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HERMAN FRANCI S MARK May 3, 1895-April 6, 1992 BY HERBERT MORAWETZ HERMAN MARK WAS WIDELY KNOWN as the father of polymer science and the contribution he macle to his chosen field was crucial in many ways. His research and inspiring teaching and lecturing were only part of his activities. Be- ing completely ~levoid of academic snobbery, Mark was equally at home at universities and inclustrial laboratories and was most influential in the phenomenal growth of the polymer industry. Deeply concerned with establishing the study of polymers as a discrete branch of chemistry, he clesignecl the first graduate curricula in that cliscipline, foun(led a poly- mer journal and monograph series, and was one of the chief architects of the Polymer Section of the International Union of Pure and Appliecl Chemistry. Because of the informality of his nature, Mark was affec- tionately called by the nickname "Geheimrat" to stress his extreme (lifference from the pompous professors who had been aclornec! with this "Secret Councillor" title. His con- stant cheerfulness reflected his enviable ability to recall the good part of his life's experience while choosing to forget all the unpleasantness. 195

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96 BIOGRAPHICAL MEMOIRS EARLY LIFE AND EDUCATION Herman grew up in Vienna as the second son of Herman Carl Mark ant! Lily Mueller. His father was a physician, and Herman was early impresser] with the conversation around the family clinner table with guests such as the psychoana- lyst Sigmunc! Freud, the dramatist Arthur Schnitzler, an ct the founder of Zionism Theodore HerzI. The musical life of the period, when Gustav MahIer was conductor of the Vienna Philharmonic, macle a great impression. Mark was also en- thusiastic about sports, particularly skiing en c! soccer, and on one occasion he was a member of the Austrian national soccer team. This idyllic life came to a suciclen enc! with the outbreak of the First World War. Mark fought on all fronts, was woundec! several times, anct was awarded fourteen medals for bravery. On one occasion, when the Italian army cap- turec! Monte Ortigora and the Austrians orclerect a retreat, Mark persuaded his superior officer to allow him to leacl a counterattack in which the strategic peak was retaken in spite of a heavy loss of life. During the final months of the war Mark was captured. He spent almost a year as a pris- oner of war in a convent near Bari; his account of the humane treatment of the prisoners in those days reads to- day almost like a fairy tale. To relieve the boredom of prison life, Mark studier! languages en c! resumed his study of chem- istry, which he hac! starter! two years earlier while recuper- ating from a battle wound. In October 1919 he Earned that his father was sick. He bribed a prison guard and took a train to Vienna. He worked on a doctoral thesis cleating with the synthesis and characterization of the pentaphenyl ethyl free radical uncler the direction of Wilhelm SchIenk. Many years later, Mark recallecl that SchIenk repeated his elemental analysis

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HERMAN FRANCIS MARK 197 before he allowed him to write up the dissertation. Mark worshipped his thesis Divisor and SchIenk was clearly most impressed with his student, since he invited Mark to come with him to the University of Berlin, where, in 1921, SchIenk was offered the chair previously occupier! by Emil Fischer. KAISER WILHELM INSTITUTE (1922-26) As it turned out, the Schienk-Mark collaboration clic! not last long. A year after Mark arrived in Berlin with his young wife, the former Mimi Schramek, Fritz Haber, director of the Kaiser Wilhelm Institute (KWI), asker! SchIenk for a modern organic chemist for a new Institute of Fiber Re- se~rch to be organized at KWI. SchIenk unhesitatingly rec- ~ ~ ~ r ~ rem 7 ommenctect aviary. anus, a period of almost unbelievable productivity started for Mark at what was then one of the leacling scientific centers in the worIct. Michael Polanyi hac] recently joined KW} ant! under his inspired leaclership a broad program of X-ray crystallographic studies was initi- ateci. Polanyi found that the X-ray diffraction from cellulose fibers indicated the presence of crystallites oriented in the direction of the fiber axis and that an analogous crystal orientation existed in metal wires. A full structure analysis of cellulose seemed beyond the experimental possibilities of the time, but Mark en cl Polanyi noted that the increase in the modulus of cellulose fibers on stretching seemed similar to the reinforcement of metal wires cluring cold- clrawing. They embarked, therefore, on a detailecl analysis of the changes accompanying the coicI-cirawing of a zinc wire. It is interesting to list some of the large number of mate- rials Mark selected for his later crystallographic studies. The determination of the hexamethyTene tetramine structure in 1923 was one of the first for a comparatively complex or-

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98 BIOGRAPHICAL MEMOIRS ganic molecule. The graphite structure (1924) later provecl important in convincing Mark (in opposition to many crys- tallographers of that time) that covalently boncled struc- tures may extend beyond the crystallographic unit cell. The oxalic acid study (1924) lee! him to conclude that "one may assume that the carboxy! group of one molecule may at- tract as well the OH of water as the hyciroxyl of another oxalic acid molecule." In his study of calome} (1926) he relater! the birefringence to the crystal structure. The crys- tallographic study of carbon c3 ioxicle ~ ~ 925, ~ 926) was aimed at the determination of the carbon-oxygen bond length. A comparison of the ethane and cliborane crystal structure (1925) showed that the two molecules hac! similar geom- etriesa result that was then quite surprising, since the manner in which the trivalent boron could form B2H6 mol- ecuTes was something of a mystery. (The discovery of the similarity of the ethane en c! cliborane structures is generally credited to S. H. Bauer's 1937 electron diffraction study, ignoring Mark's earlier work.) Considering that Mark was originally trained as an or- ganic chemist, it is striking how much of his effort cluring his years at KWl was clirectec3 at problems in physics, such as the natural width, the refractive index and the polariza- tion of X rays, the Stark effect, and the Compton effect. An important milestone in Mark's career was the meet- ing of the GeselIschaft Deutscher Naturforscher und Arzte (Society of German Natural Scientists and Physicians) hell! in Dusselclorf in 1926. At this meeting Herman Stauclinger, the champion of the concept of long chain molecules, was confronted with some of Germany's most distinguished chem- ists who viewed this idea with utmost skepticism, insisting that all effects ascribed by Stauctinger to macromolecules couIc! be explained by a colloict association of small mol- ecuTes. Mark's lecture was titIec! "Roentgenographic Deter-

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HERMAN FRANCIS MARK 199 mination of the Structure of Organic, especially Highmolecular Substances." It is important to note that the term "highmolecular" (hochmolekular) at that time carried no implication whether such substances were composed of Staudinger's macromolecules or of his opponents' colloidal aggregates. Mark reviewed his crystallographic work, stress- ing that important information may be gained from the unit cells and space groups, even if detailed molecular struc- tures are not available. As for highmolecular substances, he was not yet ready to commit himself to Tong chains but suggested that the failure of ah Lances to break un .. . . . On dissolution Into small particles "indicates that lattice forces are quantitatively and qualitatively comparable to intramo- lecular forces: The entire crystallite behaves like a large molecule." I. G. FARBENINDUSTRIE In 1926 K. H. Meyer, a director of Germany's largest chemi- cal corporation, the I. G. Farbenindustrie, invited Mark to become the director of a research laboratory of highmolecular compounds in Ludwigshafen. I. G. was a prominent pro- ducer of rayon and cellulose acetate fibers, and Mark was given full freedom to pursue fundamental studies as well as studies of spinning technology. His years at KWl had pre- pared him well for a consideration of the cellulose struc- ture. As far back as 1921, Polanyi had pointed out that the unit cell of cellulose contains four glucose residues, but although he remarked that the diffraction pattern might be consistent with Tong chains composed of glucose resi- dues, he attached no importance to that possibility. Mark made later the suggestive observation that the identity pe- riod in the fiber direction remained unchanged when cel- luTose was converted to its ethers or esters. Then, in 1926, SponsTer and Dore proposed in the United States a solu- c~

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200 BIOGRAPHICAL MEMOIRS tion of the X-ray structure in which cellulose consisted of long chains of glucose residues, but this structure was in- consistent with chemical evidence that cellulose could be clegracled to cellobiose. In a pioneering 1928 paper, Meyer ~ ~ ~ ~ ~ ~ . ~ ~ . - - . . a~u Vary solve one a~racuon pattern to yield a structure in agreement with the chemical evidence the first poly- mer crystal structure that has survives! the test of time. Another important investigation concerned Hevea rub- ber. While Mark was at KWT, one of his colleagues, I. R. Katz, made the surprising discovery that natural rubber, amorphous in the relaxer! state, exhibits a sharp X-ray ctif- fraction pattern when stretched. In his I. G. laboratory Mark followecI up this (liscovery by solving with G. V. Susich the Hevea rubber crystal structure. This result was particularly important since it settlecI, for the first time, a question of chemical constitution: It hac! been known that natural rub- ber is poly(l,~isoprene), but only the crystal structure proved that it hacI the cas configuration arounc! the carbon-carbon clouble boncI. Mark was keenly interested in the relationship between the molecular characteristics of polymers and their techno- logically useful properties. This lee! him to calculate, on the basis of the cellulose crystal structure and the energy re- quired to break its covalent bonds, estimated on the basis of spectroscopic (lata, the ultimate strength of an icleal cel- ~ ~ ~ T ~ ~ ~ r 1 _~ __ Hose cider. in this approach he was far aheac! of his time. He showed that the best industrial fiber was only about 10 percent as strong as the ideal fiber clearly owing to vari- ous defects. With Meyer's encouragement, Mark was free to pursue cluring his years in Luc~wigshafen a number of his scientific interests, which were not likely to translate into finar~cial profit for the company but which gained academic prestige for the laboratory. Thus, he carried out the first electron ~ .

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HERMAN FRANCIS MARK 20 diffraction studies of gases, determining the bond length and bond angles for molecules such as carbon tetrachIo- ride, germanium tetrachIoricle, benzene, cyclohexane, cis- I,2-ctichioroethylene and trans-l,2-dichIoroethyTene. It is of special interest that he concluded, as early as 1930, that the data for I,2-dichioroethane are incompatible with free rota- tion (i.e., that some values of the internal angle of rotation must be favored). The young Linus Pauling visited Mark's laboratory and was greatly impresser! with these studies, as he frequently recalled in later years. One of the most important contributions of the Ludwigshafen years was the writing, with Meyer in 1930, of the first monograph on polymeric compounds, "DerAufbau der hochpolymeren organischen Naturstoffe" ("The Structure of High Molecular Organic Natural Substances". It dealt with cellulose, Hevea rubber, gutta percha, starch, silk fibroin, en cl collagen on the basis of their crystallographic ant] so- lution properties. Another influential book of this period was Mark's Physik und Chemie rler Zellulose, publishecl in 1932. However, the description of this period of Mark's career would be incomplete without mention of the bitter attacks to which he was subjected on the part of Herman Staudinger. Stauclinger's highly charged emotional reaction was uncloubt- ecITy clue to his conviction that, having first proposed the existence of long chain molecules, he had created a new fertile field of organic chemistry and couch regard physical chemists ant! physicists who studier! polymers as interlopers whom he felt free of accusing of plagiarizing his icleas. The central controversy involves! Stauclinger's insistence that polymer molecules are stiff rods, whereas Mark and Meyer realized that because of the hindered rotation around the boncis in the polymer backbone they must be thought of as flexible coils. By 1932 the management of I. G. conclucled that, with

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202 BIOGRAPHICAL MEMOIRS the probable takeover of the German government by Hitler's party, Mark, as the son of a Jewish father, could not con- tinue to hold a prominent position in the company. It was characteristic of Mark that he always clepictecT the interview in which he was told that he would have to leave in the most innocuous colors. VIENNA ( 1932-38) In 1932 Mark was appointed professor of chemistry at the University of Vienna. He embarked immediately on the design of a curriculum in polymer science, the first of its kind. The research of his students dealt with the mecha- nism of polymerization en c! the viscosity of polymer solu- tions, but the most important achievement of the Vienna years was the formulation, with E. Guth, of a statistical theory of the elasticity of a rubber molecule. This proviclecl the basic icleas that lest later to the theory of crosslinkec! rub- ber elasticity. In 1935 Mark conceived an ingenious idea for combining his scientific interests with his love for mountaineering. He persuaclecl his friends at the Soviet Academy of Sciences to organize an expedition to the highest peak of the Caucasus to (letermine whether deuterium was concentrate<] in its ancient glaciers. The results were inconclusive but all mem- bers of the expedition had a wonderful time. Once again a political upheaval led to a painful change in Mark's life. In March 1938 Hitler's army occupier! Aus- tria, Mark was clismissect from his professorship anc! arrester! because of his friendship with Chancellor Dollfuss who had tried to ke ep Austria inclepen clent an c! hac! be en murclerec! by Nazi conspirators cluring an attempted coup in 1934. Mark had to use the influence of a high school classmate, now an influential man in the new regime, to be released from jail and to have his passport returned. He told me

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HERMAN FRANCIS MARK 203 that the fee demanded by the "friend" for this service was his year's salary at the university. Fortunately, Mark hacl been contacted during the previ- ous year by the director of the International Paper Com- pany plant in Hawkesbury, Ontario, who had offered him the position of research director. This offer was now re- peatecI. Mark, his wife, and two young sons left Austria for SwitzerIan(l, ostensibly on a skiing vacation, and proceecle to England. In September Mark arriver] in Canada, where he was joined by his family a few weeks later. THE AMERICAN YEARS ( 1938-92 ) Mark stayed in Hawkesbury for only two years, concen- trating on the improvement of the manufacturing of wood pulp, cellulose acetate, and viscose. The work on viscose was particularly challenging because of its recent use in tire cord, which required fibers of new exacting quality stan- ciarcis. This led also to a close relationship with the Du Pont company, which proved important when Mark clecicled that Hawkesbury diet not offer a sufficiently broad scope for his scientific interests. One of the Du Pont officers with whom Mark had dealt on the tire cord project was a board mem- ber of the Polytechnic Institute of Brooklyn and he pro- posecl that Mark combine a Du Pont consultantship with an academic appointment at Poly. In retrospect, the situation at Poly seemed far from aus- picious when Mark joined its faculty as an adjunct professor in September 1940. This was a time when a flood of refu- gees from Hitler's Europe found it next to impossible to obtain academic positions appropriate to their quaTifica- tions and experience. Mark was assigned to the Shellac Bu- reau, whose function was the testing and chemical charac- terization of shellac. However, since this material was imported from Asia, the war stimulated a search for a synthetic substi-

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204 BIOGRAPHICAL MEMOIRS tute and Mark's past experience was most valuable in that effort. His activities at Poly broaclenecI substantially as a result of research contracts with the wartime Office of Scientific Research and Development, which allowed! him to hire A. V. Tobolsky, P. M. Doty, and B. H. Zimm, none of whom hac3 experience with polymers but who later became leact- ing figures in polymer research. Mark's influence inclucec3 a number of giftec! students, such as S. Krimm and R. S. Stein, to make their career in this academically unfashion- able area. Mark also became involved in a number of rather exotic wartime projects. The most intriguing, perhaps, resulted from Mark's observation that the brittleness of ice collie be largely eliminates! by the incorporation of a few percent of sawdust. The British Military Mission in Washington, con- cernec! about the shortage of landing facilities, which lim- itecl the scope of airplane attacks against German subma- rines, hoped that a flat iceberg macle from this composition couicl be used as "an unsinkable lancling field." A prototype was in construction when a dramatic improvement in the fortunes of war lee! to the termination of this effort in Sep- tember 1942. The polymer research activities at Poly lecT in 1947 to the foundation of the Institute of Polymer Research, the first graduate program of its kincI in America. It is harct to recall tociay, when a number of distinguished programs of this kind are active at American universities, that this was highly controversial half a century ago. Mark's enthusiastic leacler- ship was essential, as were his innumerable contacts all over the world, which enabler! Poly's students to meet all the leading polymer scientists of that time. On Saturday morn- ings, symposia on subjects related to the rapidly advancing

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H E ~ M AN F RAN C I S M A R K 205 polymer research were held in Brooklyn en cl were attendecl by people from a wide area. At the same time, Mark's friendship with polymer scien- tists in all countries where polymer research was active made the polymer community an exceptionally close-knit group. Because of his inability to bear gruclges, he was most help- ful to German en cl Austrian colleagues at a time when they were frequently ostracized. He also click a great clear to bridge the gulf between the area dominated by the Soviet Union and the rest of the scientific world. He was particularly clevoted to the Weizmann Institute, created in Palestine in 1944, before the end of WorIcT War IT, and uncler his leacler- ship Poly was used to procure equipment for what became in time one of the woricl's outstanding scientific centers. Advancing age clic! not seem to slow Mark's activities. Al- though he gave up his lecture course at Poly when he turned seventy, he continued for many years to delight students and faculty by his yearly lecture on "What is new in poly- mers," in which he related what he had heard cluring his many trips overseas and in America. By his count he ma(le about 500 overseas visits, using his native Vienna as a base. He lecturecI extensively at universities and industrial labo- ratories, acted as editor of the lburnlzl of Polymer Science. and ,.. . . was a consultant to the polymer industry and the U.S. gov- ernment. He was also a most effective expert witness at a number of important patent litigations. Two experiences of his travels were specially memorable: In 1962 he was invitec! to present a lecture to the Japanese Emperor. ~ was toIct that such invitations were customary when a Nobel Prize laureate visited Japan, but that it was a unique honor in Mark's case since he clid not fall into that category. Ten years later, Mark was one of the first two American scien- tists to visit China after the communist government seized power in 1949.

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206 BIOGRAPHICAL MEMOIRS Over the years Mark became the recipient of many hon- ors. Among these were honorary degrees from the universi- ties of Liege, Uppsala, Berlin, Vienna, Madrid, Prague, and the Technion in Haifa and memberships in the Royal Insti- tute of Great Britain, the National Academy of Sciences, and the Soviet Academy of Sciences. He received the Hertz Mecial in 192S, the Nichols Meclal in 1960, the Gibbs Medal in 1975, the Humbold Award in 1978, the Wolf Prize in 1979, the Perkin Mecial and the National Medal of Science in ~980, and the Michelson-MorIey Award in ~989. His personal life was deeply affected by the cleath, after a Tong struggle with angina pectoris, of his wife Mimi in 1970. Another blow was the death of his son Peter in 1979. Dur- ing the last two years of his long life Mark lived with his son Hans, who was chancellor of the University of Texas. There ~ visited him in the spring of 1991. The Geheimrat was in a wheelchair, but there seemed little change in his spirit as he toict me about preparations for a lecture on conducting polymers. NOTE FOUR YEARS BEFORE Herman Mark's death, Jeffrey I. Seeman asked him to contribute an autobiographical sketch to the series of such memoirs of outstanding organic chemists published by the Ameri- can Chemical Society under the title "Profiles, Pathways and Dreams." Mark accepted with enthusiasm, and I had the unique pleasure to work with him on the editing of that booklet, which was published in 1993. This memoir presents a picture of Mark's vivid character that cannot be conveyed second hand.

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HERMAN FRANCIS MARK SELECTED BIBLIOGRAPHY 1922 207 .. With W. Schlenk. Uber das freie Pentaphenyl-athyl. Ber. 55:2285-89. 1923 With H. Gonnel. Roentgenographische Bestimmung der Strukturformel des Hexamethylentetramins. Z. Phys. Chem. 107: 181-218. .. With K. Weissenberg. Uber die Struktur des Pentaerithrits und eine graphische Auswertung von Schichtliniendiagrammen. Z. Physik 17:301-15. With M. Polanyi and E. Schmid. Vorgange bei der Dehnung von Zinkkristallen. S. Physik 12:58-116. 1925 .. .. With E. Pohland. Uber die Gitterstrucktur des Athans und Diborans. Z. Kristall. 62:103-12. 1926 With H. Kallman. Uber einige Eigenschaften der Comptonstrahlen. Z. Physik 36:120-42. With L. Szilard. Die Polarisation von Rontgenstrahlen durch Reflexion an Kristallen. Z. Physik 35: 743-47. Uber die rontgenographische Ermittlung der Struktur organischer, besonders hochmolekularer Substanzen. Ber. 59:2982-3000. 1928 With K. H. Meyer. Uber den Bau des kristallisierten Anteils der Zellulose. Ber. 61:593-613. .. With K. H. Meyer. Uber den Aufbau des Seidenfibroins. Ber. 61:1932- 36. .. With K. H. Meyer. Uber den Kautschuk. Ber. 61:1939-48. .. With G. v. Susich. Uber geregelte Mizellstrukturen von Kautschuk. Kolloid-Z. 46:11-21. 1929 .. With G. v. Susich. Uber die naturliche Breite der Rontgenemissionslinien. Z. Physik 65: 253-65.

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208 BIOGRAPHICAL MEMOIRS .. . With R. Wierl. Uber die relativen Intensitaten des Starkeffekts- Komponenten Hc and H~. Z. Physik 53:526-41. With R. Wierl. Starkeffektintensitaten im Langseffekt. Z. Physik 57:494- 500. Zur Theorie der Flussigkeitsinterferenzen. Z. Physik 54:505-10. The determination of particle size by the use of X-rays. Trans. Fara- day Soc. 25:387-89. 1930 With {. Hengstenberg. Ron tgenographische In tensitatsmessungen an gestorten Gittern. Z. Physik 61:435-53. With K. H. Meyer. DerAufbau der hochmolekularen organischen Naturstoffe. Leipzig: Akademische Verlagsgesellschaft. With R. Wierl. Die Ermittlung von Molekulstruckturen durch Beugung von Elektronen an einem Dampfstrahl. Z. Elektrochem. 36:675-76. 1932 .. Uber den Aufbau der hochpolymeren Substanzen. Scientia 51:405- 21. 1937 With E. Guth. Statistische Theorie der Kautschukelastizitat. Z. Elektrochem. 43:683-86. With K. H. Meyer. Hochpolymere Chemie. Leipzig: Akademische Verlagsgesellschaft. 1940 Intermicellar hole and tube system in fiber structure. [. Phys. Chem. 44:764-88. 1950 With A. V. Tobolsky. Physical Chemistry of High Polymeric Systems. New York: Interscience Publ.

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