Tribute to the support groups in the quasicrystal discovery – a 40-year anniversary

Istvan Hargittai
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On November 3, 2011, at NIST, from left to right: Istvan Hargittai, William Boettinger, Frank Gayle, Francis Biancaniello, Stephen Ridder, Leonid Bendersky, Robert Schaefer and Balazs Hargittai. Photograph by Istvan Hargittai.

Forty years ago, in 1984, a brief communication in Physical Review Letters announced the discovery of quasicrystals (not yet using this term). Three scientists joined Dan Shechtman as co-authors. Previously, associates of the then National Bureau of Standards assisted Shechtman in his experiments. In 2011, Dan Shechtman received the Nobel Prize in Chemistry for the discovery of quasicrystals. There was no doubt that he deserved it and that he deserved the prize unshared. This personal review is dedicated to his 'support cast', the members of two groups that assisted his discovery and the publication reporting it.

[image1]Dan Shechtman, 1995, in the author’s home in Budapest. Photograph by Istvan Hargittai.

Dan Shechtman’s unshared Nobel Prize in 2011 was unequivocally appreciated by those familiar with his milestone discovery and his perseverance during the preceding years. Great scientific authorities had questioned the validity of the interpretation of his observation. The award signaled the official seal of approval of the existence of quasicrystals, which he announced in 1984 [1] but had observed in 1982 (see, e.g. [2−7]).

In 1981, Dan Shechtman of the Technion — The Israel Institute of Technology — went for his first sabbatical at the National Bureau of Standards (NBS; today, the National Institute of Standards and Technology, NIST, in Gaithersburg, Maryland). John W. Cahn (1928−2016), a senior scientist at NBS, initiated his appointment. The two first met in the late 1960s when Cahn visited the Technion, where Shechtman was an engineering student in the Department of Metallurgy. At the time, Cahn was already well known for his thermodynamics of materials [8]. Their next meeting was in 1972 when Shechtman was a postdoctoral fellow at the Aerospace Research Laboratories, Wright-Patterson Air Force Base, near Dayton, Ohio.

[image2]John W. Cahn, 1995, in Gaithersburg, Maryland, photograph by Istvan Hargittai.

Their “life-changing” meeting [8] happened in 1979 when Cahn and his wife stayed at the Technion for a longer period. By then, Shechtman had become an expert in electron microscopy and developed a method for studying metallic powders by transmission electron microscopy. His research focused on rapidly solidified metallic alloys, something a group at NBS had also been working on but not very successfully. Cahn thought that Shechtman would be a good addition to the group and invited him for a talk and then for a stay at NBS. Shechtman at NBS was supported by a joint program of the Defense Advanced Research Project Agency (DARPA) and the National Science Foundation (NSF). He had freedom in choosing and executing his research projects.

Shechtman first visited NBS in the summer of 1980 and gave a talk. Then, he returned with his family in August 1981 for “two magnificent years” [8]. In 1995 he remembered: “I started by studying rapidly solidified aluminum-iron alloys. I analyzed the phases present and the solidification patterns. I collaborated mainly with members of the metallurgy group, Bill Boettinger, Bob Schaefer, and Frank Biancaniello. We wrote a series of papers together and understood rapid solidification better. It was in April 1982, half a year after I had arrived, that I discovered the icosahedral phase.” ([2], p. 84) [Conversation with Dan Shechtman (1995). Balatonfüred, Hungary].

[image3]In 1984 at NBS, from left to right: Frank Biancaniello, John W. Cahn, Denis Gratias, Leonid Bendersky, Dan Shechtman and Robert Schaefer. Photograph by H. Mark Helfer/NIST; courtesy of NIST (colorized by the Editor).

Frank Biancaniello’s role was especially important in Shechtman’s studies. He was a technician, not yet a full-fledged researcher at the time (as he became soon afterward); his tasks included the preparation of the alloy samples of various compositions for the electron microscope–electron diffraction experiments. According to the other members of the group, Biancaniello was most enthusiastic about this project. He was happy to work many extra hours, including nights and weekends, and he was as skilled as he was devoted to this work. At Shechtman’s initiative, the tests extended even outside the range of reasonable compositions — reasonable, that is, for expected practical applications. Biancaniello remembered [9]:

“Obviously, the quasicrystal discovery was the most important one culminating in Danny’s Nobel. But many other exciting projects we worked on came to fruition over the years. I’m sure you have heard of some of the bulk metallic glass research being carried out over the years, with yield strengths on the order of 1 to 2 gigapascals with no ductility. Steve Ridder and I developed a High Nitrogen Stainless Steel with a yield strength of 1.1 gigapascals with an elongation of 60%, using so-called rapid solidification technology. I only mention this in an attempt to demonstrate how intellectually stimulating these thirty years were starting with working with Danny Shechtman and continuing on to recent times. As Bill Boettinger mentioned, we worked on many projects with Danny. Steve Ridder and I did more recent research with Danny using a quasicrystal for a wear-resistant coating while doing thermal spray studies.”

Shechtman narrated in our 1995 conversation about some of the details of the seminal experiment ([2], p. 84):

“At first, I was studying rapidly solidified aluminum-iron alloy, which we thought had some commercial future. Eventually, it turned out that although rapid solidification research resulted in several useful products, it did not develop into a widespread technology. This, however, is not important for our story. In the aluminum-iron binary system, there was one metastable phase, Al6Fe, which I studied. The equivalent Al6Mn in the aluminum-manganese system is a stable phase, and I wanted to compare some crystallographic features of the two. We started, therefore, to produce a series of aluminum-manganese alloys with increasing amounts of Mn in them. Eventually, I ran wild, from a practical point of view, since beyond several percent of manganese the rapidly solidified alloy becomes brittle and therefore useless. Among the alloy ribbons that I have prepared with Frank Biancaniello by melt spinning, there were alloys which contained over 25 weight percent manganese. On April 8, 1982, as I was studying by electron microscopy rapidly solidified aluminum alloy which contained 25% manganese, something very strange and unexpected happened. It is worthwhile to look at my TEM [transmission electron microscope] logbook records of that day. For plate number 1725 (Al-25% Mn) I wrote: '10 Fold ???'. There were ten bright spots in the selected area diffraction pattern, equally spaced from the center and from one another. I counted them and repeated the count in the other direction and said to myself: ‘There is no such animal’. In Hebrew: 'Ein Chaya Kazo'. I then walked out to the corridor to share it with somebody, but there was nobody there, so I returned to the microscope and, in the next couple of hours, performed a series of experiments. Most of the needed experiments were performed at that time. A few days later, all my work was complete, and everything was ready for the announcement. Then it took two years to publish it.”

This comment that “it took two years to publish it” signified a hard time for Shechtman. The delay was not only due to the disbelief of the scientific community that the dogma about the impossibility of fivefold symmetry (and other 'forbidden' symmetries) in the world of crystals should fall. It was also that no convincing model could be constructed for interpreting the unexpected observation. At the same time, sitting on a seminal observation, he felt the necessity of communicating it to the broader community of researchers. He produced a manuscript in co-authorship with Ilan Blech (b. 1936), one of his former professors at the Technion, who devised a model to interpret Shechtman’s observation. This also meant that in Ilan Blech Shechtman found someone who shared his conviction that it indeed was an observation of a heretofore unknown structure.

They submitted their manuscript to the Journal of Applied Physics (JAP) in the summer of 1984. The disappointing editorial decision came back with a review. The Editor of JAP, Lester Guttman, wrote [10]: “Our reviewer and we both believe that your paper will not reach the most appropriate audience through this journal, and we are therefore returning your manuscript. We wish to make it clear that this is not a comment on the technical quality of your work; rather, it is an attempt on our part to try to place papers where they will be of the greatest use to the greatest number of people.” As the manuscript was more of the nature of a report in metallurgy than in physics, eventually, it was published in a metallurgy journal, Metallurgical Transactions [11]. The name of the journal was later changed to Metallurgical and Materials Transactions. In the wake of Shechtman’s Nobel Prize, the editor of this journal invited Shechtman’s three co-authors of the Physical Review Letters paper to recount their experience in that co-authorship [12]. This account was followed by a reproduction of the 1985 Shechtman-Blech paper [11].

Even before Shechtman received the letter of rejection from JAP, he showed the manuscript to John W. Cahn. Shechtman did not do this too eagerly, as Cahn’s initial reaction when he showed him the April 8 observation was rather negative. In Cahn’s words [13] [Conversation with John W. Cahn (1995). NIST, Gaithersburg, Maryland]: “One day he came into my office, and said, ‘John, what do you think of a 10-fold axis?’ I said, ‘Don’t bother me, Danny, this is clearly twinning’, and he said, ‘I don’t think so’. Then we discussed a number of experiments to decide this question. I didn’t know much about twinning, but I did know that through twinning you could get unexpected symmetries.” 

They did not talk again about Shechtman’s observation until mid-1984. In the meantime, Shechtman was back in Israel, and when he returned, he wanted to inform Cahn about the difficulties of publishing his April 8 observations. At the time, Cahn was attending a Gordon Conference in Aspen, Colorado, but when Shechtman’s word reached him, he flew back one day early from the conference. Shechtman showed him the manuscript that had been submitted to JAP but had not been rejected yet. We continue with Cahn’s own words [13]:

“I read this paper immediately and got very excited because I saw the data for the first time. I wasn’t convinced by the Blech model, but I was very much convinced by the experiments. It was obvious that it was not twinning, that it was something outside of what was known. I’m sure that had I seen the data in ’82, the same day when they were taken, we wouldn’t have wasted two years. On Friday, I met with Danny and said, this is a poorly written paper; you’re hiding this new phase. The entire paper was about experiments on aluminum–manganese. It started out by saying that we did this, we found this, and gave a list of the known periodic phases for each composition range, and buried, in half a paragraph, was a new phase, in the middle of an otherwise very conventional paper. My impression was that it was written that way to sneak it past the referee because everybody, except Blech, had told him that he had nothing. I remember that Friday going to the bosses [at NBS] and telling them that this is really something and it’s going to be big. I more or less said that we should mount a major effort; lots of people should shift because this has got to be investigated. At this stage I was not a co-author, and I did not expect to be a co-author. I told Danny that this is the wrong paper, but Danny told me that the paper had been submitted.”

[image4]Denis Gratias and Dan Shechtman in Shechtman’s office at the Technion, in January 2011, nine months before the announcement of Shechtman’s Nobel Prize. Shechtman is wearing his 'quasicrystal tie'. Photograph by Istvan Hargittai.

When the paper was rejected by JAP and published in Metallurgical Transactions, Cahn encouraged Shechtman to write “a proper paper”. To this, Shechtman said to Cahn [13]: “if you feel so strongly about it, can you write this paper?” To which Cahn replied: “Danny, this is your work; you’re making me an enormous gift.” Shechtman did not mind, and the two and a half journal-page paper was produced, though not before Cahn had invited a young French theoretician, Denis Gratias, to join them in writing the paper. Blech did not participate in producing this manuscript, but Shechtman added his name out of loyalty. Blech soon went into industry; he now lives in California. The others continued in research. Denis Gratias is currently a research director emeritus at the CNRS, the French National Center for Scientific Research. His highest recognition was his election to be a corresponding member of the French Academy of Sciences in 1994.

John W. Cahn’s co-authorship in the 1984 Physical Review Letters paper was an important event, but only one of several in his rich research career. He was born in Cologne, Germany, in a Jewish family. His father was a lawyer known for his anti-Nazi sympathy who narrowly escaped arrest upon the Nazi takeover in 1933. The family fled Germany and, after a few years in Holland, emigrated to the United States in 1939. They lived in New York City, and Cahn served in the US Army in Japan during its occupation. Cahn received a bachelor’s degree in chemistry in 1949 at the University of Michigan and a PhD in physical chemistry in 1953 at the University of California Berkeley. For the next decade, he worked in chemical metallurgy at General Electric in Schenectady and became a professor of metallurgy at the Massachusetts Institute of Technology from 1964−1978, followed by his tenure at the NBS/NIST from 1977−2007. His research results in metallurgy, non-crystalline materials, and other areas of materials science and technology were manifested in numerous publications and named effects and equations. The development of his research interests has been summarized [14]. His achievements were recognized by numerous awards and other signs of appreciation. He was elected member of the US National Academy of Sciences in 1973 and the National Academy of Engineering in 1998. He received the National Medal of Science in 1998 and the Kyoto Prize in 2011. 

When Cahn accepted Shechtman’s assertion that his observation was a discovery of a heretofore unknown phenomenon, however great Cahn’s authority was in materials science, there were more hurdles to overcome. In Cahn’s words [13]:

“At NIST, we have an Editorial Review Board. Every paper from the Institute has to be reviewed internally before it can be sent out. This Review Board was afraid of another polywater. The Bureau of Standards had been burned by polywater1 publications. The Board wanted to be on the right side this time and had asked local crystallographers to give them lectures about fivefold symmetry, why it can’t be. They were spending a great deal of time. The Board was split. My Division Chief of Metallurgy, also an old friend, said to me, ‘John, you have a wonderful reputation. Why ruin it by putting your name on something like such a paper.’ I said, ‘please, read this paper, it is very important and very exciting, and it’s not a time to be conservative.’ The Board took a very long time, they had lots of meetings, sometimes they came to me for advice but I was never present at these meetings. They carried an inquiry very carefully, and eventually they approved the paper. Finally, in mid-October, we could send off the manuscript. It came out three weeks after it was submitted.” 

After the paper was published, it generated enormous interest and an avalanche of publications. Foremost among them was a brief communication by Paul Steinhardt and Dov Levine of the University of Pennsylvania. They offered a plausible model and coined the name 'quasicrystal' [15].

As we have seen Shechtman had two supporting teams, one for his seminal experiment and one for its publication, with John W. Cahn bridging the two. The following years, however, Shechtman spent essentially as a lone hero of perseverance. There was a growing number of his supporters, but the dissenters could refer to the devastating opinion of Linus Pauling (1901−1994), arguably the most revered chemist of the time. In the fall of 1993, not long before his passing, I asked Pauling about quasicrystals. He dismissed it; not the experiment, not even the name, but the interpretation, and he did this in an uncompromising manner [16]: “As to the quasicrystals, you know that I contend that icosahedral quasicrystals are icosahedral twins of cubic crystals containing very large icosahedral complexes of atoms. It is not surprising that these crystals exist. The first one to be discovered was the MgZnAl compound reported by my associates and me in 1952. We did not observe quasicrystals of this compound, but they have been observed since then.” Even after Pauling’s death, many of his followers were reluctant to disrespect the memory of their Master by accepting Shechtman’s discovery for what it was. The Nobel Prize in 2011 ended any such hesitation.

Although solid state structures have not been in my research interest except for comparison with gaseous structures, quasicrystals have fascinated me ever since I heard about them. Curiously, I had learned about the possibility of their existence as early as 1982. I organized a lecture series for Alan L. Mackay of Birkbeck College at Eötvös University in Budapest and two of his presentations were about fivefold symmetry. Mackay warned us that if we believed the impossibility of fivefold symmetry in solid-state structures, as classical crystallography had taught us, we might let it pass us unrecognized even if we observed it (see, e.g. [17] (Conversations with Alan L. Mackay, October 1994, London) and [18]).

In 1987, I attended a crystallography meeting in Moscow in honor of Alexei Shubnikov’s centennial [19]. There, Shechtman’s discovery dominated the discussions in the coffee breaks. We met first in person in the early 1990s when I spent a month in Israel as a visiting professor at Ben-Gurion-University in Beer Sheva. This stay allowed me to give invited lectures at all major universities in Israel. During one of these presentations as I was talking at length about the significance of Shechtman’s quasicrystals, suddenly someone in the audience stood up and said: “I am Danny Shechtman.” Thus, our friendship began. In 1995, I was responsible for the scientific program of a crystallography meeting/school in Balatonfüred, Hungary, and quasicrystals received plenty of exposure with Shechtman as a star lecturer. There were other encounters but fast forward to January 2011 when at my initiative and, perhaps, at others’ as well, there was a meeting at the Technion celebrating Shechtman and his discovery. This meeting happened nine months before the announcement of his Nobel Prize. 

My son, Balazs, and I visited NIST on November 3 and 4, 2011, responding to an invitation for a presentation about Edward Teller and the other Hungarian 'Martians' of science. As our visit happened a few weeks after the announcement of Shechtman’s Nobel Prize, I gave an impromptu talk about the quasicrystal discovery as well. We spent several hours with Shechtman’s former colleagues, and we learned about the warm feelings they had toward Shechtman and their pride for having contributed to the discovery [5]. 

His former NIST colleagues have rarely figured in Shechtman’s statements. In his two-minute speech at the festive Nobel banquet on December 10, 2011, of his two support groups, he mentioned only the names of his co-authors of the seminal paper [20]. There was no acknowledgments section in his Nobel lecture [21], which my wife and I attended in December 2011 in Stockholm. Neither was there one in his Gregory Aminoff lecture in 2000 in Stockholm, which we also attended. The latter was linked to the 'Symmetry 2000' conference. Alas, Shechtman did not produce his presentation for the volumes of the proceedings of that meeting [22], just as he never wrote up his Nobel lecture for publication either (but it can be watched as a video [21]). One can only speculate that he may have had some frustrating experience at NBS that he did not wish elaborating. He acknowledged though his joint work with NBS associates in our 1995 conversation when he told me: “I collaborated mainly with members of the metallurgy group, Bill Boettinger, Bob Schaefer, and Frank Biancaniello.” ([2], p. 84). 

References

[1] Shechtman, D., Blech, I., Gratias, D. & Cahn, J. W. (1984). Metallic phase with long-range orientational order and no translational symmetry. Phys. Rev. Lett. 53, 1951–1953.

[2] Hargittai, B. & Hargittai, I. (2005). Candid Science V: Conversations with Famous Scientists, ch. 5, pp. 76-93. London: Imperial College Press.

[3] Hargittai, I. & Hargittai, M. (2000). In Our Own Image: Personal Symmetry in Discovery, pp. 157-172. New York: Kluwer/Plenum.

[4] Hargittai, I. (2011). Dan Shechtman's quasicrystal discovery in perspective. Isr. J. Chem. 51, 1144–1152.

[5] Hargittai, I. (2011). Struct. Chem. 22, 745–748. (This was based on an invited contribution to IGGERET, the Hebrew-language publication of the Israeli Academy of Sciences and Humanities.)

[6] Hargittai, B. & Hargittai, I. (2012). Quasicrystal discovery–from NBS/NIST to Stockholm. Struct. Chem. 23, 301–306.

[7] Gratias, D. & Quiquandon, M. (2019). Discovery of quasicrystals: the early days. C. R. Phys. 20, 803–816.

[8] Shechtman, D. (2016). My Memories of John Cahn, NIST.

[9] Biancaniello, F. (2011). Private communication by e-mail to I. Hargittai, November 3, 2011.

[10] Shechtman, D. (2011). Private communication by e-mail to I. Hargittai, December 26, 2011.

[11] Shechtman, D. & Blech, I. (1985). The microstructure of rapidly solidified Al6Mn. Metall. Trans. A, 16A, 1005-1012.

[12] Blech, I. A., Cahn, J. W. & Gratias, D. (2012). Reminiscences about a Chemistry Nobel Prize won with metallurgy: comments on D. Shechtman and I. A. Blech, Metall. Trans. A, 1985, Vol. 16A, pp. 1005–12. Metall. Mater. Trans. A, 43, 3411–3422.

[13] Hargittai, I. & Hargittai, M. (2000). In Our Own Image: Personal Symmetry in Discovery, pp. 165-167. New York: Kluwer/Plenum.

[14] Bottinger, W. J., Handwerker, C. A. & Gayle, F. W. (2019). John W. Cahn. Memorial Tributes. Vol. 22, pp. 38-44. Washington, DC: National Academies Press.

[15] Levine, D. & Steinhardt, P. J. (1984). Quasicrystals: a new class of ordered structures. Phys. Rev. Lett. 53, 2477–2480.

[16] Interview via e-mail with Linus Pauling in the fall of 1993. (1995). Chem. Intell. 1(1); reproduced in Hargittai, I. (2000). Candid Science: Conversations with Famous Chemists, edited by M. Hargittai, pp. 2-7. London: Imperial College Press. (Actual quote, p. 6.)

[17] Hargittai, B. & Hargittai, I. (2005). Candid Science V: Conversations with Famous Scientists, ch. 4, pp. 56-75. London: Imperial College Press.

[18] Hargittai, I. (2017). Generalizing crystallography: a tribute to Alan L. Mackay at 90. Struct. Chem. 28, 1–16.

[19] Hargittai, I. & Vainshtein, B. K. (1988). Editors. Crystal Symmetries: Shubnikov Centennial Papers. Oxford: Pergamon Press.

[20] Dan Shechtman – Banquet speech (2011). https://www.nobelprize.org/prizes/chemistry/2011/shechtman/speech/.

[21] Dan Shechtman – Nobel Lecture (2011). https://www.nobelprize.org/prizes/chemistry/2011/shechtman/lecture/.

[22] Hargittai, I. & Laurent, T. C. (2002). Editors. Symmetry 2000, Part 1 and Part 2. Proceedings from a symposium held at the Wenner-Gren Centre, Stockholm, September, 2000 (in two volumes). London: Portland Press.

 

Istvan Hargittai is located at the Budapest University of Technology and Economics, Hungary.
4 November 2024

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