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Paul Flory

 
Scientist: Paul John Flory

American polymer chemist (1910–1985)

Flory was born at Sterling, Illinois, and educated at Ohio State University, where he obtained his PhD in 1934. His career was divided between industry and university. He worked with Du Pont from 1934 until 1938 on synthetic polymers and then spent the next two years at the University of Cincinnati. After working for Standard Oil from 1940 until 1943, Flory served as Director of Fundamental Research for the Goodyear Tire Company in Akron, Ohio, until 1948. He was then appointed to the chair of chemistry at Cornell. He left Cornell in 1957 to become director of research of the Mellon Institute in Pittsburgh and, finally, in 1961, accepted the chair of chemistry at Stanford University, California.

Flory was one of the people who, in the 1930s, began working on the properties of polymers. A particular problem at the time was that polymer molecules do not have a definite size and structure; a given polymeric material consists of a large number of macromolecules with different chain lengths. Flory approached this problem using statistical methods, obtaining expressions for the distribution of chain lengths.

In further work he developed a theory of nonlinear polymers, which involve cross linkages between molecular chains. He showed how such extended structures can form from a solution of linear polymers. A particular innovation was the concept of Flory temperature – a temperature for a given solution at which meaningful measurements can be made of the properties of the polymer.

In later work Flory considered the elasticity of rubbers and similar polymeric materials. He published two authoritative books: Principles of Polymer Chemistry (1953) and Statistical Mechanics of Chain Molecules (1969). For his major contribution in the field Flory was awarded the Nobel Prize for chemistry in 1974.

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Biography: Paul Flory
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Paul Flory (1910-1985), founder of the science of polymers, was a researcher in macronuclear chemistry and was awarded the Nobel Prize in 1974.

Paul Flory is widely recognized as the founder of the science of polymers. The Nobel Prize in chemistry he received in 1974 was awarded not for any single specific discovery, but, more generally, "for his fundamental achievements, both theoretical and experimental, in the physical chemistry of macromolecules." That statement accurately reflects the wide-ranging character of Flory's career. He worked in both industrial and academic institutions and was interested equally in the theory of macromolecules and in the practical applications of that theory.

Paul John Flory was born in Sterling, Illinois, on June 19, 1910. His parents were Ezra Flory, a clergyman and educator, and Martha (Brumbaugh) Flory, a former school teacher. Ezra and Martha's ancestors were German, but they had resided in the United States for six generations. Both the Flory and the Brumbaugh families had always been farmers, and Paul's parents were the first in their line ever to have attended college.

After graduation from Elgin High School, Flory enrolled at his mother's alma mater, Manchester College, in North Manchester, Indiana. The college was small, with an enrollment of only 600. He earned his bachelor's degree in only three years, at least partly because the college "hadn't much more than three years to offer at the time," as he was quoted as having said by Richard J. Seltzer in Chemical and Engineering News. An important influence on Flory at Manchester was chemistry professor Carl W. Holl. Holl apparently convinced Flory to pursue a graduate program in chemistry. In June of 1931, therefore, Flory entered Ohio State University and, in spite of an inadequate background in mathematics and chemistry, earned his master's degree in organic chemistry in less than three months. He then began work immediately on a doctorate, but switched to the field of physical chemistry. He completed his research on the photochemistry of nitric oxide and was granted his Ph.D. in 1934.

Flory's doctoral advisor, Herrick L. Johnston, tried to convince him to stay on at Ohio State after graduation. Instead, however, he accepted a job at the chemical giant, Du Pont, as a research chemist. There he was assigned to a research team headed by Wallace H. Carothers, who was later to invent the process for making nylon and neoprene. Flory's opportunity to study polymers was ironic in that, prior to this job, he knew next to nothing about the subject. Having almost any job during the depths of the Great Depression was fortunate, and Flory was the envy of many classmates at Ohio State for having received the Du Pont offer.

Flory's work on the Carothers team placed him at the leading edge of chemical research. Chemists had only recently begun to unravel the structure of macromolecules, very large molecules with hundreds or thousands of atoms, and then to understand their relationship to polymers, molecules that have chemically combined to become a single, larger molecule. The study of polymers was even more difficult than that of macromolecules because, while the latter are very large in size, they have definite chemical compositions that are always the same for any one substance. Polymers, on the other hand, have variable size and composition. For example, polyethylene, a common polymer, can consist of anywhere from a few hundred to many thousands of the same basic unit (monomer), arranged always in a straight chain or with cross links between chains.

With his background in both organic and physical chemistry, Flory was the logical person to be assigned the responsibility of learning more about the physical structure of polymer molecules. That task was made more difficult by the variability of size and shape from one polymer molecule to another - even among those of the same substance. Flory's solution to this problem was to make use of statistical mechanics to average out the properties of different molecules. That technique had already been applied to polymers by the Swiss chemical physicist Werner Kuhn and two Austrian scientists, Herman Mark and Eugene Guth. But Flory really developed the method to its highest point in his research at Du Pont.

During his four years at Du Pont, Flory made a number of advances in the understanding of polymer structure and reactions. He made the rather surprising discovery, for example, that the rate at which polymers react chemically is not affected by the size of the molecules of which they are made. In 1937, he discovered that a growing polymeric chain is able to terminate its own growth and start a new chain by reacting with other molecules that are present in the reaction, such as those of the solvent. While working at Du Pont, Flory met and, on March 7, 1936, married Emily Catherine Tabor. The Florys had two daughters, Susan and Melinda, and a son, Paul John, Jr. Flory's work at Du Pont came to an unexpected halt when, during one of his periodic bouts of depression, Carothers committed suicide in 1937. Although deeply affected by the tragedy, Flory stayed on for another year before resigning to accept a job as research associate with the Basic Science Research Laboratory at the University of Cincinnati. His most important achievement there was the development of a theory that explains the process of gelation, which involves cross-linking in polymers to form a gel-like substance.

Flory's stay at the University of Cincinnati was relatively brief. Shortly after World War II began, he accepted an offer from the Esso (now Exxon) Laboratories of the Standard Oil Development Company to do research on rubber. It was apparent to many American chemists and government officials that the spread of war to the Pacific would imperil, if not totally cut off, the United States' supply of natural rubber. A massive crash program was initiated, therefore, to develop synthetic substitutes for natural rubber. Flory's approach was to learn enough information about the nature of rubber molecules to be able to predict in advance which synthetic products were likely to be good candidates as synthetic substitutes ("elastomers"). One result of this research was the discovery of a method by which the structure of polymers can be studied. Flory found that when polymers are immersed in a solvent, they tend to expand in such a way that, at some point, their molecular structure is relatively easy to observe.

In 1943, Flory was offered an opportunity to become the leader of a small team doing basic research on rubber at the Goodyear Tire and Rubber Company in Akron, Ohio. He accepted that offer and remained at Goodyear until 1948. One of his discoveries there was that irregularities in the molecular structure of rubber can significantly affect the tensile strength of the material.

In 1948, Flory was invited by Peter Debye, the chair of Cornell University's department of chemistry, to give the prestigious George Fisher Baker Lectures in Chemistry. Cornell and Flory were obviously well pleased with each other as a result of this experience, and when Debye offered him a regular appointment in the chemistry department beginning in the fall of 1948, Flory accepted - according to Maurice Morton in Rubber Chemistry and Technology - "without hesitation." The Baker Lectures he presented were compiled and published by Cornell University Press in 1953 as Principles of Polymer Chemistry. Flory continued his studies of polymers at Cornell and made two useful discoveries. One was that for each polymer solution there is some temperature at which the molecular structure of the polymer is most easily studied. Flory called that temperature the theta point, although it is now more widely known as the Flory temperature. Flory also refined a method developed earlier by the German chemist Hermann Staudinger to discover the configuration of polymer molecules using viscosity. Finally, in 1956, he published one of the first papers ever written on the subject of liquid crystals, a material ubiquitous in today's world, but one that was not to be developed in practice until more than a decade after Flory's paper was published.

In 1957, Flory became executive director of research at the Mellon Institute of Industrial Research in Pittsburgh. His charge at Mellon was to create and develop a program of basic research, a focus that had been absent from that institution, where applied research and development had always been of primary importance. The job was a demanding one involving the supervision of more than a hundred fellowships. Eventually, Flory realized that he disliked administrative work and was making little progress in refocusing Mellon on basic research. Thus, when offered the opportunity in 1961, he resigned from Mellon to accept a post at the department of chemistry at Stanford University. Five years later, he was appointed Stanford's first J. G. Jackson-C. J. Wood Professor of Chemistry. When he retired from Stanford in 1975, he was named J. G. Jackson-C. J. Wood Professor Emeritus. In 1974, a year before his official retirement, Flory won three of the highest awards given for chemistry - the National Medal of Science, the American Chemical Society's Priestley Medal, and the Nobel Prize in chemistry. These awards capped a career in which, as Seltzer pointed out, Flory had "won almost every major award in science and chemistry."

Flory's influence on the chemical profession extended far beyond his own research work. He was widely respected as an outstanding teacher who thoroughly enjoyed working with his graduate students. A number of his students later went on to take important positions in academic institutions and industrial organizations around the nation. His influence was also felt as a result of his two books, Principles of Polymer Chemistry, published in 1953, and Statistical Mechanics of Chain Molecules, published in 1969. Leo Mandelkern, a professor of chemistry at Florida State University, is quoted by Seltzer as referring to the former work as "the bible" in its field, while the latter has been translated into both Russian and Japanese.

Flory was also active in the political arena, especially after his retirement in 1975. He and his wife decided to use the prestige of the Nobel Prize to work in support of human rights, especially in the former Soviet Union and throughout Eastern Europe. He served on the Committee on Human Rights of the National Academy of Sciences from 1979 to 1984 and was a delegate to the 1980 Scientific Forum in Hamburg, at which the topic of human rights was discussed. As quoted by Seltzer, Morris Pripstein, chair of Scientists for Sakharov, Orlov, and Scharansky, described Flory as "very passionate on human rights…You could always count on him." At one point, Flory offered himself to the Soviet government as a hostage if it would allow Soviet scientist Andrei Sakharov's wife, Yelena Bonner, to come to the West for medical treatment. The Soviets declined the offer, but eventually did allow Bonner to receive the necessary treatment in Italy and the United States.

Flory led an active life with a special interest in swimming and golf. In the words of Ken A. Dill, professor of chemistry at the University of California, San Francisco, as quoted by Seltzer, Flory was "a warm and compassionate human being. He had a sense of life, a sense of humor, and a playful spirit. He was interested in, and cared deeply about, those around him. He did everything with a passion; he didn't do anything half way." Flory died on September 8, 1985, while working at his weekend home in Big Sur, California. According to Seltzer, at Flory's memorial service in Stanford, James Economy, chair of the American Chemical Society's division of polymer chemistry, expressed the view that Flory was "fortunate to depart from us while still at his peak, not having to suffer the vicissitudes of old age, and leaving us with a sharply etched memory of one of the major scientific contributors of the twentieth century."

Further Reading

Morton, Maurice, "Paul John Flory, 1910-1985, part I: The Physical Chemistry of Polymer Synthesis," in Rubber Chemistry and Technology, May-June, 1987, pp. G47-G57.

Seltzer, Richard J., "Paul Flory: A Giant Who Excelled in Many Roles," in Chemical and Engineering News, December 23, 1985, pp. 27-30.

 
Columbia Encyclopedia: Paul John Flory
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Flory, Paul John, 1910-85, American chemist, b. Sterling, Ill., Ph.D. Ohio State Univ., 1934. Flory was a researcher with the DuPont Company (1934-37) and a professor at the Univ. of Cincinnati (1937-40). He then worked for Esso (now Exxon) Laboratories (1940-43) and Goodyear Tire and Rubber Company (1943-48). Flory returned to academia as a professor at Cornell Univ. (1948-57), the Mellon Institute, Pittsburgh (1957-61), and Stanford (1961-85). Flory won the 1974 Nobel Prize in Chemistry for theoretical and experimental achievements in the physical chemistry of macromolecules. Flory developed concepts to explain the behavior of polymer molecules, including identification of the theta temperature, now known as the Flory temperature, where the molecule assumes a kind of ideal state. This concept enables useful comparisons to be made among different types of polymers.
Wikipedia: Paul Flory
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Paul John Flory

Born June 19, 1910(1910-06-19)
Sterling, Illinois
Died September 9, 1985 (aged 75)
Big Sur, California
Nationality United States
Fields Physical chemistry
Institutions DuPont, Stanford University, Carnegie Mellon University
Alma mater Manchester College (Indiana) and Ohio State University
Doctoral advisor Herrick L. Johnston
Known for Polymers
Notable awards Nobel Prize for Chemistry (1974)
Perkin Medal (1977)
Priestley Medal 1974

Paul John Flory (June 19, 1910September 9, 1985) was an American chemist and Nobel laureate who was known for his prodigious volume of work in the field of polymers, or macromolecules. He was a leading pioneer in understanding the behavior of polymers in solution, and won the Nobel Prize in Chemistry in 1974 "for his fundamental achievements, both theoretical and experimental, in the physical chemistry of macromolecules."

Contents

Biography

Early life

After graduating from Elgin High School in Elgin, Illinois in 1927, Flory received a bachelor's degree from Manchester College (Indiana) in 1931 and a Ph.D. from the Ohio State University in 1934. His first position was at DuPont with Wallace Carothers.[1]

Polymer science

Flory's earliest work in polymer science was in the area of polymerization kinetics at the DuPont Experimental station. In condensation polymerization, he challenged the assumption that the reactivity of the end group decreased as the macromolecule grew, and by arguing that the reactivity was independent of the size, he was able to derive the result that the number of chains present decreased with size exponentially. In addition polymerization, he introduced the important concept of chain transfer to improve the kinetic equations and remove difficulties in understanding the polymer size distribution.

In 1938, after Carothers' death, he moved to the Basic Science Research Laboratory at the University of Cincinnati. There he developed a mathematical theory for the polymerization of compounds with more than two functional groups and the theory of polymer networks or gels.

In 1940 he joined the Linden, NJ laboratory of the Standard Oil Development Company where he developed a statistical mechanical theory for polymer mixtures. In 1943 he left to join the research laboratories of Goodyear as head of a group on polymer fundamentals. In the Spring of 1948 Peter Debye, then chairman of the chemistry department at Cornell University, invited Flory to give the annual Baker Lectures. He then was offered a position with the faculty in the Fall of the same year. There he elaborated and refined his Baker Lectures into his magnum opus, Principles of Polymer Chemistry which was published in 1953 by Cornell University Press. This quickly became a standard text for all workers in the field of polymers, and is still widely used to this day.

Flory introduced the concept of excluded volume, coined by Werner Kuhn in 1934, to polymers. Excluded volume refers to the idea that one part of a long chain molecule can not occupy space that is already occupied by another part of the same molecule. Excluded volume causes the ends of a polymer chain in a solution to be further apart (on average) than they would be were there no excluded volume. The recognition that excluded volume was an important factor in analyzing long-chain molecules in solutions provided an important conceptual breakthrough, and led to the explanation of several puzzling experimental results of the day. It also led to the concept of the theta point, the set of conditions at which an experiment can be conducted that causes the excluded volume effect to be neutralized. At the theta point, the chain reverts to ideal chain characteristics - the long-range interactions arising from excluded volume are eliminated, allowing the experimenter to more easily measure short-range features such as structural geometry, bond rotation potentials, and steric interactions between near-neighboring groups. Flory correctly identified that the chain dimension in polymer melts would have the size computed for a chain in ideal solution if excluded volume interactions were neutralized by experimenting at the theta point.

Among his accomplishments are an original method for computing the probable size of a polymer in good solution, the Flory-Huggins Solution Theory, and the derivation of the Flory exponent, which helps characterize the movement of polymers in solution.

The Flory convention

see Flory convention for details.

In modeling the position vectors of atoms in macromolecules it is often necessary to convert from Cartesian coordinates (x,y,z) to generalized coordinates. The Flory convention for defining the variables involved is usually employed. For an example, a peptide bond can be described by the x,y,z positions of every atom in this bond or the Flory convention can be used. Here one must know the bond lengths li, bond angles θi, and the dihedral angles φi. Applying a vector conversion from the Cartesian coordinates to the generalized coordinates will describe the same three-dimensional structure using the Flory convention.

Later years

He accepted a professorship at Stanford University in 1961, became the Jackson-Wood Professor there in 1966 and retired from there in 1975. He was awarded the Nobel Prize in Chemistry in 1974 "for his fundamental achievements, both theoretical and experimental, in the physical chemistry of macromolecules." He remained active after his retirement, and consulted for IBM for some years. He and his wife Emily Catherine Tabor (now deceased) had three children. He died of a heart attack in Big Sur, California in 1985.

Bibliography

References

  1. ^ * Morris, Peter J. T. Polymer Pioneers: A Popular History of the Science and Technology of Large Molecules Center for History of Chemistry, Philadelphia (1986) p. 70-73

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