TEM (Transmission Electron Microscope) photograph. I envisaged the possibility of very thin carbon nanotubes. Here you can read “mince cylindres” (thin cylinders). We had found the possibility of very tiny tubular structures.

BBV : Why did Mrs Oberlin signed this notebook in 2002 ? Was there a priority controversy ?

ME : Because I visited her in France last June. And because people said you should get the evidence that you had observed such nanotubes in 1975.

BBV : So nanotube was not discovered in 1991 by S. Iijima in his paper in Nature as people usually say..

ME : People say that Iijima clarified the structure of nanotubes. But Endo observed them in 1974. This is a recent understanding. I clarified the growth mechanism and the mass-production of a thick fiber out of a very thin cylinder.

BBV : The irony is that I came in touch with you through MIT thanks to Millie Dresselhaus and not through your French connection although I live in France.

ME : Mrs Oberlin lives near Montpellier in a mountainous area. She is now 75 year old. She gave me many evidences that I observed nanotubes in 1975.

BBV : Do you also know Bernier in Montpellier ?

ME : I know him but I am not as friendly with him as with Mrs Oberlin. He is a newcomer in science while I have been in carbon science for 30 years.

In my process the carbon nanotube is essential to grow the fiber but we can easily extrude the carbon nanotube. Now we can easily expand the technology to make carbon nanotubes. Several companies such as Showa Denko manufacture carbon nanotubes based on my method. Recently in order to make electronic circuit with carbon nanotubes people used this catalytic process. They put the small particle of iron on the electrode and expose this substrate to hydrocarbon to grow the nanotube. Here is a nanotube paper I am not too happy with ; they don't cite my old paper. Many people are not fair. They only take into account recent science and never go back to older papers…

Anyway this catalytic process is now applied in the mass-production of carbon nanotubes, whether they have single wall or double wall. To me it is very important to produce carbon nanotube and use them for practical applications. So coming back to your question about the date of discovery of nanotubes : in 1975 there was no practical use of carbon nanotubes. The interest was in carbon fibers. So we designed a process to get a thicker fiber.

BBV : When did the interest shift from fibers to nanotubes ?

ME : Carbon nanotubes quickly developed after the discovery of C60 in 1985. But they still have no practical application because they are still high cost. For carbon fibers, by contrast, we already had the technology, the know how to produce them. However my nanotubes are already commercialized for Lithium ion batteries since the late 1980s (figure 6). It is useful to provide safe small-size batteries for mobiles and camcorders. For safety reasons it is better to use only Li+ instead of metallic lithium. For this, we need to intercalate carbon at the anode. Almost most of the Lithium ion batteries manufactured in this country use my fiber in the anode. It is the only material that can work in this application. There is no alternative, no substitutional material. Only my product. So finally what the Japanese companies produce is based on my carbon nanotube.

Figure 6. Mass-producing and commercializing Multi-wall carbon nanotubes since 1988

Courtesy of Morinobu Endo.

BBV : Which Japanese companies manufacture the Li-ion batteries with your patent ?

EM : Many companies (Sony, etc). But, now this is not my patent. It is the company who manufactures my fiber who owns the patent. Only the production system is my patent. And I am happy with that. Even French companies like Alcatel who have a battery division need to use my fiber. Recently we got the allowance to export this material abroad. The Ministry of Industry (MITI) gave us permission to export this material. Now Alcatel and a number of American companies can use my material.

BBV : Do you mean that a Japanese company cannot export one its products without permission from the Ministry of Industry ?

ME : It is only for strategic materials with potential military applications because it is a strategic material for military uses (although I don't know which one). In such cases we are under the control of ICOCOM. Anywhere we can get such allowance.

BBV : Coming back to the earlier period of carbon science, what was your reaction and the reaction of your colleagues in 1985 to Curl's, Smalley's and Kroto's paper on the fullerene structure ?

ME : I felt very nice because it was familiar to me. I was very excited with that kind of nanosize particles.

BBV : After this publication did you get more funds to start research programs on nanotechnologies ?

ME : There was an impulse to work on nanotechnology. And the government gave us substantial funds. 95% of the research budget went to nanotechnologies.

BBV : If you get such substantial funds from government do you also have support from industrial companies ?

ME : Most of my research is supported by industrial companies. Only a small part of the basic science is supported by MITI. For carbon nanotubes we work in close collaboration with industrial companies. We have a very nice cooperation. We are always aware of pratical purposes. So in my research science and applications are closely intertwinned. It is our policy.

BBV : But industrial companies have their own research laboratories ?

ME : Yes, we collaborate with them. Presently I have about 100 collaborators who run joint projects with me. More exactly, I should say 50 researchers who come to join me. It becomes big science when you want to reach the commercial applications because you have to do all kinds of tests : safetyness, production cost, optimizing the size, the diameter of the fiber, its packing...It requires a lot of time and a lot of money. The PAN-fiber, for instance, was designed in 1965 and Toray spent more than 20 years of R&D before the commercialization of PAN fibers in the early 1990s. For the batteries we took 7 years.

BBV : Do you have a kind of division of labor with Research conducted in academic laboratories and development in industrial laboratories ?

ME : We have a lot of feedback. For any specific material we need a lot of time and money. Carbon fibers still need a lot of additional technology for commercial mass-production.

BBV : So your financial resources come both from industry and from government ?

ME : Fortunately we get a lot of money from industry because I contributed a lot to industrial applications. We also get money from the Ministry of education for scientific development. I am acting as a bridge between science and industry, and also as an interprter for tax-payers. We do a lot of coordination with social demand, between university and industry and also of education for industry. We are very busy.

BBV : In your career is there a close connection between teaching and research ? In particular how important was the book on carbon that you co-authored with Stan Mrozowski and Millie Dresselhaus ?

ME I have been deeply encouraged by Millie Dresselhaus. Our book was not intended as a textbook. Rather it was a review book. When it was published in 1996 most of the people were rather interested in fullerenes. This book triggered the interest in nanotubes. The publisher Pergamon is very active in carbon science.

BBV : As historians of science and technology, we learn a lot from success but failures are even more illuminating for us. Would you tell mes about a case of failure in your career or in your field ?

ME : I don't remember any project of mine which failed. I spend a lot of time selecting my research projects. It is important because lot of Japanese companies trust me. I have no right to fail. Every problem has a solution. In a sense the tiny cylinder of the nanotube is a miracle. How can we control particles at the nanosize !

Carbon is an old but new material. Professor Kroto who got the Nobel Prize in 1986 said in his Nobel address : the 21st century will be the century of carbon. I believe that. Carbon is a key material. Carbon fibers and carbon nanotubes are vital in three respects : for energy, fuel cells in particular ; for information technology (mobiles and computers) ; for environment, especially for the purification of air and water. The question of water is crucial : 2 million of people die every year from impure water and 20 million are sick from impure water.

BBV : How can you use carbon for the purification of water ?

ME : It is possible. We can use activated carbon to take off bacteria. Developing countries need clean water at a reasonable cost. So carbon is and will be in the future a key material. My own research is focussed on carbon nanotubes, their action, their preparation, growth mechanism, control of the structure and applications. We study batteries, new devices for energy storage in new cars, devices for water purification for the developing countries.

BBV : You mean that in one laboratory you can afford to conduct all these projects altogether ?

ME : Yes, as they are all related to carbon. Carbon and its properties are important everywhere. I'll show you a very nice table. Carbon is not the most abundant on the earth like silicon. It is only 0.04% of the material resources. But carbon is localized, concentrated in some places so that it is easily accessible and easy to extract.

BBV : How many people are working in your laboratory ?

ME : I have 25 people including students and post-doc. We have ten research projects. They come from materials science, electronics or electrical engineering, physics and two post-doc chemists.

BBV : Do you have financial constraints for the purchase of laboratory equipment ?

ME : We have few constraints to buy instruments. For instance, we have got a very sophisticated Transmission electron microscope, all computerized (figure 7). It is a unique model made by a Japanese instrument maker. It has three functions : EDX (Energy-dispersive X-ray spectroscopy), EELS (Electron energy loss spectroscopy), and Mapping.

Figure 7. Endo's Lab TEM

BBV : Did you acquire it with industrial funds or state money ?

ME : It was state money. We also have various analytic instruments for carbon materials such as STM (scanning tunnelling microscope), TGA (thermal gravimetric analysis), FE-SEM (Field emission scanning electron microscope), Thermal conductivity analyser, Raman, XRD (X-ray diffraction), pore distribution analyser, etc.

BBV : Do you have a lot of routine reporting to your sponsors ?

ME : We have obligations towards the university. The annual report mentions how much money I get from the Ministry of Education. But how much support I get from industry this is included in the global amount of subsidies provided to the university. The annual report does not mention openly how much Endo gets from industry. I think I am one of the most funded.

BBV : Publishing or patenting ? What is the priority ? Which one is the most important for the credit and reputation of a laboratory in materials research in this country ?

ME : It is now the Japanese policy that patenting and publishing should run parallel. For me publication is more important. But as part of the national community I should keep a balance between publications and patents. The Ministry of Education recognizes and rewards patents.

BBV : Do you file patents in your own name ?

ME : It depends. If the research project was financed with state money as a national project, then the patent is a state patent. If the patent comes out of a project financed by industry or by the university then it is your individual patent.

BBV : Who gets the royalties ? you or the university ?

ME : We have a judge who decides. If we invent a product with funds from the unviersity, most of the time it belongs to ourselves.

BBV : The patent on vapor deposition carbon fiber belongs to yourself ?

ME : Yes it is my patent.

BBV : Do you have international collaborations : in which countries ? How much do they matter ?

ME : With Millie Dresselhaus, it is a private collaboration. I also have collaborations with Sussex University (U.K.) and with Mexico. In France I have friends but no more collaborations.

BBV : Did you notice differences in the research styles of various countries ?

ME : I cannot see any difference in research styles. The Japanese style is very much americanized. Or rather, our style is between the French and the American styles.

BBV : What is the French style ? And how would you characterize the American style ?

ME : American style is top-down with the state at the top. French style is rather bottom-up. In Japan it is half-half. I feel rather close to the French style but for patenting we are more like the USA. In France it is difficult to file a patent.

BBV : You have spent 30 years on one single material, carbon. But do you think that the materials generic perspective with its basic notion of structure, properties, performances and process, is useful for your research ?

ME : I think that I have a very general concept of carbon. I generalized the concept from structures to properties. Process is very important to get up with the structure in the case of carbon. Carbon science developed by studying its structures but now processing is important. You get different structures with different processes.

BBV : What aspect is the more important for you ?

ME : I am neither a specialist in processing, nor a specialist of structures. I am a carbon scientist.

BBV : What is the place of materials science in general and carbon science in particular in Japan ?

ME : Unfortunately carbon is a minor field. Semiconductor is the major field. In the minor field of carbon I should say I am number 1 or number 2.

BBV : Does carbon science attract students ?

ME : Yes many students come to work with me, because we have advanced equipment and there are job opportunities in this country : in car companies or electric companies.

BBV : Where do you locate the leading centers in the field of carbon science ?

ME : The major countries are Japan, USA, France and Germany. Then come India, then China, England and Canada.

BBV : Do you see Japan as the leader ?

No. Japan, USA, France and Germany are at the front. It depends on the field. Certainly Japan produces 70% of the carbon fibers by the aerospace applications in the USA.

BBV : Where do you locate the strengths and weaknesses of Japan ?

ME : The human network is too strong. More open competition like in the USA would be necessary. In France the system is too centralized, too concentrated.

Fin de l'enregistrement

Pour citer l'entretien :

« Entretien avec Morinobu Endo », par Bernadette Bensaude-Vincent, 26 août 2002, Sciences : histoire orale, /spip.php ?article8.

Pour citer l'entretien :

« Entretien avec Morinobu Endo », par Bernadette Bensaude-Vincent, 26 août 2002, Sciences : histoire orale, https://sho.spip.espci.fr/spip.php?article8.

Lieu : bureau de Moronibu Endo, Endo lab, Université de Shinshu, Department of electrical and electronic engineering, Wakasoko, Nagano-shi 380-8553, Japon.

Support : enregistrement sur cassette.

Transcription : Bernadette Bensaude-Vincent.

Édition en ligne : Sacha Loeve.