February, 1929
I N D U S T R I A L A N D ENGINEERING CHEMISTRY
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PERKIN MEDAL AWARD The Perkin Medal for 1929 was presented t o Eugene C. suilivan, president of Corning Glass Works, Corning, N. Y . , on January 4, 1929, a t the joint meeting of the American Section of the Society of Chemical Industry, the AMERICAX CHEMICAL SOCIETY,the Societe de Chimie Industrielle, and the Electrochemical Society, in New York City. The program included an account of the early days of the medalist, by Alfred H. White, and of his accomplishments, by Arthur L. Day, followed by the presentation of the medal by a’illiam H. Nichols, and its acceptance by the medalist. Doctor White’s remarks were in part as follows:
Applied Chemistry.” It was founded in 1906 a t the time of the Perkin semi-centennial celebration of the coal-tar discoveries, the first medal being awarded to Sir William H. Perkin himself. The previous Perkin medalists are given below: DATEOF AWARD
It was formerly said in business circles t h a t the man t o be picked for the president of a company should be a hard-headed, practical man who had worked up from the position of office boy. Later the trend seemed to be toward the promotion of attorneys or salesmen, and now we are coming to the period when the scientist with a rich background of experience as well as scientific knowledge is considered the logical man to promote to an executive position. Doctor Sullivan is one of the pioneers in receiving this recognition. His father was foreman of the composing room of the Chicago Tribune, and while still a small boy Eugene learned to set type and to read proof. During his high-school course he spent his Saturday nights as a proofreader on the Tribune, and the money which he saved a t that time and which he earned in a similar position during vacations furnished most of the funds for his college course. Graduating from the course in chemistry at the University of Michigan in 1894, he was employed first in a dynamite plant and later in one which made baking powder. The desire for further study took him to Germany in 1896 where, after a semester with Nernst in Gottingen, he studied with Ostwald in Leipzig and received his Ph.D. in 1899. Returning t o the United States, he sepnt four years teaching analytical chemistry a t the University of Michigan. Promotion was slow at the university and Doctor Sullivan resigned in 1903 t o become a chemist with the United States Geological Survey. After five years he resigned that position to go to the Corning Glass Works as chief chemist, where he gradually built up the wonderful research division which has done so much t o bring ,American glass to the respected position which it now occupies. Starting in the laboratory, he gradually rose to have charge of the raw materials and melting of the glass and was successively promoted to be vice president, and in 1928 to be president, of the company. The Perkin Medal is awarded “annually t o the American chemist who has most distinguished himself by his services t o
1907 1908 1909 1910 1911 1912
AWARDED TO Sir W. H. Perkin J. B. F. Herreshoff Arno Behr E. G. Acheson Charles M. Hall Herman Frasch
1913 1914 1915
James Gayley John W. Hyatt Edward Weston
1916
L. H. Baekeland
1917 1918
Ernest Twitchell Auguste J. Rossi
1919 1920
Frederick G. Cottrell Charles F. Chandler
1921
Willis R. Whitney
1922
William M. Burton
1923
Milton C. Whitaker
1924
Frederick M. Becket
1925
Hugh K. hloore
1926 1927
R. B. Moore John E . Teeple
1928
Irving Langmuir
PRINCIPAL
FIELDS OF
INVENTIONS
Discoverer of first aniline color Metallurgy: contact sulfuric acid Corn products industry Carborundum; artificial graphite Metallic aluminum Desulfuring oil and subterranean sulfur industry Dry air blast Colloids and flexible roller bearings. Electrical measurements; electrodeposition of metals; flaming arc Velox photoprint paper; bakelite and synthetic resins; caustic soda industry Saponification of fats Development of manufacture and use of ferrotitanium Electrical precipitation Noteworthy achievements in almost every line of chemical endeavor Development of research and application of science to industry Achievement in oil industry; efficient conversion of high-boiling fractions into low-boiling fractions Great constructive work in field of applied chemistry Process for extraction of rare metals from ores; manufacture of calcium carbide; processes for reduction of rare metals and alloys Electrochemical processes for caustic soda, soda, and chlorine; production of wood pulp; hydrogenation of oils, etc. Radium, mesothorium, and helium Significant scientific, technical, and administrative achievements, particularly the economic development of an American potassium industry a t Searles Lake, Calif. Atomic hydrogen and its application. to welding
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The Many-Sidedness of Glass Eugene C. Sullivan CORNINGGLASSWORKS,CORKING,N.
NY results achieved a t Corning have come, not from one mind and one pair of hands, but from many minds and many hands working in cooperation. First, tribute should be paid to the men who were clear-sighted enough t o plant their money in the field of research at a timetwenty years or more ago-when visibility of dividends from that field was far lower than today. The research organization a t Corning, which has actually done the work, is made up of men willing to devote their efforts unselfishly to the common good. Some of the members of the research staff whose names should be mentioned are W. C. Taylor, chief chemist; J. T.Littleton, Jr., chief physicist; H. P. Gage,
A
Y.
chief of the Optical Laboratory; George V. McCauley, Gordon S. Fulcher, Harrison P. Hood, Rowland D. Smith, and the list could easily be extended. A competent engineering and mechanical development force has contributed also valuable advice and assistance; and, finally, the men who are most intimately familiar with glass, many of whom have given a lifetime to intelligent study of their material long hours every day, year in and year out-the superintendents and foremen and glass workers-we have found ready to meet the technical man more than half way, and eager t o contribute the observations for which they have such unexcelled opportunity. Old notebooks still in existence indicate that there always was
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research a t the Corning Glass Works. In its modern phase it began some twenty-five years ago when a representative of the company stepped into the laboratory of a consulting chemist in New York City and inquired, “Tell me, is it true that a chemist by analyzing a glass can say what materials have been put into it?” The chemist’s reply, “Oh yes!” was perhaps a trifle more confident than the situation warranted, yet that “yes” led Corning to undertake analyses of glass and raw materials and later to establish a one-man laboratory.
Vol. 21, No. 2
container, and in the service for which it was intended, for lantern globes, practically no difficulty was caused by the infirmity described. Another glass of higher expansion had been developed for chemically-resistant containers such as battery jars, and it was the effort to unite in one glass the good qualities of the two which led ultimately to the Corning super-resistant glasses. Glass for Baking Dishes
For several years after the advent of the .first super-resistant glass a t Corning, it was felt that we had in hand a new substance Corning has always manufactured railroad glassware, and the which might prove serviceable in various fields if only the proper first request made of the new laboratory was for a better lantern application could be found. The suggestion that the glass might globe for trainmen. A lantern globe frequently becomes over- be a suitable material for baking dishes for domestic use was heated in one spot by the oil flame playing directly on it, and therefore welcomed, and in spite of early misgivings over the glass thus overheated taken outdoors into radical step of putting glass into kitchen rain or snow may crack a t a time when a stoves, the venture has been a success. lantern signal is a matter of human life or One reason for hesitancy in offering glass death. for oven use was that we thought food The glass produced in response to this would bake very slowly in thick-walled demand had a low expansion codlicient, dishes of low heat conductivity, and the and in thermal endurance-that is, its ability first reports of faster baking in glass than to stand rapid temperature changes within metal were scarcely credited. The fact out breaking-it has scarcely been excelled was soon definitely established, however, among glasses produced in large commercial and there could be but one explanation quantity. -namely, that baking is a process of radiaIn view of the smallness of the change in tion from the oven walls rather than convolume caused by heating or cooling, the duction or convection. The surface of the expansion coefficient is a rather surprisingly metal dish throws back by reflection most significant factor in defining the service to of the heat rays striking it, whereas glass which a glass may be put. A pie plate, for reflects not over 10 per cent, and the high instance, 9 inches in diameter, of ordinary reflecting power of the metal evidently glass, contracts 0.009 inch when cooled from slows down the heating of its contents t o the boiling point to the freezing point of an extent not compensated by its thinness and high conductivity. Baking in metal water. A similar plate of low-expansion glass would contract 0.003 inch. The difactually is made more rapid by placing a glass plate under the metal dish. Curiously ference between the two glasses in amount Eugene C. Sullivan of contraction is only 0.006 inch, or the enough, cooling is slower in glass. The thickness of a visiting card, spread over 9 inches of diameter; cooling of a dish taken from the oven involves lower temperayet the ordinary glass plate heated to 100” C. and plunged tures than the heating, and the determining factor here is not radiation but the slow movement of heat through the thick glass. into ice water will crack while the low-expansion glass will stand a similar plunge from much higher temperatures. Laboratory Glassware Fortunately, in view of the importance of controlling this property of thermal endurance, the expansion coefficient of glasses As i t became evident that successful glasses for baking dishes can be varied in a wide ratio by suitable changes in chemical must possess not only very low expansion coefficient but also composition. Commercial glasses have linear expansivi ty ranga very high order of resistance to chemical corrosion, it was ing from three-millionths to eleven-millionths, these fractions realized that such glasses would be well fitted for laboratory use. representing the extent to which the length increases or decreases The field of laboratory glassware was, however, not alluring on heating or cooling one degree Centigrade. Where ordinary commercially, and it was only in response t o a rather insistent glass expands ten-millionths, metallic copper expands seventeen, demand, when imports of glass ceased during the war, that iron twelve, and platinum nine, this being also the figure for Corning entered upon the manufacture of beakers and flasks. certain lead glasses which are readily sealed t o platinum. For The ware was found to be less attacked by water than any other the Corning super-resistant glasses the value is around three, and and thanks to its low expansion coefficient i t could be made thicksome of these glasses seal readily t o porcelain, tungsten, and walled, therefore rugged, and yet could survive the shocks of molybdenum, which have expansion coefficients of four to five rapid heating and cooling in laboratory manipulations, to meet on the same scale. which glassware of higher expansion had had t o be very thin and For wider applications our first lantern-globe glass suffered therefore fragile. The chemists of the country received the ware under one serious drawback-it was slowly but completely soluble very cordially and have paid it the high compliment of subjecting in water at ordinary temperatures. Used as a container for i t to service more and more strenuous, with consequent occasional water it would absorb the liquid into its surface, and the swelling disaster. It has become necessary t o put out reminders that, and tension which resulted as the water penetrated further and after all, the ware is glass and that if overheated in a hot flame it takes on strain which may cause it to break a t a most unexpected further would finally cause the glass to fly to pieces in a miniature moment. explosion. Indeed, the rapidity with which the glass gave off An outgrowth of the use of Pyrex beakers and flasks is the boric acid to water led to the suggestion that the fault be exploited application of Pyrex tubing t o ordinary laboratory glass-blowing. as a virtue. It was proposed that we market sanitary tumblers, advertising them as “germproof” by reason of the antiseptic Orders for Pyrex tubing for common use were referred by the properties of the boric acid. The glass was never offered to the factory in the beginning to manufacturers of lime glass in the public, however, in a form in which i t could possibly be used as a bellef that there was no need in such cases for Pyrex tubing. It First Research o n Low-Expansion Glass
February, 1929
INDUSTRIAL AND ENGINEERING CHEXISTRY
is true, however, that with the low-expansion tubing not only less glass-blowing skill and less care are required, but subsequent breakage is less likely from strain introduced during working, and hence the low-expansion tubing has come into very extensive use for laboratory glass-blowing. O t h e r Applications of Low-Expansion Glass I n addition to their application in the field of laboratory ware various unanticipated merits of the Corning low-expansion compositions have come t o light in course of time. The hardness of these glasses in the sense of resistance to scratching is greater than that of common glass and they resist certain types of abrasion much better than steel. The unusual hardness has led to the use of Pyrex reels for winding silk, such reels wearing away rapidly when made of other materials. I n general, hardness in glasses can be made to vary in about a 2 t o 1 ratio, the hardest glass being harder than quartz or iron and the softest somewhat harder than the soft mineral fluorite. The chemical resistivity and low expansion coefficient of the new glasses suggested their employment in the field of hightension electric insulation. They were found to have suitable dielectric strength or puncture strength, from 15 to 35 per cent higher than that of the ordinary material, which is a wet-process porcelain. Other favorable qualities were soon discovered. Exposed to direct sunlight the temperature of porcelain insulators rises several times as much as that of Pyrex insulators. The transparent material therefore lessens such breakage as takes place on mountain power lines, when the sun sets quickly behind a western range and the insulator is chilled by a cold wind. An outstanding virtue of the glass is its survival of the fiery ordeal of a power arc, which shatters porcelain instantly. The heat of the arc melts a thin surface film of glass, but the insulator continues to perform its function. A modified form is a nostatic insulator which eliminates corona discharge, thereby incidentally lessening operating difficulties and a t the same time raising the puncture strength. For radio insulation some of the Pyrex compositions are found to possess rather unique properties which protect the already attenuated radio currents against leakage and dielectric loss. The power loss is lower than that of other materials suitable for radio insulation, with the possible exception of fused quartz, being only a small percentage of that of such insulating substances as ordinary glass, porcelain, hard rubber, and phenolic compositions. Physical Properties of Glasses With regard to glasses in general, it is only in recent years that the individuality of the members of the glass family is becoming known. To many people glass is glass, and that's the end of it. Actually glass is a many-sided material. A more general recognition of the wide range of physical properties which are a t our disposal in glasses would lead undoubtedly t o special glasses developed for specific purposes becoming useful additions t o the materials now serving industry. By adjustment of chemical composition most of the properties of glass can be changed in the ratio of 2 t o 1 and some in a very much greater ratio. To a surprising extent these properties approach or even overlap those of the metals.' Not only are the virtues of glass not fully appreciated, but all too frequently it is actually maligned. For instance, when properly made it does not merit its reputation for lack of strength. In strength glass under certain conditions equals iron. Its tensile strength in laboratory measurements ordinarily is about 10,000 pounds per square inch, which means that, provided the laboratory strength could be maintained in large-scale tests, a freight car or its load, say 40,000 pounds, could be supported An interesting comparison between properties of glass and other materials is contained in a paper on the physics of glass by George Gehlhoff, of Berlin, in February, 1928, and printed as manuscript.
179
by a glass bar 2 inches square. It is possible to prepare glasses by special heat treatment, the so-called case-hardening process, which show tensile strength near that of wrought iron, which is about 50,000 pounds per square inch. This is not new, for casehardened glasses were the subject of patents issued some fifty years ago. For various reasons they have not proved generally practical. The resistance of glass to crushing pressure is very great. Provided again that laboratory measurements held good in largescale operations-which, of course, they do not-350 tons, eight loaded freight cars for instance, balanced on a 2-inch cube of the strongest glass might be just sufficient to crush it. The compression strength of glass is greater than that of ordinary structural materials such as granite, concrete, or vitrified brick. Even cast iron yields under three-fourths the pressure required to crush glass. In general, glass maintains its shape under pressures which cause metals to flow like putty. In resistance to distortion under stress (Young's modulus) glasses can be varied in the 2 to 1 ratio. At its highest this property in glass is higher than that of aluminum and, strange to say, approaches that of cast iron. A t its lowest it is lower than most of the metals. The specific gravity of ordinary lime glass is close to that of metallic aluminum and of the common rock-forming minerals. It can be made to vary in a ratio of about 3 to 1-namely, from 6.33 to 2.14. The glasses sold under the Pyrex trade-mark are among the lowest. The highest is almost up to that of gray cast iron, which may be as low as 7. The surface tension of glass a t its melting temperature-namely, its tendency to form into drops-is twice that of water and less than one-third that of mercury. In specific heat ordinary glass is near aluminum and about twice iron or copper. Heat conductivity, of course, is far below the metals. However, in consequence of surface conditions heat transfer through a copper condenser is only two and one-half times that through a Pyrex condenser, although the heat conductivity of copper is some three hundred times that of the glass. The annealing temperature of glass-that is, the temperature a t which strain is relieved-is 400" to 600" C., somewhat higher than that for steel, which is between 200' and 500' C. Glass on cooling passes through a recalescence a t a temperature close to one of the recalescence points of steel, 487" C. In its effect on the velocity of light as shown by the refractive index, glass varies between 1.46 and 1.96. Water is somewhat below the lower figure. Diamond is far above the high figure, hence the superior brilliance and sparkle of the precious stone. In dispersive power, however, some glasses considerably excel the diamond, the figures for glass ranging between 29 and 70 while diamond is 56. With regard to absorption and transmission of radiation, there is a multitude of practical possibilities in the peculiar properties possessed by glass. There are glasses which transmit visible light but no infra-red and others that transmit infra-red and no visible. At the other end of the spectrum a recent development is a glass which transmits the ultra-yiolet of sunlight as well as quartz. There are other glasses which transmit some ultraviolet and no visible, and still others that transmit visible and no ultra-violet. The last named has found application in the transparent cylinder of the roadside gasoline pump, to protect the gasoline from the short wave-length rays of the sun, which would turn i t yellow and cloudy. In the visible spectrum glass color filters can, of course, be had of great variety for a multiplicity of purposes. Unsolved Problems After all, not much more than a beginning has been made on the chemistry and physics of glass. We know practically nothing
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of the chemical constitution and structure. A glass melted from moist raw materials differs in working quality from a glass melted from the same materials dry. Chemically they do not differ. Two glasses otherwise identical, both without visible strain, will have different viscosities, depending on heat treatment. What structural differences exist among these glasses identical in chemical composition yet unlike in physical properties, we do not know. Nor has a systematic determination been made of equilibrium conditions among glass components. Investigation of these subjects and others as purely scientific problems undoubtedly would yield results of immediate practical application. A major task of the glass technologist today is the delivery to glass-working machines of material that is both homogeneous and uductuating as t o chemical composition, as t o temperature, and as t o physical properties. The hand worker can adapt his manipulation t o a varying material. For the machine the material should be constant. Present glass-melting methods are poorly adapted for delivering such a product. One reason why glass is not homogeneous is that it dissolves the clay walls of the tank. A long step toward meeting the crying need of the industry for a suitable refractory in which t o melt glass has been taken by Doctor Fulcher, inventor of cast refractories, which are aluminum silicates and refractory oxides handled as in iron foundry practice, the material being melted in an electric furnace and cast in molds for tank blocks and other shapes. The cast block is more resistant t o the corrosive attack
VOl. 21, XO. 2
of glass than the ordinary clay block, which lasts in exposed positions a t best a year and sometimes only a few months. Lack of homogeneity is caused also by temperature differences in the glass, and such differences, as well as an excessive waste of fuel, are t o be laid t o the conventional design of the glass-melting tank. I n the melting process, which is a large item of cost, only about 10 per cent of the coal used is actually required t o raise the raw materials t o temperature and to melt them. Ninety per cent of the heat value is lost. The excessive consumption of fuel is caused chiefly by the practice of maintaining a t or near melting temperature a mass of glass out of all proportion to the quantity actually being worked. For machines working, say, 50 pounds a minute we hold 6000 times that amount, or 160 tons a t white heat 24 hours a day, 7 days a week, and thus cause losses by radiation and otherwise amounting t o many times the total heat theoretically required. An abundance of interesting and fundamental work, then, remains t o be done in glass, both in pure science and in its application. One of my fellow students in Ostwald’s laboratory, in Leipzig, thirty years ago, who was laboring as we all were to give birth to something that might charitably be regarded as a contribution to science, was in the habit of lamenting bitterly that the easy things had all been done. In glass not even the easy things have all been done, and help is needed from those who like t o do the hard things. To workers in science we suggest the field of glass investigation as attractive and worthy.
CHANDLER LECTURE The Chandler Lecture for 1928 was delivered at Columbia University on December 7, by John Arthur Wilson, of Milwaukee, Wis., chief chemist of A. F. Gallun and Sons Company and consulting chemist and director of research for the Milwaukee Sewerage Commission. In presenting the medal t o Mr. Wilson, Dean George B. Pegram stated that the medalist was best known “for the way in which he has applied the most modern concepts of chemistry to one of the oldest industries, the making of leather,” and described his achievements as follows:
The Charles Frederick Chandler Foundation was established in 1910, when friends of Professor Chandler presented to the trustees of Columbia University a sum of money, and stipulated that the income was to be used to provide a lecture by an eminent chemist and also a medal t o be presented t o this lecturer in further recognition of his achievements in the chemical field. The previous lecturers, with the titles of their lectures, are as follows: 1914
L. H. Baekeland
Mr. Wilson’s published researches in physical chemistry, colloid chemistry, and the chemistry of proteins ; his application with great daring and acumen of wide and exact knowledge of the most modern advances in chemistry to the complex problems of leather chemistry, resulting in valuable improvements in processes; and his distinguished public service in introducing improvements in the process of sewage treatment that has not only made operable a sewage disposal plant for his own city of half a million people which is a valuable object lesson for all our cities, but has made it operable in such a way that it may soon be returning revenues to the city, are achievements that have placed him in the front rank of chemists.
1916
W. F. Hillebrand
1920
W. R. Whitney
1921
F. G. Hopkins
1922 1925
E. F. Smith R. E. Swain E. C. Kendall
1926
S. W. Parr
1927
Moses Gomberg
1923
Some Aspects of Industrial Chemistry [Vol. 6 769 (1914)l Ou; Analytical Chemistry and Its Future [Vol 9 170 (1917)I The Lktl;st Things in Chemistry [Vol. 12, 599 (1920)l Newer Aspects of the Nutrition Problem [Vol. 14, 64 (1922)l Samuel Latham Mitchill-A Father in American Chemistry [Vd. 14, 556 (1922) ] Atmospheric Pollution by Industrial Wastes [Vol. 15 296 (1923)l Influence hf the Thyroid Gland on Oxidation in the Animal Organism [Vol. 17,525 (1925) The Constitution of Coal-Having Speciall Reference to the Problems of Cirbonization [Vol. 18, 640 (1926)l Radicals in Chemistry, Past and Present [Vol. 20, 159 (1928)l
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Chemistry and Leather John A r t h u r Wilson A. F. GALLUN& SONSCOMPANY, MILWAUKEE, WIS.
S
INCE the dawn of civilization, leather has been one of the world’s most important commodities. It has become so much a part of our everyday life that we should find ourselves in a quandary if it were suddenly taken from us. And yet, after thousands of years of daily use, its properties remain but poorly defined. Leather is not a simple and homogeneous material of definite properties. On the contrary, it is of very
variable chemical composition; it has an exceedingly complex and variable physical structure; and every variation in composition or structure causes some corresponding change in properties and in serviceability. Unfortunately, the relations involved are not yet well understood. Occasionally we find glaring examples of the far-reaching effects of our ignorance in this respect. It will be sufficient t o cite one.
