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OCR for page 195
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
OCR for page 196
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
OCR for page 197
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-
etries—a 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-
OCR for page 199
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
~ .
OCR for page 201
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
OCR for page 202
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
OCR for page 203
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
OCR for page 205
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.
OCR for page 206
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.
OCR for page 207
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.
OCR for page 208
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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Representative terms from entire chapter:
crystal structure
