The Legend of Professor H. Mark of NYU Tandon School of Engineering

Herman Francis Mark was a legendary professor in the history of the Polytechnic Institute of Brooklyn (PIB, now the NYU Tandon school of Engineering). He joined PIB in 1940, making immense contributions to the institution during its “Golden Age”, and maintained a deep bond with the school for over fifty years. Universally acclaimed as the “Father of Polymer Science,” Herman Mark is the subject of this article, which not only highlights the outstanding contributions he made specifically to the Tandon School but also endeavors to present his legendary life from a broader perspective — encompassing his work in education, scientific research, and industrial application, as well as the exceptional service he rendered to the U.S. government during World War II.

Herman Mark was a Jew born in Vienna, Austria on May 3, 1895. He grew up in the vibrant city and earned his doctorate in organic chemistry from the University of Vienna in 1921. It was during his studies at the University of Vienna that Mark began his research on various polymer materials, with cellulose being one of the most famous natural polymers he studied.

At the time of Mark’s graduation, his doctoral advisor Wilhelm Schlenk accepted a position as Head of the Chemistry Department at the University of Berlin, Mark followed Schlenk to the University as a post doctoral instructor.

一. Herman Mark’s Outstanding Scientific Achievements

Opportunity always favors the prepared mind; in the Summer of 1922, the newly established Kaiser Wilhelm Institute (now Max Planck Institute was seeking an organic chemist with a background in plant fiber research, and H. Mark was fortunate enough to be selected. At that time, Michael Polany had also just joined the institute; as a pioneer in the field of X-ray diffraction, he initiated a comprehensive X-ray crystallography research program. Under Polanyi’s leadership, Mark served as the project’s lead investigator. After nearly two years of rigorous experimentation and research, the team led by Herman Mark achieved a breakthrough. Virgil Percec, a renowned American chemist and professor at the University of Pennsylvania, offered the following assessment: “In 1924, Mark demonstrated that cellulose fibers showed crystallites oriented in the direction of the fiber, analogous to the crystal orientation in metals. This indicated that covalently bounded structures could extend beyond the crystallographic unit cell, in agreement with the macromolecular concept advanced by Staudinger (1953 Nobel Prize Winner). In 1926, during the Society of German Natural Scientists and Physicians Conference in Dusseldorf, Mark presented the lecture ‘Determination of the structure of organic, especially high molecular mass substances by x-ray. Studies’ and met Staudinger." (1)

To clearly articulate Herman Mark’s outstanding contributions to macromolecular science, we need to understand the broader context. Our ancestors learned to use naturally occurring polymers such as cellulose and proteins as materials long ago. Wood, paper, cotton yarn, and silk are good examples. However, it wasn't until the early 20th century that the European scientific community began to pay widespread attention to polymer chemistry. Here we must mention the contribution made in this field by two individuals: the German Chemist Hermann Staudinger and the protagonist of this article, Herman Mark.

Staudinger (1881-1965) was a German organic chemist who demonstrated the existence of macromolecules, which he characterized as polymers. For this work he received the 1953 Nobel Prize in Chemistry. In 1920, in his famous paper “Über Polymerisation” (2) (On Polymerization), Staudinger stated that substances such as polystyrene, polyvinylchlorides, and rubber, were composed of polymer chains with very high molecular weights. Each chain in these ‘high polymers’ could contain over 100,000 atoms — these were huge molecules. Moreover, in 1922, Staudinger proposed the concept of macromolecules. He proposed that macromolecules were long- chain molecules of identical or nearly identical units that were linked by covalent bonds, but without much proof to back up his proposal. Today it is known that many of Staudinger's ideas were essentially correct, but in the 1920s, modest chemists disagreed with him. They viewed macromolecules as colloidal aggregates of small molecules and did not believe that covalent bonding was involved. Stauginger’s ideas were gaining popularity, but it was a 1928 paper by Herman Mark and Kurt Meyer that finally convinced chemists that Staudinger had been right, Mark and meyer used X-ray crystallography to probe the structure of a crystallized polymer and found that polymers were indeed long-chain molecules in which repeating units were lined by covalent bonds.

二. Herman Mark’s Outstanding Contribution to the Industrialization of Polymers: Synthetic Rubber

H. Mark can be considered the first person in the 20th century to integrate scientific theoretical research with industrial practice in the field of polymers, and no one can surpass him. According to the Herman Mark Special collection in the Poly Archives, H. Mark made as many as 38 significant contributions in polymer science: (3)

Contributions to science by Herman F. Mark

H. Mark’s application of scientific theory to industrialization began with the joining I.G. Farben. In late 1926, Chemist Kurt Meyer of I.G. Farben offered H. Mark the assistant director of research and head of the physics department at one of the company’s laboratories in Ludwigshafen; however Mark did not actually begin working there until early 1927. As H. Mark himself recalled, this took place in January 1927. “I joined I.G. Farben-Industrie in January, 1927.” (4) Prior to joining I.G. Farben, H. Mark utilized X-ray diffraction techniques to demonstrate that natural rubber, cellulose, and proteins are composed of massive, long-chain macromolecules; this revolutionary discovery laid a crucial scientific and theoretical foundation for the purposeful synthesis of polymeric materials at I.G. Farben, which was Germany's Largest Chemical company. Mark’s job was to find ways to make polymer-based commercial products and stronger and more durable materials. He used every new technique available, pioneering the application of X-ray diffraction, electron diffraction, and spectroscopy to fiber studies. The Mark group used cellulose as a raw material to create industrial quantities of cellulose acetate (a substitute for silk).

H. Mark’s greatest contribution at the I. G. Farben was his work on synthetic rubber. According to H. Mark’s recollection, “Afterwards, the first truly synthetic rubbers, Buna-S and Buna-N were prepared by I.G. Farben. The preparation of these rubbers was the first copolymerization carried out with sodium (as the initiator). Natrium is the German word for sodium so the material was called Buna-N. Buna-N was a butadiene-acrylonitrile copolymer, and Buna-S a copolymer of butadiene-styrene." (5) In fact, Michael Faraday had shown in 1829 that rubber had the empirical formula C5H8. In 1860, Greville Williams obtained a distilling

Liquid with the same formula by rubber; he called it “isoprene”. Synthetic rubber technology started in 1879, when Gustave Bouchardat found that heating isoprene with hydrochloric acid produced a rubber-like polymer. However, Bouchardat had obtained isoprene from natural rubber; the first truly synthetic rubber was made by William Tilden three years later. Tilden obtained isoprene by cracking turpentine, but the process of converting it to rubber took several weeks. In 1911, Francis Matthews and Carl Harries discovered, independently, that isoprene could be polymerized more rapidly by sodium. In 1906 scientists at the Bayer company in Germany embarked on a program to make synthetic rubber. By 1912, they were producing methyl rubber, made by polymerizing methylisoprene. Methyl rubber was manufactured on a large scale during World War I, when a blockade halted the import of natural rubber to Germany. Because methyl rubber was an expensive and inferior imitation, production was abandoned at the war’s end.

I.G. Farbeninsustrie truly began its research into synthetic rubber in the summer of 1926, under the leadership of chemist Kurt Meyer. However, the project team was led by H. Mark. Mark’s team utilized modern X-ray diffraction techniques to investigate the structures and properties of natural polymers, such as strength, elasticity, softening point etc., thereby paving the way for the synthesis of artificial rubber, fibers, and plastics. H, Mark also made pioneering contributions to polymerization technology: 1. He investigated and utilized "peroxides" as initiators for polymerization reactions. In an interview with Allan Stahl in 1979, Mark detailed to process involved in this aspect (6):

2. H. Mark developed a catalytic method for the production of styrene, enabling its large-scale, low-cost manufacture and directly resolving the critical raw material issue for the synthesis of styrene-butadiene rubber.

When the Nazi regime seized control of the I.G. Farben company, and subsequently annexed Austria in March 1938; H. Mark, despite finding himself in grave danger, published an article titled “Natural and Artificial rubber: the Elasticity of long-chain Molecules” (7) in the journal <<Nature>> on April 16, 1938, with the aim of placing synthetic rubber technology at the service of all humanity. In the 1938 article, Prof. H. Mark built the foundation for understanding polymer chain flexibility crucial for the development of synthetic rubber.

When Herman Mark arrived at the Polytechnic Institute of Brooklyn in 1940 to serve as an adjunct professor in the Department of Chemistry, World War II was in full swing. With Japan having seized control of Southeast Asia — and, by extension, the majority of the world' s natural rubber sources, the United States was facing a severe rubber shortage. At the time, the U.S. The Shellac Bureau was actively seeking substitutes for natural rubber; consequently, H. Mark was appointed as a director under the directorship of William Gardner. To provide the U.S. government military, industry and academic institutions — such as universities — with knowledge regarding synthetic rubber, H, Mark published a lengthy Paper titled “Some Scientific Aspects of Synthetic Rubber Problem” (8) in the journal << American Scientist>> in April 1943, offering a comprehensive overview of the scientific principles of synthetic rubber. This contribution played a role in helping the United States secure victory in World War II

三. Herman Mark’s Greatest Contribution lies in the Field of Education

In 1932, as the Nazi Party assumed power in Germany, H. Mark returned to the University of Vienna as a professor of chemistry and later became director of the first chemical Institute, a position he held in 1938. Mark was acknowledged both as an industrial chemist as well as an academic. He had realized very early the importance and advancement of polymer chemistry as a new branch of the subject. Therefore, after returning to the University Mark re-organized the “First Chemical Laboratory,” At that time structural Chemistry was an unusual, one might say, a marginal field of academic research. Structural was at the time an industrial domain; academically it was not yet considered a serious discipline. Nevertheless, H. Mark introduced x-ray analysis, as a pioneer in applying modern physics to chemistry, and concentrated on the design of the academic curriculum for polymer technology.

When H. Mark was appointed professor in the University of Vienna, he switched over to basic research, he concentrated upon the mechanisms of polymerization to determine the relationship between molecular weight and viscosity. Mark also initiated the statistical treatment of macromolecular substances. The most important achievement was the formulation of statistical theory of the elasticity of rubberlike molecules and the mechanical properties of rubber.

In 1942, Herman Mark became the first full-time professor of polymer chemistry at the Polytechnic Institute of Brooklyn. He quickly began formulating a curriculum for the teaching of polymer chemistry. In addition to undergraduate education, and with the aim of serving master’s and doctoral students, PIB established the Polymer Research Institute (PRI) in 1946. “Under Mark’s active leadership, PRI quickly grew and attracted first-class scientists, students, and postdoctoral researchers from all over the world, including Great Britain, India, France, Israel, Italy, Japan, and the Soviet Union.” (9) The institute is not only the first polymer research institute in the United States, but it is also renowned worldwide. “With professor Weber, Othmer, Mark and Frankuchen teaching the gifted scientific minds of the time, it was the beginning of the Institute's golden years.” (10)

In fact, PRI changed the way industry approached polymer science. Following PRI’s lead, numerous companies began polymer programs, including Dow chemical, Phillips petroleum, Rohm and Haas, and Shell Oil. Many of these were started by scientists who had studied or taught at PRI. Without PRI’s influence, polymer science would not have advanced at such an accelerated rate. To this end, on September 3, 2003, the American Chemical Society designated Herman Mark and the Polymer Research Institute as a “National Historical Chemical landmark.”

H. Mark can truly be said to have students and disciples spanning the globe; he experts and immensely broad influence within the field of polymer chemistry worldwide. To help spur worldwide communication, H. Mark founded the"Journal of Polymer Science” in 1946. So,
“Many scientists, who later became world-famous have been students of Mark, for instance: Edward Teller, Leo Szilard and Mark Perutz. The double Nobel Prize winner Lines Pauling declared himself repeatedly ‘deeply indebted’ to Mark, “I think of him, with affection and admiration, as a pioneer in modern structural chemistry and an important early contributor to its development.” (11)

In fact, Herman F. Mark had received more than a dozen honorary doctoral degrees. He was also an elected member of more than two dozen Academics of sciences and he had received the highest awards world wide, with one exception, the Nobel Prize.

Note (References)

1. Percec, V. (2023). Herman F. Mark: Pioneer in structural chemistry, molecular biology, and polymer science. ScienceDirect, 9(12), 3386-3393. https://www.sciencedirect.com
2. "Uber Polymerisation." Poly Archives, Box 13, Folder 23. Bern Dibner Library, NYU Libraries, Brooklyn.
3. "Significant Contributions of H. Mark in Polymer Science." Poly Archives, Box 13, Folder 21. Bern Dibner Library, NYU Libraries, Brooklyn.
4. "An Interview with Herman F. Mark by G. Allan Stahl, 1979." Poly Archives, Box I, Folder 43. Bern Dibner Library, NYU Libraries, Brooklyn.
5. "An Interview with Herman F. Mark by G. Allan Stahl, 1979," page 5. Poly Archives, Box 1, Folder 43. Bern Dibner Library, NYU Libraries, Brooklyn.
6. "An Interview with Herman F. Mark by G. Allan Stahl, 1979," page 5. Poly Archives, Box 1, Folder 43. Bern Dibner Library, NYU Libraries, Brooklyn.
7. "Natural and Artificial Rubber: The Elasticity of Long-Chain Molecules." Poly Archives, Box 11, Folder 20. Bern Dibner Library, NYU Libraries, Brooklyn.
8. "Some Scientific Aspects of Synthetic Rubber Problem" by H. Mark. American Scientists, vol. 31, April 1943. Bern Dibner Library, NYU Libraries, Brooklyn.
9. "Charging the World." Polytechnic University, page 154.
10. "Charging the World." Polytechnic University, page 142.
11. Feichtinger, Johannes. "Herman F. Mark (1895-1992): Viennese-Born Ambassador of Macromolecular Research." In the 6th International Conference on the History of Chemistry, 219. https://www.academia.edu