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WHITTINGHAM Stanley, 2000-10-30

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Michael Stanley Whittingham is one of the main figures in the history of rechargeable batteries. From the late 1960s until now he has examined promising materials for use as cathode, anode, or electrolyte. He pioneered the use of titanium disulfide for cathodes, now commonly used. He also initiated the concept of intercalation. This term refers to the insertion of positively charged ions into the cathode material. In a rechargeable battery, Li+ ions are typically inserted between layers of the titanium disulfide cathode while the battery is being charged, and then de-intercalated during discharge. That the process of intercalation and de-intercalation of ions leaves the basic structure of the host material intact, so that the charge and discharge can take place repeatedly, was an understanding forged in the 1970s and early 1980s, and in which Whittingham played an important role. He has also been prominent in the field through the editing of its main journal, Solid State Ionics, from its inception in 1981.

Whittingham went into management for a number of years (1984-1988), while the field forged ahead. Japanese companies, in particular, made great strides in the commercialization of lithium titanium disulfide rechargeable batteries. When he rejoined battery research, the Japanese lead was becoming dominant, embodied in a raft of patents.

Since 1988, Whittingham has explored further materials with a view to improving batteries still further, both with regard to size and to performance. This will not change drastically the way in which the energy economy is currently organized (for example, the electrical vehicle is not around the corner), but smaller and more powerful batteries will impact upon the cost and design of portable electronics.

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« Entretien avec Michael Stanley Whittingham », par Bernadette Bensaude-Vincent et Arne Hessenbruch, 30 octobre 2000 Sciences : histoire orale,


Entretien avec Michael Stanley Wittingham, par Bernadette Bensaude-Vincent et Arne Hessenbruch, 30 octobre 2000

Lieu : SUNY Binghamton

Support : enregistrement sur cassette

Transcription : Bernadette Bensaude-Vincent et Arne Hessenbruch

Edition en ligne : Sophie Jourdin

STANLEY WHITTINGHAM (SW) : I graduated with a PhD in solid-state chemistry (from Oxford).

BERNADETTE BENSAUDE-VINCENT (BBV) : So you were trained as a chemist, mainly ?

SW : Yes.

BBV : And why did you go to Stanford, with Prof. Huggins ?

SW : Because in my time almost everyone from Oxford came to the States for one or two years. That was expected if you wanted an academic or an industrial job. It changed a lot... 1968. And why Stanford ? It was on the West Coast, California had sun.

BBV : And your PhD was on tungsten bronzes ?

SW : That’s right : tungsten oxides and tungsten bronzes.

BBV : And how did you choose this topic ? It was not that popular ?

SW : No, I think Oxford always had a very active program in solid state. There were three or four faculty there interested in solid-state.

BBV : Who was that ?

SW : Peter Dickins was my advisor ; and J. S. Anderson was head of the department. And Jack Lunette was also there, and he was interested in the theory of calxes. So initially we were studying (?) catalytic activity, and how all that changed with the changes in the electronic properties of the material. There was a great deal of interest in the crystal structure, or rather the band structure, that controls the catalytical activity.

BBV : So it was mainly for catalysis in Britain ?

SW : Right. And we chose a very, very simple reactant : mainly oxygen atoms, and we just looked at how they recombine at the surface. And this was at the time of Sputnik and the US Air Force paid for the research.

BBV : Even the research conducted in Oxford ?

SW : They paid through their London office. Because they were interested in how various species (?) reacted outside their space ships.

BBV : So it makes sense in fact.

SW : Right. And that was the topic of my masters degree mainly. And then we looked at the same materials as catalysts potentially for gas production. And the Gas Council paid for that research. But within a few months of me starting the research, they struck natural gas in the North Sea.

BBV : And you stopped the project ?

SW : No, they said : we are not really interested in what you are doing anymore, but you have got the money. Do what you want and don’t bother us too much.

BBV : And in those days money was easy to get ?

SW : Oh yes, you turned down money in those days.

ARNE HESSENBRUCH (AH) : You mean this was the case between the oil crisis and the discovery of natural gas in the North Sea ?

SW : No, they discovered gas in the North Sea before the 1973 oil crisis.

AH : Why did the money flow easily ?

SW : Well, the money came from the Gas Council and they made gas basically from coal. So they wanted a better catalyst to convert. Natural gas avoids all that messy stuff. The rest is really history. London cleaned itself up because they stopped burning coal.

BBV : And then, when you moved to Stanford who was there ? And how was the lab ?

SW : I worked for Bob Huggins there. And that was quite a switch. In England, France, and Germany, solid-state chemistry was a respectable subject. Chemistry departments did solid-state chemistry. In the US you could count the number of solid-state chemists on the fingers of one hand. So I went to a materials science department, not to a chemistry department.

BBV : Was Huggins considered a solid-state chemist ?

SW : He was a materials scientist with a PhD form MIT and he set up a new centre for materials research at Stanford. His interest was in solid-state electric chemistry ; how ions move in solids and things like that. And at that time the Ford Motor Company had just discovered that sodium ions move very fast in a material called beta-alumina. Sodium ions move almost as fast in that solid as they do in a liquid.

BBV : So it was the time of the beta-alumina ?

SW : Yes. Ford published their data in 1967, and I went to Stanford in 1968.

BBV : Did you continue your research on tungsten bronzes there ?

SW : Yes and no. I measured the conductivity of beta-alumina. That is what we tried to do. We has to have electrodes that were reversible to electrons, so we could get a current, and to the ions that were moving. So we paid attention to bronzes that had sodium in them, to metallic conductors, to see if they would make good electrodes. So we have narrowed the Oxford work into the Stanford work.

BBV : And how did you develop the batteries using tungsten bronzes.

SW : I arrived at Stanford in February. In May or June of that year Bob Huggins left to go to Washington to run this whole suite of advanced research centres of materials (?) of which MIT is the last surviving. So he went there and manned those for about two and a bit years. I remained at Stanford and continued my research on the basics. And about the same time, there were others in the medical field who were interested in batteries for pace makers and things like that and there was a number of good silver iodide conductors... (?). And it struck us that sodium or potassium had an advantage over silver because they yield a bigger current. And that is where we got the interest in actually using them. Beta-alumina as the electrolyte and we thought of sodium and some oxides as the electrodes.

BBV : And how did you come to your favourite, titanium disulfide ?

SW : Ah, that is a jump.

BBV : Yes, because you took the patent out in 1973.

SW : Right. While I was at Stanford a number of other people, in particular Hector Ball, who was Professor of Applied Physics and associated with the Materials Department. He was contacted to find people to go to Exxon who were starting up a new corporate research lab. Exxon really had very few chemists and physicists at the time. So I did an interview at Exxon and one at Cornell, and I was offered a job in the Materials Science Department at Cornell, not the Chemistry Department. About a third or a half of the faculty in Materials Science Departments in the US are physicists and chemiusts... they have PhDs in physics or chemistry, not in materials science.

BBV : Incidentally, do you think that physicists have had an impact on your field ?

SW : Oh yes. At Exxon they made me a very nice offer. What they had built up was an interdisciplinary group. It was led by Fred Gamble, who had also come from Stanford. His interest was in superconductivity. And that was the first wave of superconductivity. What we tried to do then was to look at (?) tantalum disulfides. And by intercalating different molecules between the sheets of tantalum disulfide we could change the superconductivity transition temperature. So, tantalum sulfide became superconducting, I think it was at 0.8 degrees Kelvin. By putting in different molecules you could raise it to about 6 Kelvin. It turns out that the one that could raise it the highest was potassium hydroxide. And my first job was to try to understand what was going on. And what I found out was that basically potassium ion structure was particularly stable in TaS2-... It behaved like a salt ... there was again of energy ... (?).

AH : Where was this new Exxon lab placed ?

SW : It was across the street from a refinery in Linden, New Jersey, along with a raft of other chemical and solids research labs. Basic research. And the goal was to be prepared since oil was soon going to run out. My part was energy-related systems, other than petroleum and chemicals.

AH : It was set up in 1972 and you were there from the very beginning ?

SW : It may have been set up in 1971, but basically yes.

BBV : How many people worked with you on this project ?

SW : The group headed by Fred Gamble : there was about six of us. Each one of us had a different background. Fred Gamble himself was something like a physical chemist, there was an organic chemist, some were physicists.

AH : Presumably you had plenty of funding for equipment and the like ?

SW : In those days, if you needed something for your research you asked for it, and it would be there in a week. Money was no issue. They invested in a research laboratory like they invested in drilling oil. You expect one out of five to pay off.

BBV : Was it perceived as a long-term project ?

SW : Yes.

BBV : And what did that mean : 10 years ?

SW : 5-10 years. Industry has changed considerably since then. I would say after about 7 years they began to ask : well, what is going to come out of this ? By that point we had moved from tantalum sulfide, which is really no superconductivity material. We were looking at lighter materials : titanium sulfide. And we were looking at lithium, not potassium, because it turns out that potassium is very dangerous. And some time in this period a Japanese company had come out with a carbon fluoride battery which they used for fish floats. They fish at night and they need to see where their floats are. And that was a primary battery. This was the beginning of interest in lithium batteries.

BBV : So the initial interest came from Japan ?

SW : Well... we thought we could do something better. It was a high-voltage, one-shot, then you throw it away. And Exxon was only interested in rechargeable systems. They were looking to the electrical vehicle.

BBV : From the very beginning ?

SW : As soon as we started. We were only in energy, but we told them that we may have a battery and they immediately jumped to the notion of an electrical vehicle. And they in fact built – well it must have been in the mid-1970s – a 3W and diesel hybrid vehicle running on the roads.

AH : Presumably the Japanese were also interested in the EV at this early stage ?

SW : No, they were not interested at all. In the mid-1970s some Japanese companies started selling calculators with solar systems built in.

AH : In other words, they focused only on smaller batteries than those employed for vehicles ?

SW : Yes. And it is important to make the point that no battery company came up with any inventions. Every invention coming from Japan came not from a battery company. They had a device they wanted to take to the market. Sony, Sanyo. It is a straight busines. They do not stray from where they have been.

BBV : And from where did you get your techniques in intercalation chemistry ? Did you receive training in this already in Oxford ?

SW : Well, the tungsten bronzes are quite similar in this respect sodium, lithium, or hydrogen in and out. There was interest in electrochromic displays in the late 1960s early 1970s and so we were all familiar with them. You have tungsten dioxide and you put in in acid adding a bit of zinc. It generates atomic hydrogen and turns into a solid going from yellow to blue.

BBV : Yes, but when the mixed conductors started, I think there was something of a change in intercalation chemistry.

SW : Yes.

BBV : Was there any feedback from your research at Exxon to intercalation chemistry ? Or was it isolated as a completely industrial research lab ?

SW : No, I think we had a huge impact. At the time Bell Labs were doing similar things. They were located close to us, they were a similar group, also with many individuals from Stanford. We were competing head-on for a while, also in publications. If you look at our publications on the battery, you will see a lot of basic science with no mention of batteries at all. Exxon clearly did not want to disturb their aura (?).

AH : What journals did you publish in ?

SW : Electrochemical Society, Materials Research Bulletin. But the electrochemical stuff came after the basic stuff. So much of the basic stuff went into the MRB which had a very strong reputation in those days.

BBV : So, you have been working on titanium sulfide for many years ?

SW : I started working on that when I joined Exxon in 1972, already in October. As soon as we started work on it we realized that it had very interesting physical properties. So my colleagues like Art Thompson ... (?). After a year we knew about that material than anybody in the world.

AH : May I ask a couple of questions about the early period before we get advance too far chronologically ? Would you please contrast the appearance of the labs at Oxford, Stanford and Exxon ?

SW : Sure. Oxford was an organic chemistry lab. We were in the old wing of the building, built probaly at the beginning of the last century. The walls are three feet thick. There was mercury all over the floor and under the floorboards. It was an antique place. But most of the facilities were there. It was all set up for solid-state work, because the head of the department was a solid-state chemist. We had some of the first NMR ... (?). It was, I would not say state of the art but, pretty good for those days. And what people don’t realize is that there was no such thing as an electronic calculator. The computer we used took up a whole Victorian house and it had less power than one of those [pointing to a PC].

AH : What was your working day like ?

SW : If you were running an experiment you stayed there. There was no computer. If you were lucky you had a chart recorder. change temperatures... (?) You built your own equipment, you could not buy it.

BBV : Was the equipment different in Stanford ? Was it a shock ?

SW : Stanford was a new building. The Center for Materials Science had been built just a few years earlier. The building was new, most of the equipment was fairly new, though soime of it was surplus from (?). But the change was more going from a chemistry department to one of materials science. There were no fume hoods in the buildings. It was much more electronically oriented and obviuously the computers at Stanford were then better than those at Oxford. And after maybe a year there, a hand-held calculator costing about $95 came out. ..... (?)

BBV : And that was important for your own field ?

SW : Yes, because we wanted to measure how fast ions move. We made the first measurements over the first 5 or 10 seconds. You can do it with a chart recorder but it is very difficult.

BBV : And at Exxon ? Did you have everything you needed ?

SW : You had everything you wanted within reason. It was a new set-up and wanted to get it going right. Their attitude was that our time was much more expensive than the equipment.

AH : Were there more technicians at Exxon than the other two places ?

SW : No, I would say it was almost the opposite. Oxford had more support staff than any place in the US. We had a huge machine shop, a huge glass-blowing shop. And you had the old business of artisans in what were called shops. They would do new things for you, but they expected you to do anything routine by yourself. If it was complicated, they would do it for you.

AH : And in the US you would buy in ?

SW : Yes, there you tended to buy stuff. There was some support staff but nowhere near the same. These days there is almost no support staff.

AH : But the impact of the computer has generally speaking been more marked in later periods than the one we are talking about now, right ?

SW : Yes, when did the PC arrive ?

AH : I think it was about 1986.

SW : And I was at Exxon from 1972 to 1984. We came up with a battery patent early on. We had an incredibly good patent attorney. They would write up your invention and then ask you : why can’t you do it this or that way ? And they came up with ideas for building a battery fully charged or fully discharged. TiS2 patent... (?)

BBV : And did you publish more patents or more articles during your time at Exxon ?

SW : More articles because one of the goals was to get Exxon better known as a research institution so they could hire better scientists. And there was some pride with the president of the company that he wanted to compete against Bell Labs. So he wanted us to be perceived as the labs of the energy business. One of the presidents was E.B. David (?) who subsequently became head of the board of Science Advisors or something like that. He wanted Exxon to be known as the best place in the world.

BBV : So they valued research over patents ?

SW : Both.

BBV : Was not there a tension between the two in the disclosure of results ?

SW : Yes. The publications did not mention batteries at all. So we made materials and we described how we made them. We then discussed their scientific behaviour, how they reacted with water, their thermodynamics. But anyone smart enough would know what we were doing. They soon caught on. And I think about 1975 or 1976 when the first patent started coming out we released the first paper in Science Magazine. And about the same time we also published ... (?). Because up to that time people in the battery business did not know what intercalation was. ...

BBV : Did you attend the Belgirate, Italy, meeting in 1973 that purportedly is the founding event of the community ?

SW : Yes, I gave two papers both of which went very well. And the other thing I remember is that Carl Wagner attended that meeting. He was very old. He basically put the field of corrosion on a scientific basis. He ought to have received a Nobel Prize.

BBV : Were there more Europeans there ?

SW : It was organized by Europeans, and I think there were more Europeans. And I remember that I was there with my wife and two young children. We bailed out half a day early because they said it was going to snow in the Alps, in order to go back to England.

AH : Were there any Japanese present ?

SW : Yes, I think there were a few.

AH : So you agree with the interpretation that this was a founding meeting ?

SW : Yes.

AH : One might also point to the beginning of the journal Solid State Ionics (1980) as the origin of a community ?

SW : Yes, but by that stage we were already having annual meetings.

BBV : Did the journal make any difference ?

SW : Do you want a bit of history of the journal ? The North Holland folks then had an office in the US. I lived in New Jersey two miles away from the publishing editor. They published the Belgirate proceedings. And this editor said : we need a journal in this field. I was one of those who said : no we don’t.

AH : Why did you think that ?

SW : I thought there were too many journals already, even at that time. There were few compared with today of course, but even so. So he said, you prove that to us and we will pay you to do it. So Hans Becker (?) and I sent out a mail to everyone in the community, saying North Holland was going to start this journal and was there any interest ? I fully expected to get negative feedback hbut 95% wanted it. So North Holland played every nice game and we could not say no.

AH : Did the journal then not change anything much ?

SW : Yes, the journal changed a great deal because it pulled all the papers together in one place. Remember in those days there were no journals such as Chemistry and Materials. Solid-state chemistry had just started and that was more high-temperature. And there was the Materials Research Bulletin. So papers were all over the place. So they convinced us to go with it. I had my arm twisted to edit it. Within one year we went from single-column to double-column format and larger-size paper. It basically took off straightaway.

BBV : The whole community decided to publish in this journal instead of in the others you mentioned ?

SW : Yes. They kept publishing in other journals also, but they knew that here they would have their stuff recognized .

BBV : Was it a fast publication ?

SW : Five months. The goal was to get it out quickly. In those days the Materials Research Bulletin got things out in two months.

BBV : Let us come back to your career. Why did you leave Exxon in 1984 ?

SW : Exxon had one good thing about them. It was run by scientists and engineers, not by lawyers or MBAs. I will give you an example. When we had come up with the battery, the board of directors came to the lab to listen to us. And they then said here is the money, now go and do it. So they built an applied film group costing millions of dollars, a very good one. It was like a poker game : well we make a big dollar or we loose it. Their philosophy was that if you were a good scientist then you would also be a good director. So within a few years I became a lab director. I am not sure exactly when but at some stage they said : now you have shown that you can manage something you know, so we will now send you off to manage something you do not understand. That is why I went to an engineering facility, where I headed their chemical engineering. I was responsible for technology, for synthetic fuels in those days, chemical plants, raffineries. It sounded challenging at the time and I stayed there four years. At that time began the shale oil and coal gasification (?). It was a booming period. My job was to employ as many chemical engineers as I could lay my hands on. But soon the writing was on the wall and the slump was coming. We started laying off people. We went from roary-rosy days to (?). And I was doing no science myself then. I missed that and that is why I went to Schlumberger. My first boss at Exxon went to the Metallurgical division there.

BBV : What kind of research did you do there ?

AH : It was 1984-1988.

SW : Right. Schlumberger was in Richfield, CT, the lab was built and designed by a famous architect called Johnson, from Texas. One or two stories, glass, a very pretty building. You could not have your names on the doors or pictures on the walls unless they’d approve them. Schlumberger was then the Rolls-Royce of the oil field. They built very expensive analytical equipment which they put down oil wells to determine whether there was in fact any oil down there, what the rock foundations were like. They would put these probes worth millions of dollars down the well, pull them up very slowly and you would get wiggles and charts and things like that. And if they could reproduce the wiggles they would sell it. It was a very low-key company. In those days they probably made more money than all but two or three of the biggest oil companies. What they did not have was chemists, those who tried to understand what these measurements actually meant. They did have a large number of physicists and electrical engineers building the instruments. Then they decided to build up a basic rock science group, the job of which was to try to understand what was measured. And I went as head of the group, to bild up the chemistry activity with the engineers. One of the biggest electrolytes in the world is clay. It is clay in the formations that causes various forces to be formed in the earth and you can measure them.

AH : So you were not really moving to something completely new. This is the link to your previous field.

SW : Yes, but I had been doing management. At Schlumberger I was dealing with chemical engineers. But as my wife said, I was doing far too much travel. Schlumberger had labs in Texas, Connecticutt, Tokyo, Paris, and Cambridge, England. During my first year I was in the US maybe half of the time.

BBV : Is that why you stayed only four years there ?

SW : When I went there it was a booming organization run by a Frenchman (Ludeau ?). A whole book has been written about him. He died, and his chosen successor failed. There was a palace revolution. And a Scotsman was in charge, Ewan Baird (?), I think he is still in charge. At that point they were building a new chemistry facility in Richfield. They had put the foundations in, and he came in one day and said, no. Construction stopped. He ordered people back to basics. Schlumberger also had some TV stations back in France. They invested in other things. It was as if they only wanted to have Nobel Prize scientists : only the best was good enough. They did hire some outstandingly strong theoretical physicists. We looked at how oil flows through sandstone in rocks. Sprinkering (?) techniques ..very similar to how snowflakes build up on the window. Some people there did not like it : why are you doing this ? There was a reaction against basic science and people wanted to get back to building and improving equipment.

AH : Was the basic stuff modelling ?

SW : Yes, there was a strong modelling component and a measurement component. At that time we had about 30 people in this basic science group. We were told basically that we could become engineers or leave. We were given about 18 months. They were very generous. Some of the best people were in their 20s. Three of them were offered tenured professorships within a month.

AH : This is also the period of change from the mainframe to the PC.

SW : Yes, and Schlumberger was big on that. They had a Cray computer and Macintoshes. The theorists wrote their programs on the Macs and ran them on the Cray. Schlumberger also had e-mail, around the world. We were in touch with the Japanese and the French. That was really the first time that I used e-mail. They were well ahead.

AH : This must have been towards the end of your time there ?

SW : They had it from the beginning. Remember, they were well versed in how to get electronic information.

BBV : Did you go straight from Schlumberger to SUNY Binghamton ?

SW : Yes. At that time I decided that US industrial research activites had started on a down hill. Exxon had cut back on their basic research by about 50%. Seven years earlier they had doubled basically overnight. Then they had said : what would you do if we gave you twice as much money ? Give us a plan by Monday (that was on Friday). In my recollection we worked all that weekend. Within a week we had the doubled size.

AH : How would you account for the change in atmosphere, for the downturn in the mid-1980s ?

SW : A number of things : 1) oil prices had been going up but then they dropped ; 2) MBAs started getting into the business (short-termism ; now the stock price is more important than everything else) and then they looked hard at basic research. With regard to Exxon : it is a mammooth company. The corporate labs were under $50 million. When they doubled it, it got above $50 million. They rounded everything off into hundreds of millions. Anything under $50 million just did not appear in the balance sheet. 3) When the oil price went down there was no longer a sense of crisis. So you do not need any longer to investigate all the alternative forms of energy. Exxon had gone into solar, batteries, computers, a chip company. But Exxon did not really have the management expertise. At about that time Exxon sold all their battery technologies. They licensed them to a Japanese company, one American and one European. I think it was Sony in Japan. Exxon said : you mean you can not make $100 million a year on this ?

AH : It would seem that the price of oil is a really good indicator of the field of solid-state ionics ?

SW : Yes. When Exxon got out, the whole field got out. The federal government cut funding, thinking that if Exxon was not interested, then why should we be.

BBV : So how did the field continue ? Where did the incentive come from ?

SW : Europe was continuing. The Japanese had our technology. There were a few problems with it. They wanted a safe anode ; they could not use pure lithium. ... (?) John Goodenough came up with cobalt oxide. That is almost double the voltage. Sony combined that with an interpolation compound of graphite as the anode ; and came out with what is called (?). The Japanese now have some 90% of the market for all lithium rechargeables. Sony has the primary licence making sublicenses. I think the patent is running out any day now. A number of companies toyed with getting into the business. Eveready two years ago started a plant and found that they could buy the batteries cheaper in Japan than they could build them themselves. The Japanese just have such a long lead time.

AH : Your personal choice of going back to academia. There was no future in industry you said...

SW : There was no future in industry and I wanted to do my own thing. In the mid-1970s 9 out of 10 solid state chemists were in industry. About that time chemistry departments in this country suddenly realized that this is a field. We want these people. Now, 9 out of 10 are back in academia.

AH : What impact did the return of solid state chemists to academia have upon the field ?

SW : In 1987 superconductivity happened. All solid state chemist jumped on board. The result was this symposium. Meeting in New Orleans. The largest room in New Orleans was not big enough.... [too much noise]

BBV : The field suffered from the cold fusion affair ?

SW : Yes and no.... [too much noise] few people got involved in cold fusion

AH : Characterization ?

SW : Computerization has accelerated the getting of measurement results.

Most of these batteries have maybe one or two years. They last as long as the product itself. As far as environmental concerns : they are pretty darn good. [noise]

AH : Hybrid vehicles ?

SW : They are there. The Japanese have them. All that is needed is the political will to factor in the environmental advantages.

BBV : Oxide markets ?

SW : Electrochromic displays.

AH : Optimism when you started ?

SW : Optimism fuelled by end of oil. Now the end of oil is not in sight. But batteries are needed in the small electronic devices. The EV is not everything.

AH : Whom should we talk to : Frank, John Goodenough, Michel Armand.

BBV : Hagenmuller ? Steele ?

SW : Steele is still active.

AH : Fuel cell relevance ?

SW : Fuel cells are much more active in Europe than in the US.

AH : For political reasons ?

SW : No, .. [noise]

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