Is There a Sulfur Shortage? - C&EN Global Enterprise (ACS

Τ H t CHEMICAL W O R L D THIS WEEK Is There α Sulfur Shortage? For the present? N o . All forms? a long time. Frasch process? Eventually mediately

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VITTITH the alleviation of the sulfur short*^ ages which have occurred over the past two years, sulfur users are once again drawing normal breaths. For the imme­ diate present, the sulfur picture is not too disturbing. More sulfur has become avail­ able, domestic and international allocations have gone, and price ceilings are off. Ex­ port shipments still remain limited, how­ ever. Since OPS ceiling prices were lifted in March, the price of sulfur has risen $3.50 to $5.50 a ton for low-cost sulfur, but, on the other hand, Frasch sulfur consumers who were forced to turn to high-cost or black-market sulfur at $100 a ton or over are no longer faced with this necessity. This does not mean that high-cost sulfur is being entirely displaced, however. Many special areas will always create a demand for this type. A steady rate of increasing demand is seen for both highcost and low-cost sulfur in the long run. In retrospect, the sulfur shortage was not as severe nor as fearsome as was first believed. National Production Authority statistics show that the over-all usage cut­ back amounted to a little less than 10% of demand. Everyone felt the pinch, of course, but rarely was it fatal. The opin­ ion of many sources now is that the strained position of sulfur was not caused by a sudden run-out in resources but by a series of unpredictable events affecting production. In general, it is felt that the unbalanced position of sulfur was caused by three factors: 1. a depletion of mine stocks despite a record tonnage in World War II and without normal chances to re­ stock, 2. the high demand for sulfur by free nations in their postwar build-up, and 3. the sudden demands brought about by the Korean mobilization. A certain amount of recuperative time was needed by the sulfur industry to re­ organize for accelerated production and to assess the world demand picture after World War II. That time was not found. It is now felt in many places that the ac­ celerated production programming of the last two years, coupled with allocations, has provided some of this time. The abil­ ity of production to meet the demand of consumers would certainly indicate this fact. With these kinks being ironed out by the industry and consumers alike, no im­ mediate recurrence of the shortage is be­ lieved to be in the offing. It has been pre­ dicted that in the future, should sulfur consuming industries again expand at a rapid rate, the sulfur situation might again become tight. Other sources advance the theory that hoped-for production of Frasch-process sulfur in Mexico will di­ minish this fear. With Frasch sulfur so low in cost ($25 to $27 per ton at the port), it is obvious that no sulfur consumer is going to think AND

E N G I N E E R I N G

NEWS

U.S. SULFUR POSITION Million Long Tons

1935

1940

1945

1950

52 53 EST. £ST.

of other, high-cost sulfur ($35 to $110 per t o n ) if he can get Frasch sulfur. The great question raised in the minds of consumers by the shortage is: How long can Frasch sulfur be relied upon? This might almost be called the $27 question. The International Materials Conference states that free world production of crude sulfur -was 6.14 million long tons in 1951 and about 6.4 million long tons in 1952, and estimates 1953 production at 6.9 million. On the other hand, at the height of the crisis IMC calculated world requirements for 1951 as 7.1 million long tons. At that time they advanced a figure of 7.4 million long tons for 1952. Early in 1952 they revised this estimate downward, and current figures show that the actual demand for sulfur in 1952 barely reached 6 million long tons. In short, production more than balanced demand in 1952. IMC now estimates that 1953 demand will be only about 6.9 million long tons. These figures led them to remove sulfur allocations early this year (Feb. 2,8). As evidence for these figures, IMC said actual demand had declined in 1952 because of increased use of other sulfur-bearing materials, conservation measures, and a decline in the level of industrial activity. Over-production in this country has enabled Frasch process operators to build up their stocks on hand by about 400,000 long tons in the past two years, although this is still about 2 million tons short of the 5 million tons on hand before World War I I . Decline in demand, allocations, and full production schedules have made this possible. It is estimated that the Frasch sulfur mines which existed in 1950 cannot produce more than 1 to 2 % over what they are n o w producing. If these were the only V O L U M E

3 1,

NO.

19

sources of low-cost sulfur, production expansion based on Frasch sulfur would be at a stalemate. If the production from a dome such as the Boling Dome, which produced nearly half of 1950's Frasch sulfur, were to dry up, the sulfur outlook would again be serious if there were no other source upon which to rely. This is not the case. During 1952, Freeport Sulphur brought into production its Bay St. Elaine Dome, La., with some 100,000 tons of additional capacity. Jefferson Lake Sulphur has added its Starks Dome, La., plant with about 80,000 tons annual capacity. Texas Gulf Sulphur has built a 250,000-ton plant at the Spindletop Dome and in December 1952 brought in its 150,000-ton expansion at Moss Bluff, Tex. The latest plant reported open is the Freeport Chacahoula Dome, La., with an annual capacity estimated in excess of 100,000 tons. Still under development are Freeport's Garden Island Bay, La., and Nash, Tex., domes. However, the U. S. is no longer the only source of Frasch sulfur now that Mexican deposits are being developed. Prospecting has been aggressive in Mexico, and much of the subsequent development has been backed by the Export-Import Bank of Washington. The accompanying map shows the location of suspected or known Mexican deposits obtainable by the Frasch process. Mexican Gulf Sulphur has a $5.5 million plant under construction on the San Cristobal Dome -with an expected capacity of 200,000 tons per year. It is expected to be ready to go on stream about July 1 of this year. Pan American Sulphur has raised nearly $7 million and will shortly begin construction of a 500,000-ton-peryear plant at Jaltipan, where some 70 wells have proved a deposit of 7.2 to 11.8 milMAY

11,

1953

lion tons. Gulf Sulphur Co., another firr** operating in the same area of Mexico's Isthmus of Tehuantepec, reports that a drilling of 18 wells on its Salinas holdings has yielded a geologic estimate of over 8.9 million long tons on one section of their property. Other drillings have been made by other firms but no reports of the findings are adequately known. On the other hand, in the spring of 1951 a Mexican firm placed in production a sour gas sulfur recovery plant which is now operating at a recovery rate of 120 tons per day from a weak gas. Such actions are felt by some to be indicative of a far reaching trend. Not enough prospecting' has been done so far, so as yet no estimate is forthcoming as to the amount of Frasch sulfur in Mexico. It is interesting to note that two companies, Gulf Sulphur and Mexican Gulf, have begun development of their plants on the basis of findings on 1 ancl 8r/r of their properties, respectively. However, it is warned that these percentages arc not valid tools for predicting what may still be underground in Mexico. If the large capacity indicated is found, Mexico will become a large exporter of Frasch sulfur, even though some of it may be absorbed by the growing needs of that country. These figures indicate the availability of enough new capacity in the near future to provide more than the highest 7.4million-ton annual requirement estimated by IMC. If the trend in positive results from prospecting continues, more Frasch sulfur may be uncovered in the near future, enabling production to keep pace with expanding demand for some time into the future. This immediately raises the question of* how long Frasch sulfur, that pure, relatively cheap commodity, will be available. No one can answer that because no one knows. Too many unknowns are in the picture. The extractable tonnage of brimstone in a given dome is impossible to assess exactly. Not only is it difficult to know when mines approach exhaustion, but it is even difficult to predict the rate of production a year or two ahead. Major producers of American crude sulfur have indicated that some of their mines have been operating at a declining rate. Moreover, U. S. operators no longer look on American Frasch sulfur as unlimited and hold out little hope of discovering much more in continental U. S., although another big sulfur strike is by no means impossible. Until more Mexican prospecting results are in, no one can gues& the full extent of the Frasch sulfur potential. Some informed sources give a tentative estimate, established more by guess than by actual figures, that supplies might last from 10 to 25 years. It is not inconceivable that the figure might even be higher. This figure is for normal consumption and expansion. It should be emphasized that it is only a guess. There is a lot of sulfur in the world, enough for a long, long time, but not all of it can be mined by the Frasch process. 1969

THE CHEMICAL WORLD THIS WEEK

NEW PRODUCTION CAPACITY—1952 Thousands of tons • Expected

Actual N e w Capacity

1.105.000. 1,516.000

FRASCH

MINED

GASES

PYRITES

GASES

SULFUR MINERALS Brimstone Other

BRIMSTONE High-cost sulfur, selling anywhere from $35 to $110 a ton, is plentiful. More and more high-cost plants a r e being developed. Frasch sulfur as a source can b e seen as slowly t a p e r i n g off, with other sources taking its p l a c e in the foreseeable future. This, of necessity, leads to what can b e called the $ 3 0 to $35 question, especially for those desirous of planning more than 20 years a h e a d . Frasch sulfur, t o use an average figure, now markets at t h e port for nearly $27 per ton. This is exclusive of transportation costs. If the sulfur has to be moved any great distance, transportation costs, which have considerably changed the market for m a n y commodities, seriously affect the total cost. Compelling alternatives would b e open to the chemical industry if the price of Frasch sulfur were to go up to $30 to $35 per ton. Such alternatives would be n o t a b l y in t h e fields of pyrites, recovery from sour gas, smelters, surface deposits, a n d oil refineries (C&EN, May 28, 1951, p a g e 2 1 2 8 ) . A consumer, distant from his Frasch sulfur* source but near a good reserve of pyrites c o u l d stand to profit by a switch under certain conditions. Before OPS lifted ceiling prices a n d when Frasch sulfur was at $20 to $22 per ton, a consumer's $10 to $ 1 5 transportation charge would m a k e his final cost $30 to $37 per ton. Economics might tell him pyrite roasting would cost $40 to $42 per ton plus the h e a d a c h e of having to manage t h e plant a n d convert his process lines. Present p r i c e o f $27 per ton puts the distant c o n s u m e r at the borderline between deciding i n favor of Frasch process or high cost sulfur. Usually, the additional expense of converting, coupled with a man-

1970

OTHER SULFUR

TOTALS

agement headache, has kept consumers in the Frasch market. However, that headache might be well worth while should t h e price of sulfur go to $30 to $35 p e r ton with subsequent final cost at $40 to $50. T h e n the consumer might stand to be $2.00 to $10 ahead on every ton if he switched to "high-cost" sulfur. Again, with a run-out in Frasch sulfur possible within a half a century, some sulfur experts have advocated that establishment of a recovery plant now, with an eye to keeping it expandable, might be a good move. Not only would a company firmly establish itself as a supplier of the future, but it would also set up a means of security for the children and grandchildren of the owners. I M C has quite definitely stated that non-Frasch sulfur production should b e encouraged. N o indication is seen for the price of sulfur to go d o w n or to hold its present level. In fact, no indication is seen for it not to go a little higher. If it should, the price rise will b e an encouragement for marginal producers like those mentioned in the preceding paragraph. Moreover, with the recent export limit (960,000 tons per year ex C a n a d a ) set for crude sulfur by the Office of International T r a d e , countries which until now have been importers of Frasch sulfur may find the limit, coupled with a price rise, highly conducive to turning toward other forms of recovery from native resources. Langbourne M. Williams, president of Freeport Sulphur Co., has told of 100 n e w sulfur projects begun since t h e shortage (C&EN, July 28, 1952, page 3 0 9 4 ) . Of these, 94 are for the recovery of sulfur in one form or another by methods other than the Frasch process. Since that time,

CHEMICAL

many companies have given u p their projects while other newcomers h a v e initiated them. T h e easing of the shortage is believed responsible for this state of flux. Surprisingly enough, the free world grand total of expected new sulfur capacity by 1955 over t h e known capacity of 1950 is now higher than was predicted a year ago. According t o the best guesses by many other informed business sources, and guesses which take into account t h e present state of flux occasioned b y t h e easing of the shortage, t h e new grand total is more nearly b e t w e e n 4.25 and 4.75 million long tons as against Freeport's previous estimate of 4.04 million tons of new capacity. The principal reason for this increase appears to b e the projected development under way in Mexico. On t h e other h a n d , rough estimates of the new capacity actually starting to come on stream in t h e past year are not u p to the predicted capacity. Sulfates (principally gypsum), ai*e the only group which have exceeded their estimate. T h e principal reason for this excess is the swift development of the Sindri, India, fertilizer plant. However, since sulfur development is a comparatively slow process that takes time to build m o m e n t u m , a snowball effect is expected to occur which will more than meet predictions. In fact, many of the plants slated to b e in production b y the end of the year by estimates h a v e only been a montH or two late. Pyrite capacity is being enlarged b y almost every c o u n t r y in the free world. New capacity hv 1955 is estimated to b e an over-all 1 million long tons. In t h e past year, the petroleum industry, a big consumer of sulfur, has produced 20,000 tons m o r e sulfur by recovery from refinery gases than it has consumed. Similarly, sulfur from smelter gases has already enlarged its prediction by some 60,000 tons. On the consuming end of the picture, one significant fact stands out from the others. Many consumers, frightened by the shortage, h a v e been quietly casting about for other means of arriving at their end product without calling on sulfur or sulfuric acid. This has been especially noticeable in fertilizers and plastics. In other cases, sulfur consumers w h o have a great amount of sulfur as by-product in their waste "have been developing means of recovering this sulfur for re-use or as a marketable p r o d u c t . As these conservation and alternative means begin to play a part in the over-all sulfur picture, it is hoped t h e consumption increment, w h i c h has been alarming ever since 1940-41, should find a more gradual ascent indicative of normal production, consumption, a n d expansion rather than the zooming one it has held. Should another mobilization emergency occur, any predicted length of supply indicated by current knowledge might b e cut drastically. In such a case, one man's guess is as good as another's.

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ENGINEERING

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REYNOLDS E X C L U S I V E V O L U M E

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» »

ALUMINUM

A G E N T S »

» M A Y

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FOR 1953

B E N S O N

C H E M I C A L

D R U M S 1971

THE CHEMICAL WORLD THIS WEEK

Leo Brewer (left) of University of California receives Baekeland Medal from John Lee, chairman of the ACS North Jersey Section. Looking on is George Baekeland, son of the chemical pioneer in whose honor the award is named C&EN REPORTS: ACS North Jersey Section, Baekeland Award

High-Temperature Chemistry Is Still in Early Infancy Stars provide molecular behavior at

important elevated

NEWARK.—Chemistry today in the 2000° to 3000° IC. range is similar to chemistry at conventional temperatures in the days when researchers debated whether the formula for water was H 2 0 or HO and when very little was known about the important oxidation states of most elements. This observation was made by Leo Brewer of the department of chemistry of the University of California, speaking at the Leo Hendrik Baekeland Award meeting held here on April 27. The award, a gold medal and $1000 presented once every two years by the ACS North Jersey Section, is sponsored by the Bakélite Co., a division of Union Carbide and Carbon Corp. As fifth winner of this award, Dr. Brewer is honored especially for his research at High temperatures. If asked why industry does not consider more seriously the possibility of carrying out chemical processes at elevated temperatures, most chemists would say that it is too difficult to produce high temperatures or that it is too difficult to develop the necessary materials of construction for high-temperature systems. Actually, the main obstacle, said Dr. Brewer, is the lack of information about the types of compounds that can exist at high temperatures and, therefore, the kinds of reactions that are likely to occur. In determining the possible gaseous molecules that may be present in high-temperature systems, the researcher finds that conventional chemistry is of little help. 1972

information temperature

about

At high temperatures, the conventional oxidation states of an element may be unimportant, and oxidation states never encountered at low temperatures are often the important ones. For example, aluminum has a 3 + oxidation state under ordinary conditions. On the other hand, at very high temperatures, aluminum compounds usually have oxidation states of 1+ and 2-\-. When beryllium oxide was proposed as a suitable high-temperature pile material, who would have expected that beryllium hydroxide gas would be so stable at high temperatures that the oxide would rapidly vaporize in the presence of steam? Still, Grossweincr and Seifert recently found this to be true. At ordinary temperatures, sodium is so highly reactive that few chemists would have guessed off-hand that sodium vapor would be quite stable in the presence of oxygen at elevated temperatures. We are so accustomed to the platinum metals being inert that it is surprising to find that these substances become rather good reducing agents at high temperatures, said Dr. Brewer. Thermodynamic Data. It is often assumed that valuable information about high-temperature systems can be obtained by means of thermodynamics. Using thermodynamic data for known compounds, the investigator can calculate their contribution to chemical systems at high temperatures. If these compounds are the only important ones present, the calculaC H E M I C A L

tions will be quite useful. The difficulty, said Dr. Brewer, is that, in many instances, new compounds that are unknown at lower temperatures predominate at high temperatures. Thus, the neglect of these compounds often makes the usual thermodynamic calculations completely worthless. A popular assumption is that, at very high temperatures, all molecules are relatively simple. If this were so, said Dr. Brewer, the molecules to be considered in a given system would be exceedingly restricted. That this is not the case is clearly established by a study, for example, of the cuprous chloride system. In the gaseous state, cuprous chloride is mainly C113CI3. At 1632° K., the saturated vapor contains 0.89 atmosphere of Cu3Cl3 and only 0.11 atmosphere CuCl. The large proportion of this more complex molecule at high temperatures could not have been predicted, he said. Sodium vapor in equilibrium with liquid sodium is predominantly monatomic sodium. At 370° C , only 1.2% of the dimer Na2 is found. At 800° C , 8%? Na 2 is present in the vapor. At higher temperatures, the percentage of dinner increases still further. Thus, in general, if a vapor in equilibrium with a solid or liquid at relatively low temperatures contains mainly a monomer in the presence of a small amount of dimer, a rise in temperature will always cause an increase in the percentage of dimer. Astronomical Clues. Because of the difficulty involved in carrying out experiments at high temperatures, no possible clues from research of any type should be over looked, Dr. Brewer emphasized. In particular, astronomical and geological evidence can often be of great help in the identification of molecules important in high-temperature systems. From the molecules observed in the spectra of the stars, for example, extremely valuable information can be derived that might never be found in the laboratory. In the search for stable gaseous hydroxides, for example, evidence obtained from hot springs and fumeroles should not be overlooked. As knowledge of high-temperature systems is gradually accumulated, it becomes increasingly clear that conventional chemistry must be relearned. In everyday chemistry, said Dr. Brewer, molecules such as CH, CN, CF, CF 2 , OH, C2, CS, and ALO are regarded as extremely unstable, with only very fleeting lifetimes. On the other hand, molecules such as CH4, CF*, H2O, CS-, and Al 2 0 3 are considered quite stable. At high temperatures, the situation is completely reversed. Thus at elevated temperatures, there is little difference between the stability of radicals and the stability of molecules with completely paired elections. Such molecules as C2, TiO, and MgO can be found either in radical forms with unpaired electrons or in nonradical forms with completely paired electrons— with almost the same energies and stabilities. The study of high-temperature systems, AND

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Honeywell B R O W N

V O L U M E

3 1,

NO.

19

M A Y

I N S TRR UU ΜM Ε E Ν N Τ T S

1 1 , 1 953

H 1973

THE CHEMICAL W O R L D THIS WEEK said Dr. Brewer, has been greatly accelerated b y activity in the field of high-temperature refractories. I n the past few years, many laboratories have b e g u n studies of high-melting borides, carbides, nitrides, suicides, and sulfides—materials that may b e used to supplement the conventional oxide refractories. This arsenal of n e w materials will permit many studies to b e conducted that could not possibly have been carried out previously because of a lack of container materials. In studying high-temperature systems, the chemist often finds himself in the position of t h e ancient alchemist striving to produce t h e universal solvent. W h a t troubled him most was the problem of containing the universal solvent should he ever succeed in preparing it. At high temperatures, most systems a r e practically universal solvents. As a result, t h e selection of a suitable container material often takes more time and effort than t h e actual experimental measurements. T h e newer materials, however, are greatly easing this problem, h e added. In the future, high-temperature industrial processes will become relatively commonplace, Dr. Brewer predicted. For many years, the steel industry has been successfully operating at temperatures just below 2000° K. As vital information about chemical behavior at these temperatures is steadily accumulated, many more processes are certain to b e carried out near 2000° K. COILS! AMME1

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1974

The Cover

Baekeland A w a r d to Brewer for Leadership in Thermodynamics τ

ΕΟ BREWER, winner of the Leo

Hen-

*~* drick Baekeland Award, is de­ scribed b y a coworker and colleague as . "a man with great scientific curiosity and a keen mind which borders on bril­ liance." From this description, and t h e fact that he is pushing an ambitious re­ search program with exceptional energy, it is no wonder h e was chosen to receive the award to stimulate the creative talents of young American chemists. H e was born in 1919 at St. Louis, and at t h e age of 21 received his B.S. at CalTech. Three years later, in 1943, he received his doctorate at t h e Uni­ versity of California, where h e h a s been on the faculty since 1946. D u r i n g 1 9 4 3 46, he was a chemist for the Manhattan District Project, doing research on high temperature thermodynamic properties of compounds. His compilations of fundamental data were already paying dividends at that time. It was there h e began his acquaintanceship with F. A. Jenkins, spectroscopist, that was to lead to their collaboration, along with Paul Gilles, in a classic piece of research on a controversial subject, heat of sublima­ tion and vapor pressure of carbon. His sabbatical leave during t h e fall and" winter of 1950 was spent as a John Simon Guggenheim Memorial Fellow visiting laboratories in Europe special­ izing in spectroscopy a n d high tempera­ ture chemistry. H e presented several lectures and papers there and at t h e end of October went to London to the laboratory of A. G. Gaydon of the department of chemistry, Imperial Col­ lege, for further research. T h e comple­ tion of their work, t h e spectroscopic study of cyanogen flames, heralded the solution to another controversial sub­ ject, that of t h e dissociation of the nitrogen molecule. Another paper, "Thermodynamics of Gaseous Cuprous Chloride Monomer and T r i m e r " p u b ­ lished in 1950, gives evidence of a highly developed technique, and the introduction to methods of interpreta­ tion which will prove useful in many high temperature problems. His work on the preparation and manufacture of D r . Brewer examines and checks dimen­ sions of cerium and thorium sul­ fide crucibles which a r e used for containers in high temperature studies

cerium a n d thorium subsulfide refrac­ tories for handling the more electro­ positive metals was a most significant contribution in high temperature thermodynamics and serves to further substantiate his position as that field's leading researcher in t h e past decade. Dr. Brewer's choice of highly im­ portant problems for his experimental work h a s interested not only chemists but astronomers as well. H e is vitally interested in chemical thermodynamic laboratory studies of systems under temperature conditions approaching that of t h e exteriors of the cooler stars, our sun included, and has been en­ gaged in obtaining special absorption coefficients, h e a t s of formation, and other thermodynamic data that h e be­ lieves will make possible t h e quantita­ tive determination of t h e various atomic and molecular species in t h e starry at­ mospheres when combined with t h e astronomer's d a t a on star spectra. He h a s published altogether 37 papers, most of which represent simi­ larly important contributions to funda­ mental inorganic chemistry at high temperatures. His combination of sound knowledge with ingenuity and experi­ mental skill h a s resulted in his solving difficult problems. During the w a r h e developed an entirely n e w refractory for handling plutonium that had baffled other expeiimentors. Although his work occupies a major part of his day, Dr. Brewer is devoted to his home too. In 1945, he married a native Californian, Rose Strugo, a n d they n o w have a 16-months old daughter. During his carefree under­ g r a d u a t e years, h e was an ardent track man. Now, he has b e c o m e a typical Californian, having lived there since 1929, and devotes his nontechnical reading to books on plant life, in order to improve his extensive collection of indigenous plants surrounding his oneacre estate i n Orinda. Not the least of his virtues is his reputation as a jack-ofall-trades, as far as t h e maintenance of his ho>me is concerned. Without a doubt, his skill as an amateur p l u m b e r and electrician is a mere reflection of his abilities i n t h e laboratory. As a teacher, Dr. Brewer is noted for his humor, patience, a n d his encour­ a g e m e n t to students to enter into dis­ cussions. The urge to experiment with which h e imbues students keeps pace with h i s own prowess in research, a n d indicates even greater advances to come in the high-temperature field.

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V O L U M E

3 1,

NO.

19

MAY

11,

1953

1975

THE C H E M I C A L W O R L D THIS WEEK

Floyd A. Hummel ( right ) of Penn State receives the Purdy Award for his work on the properties of synthetic lithia minerals. W. E. Cramer, president of American Ceramic Society, presents award while Harry Thiemecke of Homer Laughlin China Co. looks on C&EN REPORTS: American Ceramic Society

Silicon-Based Cermets M a y Be Useful in Aircraft Engines N e w torsional device introduced for measurement of viscosities at elevated temperatures NEW YORK.—The possible use of silicon as a component of cermets for hightemperature applications in aircraft engines has been suggested by Berthold C. Weber of Wright Air Development Center. Speaking before the American Ceramic Society, Dr. Weber indicated that silicon might be especially useful in turbine buckets because of its low specific gravity of 2.33, which is lower than that of aluminum. Silicon has a linear expansion coefficient of 1.95 X 10 e up to 100° C. and 3.27 X 10° at 1000° C. Its melting point of 1420° C. lies well within the range of refractory materials. If this metal could be combined with ceramic materials, thus creating a cermet having similarly favorable properties, silicon could become an important engineering material, said Dr. Weber. Little -work has been done on the use of this element in combination with ceramic materials, although Hauser in Switzerland has described the use of silicon as a metal addition to stoneware bodies employed as heating and cooling aggregates. His best results were obtained by firing these stoneware-silicon cermets at somewhat below the melting point of silicon in an industrial kiln having an oxidizing atmosphere. The thermal conductivity of these cermets was between four and 15 times greater than that of porcelain. Dr. Weber's talk was presented at the 1976

American Ceramic Society's 55th annual meeting held here on April 26 to 30. Attended by over 2000 persons, the program was highlighted by the presentation of the Purdy Award to Floyd A. Hummel of Pennsylvania State College. Dr. Hummel was honored for his report on thermal expansion properties of synthetic lithia minerals. Honorary membership in the American Ceramic Society was granted to Jesse T. Littleton of Corning Glass. Winner of the society's Binns Medal was Walter A. Weldon, formerly with General Electric and now with the United Nations in India. Porcelain-Silicon. Discussing previous experiments conducted at Ohio State University, Dr. Weber indicated that a highrefractory porcelain-silicon body can be satisfactorily fired in an oxidizing atmosphere at 1520° C, which is 100° C. above the melting point of silicon. Various ceramic components, including cordierite, spoclumene, and other materials having low thermal expansion, were tried in combination with silicon. However, all these hodies contained a glassy phase exhibiting poor resistance to thermal shock. A silicon-based cermet should b e produced without a glassy phase, said Dr. Weber. To accomplish this, a study was made of the properties of silicon-based cermets formulated with either titanium dioxide or titanium carbide. Tests were also made on silicon in combination with both titanium carbide and titanium suiC H E M I C A L

cides. The experiments were conducted in a variety of firing atmospheres. A cermet mixture of 80% silicon and 20 r i: titanium dioxide by weight was fired in an oxidizing atmosphere at 1520° C. Chemical analysis indicated that 7 1 % by weight of the total silicon was present in the metallic state, while 29% by weight had been oxidized to silicon dioxide. No titanium dioxide could be detected by \-ray analysis. Besides traces of titanium disilicide, only silicon and a-cristobalite were found. This cermet exhibited outstanding resistance to oxidation. A study of the mechanical and physical properties of this material is still in progress, said Dr. Weber, and its suitability as a turbine blade material will be reported later. Another promising cermet is formed by the combination of silicon and titanium carbide, fired either in vacuo or in a helium atmosphere. A series of silicontitanium carbide mixtures has been studied and the fired reaction products analyzed by x-rays. A mixture composed of 41.6% titanium carbide and 58.4% silicon by weight produced a dense, well-sintered body when fired at 1730° C. in a helium atmosphere. This cermet also exhibited good oxidation resistance. X-ray analysis indicated that the cermet was essentially free of silicon and titanium carbide, the starting materials having been converted to silicon carbide and titanium disilicide. This material, now being studied for possible use in the high-temperature field, is unique among cermets in that none of the starting materials is present in the fired product. The end-product contains 72.2% titanium disilicide and 27.87' silicon carbide by weight. Currently in progress is an investigation of cermet combinations of titanium carbide and various titanium suicide's, among which Ti.-^Sia appears especially promising because of its high melting point of 2120° C. Viscosity at High Temperatures. An apparatus developed for the measurement of viscosities at high temperatures was described by R. H. Meinken, H. T. Smyth, and H. S. Skogen of Rutgers. The liquid under study is held in a molybdenum cup, 3 inches long and 0.75 inch in diameter, with a wall thickness of 5 mils. By means of an electromagnetic device, a sinusoidally varying torque of adjustable frequency ( 1 to 5 cycles per second) and several degrees amplitude is applied to the cup. The resulting torsional amplitude of oscillation is a measure of the viscosity. For use in a high-temperature furnace, a capacity pickup has been developed that allows the motion of the cup to be recorded electrically on the same chart as the value of the applied torque. As a result, the complete phase and amplitude relations between the torque and angular movement can be obtained. Plastic Deformation. The bending of corundum, periclase, and rutile single crystals has been carried out at elevated temperatures by J. B. Wachtman, Jr., and L. H. Maxwell of the National Bureau of AND

E N G I N E E R I N G

'NEWS

Why Norton seamless tubes give you better filtration O n l y N o r t o n ALUNDUM tubes h a v e t h e seamless construction that means more u n i f o r m filtration a n d e n a b l e s faster, m o r e t h o r o u g h c l e a n i n g . A n d like all N o r t o n p o r o u s mediums they're made with the p a t e n t e d controlled structure p r o c e s s that a s s u r e s even d i s t r i b u t i o n o f p o r e s — i n t h e size a n d o p e n - p o r e r a t i o t h a t b e s t meets your needs.

Cost-cutters over a wide job range I n a n y form, N o r t o n p o r o u s m e d i u m s h a v e e x c e p t i o n a l r e s i s t a n c e to b r e a k a g e , c h i p p i n g a n d acid a n d alkaline c o n d i t i o n s . T h e y ' r e d e s i g n e d to p e r f o r m b e t t e r , last l o n g e r a n d c u t y o u r o p e r a t i n g c o s t s in a w i d e variety of chemical field a p p l i c a t i o n s . F o r e x a m p l e : filtering water o r solvents . . . c u t t i n g oils, wine a n d o t h e r liquids . . . r e c l a i m i n g c l e a n i n g fluids a n d i n d u s t r i a l w a s t e . . . in boiler feed w a t e r t r e a t m e n t .

Get the whole story S e e y o u r N o r t o n R e p r e s e n t a t i v e for c o m p l e t e facts o n h o w y o u can g e t m o r e savings a n d satisfaction w i t h N o r t o n p o r o u s m e d i u m s . O r write d e s c r i b i n g y o u r requirements,

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N O R T O N C O M P A N Y , WORCESTER 6, MASSACHUSETTS VOLUME

3 1, N O . 1 9 » » *

. M A Y 11, 1 9 5 3

1977

THE CHEMICAL WORLD THIS WEEK C & c N REPORTS: N a t i o n a l A c a d e m y of Sciences

Chemists and Physicists N e e d e d to Help Solve Riddle of the Cosmos A s p a r t i c a n d glutamic culture m e d i a containing E. co/i

Berthold C. Weber (right) of AVrigint Air Development Center shows sample of silicon monoxide cermet material to Ή. F . McMurdie, National Bureau of" Standards Standards. All of these crystals sHowed appreciable plastic· deformation. Untile was readily deformed at 600° G, c o r u n ­ d u m at 900° C., and periclase a t 1100° C. Slip lines were visible on all three mate­ rials. W h e n corundum single crystals were tested in tension at elevated tempera­ tures, the resulting creep curves showed as much as 3.5 Γ γ tensile strain a t 1000° C. Zirconia Stabilization. The stabilization of zirconia with magnesia and calcia w a s outlined b y Eugene Ryshkevvitcli o f t h e Wright-Patterson Air Force r3ase. Com­ plete stabilization was obtained with 15 mol % of MgO and CaO, separately or together. By the use of a polarizing m i ­ croscope a n d x-ray analysis, n o decromposition of MgO-stabilized zirconia co-uld be detected in cycling tests up t o 1400° C. Glass A t t a c k e d by Acid. T l i e action of hydrochloric acid solutions on borosilicate and soda-lime glass bottles w a s discussed by F. C. Raggon and F . R . Bacon of Owens-Illinois Glass Co. P i v e lots of commercial bottles were exposed to 0.0O02 to 6.0 Ν hydrochloric acid a t 70° C. for seven days. T h e contents of cadi bottle were then analyzed for sodium oxide a n d silicon dioxide. With increasing c o n c e n ­ trations of hydrochloric acid, the extrac­ tion of sodium oxide increased for t>orosilicate bottles b u t was practically constant for soda-lime bottles. The e-xtraction of silica increased with both types of "bottles, although the increase for borosilicate bottles w a s more pronounced. Synthetic Mica. A comparison of t h e dielectric properties of hot-pressed syn­ thetic mica with those of other c e r a m i c insulating materials was m a d e b>/ J. E. Comeforo and R. A. Hatch o f the Bureau of Mines. Special attention was p a i d to the variation of these properties with temperature u p to 400° C. Power factor and dielectric constants were measured at 1 megacycle, and t h e v o l u m e re-sistivity was determined on a d.c. resistance bridge with a voltage of 22.5 volts.

1978

W A S H I N G T O N . - A s t r o n o m y , the science which has delved hundreds of light years into space, has now encountered so m a n y diverse problems related to the solar sys­ tem that there is an urgent need for spe­ cialists in chemistry and atomic physics to turn their attention to these matters. Otto Struve, University of California, Berkeley, Calif., made a formal appeal to these spe­ cialists at the 1953 meeting of t h e N a ­ tional Academy of Sciences when it con­ vened at the academy's building here April 27 through 29. Harold C. Urey, University of Chicago, Chicago, 111., is one of many chemists w h o has already turned his attention to these problems. For some time he has been con­ cerned with the evolution of the earth to its present state. In his paper before the academy he demonstrated his thermody­ namic conclusions t h a t the earth's crust appears to have been several hundreds of degrees cooler than previous estimates have ,indicated. In another field, Alexander Hollaender, biochemist at Oak Ridge, Tenn., reported an as yet imperfectly defined extract from meats and yeasts that has been shown to reduce radiation damage to living cells. So far only small amounts have been re­ covered and have been proved solely on relatively simple cell life. While the postradiation treatment sub­ stance may never prove beneficial itself in

acids

formed

in

simple

treatment of man exposed to damaging radiation, its study may help scientists u n ­ cover t h e mechanisms of harm. It is then hoped that this knowledge will lead to other means of treating such exposures for man. Amino Acids from E. cofi. From t h e Carnegie Institution, Washington, D. Q , came a p a p e r by E. T. Bolton, R. Britten, a n d D. B. Cowie on the synthesis of t h e aspartic and glutamic families of amino acids b y Escherichia colt. Some 6 0 % of t h e protein produced in simple culture media was amino acid. They demon­ strated the relationships between the fami­ lies and among the members of each by the use of the isotopic competition method. John W . Graham, also of the Institution, gave t h e results of a study of the physical a n d chemical properties of several preCambrian diabase dikes and proposed a mechanism of formation which would demonstrate how some of these forma­ tions might acquire the inverse magnetiza­ tion they n o w possess. Sterling B . Hendricks and H. A. Borthwick, Department of Agriculture, Beltsville, Md., told how they found the photoreaction controlling photoperiodism in plants, germination of some seed, etiola­ tion changes in seedlings, and many other morphogenic responses, to be the rever­ sible isomerization of the light-sensitive pigment.

Ν AS honored Alfred N. Richards ( l e f t ) , University of Pennsylvania, first winner of the Kovalenko Medal, Franco Rasetti, Johns Hopkins, winner of the Walcott Medal, and Lloyd W . Stephenson, U. S. Geological Survey, winner of the Thompson Medal

CHEMICAL

AND

ENGINEERING

NEWS

Operator transfers evacuated retort from heating to cooling station of Stokes Vacuum Annealing Furnace, designed and built for the processing, annealing and other heat treatment of titanium, zircon'um, hafnium, copper a n d other metals.

One of the uses for the complete custom-built installation of Stokes vacuum freeze-drying equipment in Pitman-Moore Company's new million-dollar plant at Indianapolis, Ind. is to produce gamma globulin to combat poliomyelitis. One of the steps is drying the material from its frozen state. Operators are shown removing trays of gamma globulin from Stokes freeze-dryers. Temperatures are as low as 40° below zero F. during part of the freeze-drying cycle.

Installation of Stokes Rotary Vacuum Dryers used by Metals Disintegrating Co., Berkeley, California, for drying of aluminum powder. Highly oxidizable materials can be handled without any danger of\ combustion or explosion when they are processed under vacuum.

Vacuum at Work Diesel locomotive armature being removed, after impregnation, from Stokes high vacuum impregnating tank in the San Bernardino, Calif., plant of Atchison, Topeka & Santa Fe Railway. Electric motors for the Santa Fe's "Chief" and "Super Chief" develop such excessive heat that ordinary insulation v/ould swell or burst, causing the rotors to "freeze" in the mounting. By impregnating these rotors with protective resins under high vacuum in Stokes impregnators, each turn of wire is held in place, motors operate without interruption.

Diesel locomotive motors, paper and metals, medicines, electrical parts, toys . . . are but a few in a wide range of products which are processed in vacuum for the good of mankind and the profit of business. The application of vacuum engineering to industry is a major function with Stokes engineers. And naturally so, for it is at Stokes' that many of today's accepted procedures of vacuum processing had their inception during the last fifty years. Stokes is FIRST in Vacuum . . . first in the design and manufacture of practical vacuum processing equipment. . . and Stokes engineers are available for consultation on opportunities to apply vacuum processing to your business. F. J. STOKES MACHINE COMPANY, PHILADELPHIA 20, P A .

STOKES MAKES: High Vacuum equipment. Vacuum Pumps and G a g e s / I n d u s t r i a l Tabletting, Powder Metal and Plastics Molding Presses/Pharmaceutical Equipment

VOLUME

3 1,

NO.

19

*

»

» > MAY

11,

1953

1979

THE CHEMICAL WORLD THIS WEEK C & E N REPORTS: A m e r i c a n Physical S o c i e t y

Little increase in World's Tritium Supply Seen During Atomic A g e Intermetallic compounds seen with wide range of properties suitable for tailor-made semiconductors WASHINGTON.—Discounting some opin­ ions that tritium h a d not existed before the explosion of the first atomic b o m b , \V. F . Libby believes that there has been little or no increase in quantity of this form of heavy hydrogen in the past 20 years. His studies of naturally occurring tritium in " o l d " water have brought him to this conclusion. He cited assays of water taken from closed cisterns and sealed water heaters to confirm this opinion be­ fore a meeting of t h e American Physical Society held here April 30 to May 2. T h e geochemical studies carried out by Dr. Libhy at the University of Chicago have included assays of water sampled from all over the world. Although some rather wide variance was found between samples, h e feels that this is only a meas­ ure of the length of time t h e water vapor has been in t h e air, not a n y inherent dif­ ference in locale. His most extensive tests have been on water obtained from Lake Michigan a n d its watershed and the lake which feeds t h e Norse-Hydro deuterium plant. Lake Michigan water shows a trit­ ium content five times t h a t of the Nor­ wegian one, perhaps because water from the latter comes from Atlantic evaporation. Lake Michigan makes an unusually good water source, not only because of its prox­ imity to Dr. Libby's laboratory, b u t also because of its high evaporation rate ( a n d that of its watershed) and the rather complete mixing of the water with the lake's complete turnover every year. Some speculation was aroused at t h e meeting about the m e a n i n g of some of the results which Dr. Libby obtained last fall in Chicago. Assuming t h e conventional theory for t h e formation of tritium—cosmic ray action in the u p p e r atmosphere—his group h a d assayed rain w a t e r following a drought in t h e mid west. A fairly high concentration of tritium w a s found in t h e first rain fall in mid-October. This value gradually went up with each rain during the following month to almost three times that value in samples taken the third week in November, then trailed off to normal. Dr. Libby gave as an explanation for this the length of time the water vapor had been exposed to cosmic rays in t h e air, during t h e long lack of rain. Opposing this explanation w a s speculation t h a t t h e increase in tritium had followed t h e ex­ plosion last fall of a n atomic device which was r u m o r e d to h a v e b e e n a prototype hydrogen b o m b . Speaking at the same symposium with Dr. Libby, L. T. Aldrich of t h e Carnegie

1980

Institution o f W a s h i n g t o n described t h e n a t u r a l variations in a b u n d a n c e of iso­ t o p e s . His w o r k o n the dating of minerals by isotope v a r i a t i o n h a s led to t h e as­ signment of different dates to various geo­ logical eras. In fact, b e said that recent information of t h i s type b a d led to the conclusion t H a t b e was 1.5 billion years o l d e r than h o had thought—assuming that all atoms a p p e a r e d simultaneously. Dr. Aldrich's c h e m i c a l separation techniques h a v e made it possible for him to date s a m p l e s u s i n g an internal standard in t h e form of different isotope ratios. H e feels that in addition to r u b i d i u m it will be possible in t r i e future to use calcium and potassium f o r d a t i n g different types of material. In+ermef α Iltc Compounds. At another symposium t h e p o t e n t i a l use of semicon­ d u c t i n g i n t e r m e t a l l i c c o m p o u n d s as tran­ sistor materials w a s discussed by R. C. B r e c k e n r i d g e of t h e National Bureau of C & E N REPORTS:

S t a n d a r d s . l i e described w o r k d o n e a t NBS a n d elsewhere on t h e s e materials. After giving data on c o m p o u n d s tested b y Lis group—including a l u m i n u m , gallium, a n d i n d i u m antimonides—he p o s t u l a t e d t h e existence of a great n u m b e r of such semi­ c o n d u c t i n g materials. H e suggested that such combinations of a G r o u p I I I ele­ m e n t w i t h a G r o u p V often gives a semi­ c o n d u c t i n g material with a diamondlike z i n c b l e n d e crystal structure. T h e naturally occurring G r o u p IV semiconductors—sili­ con, g e r m a n i u m , a n d gray tin—have a lat­ tice structure of this type. H e suggested further t h e possibility of similar inter­ metallic structures of t h e fluorite t y p e . Citing resistivity a n d carrier mobilities found in t h e materials u n d e r study, D r . Breckenridge indicated t h a t there is a n almost unlimited future for materials of this t y p e for use in s e m i c o n d u c t i n g devices. T h e r a t h e r wide differences in properties found in materials already d e v e l o p e d i n ­ dicates t h a t a m o n g t h e great n u m b e r which are yet to b e s t u d i e d almost a n y desired combination of mobility and t e m ­ p e r a t u r e r a n g e will b e found. I m m e d i a t e needs include h i g h e r mobilities for h i g h frequency uses, a n d h i g h e r useful t e m ­ p e r a t u r e s , since conventional semiconduct­ ing materials such as germanium are i n ­ operative above about 50° C. W i t h a n u m b e r of these intermetallic c o m p o u n d s available it will t h e n b e possible to c h o o s e one with t h e desired properties for u s e in semiconducting devices.

N a t u r a l G a s o l i n e A s s o c i a t i o n of

America

Absorption Index Basis of N e w Shortcut G a s Analysis Butane supply expected to continue to exceed d e ­ mand even if gasoline specifications are changed H O U S T O N . - D e t e r m i n a t i o n of the h y d r o ­ c a r b o n c o m p o s i t i o n of natural gas using a n e w m e t h o d w a s described by T. W . Legatski, P h i l l i p s Petroleum Co., before t h e annual meeting of the NGAA. T h e a s s a y is w i t h i n a few per cent of the true v a l u e obtained b y low t e m p e r a t u r e frac­ t i o n a l analysis, a n d requires only an hour's t i m e . Mr. Lcgatski first described a test to d é t e r m i n e w h a t he termed the absorpt i o n index. This is t h e equilibrium press u r e in p o u n d s p e r square inch absolute d e veloped w h e n 4 0 volumes of a gas sample a r e mixed Avith one v o l u m e of pure n-oct a n e at 7 6 0 m m . mercury initial pressure a n d 100° F . C o m p a r i s o n of the absorpt i o n index o f 34 samples with analyses run b y conventional methods showed this value t o b e directly r e l a t e d to t h e " b u t a n e s a n d heavier'* c o n t e n t of natural gas in mole p e r cent. A sample b o m b c o n t a i n i n g the gas is brought t o 100° F. i n a constant t e m p e r a -

CHEMICAL

t u r e b a t h and t h e pressure is adjusted so that the initial pressure after addition of solvent will be approximately 7 6 0 m m . mercury. T h e b o m b is t h e n removed from t h e b a t h , solvent is a d d e d , and t h e b o m b is r e t u r n e d to the b a t h after shaking. Shaking is continued at 5 - m i n u t e intervals a n d the equilibrium pressure r e a d after 3 0 m i n utes. Absorption indexes may b e used, if t h e specific gravity of t h e gas sample is also known, to d e t e r m i n e the a p p r o x i m a t e c o m position of the gas. T h e chart which M r . Legatski showed has as ordinate an e m pirical scale closely related to the reciprocal of t h e absolute boiling points of h y drocarbons in n a t u r a l gas, and as abscissa cumulative mole p e r cent plotted on t h e last half of a probability scale. Gas analyses plotted on this graph a r e straight lines, and specific gravity and absorption index m a y be used to locate a n d determine the slope of t h e line r e p r e s e n t i n g the gas un-

AND

ENGINEERING

NEWS

Anatber Jiew development using

B. F. Goodrich Chemical

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pressure-sensitive

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ERE'S a plastic tape that makes short work o f troublesome plating problems, even o n irregular surfaces or "hard-to-do" parts. I t is backed with a G e o n vinyl plastic film, giving it many extra advantages that save time and money. T h e tape h a s a strong adhesive, clings tightly t o surfaces. Cleaners or plating solutions can't c r e e p under it. Cpnforming snugly t o uneven surfaces, the tape w h i s k s off cleanly w h e n the j o b i s d o n e .

And l o o k at t h e advantages o f this tape! T h e G e o n plastic b a c k i n g withstands hot o r c o l d cleaners, remains pliable under l o n g i m m e r s i o n in plati n g solutions. G e o n resists acids, alkalies, water, many chemicals, stands u p even in hard chrome plating. What G e o n d o e s for this plastic tape may start y o u t h i n k i n g h o w G e o n can h e l p you improve o r dev e l o p m o r e saleable products. T h e r e are many versatile G e o n materials, a n d we'll h e l p you select the o n e best suited t o your n e e d s . For technical in-

formation, please write Dept. G A - 5 , B. F. Goodrich Chemical Company, R o s e Building, Cleveland 15, O h i o . Cable address: G o o d c h e m c o . In Canada: Kitchener, Ontario.

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GEON RESINS · GOOD-RITE PLASTiCIZERS . . . the Ideal team to make products easier, better and more saleable. GEON polyviny! materials V O L U M E

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HYCAR American rubber »

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GOOD-RITE chemicals a n d plasticizers

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H A R M O N colors 1981

THE CHEMICAL WORLD THSS WEEK d e r tests. Absorption index a n d specific gravity scales are constructed a n d superimposed on the graph. A straight line passed through the specific gravity a n d absorption index determined for a particular gas indicates the probable composition of the natural gas. Carbon dioxide and hydrogen sulfide must be removed from the gas sample before absorption index is determined, b u t nitrogen has no significant effect. In specific gravity determinations a correction for nitrogen must be made after removal of the other two nonhydrocarbon gases. Pointing out that this method is n o t a siibsitute for low-temperature fractionation, Mr. Legatski stressed its value w h e r e approximate compositions must b e known quickly, a n d showed conclusive evidence of its accuracy to within -±5r/r of the true composition for groups of gases, and i t 10% for single hydrocarbons. Heavy H y d r o c a r b o n s in Residues. For determining low concentrations (in the order of 0.01 mole per cent) of heavy ends in residue gases, beyond the limits of ordinary fractional distillation, C. J. Newton, Magnolia Petroleum Co., offered an infrared charcoal adsorption method, in which t h e hydrocarbons from a measured volume of gas, adsorbed on a charcoal bed, are desorbed with a solvent having a negligible light absorption in the infrared a n d a boiling point below the lowest constituent to be measured. Hydrocarhons boiling below the solvent are fractionally distilled, and concentration of those remaining is determined b y measuring t h e light absorption at 3.38 microns and reading from a calibration curve. ' Butane P i c t u r e Not Good. W h a t will happen to the butane picture in the next few years? Of the total b u t a n e production from refinoiy and natural gasoline and recycling operations in 1952, estimated at 880,000 barrels per day, R. A. Steel, Standard Oil Co. ( I n d . ) , said that only about 6 0 % was utilized in salable products. Because there was no market outlet, 267,000 barrels per day, potentially recoverable, were not recovered. By 1955 Mr. Steel said, when petroleum refiners a r e expected to have an effective crude refining capacity of 8.3 million barrels per day, there will b e a net excess increase of 12 thousand barrels of butane per day. T h i s effect is broken down as follows: C h a n g e in Butane Effects of New Availability, Refining Thousands of BarCapacity rels per d a y Catalytic reforming 12 Thermal reforming -17 Catalytic cracking 61 Thermal cracking -13 Alkylation -24 Polymerization -6 Total refining effects 13 Increase in rubber a n d chemicals -4 Increase in natural gasoline 3 Total increase in excess b u t a n e 12

1982

Increasing t h e allowable Reid vapor pressure of motor gasoline by two pounds would allow incorporation of 100,000 barrels p e r day additional butane. Aviation gasoline offers a very discouraging picture, however, and jet fuels are even less promising as possible butane outlets. T h e indicated surplus is still so large, Mr. Steel said, as to furnish a strong incentive to develop outlets peculiarly favorable to the Ci Hydrocarbons. Such outlets, he suggested, might b e in the eventual largeseale- use of internal combustion turbines on t i i e ground, in increased use of liquefied petroleum gases for power and heat generation, and as a fuel for self-propelled railway vehicles. S u l f u r Recovery. Improved economic conditions for sulfur recovery exist today, answered J. L. Parker, The Girdler Corp., at t r i e quiz: session on operations. It is possible today to operate a plant economically for recovering as low as 5 tons of sulhir p e r day, if a full-time operator is'required on a 24-hour basis, Mr. Parker said.

C & E N REPORTS;

Cost of production will b e about $15 per ton, with lower cost if the plant is operated in conjunction with a gasoline plant, therefore not requiring full-time operating attention. LPG T r a n s p o r t a t i o n . W h i l e liquefied petroleum gases are transported now as constitutents of natural gas, they have not been extracted at t h e end of t h e line b e cause Federal Power Commission rulings have provided no incentives and because of heating value specifications, said J. T . Russell, Panhandle Eastern Pipeline Co. Transportation of L P G in t h e vapor state by gas pipeline will be competitive with transportation by products pipeline only if the F P C allows allocation of service charges on a volume basis. Pointing out the advantages of vapor state transportation of L P G as affording greater economy in certain circumstances, and increased availability, he cited as evidence of t h e tremendous quantities that could b e transported b y gis pipeline the figure of 9.2 gallons p e r 1000 cubic feet of gas.

J o i n t M e e t i n g , American I n s t i t u t e t h e Chemical institute of C a n a d a

of

Chemical

Engineers

and

Engineers Advised to Keep The Reader in Mind In his w r i t i n g , a n e n g i n e e r must r e m e m b e r terests a n d b a c k g r o u n d of the nonspecialist T O R O N T O . - " Y o u a r e not making a literary contribution to posterity; you are serving the person or persons who will read w h a t you w r i t e , " A. J. Johnson, Shell Development Co., told t h e 500 chemical engineers attending the joint conference of thr^ American Institute of Chemical Engineers and the chemical engineering division of the Chemical Institute of Canada, held h e r e April 26 t o 29. Mr. Johnson, speaking at the symposium on communications for action in a n organization, went on to say that too many engineers write for the nonspecialist just as they write for a fellow-specialist; they assume the reader has all the background information necessary for understanding t h e subject under discussion. T h e result: The reader draws a blank. U s e of short and familiar words with specific meanings increases readability; l o n g involved sentences decrease it, he s a i d . Abstract words are sometimes the ref u g e of the m a n w h o is short of facts, but d o e s n ' t want t o admit it. If the facts are available, express them in lively words t h a t are t o t h e point. Use of visual aids is anotber means of putting the point across to the reader, he continued. Research R e p o r t s . Progress reports ha^/e only a limited place in Shell's reporti n g system, according to Mr. Johnson. At o n e time, full progress reports were pre-

CHEMICAL

the i n -

pared regularly on every project, in addition to summary progress reports. This resulted in the delay of definitive reports, usually issued at the conclusion of a proiect or a clear-cut phase of it, because of t h e bulk of progress reports in process. Shell's solution has been to concentrate efforts on promptly issued, definitive reports—self-contained and suitable for action—and brief summaries of progress at flexible and realistic intervals. Accounting. In most industries it is t h e engineer who is t h e economist, according to C. F . Braun of C. F . Braun and Co. It is t h e engineer who makes the recommendations as to plant, process, and product. T h e first place the engineer looks for h e l p is the company accounting records a n d w h a t he finds is an antiquated system u n e q u a l to the dynamic needs of modern industry, he said. Accountants, like scientists and businessman, must learn to speak and write in understandable terms. Only through his own extensive participation, both in setting up and operating t h e accounting system, can the engineer hope t o get what he needs, w h e n h e needs it, and in language he can understand, Mr. Brown stressed. If the engineer is to make bis proper contribution to industrial economics and to management, he must dem a n d a n d assume a full share in this important form of corporate communication.

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ENGINEERING

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THE

120 B R O A D W A Y ,

NEW

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VOLUME

3 1,

NO.

19

» MAY

1 1 , 19 5 3

1983

THE CHEMICAL WORLD THIS WEEK industry that newcomers to this business may run into obstacles in processing. Polymerization of pure ethylene always is difficult. A large plant investment also is demanded in order to achieve production of a material of uniform molecular weight. Carbide states that its method and equipment are both unique. Essentially, it is a high pressure process employing continuous pressures up to 35,000 pounds per square inch, and in the case of polyethylene this pressure has to be exerted continuously throughout a 24-hour cycle. Pan A m Plans East C o a s t Refinery

Shipments of Bakélite polyethylene resin will probably reach 250 million pounds annually by 1955—some 25 times the U. S. production of only 10 years before. The company is now expanding one plant and building three others—one in California and two in Texas—to bring its production to double present U. S. total

INDUSTRY

Polyethylene Strides A h e a d With C a p a a t y Due to Q u a d r u p l e "PLANT expansions by Bakélite a n d other companies will bring polyethylene capacity in this country to well over 500 million pounds annually in 1955, in contrast to the estimated 125 million in 1952. They will also bring six or seven new producers into the market which up to now has been supplied only b y Bakélite (through Carbide and Carbon Chemicals) and Du Pont (see page 2023). Among other outstanding projects are those of Monsanto and Spencer Chemical. The former will enter polyethylene production early in 1955 with a plant in Texas for the production of 66 million pounds annually. Monsanto has projected a further increase of 509c in capacity in 1957, and upon completion of the program Monsanto expects its polyethylene capacity will represent 20r'r of national capacity, or 22% of potential market sales. It is understood that Monsanto perfected its process for polyethylene after three years of research. The company has provided for the additional ethylene that will be needed by its Texas project. Capacity of the Spencer Chemical plant at Orange, Tex., will be 45 million pounds. According to present plans tlie project should be ready in the spring of 1955, and Imperial Chemical Industries, Ltd., holder of the basic polyethylene patents, will aid in the design. Gulf Oil Co. meanwhile promises to play an important role in the chemical industry's polyethylene program as a supplier of ethylene from its refinery at Port Arthur, Tex. This plant is said to have 1984

about 180 million pounds of ethylene for sale to chemical processors, and it is presently meeting the ethylene needs of Ethyl, Koppers, Du Pont, Monsanto, and Allied Chemical & Dye. This has proved so successful that Gulf is reported lining up customers for another 180-million-pound unit. Each of the three new plants in the Bakélite program will have capacity for the production of at least 60 million pounds of polyethylene a year. It will bring the company's over-all polyethylene capacity up to 250 million pounds, or 25 times the amount that was produced and sold in 1945. The production unit, Carbide and Carbon Chemicals, was among the first to arrange with ICI for wartime production of the plastic for military cables and other insulation. Both Du Pont and Carbide were to discover later that market potentials for polyethylene insulation were rapidly being outweighed by demands for the resin in the packaging field, especially "squeezable" containers. Other polyethylene projects are planned by Dow Chemical and National Petrochemical ( Natiorfal Distillers and Panhandle Eastern). National Petrochemical, Dow, American Petrochemical, and Spencer' Chemical were the original participants in the polyethylene expansion organized by ICI. More recently, however, American Petrochemical, a company organized by Firestone Tire and Cities Service, reportedly withdrew from the arrangement (C&EN, May 4, page 1843). The idea is put forward by some in the CHEMICAL

Pan American Refining Corp. is actively developing possible plant sites for a new refinery on the East Coast. At the present time options have been obtained completely covering two sites and the company is in the process of obtaining options on a third site. These sites are located near Pedricktown, N. J., on the Delaware River; Talbot County on the Eastern Shore of Maryland; and Portsmouth, R. I., on Narragansett Bay near Providence. It is estimated that the refinery will cost in the neighborhood of $20 million to construct, and that it will process about 25,000 barrels of crude oil a stream day. Isocyanate Plant Planned b y Monsanto The phosphate division of Monsanto Chemical Co. is planning to build multimillion dollar facilities for the production of isocyanates. The new plant will expand the present production capacity of the company for isocyanates. It will follow nearly 10 years of research, pilot plant investigation, and sales development effort, involving the solution of chemical and engineering problems of isocyanate manufacture. Location of the plant has not been announced. Promising among uses for isocyanates are synthetic rubbers and isocyanates based foamed-in-place plastics. Koppers Opens P o r t A r t h u r Ethylbenzene Plant The proverb "if the hill will not come to Mahomet, Mahomet will go to the hill," is well illustrated in the opening at Port Arthur, Tex., of the sixth plant of The Koppers Co.'s Chemical Division. Koppers needed additional ethylbenzene for expanded styrene and polystyrene operations at its Kobuta plariF near Pittsburgh, Pa. Ethylene was available in quantity from Gulf's new facilities at Port Arthur. Economic studies showed feasibility of collecting benzene requirements from Eastern and Southern coke plants, shipping the benzene down the Mississippi by barge to Port Arthur for combination with ethylene, piped from Gulf Oil Corp.'s refinery. Ethylbenzene is returned by the same barges to Kobuta for dehydrogenation to styrene. Ethylene and benzene are reAND

ENGINEERING

NEWS

3

OUT OF M O R E T H A N

3500 the fact that it would contain o n e gram more of O 3 than would 2 3.84 grams of ordinary pure barium carbonate. The customs of the stable isotope trade may seem a trifle irregular to laboratory purchasing agents, but to people equipped with a mass spectrometer and eng a g e d in tracer studies where radioactivity is not permitted, it will be gratifying news that w e have slashed prices o n this as well as the other three C 13 -enriched Eastman Isotope Concentrates. Write, if interested in the details. A l i p h a t i c aromatic . · .

oil. T h e procedural abstract w e can send you g o e s into further details. In case you don't happen to like caraway seeds, w e hasten t o affirm that the procedure covers essential oils in general.

T o capture ketones. NHNHÎ

S0 3 H

p- Hydra zino ben zenesu Ijon tc A cid (Eastman 1 1 2 9 ) is a g o o d reagent For the i s o l a t i o n of k e t o n e s . Let us say you w i s h t o demonstrate the particular k e t o n e setup whence arises the subtle flavor that makes caraway seeds, such as seen enlarged above, taste so g o o d in c o o k i e s or i n fresh rye bread ( t w o slices o f the latter constituting the cortex o f a h o t corned beef sandwich, perhaps?). T h e aforementioned c o m p o u n d (formerly called IPhenylbydrazine-p-mlfonic Acid'and never r e c o m m e n d e d i n sandw i c h e s ) has t h e useful property of Forming easily cleaved condensat i o n products with ketones but d o e s not react a t all with aliphatic aldehydes. F r o m the cleavage of t h e condensation products, yields o f 70% and better are reported, ^fou cannot d o this with aromatic aldehydes because they give only addition compounds that are not converted i n t o true condensation products by splitting off water. Thus you have a reagent for the separation o f aliphatic and i s o cyclic ketones from caraway seed

ÎÎËDIPU

The price of excess . . .

Barium Carbonate (Eastman C 13 6 0 2 0 ) has been cut in price by 60%. Instead of $ 4 0 0 per gram of excess C 13 , it's d o w n to $ 1 6 0 . T h i s is strange talk about a salt available o n the market for less than a nickel a pound, but this is very special barium carbonate. Sixty t o seventy per cent of the carbon atoms in it are of the C 1 3 species, as compared with the \.\% abundance of this species of carbon atom ordinarily encountered wherever carbon occurs. W e ask purchasers of it to specify· not h o w much barium carbonate they want or even h o w much C 13 they want (there is, of course, plenty o f C 13 all about you), but the weight of excess C 13 desired. T h e commodity itself is of n o special value; it's the excess that matters. At 6 5 atom per cent C 13 , w e would supply you with 2 3.84 grams of Barium Carbonate, and its sole virtue would be

3 1,

NO. 19 »

You'll find more than 3 5 0 0 other readily available organic chemicals in our List N o . 38. If you haven't a copy, write to Distillation Products Industries, Eastman Organic Chemicals Department, Rochester 3, N . V .

Eastman Organic Chemicals A l s o . . . v i t a m i n s A a n d Ε in b u l k . . . d i s t i l l e d

Distinction Products industries VOLUME

1-Phenyldodecane (Eastman 6 8 1 6 ) could become the point of departure for an idea of which it is later said, "Why didn't I think of that?" (The g o l d e n thought concerning it has not occurred to us, either.) Look at the structure above—a hammer with a benzene ring for a head and a straight, saturated Ci2 chain for a handle. Physically it is a slightly viscous liquid that melts at —5.5 to — 3 C and boils at 1 7 9 to 180 C when pressure is reduced to 1 3 mm Hg. Density runs about 0.86. The compound is mentioned here because recently w e found a rather efficient synthesis for it and added it t o our list. W e can sell you a little of it now, and should you be fortunate enough to c o m e up with a reason for requiring it in larger-than-laboratory quantities, w e hope you will find it profitable to let us make it for you.

MAY

11,

is a division o f 1953

monoglycerides

Eastman Kodak Company 1985

THE CHEMICAL WORLD THIS WEEK

Nerve center of the Koppers ethylbenzene plant at Port Arthur, Tex., is this central control room. At the desk in the center, an operator can determine the exact ternperature at 72 spots throughout the plant''s operating unit and auxiliary equipment acted in the conventional Friedel-Crafts reaction using aluminum chloride catalyst. T h e new Williams Plant, n a m e d for J. F . Williams, Jr., formerly Koppers' president, and now a m e m b e r of the board of directors, has a design capacity of 9 0 million p o u n d s of ethylbenzene annually, and preliminary operations indicate that production at 115% capacity will b e possible. T h e plant occupies only a small part of 1040 acres which Koppers owns at Port Arthur. W h i l e there are no immediate plans for further expansion, D a n M. Rugg, vice president in charge of t h e chemical division, said that Koppers considers Port Arthur a most inviting location for future expansion in the chemical field. Dedication of the first unit of the Williams Plant of Koppers Co., Inc., was held April 29 at Port Arthur, Tex. Begun in mid-1951, the plant was designed a n d erected b y Koppers E n g i n e e r i n g and Construction Division. Partial production b e gan in mid-1952 w i t h full production attained in March of this year. Dedication ceremonies included a luncheon and plant tour attended by nearly 200 guests, including local businessmen and suppliers and contractors who contributed to the plant's construction and o p eration.

actions was to ask Secretary of Defense Charles E. Wilson to withdraw his recent order requiring his approval of all research contracts placed with government agencies other than t h e D e p a r t m e n t of Defense itself. T h e order in question is generally believed to b e directed against t h e placing of research contracts at t h e Bureau of Standards. Keith J. Laidler, Catholic University and consultant to the Small Business Committee, in his first public statement since writing an evaluation of t h e M I T report on AD-X2 last December, said that while h e did not have reason to doubt the integrity of t h e bureau, he "cannot fail to conclude that the small group of (Bureau

of Standards) scientists involved have allowed their preconceived notions to cloud their judgment." Dr. Laidler said that in the face of M I T evidence, bureau statements that t h e material ( A D - X 2 ) is worthless are "utterly unreasonable." Allen V. Astin, director of the Bureau of Standards, in a recent talk before t h e American Physical Society defended t h e bureau against a charge made by Secretary of Commerce Sinclair Weeks w h o stated that the Bureau's work on battery additives lacked objectivity. Without r e ferring directly to the battery additive matter, Dr. Astin said that the b u r e a u stresses reliability and accuracy in all its operations. Several more scientific societies h a v e come to the support of Dr. Astin and t h e Bureau of Standards. They have expressed a view concerning the necessity for h a v ing government scientists remain free of political influence. T h e American Physical Society, t h e Federation of American Scientists, and t h e National Academy of Sciences h a v e all m a d e statements in this regard. T h e physical society affiimed its belief in t h e integrity of the bureau's work. T h e FAS requested the President to clarify his attit u d e toward science in government. T h e National Academy supported the stand of its president, Detlev W . Bronk, w h o asked that Dr. Astin b e retained until a careful study of all questions involved h a s been completed. In a related development, Sen. Harley M. Kilgore ( D . - W . Va.) recommended that an unequivocal policy of no politics in science b e adopted. H e suggested t h a t the Bureau of Standards b e removed from

Explosion Rips American Resinous Chemicals Firemen pour water on the smoldering ruins of the American Resinous Chemicals Corp. main plant after an explosion ripped through the building April 30. One person was killed and 24 were injured, seven critically. The plant, located in Peabody, Mass., was operating under defense contracts. When this picture was taken police were searching the ruins for additional victims of the thunderous explosion

GOVERNMENT Astin Case Continues To Simmer Comments, pro a n d con, concerning t h e controversy over the battery additive, A D X2, and its subsequent developments, continued d u r i n g the past week. T h e committee to appraise operations of the Bureau of Standards h e a d e d b y M. J. Kelly, president, Bell Telephone Laboratories, h a s started work. One of its initial

1986

CHEMICAL

AND

ENGINEERING

NEWS

at your finger tips...

P. 5 |s.P Phenyl», y». lohcxinr and bicyclohexyl *re high boiling, colorless, oily liquid^, free from obieuionablr odor and relatively tree Irom toxicity

Structurally, phenylcyclohexane i-> composed of one aromatic six membered carbon ring and one aliphatic (hydrogenated) six membered carbon ring

Bicyclohexyl ι» composed of two aliphatic MX membered high boiling >olvenu and compa

NEW BULLETIN GIVES IMPORTANT

tibilizing agent- and penetrating agents

Intere-trng derivative- can be made from phenyh.yclohexan| by sulfona

FACTS O N

tion. nitration, halogenation and condensation with reactive cnerr.ica! agents

PHENYLCYCLOHEXANE

A N D BICYCLOHEXYL

Interested in high-boiling solvents, corapa-tibilizLig agents or penetrating agents? If you are, Monsanto's new technical bulletin on phenylcyclohexane and bicyclohexyl will be of great interest to you. These compounds sure higtiboiling, colorless, oily liquids, free from objectiona­ ble odors and believed relatively free from toxicity. Structurally, phenylcyclohexane is composed of one aromatic six-membered carbon ring and one ali­ phatic (hydrogenated) six-membered carbon ring. Bicyclohexyl is composed of two aliphatic sLx-membered carbon rings (both saturated with hydrogen). Both products are suggested for use as high.-boilirig solvents and compatibilizing agents and n.onpolar penetrating agents for metallic and other surfaces. They also show promise oi many other profitable applications. The new bulletin covers in concise, compact form the physical and chemical properties, typical re­ actions and other important information o n these two compounds. A useful bibliography is also given. For your copy mail the coupon today.

it

ÎBONSANÎÔ

DISTRICT SA.L.ES OFFICES: B i r m i n g h a m , Boston, C h a r l o t t e , Chicago, Cincinnati, Cleveland, Detroit, Los Angeles, Mew York, Philadelphia, Portland, Ore., S a n Francisco,Seattle, Twin Citie3. I n Canada, Monsanto Canada Limited, Montreal.

[ CHEMICALS -PLASTICS'

SERVING INDUSTRY

WHICH SERV£S MANKIND

M O N S A N T O C H E M I C A L COMPANY Phosphate Division 1700 South Second Street St. Louis 4, Missouri Please send me Technical Bulletin No. P-110 on phenylcyclohexane a n d bicyclohexyl. Name

Title....

Company Street City

V O L U M E

3 1,

NO.

19

MAY

11,

1953

Zone

State

1987

THE CHEMICAL WORLD THIS WEEK the Department of Commerce and m a d e a s e p a r a t e agency t o be placed under the guidance of outstanding, scientifically trained men from government, industry, a n d the universities.

Agreement on Bolivian Tungsten T h e Bolivian government has entered into an agreement with General Services Administration and the former owners of t h e now nationalized Patino mines for the sale of tungsten ore to the United States Government according t o an AP dispatch in the Wall Street Journal. T h e dispatch stated further that similar agreements are being worked out with t h e former owners of the Ilochschild and Aramayo mines. T h e agreement calls for the Bolivian government to indemnify the former owners out of the proceeds of the sale of t h e ore. Ten dollars a ton will b e given t h e former owners and a like amount will b e set aside to pay off a loan made by the export-import bank for the development of ore production. General Services Administration ad­ vised C&EN that GSA entered into con­ tracts with five tungsten producers early in 1952. Nationalization and other factors p r e v e n t e d t h e owners from complying w i t h production requirements of t h e con­ tracts. The contracts, however, d u e to other provisions, d i d not lapse and they a r e n o w being r e n e w e d . T h e price of t u n g s t e n in the contracts is from $62 to $ 6 3 a ton for ore containing 19c tungsten. T h i s price is about $20 a ton above cur­ r e n t market prices. Reconstruction Finance Corp. spokesn i e n state t h a t once t h e Bolivian govern­ m e n t reaches agreement with the former owners of t h e tin mines, w h o generally a r e t h e producers of tungsten, and the State Department gives its approval, R F C c a n enter into negotiations with t h e Boliv­ i a n government o n a long term contract f o r the purchase of tin.

Five Magnesium Plants Closed Five of t h e Government's six magnesium plants will b e taken out of production as t h e result of a review of current and fu­ t u r e requirements b y t h e Munitions Board, according t o W. E. Reynolds, commis­ sioner of Public Building Service. The plants being closed are at Painesville, Ohio; Canaan, Conn.; YVingdal, X . Y.; Manteca, Calif.; and Spokane, Wash. The plant at Velasco, Tex., which pro­ duces magnesium from seavvater and is o p e r a t e d b y Dow Chemical Co., will b e k e p t i n operation. Keeping t h e Velasco plant in operation a n d s h u t t i n g down t h e other five, which h a d a combined rated capacity of approxi­ m a t e l y 116,000,000 pounds a year, was t r i e "most practicable and economical" way

1988

of meeting remaining requirements for magnesium and at the same time bringing production down to t h e desired level.

A l k y l a t e Expansion Goal Set An expansion goal for alkylate has been established by O D M , which calls for an increase in production capacity of 30,000 barrels of alkylate per day. The expansion to b e completed by Jan. 1, 1955. The 30,000 barfels increase will be in addition to existing facilities and to new facilities on which construction already has been undertaken. Alkylate, which is m a d e from crude petroleum, is t h e primary ingredient of aviation gasoline.

Primary Nickel Consumers M e e t with NPA XPA officials will soon take action to amend the regulation controlling nickel so that the material will be distributed only to persons w h o h a v e established base period usage and intend t o use their al­ lotted nickel in their own plants. This was announced at a meeting with the advisory committee of the Primary Consumers of nickel for chemicals and electroplating industry in Washington, April 19. Industry will send some of their best

qualified employees to Washington within the next few weeks to assist in clearing u p the backlog of requests for assistance and other pressing matters involving distribu­ tion of nickel.

No Let-up Seen f o r N e w s p r i n t T h e precarious balance b e t w e e n news­ print production and t h e growing d e m a n d will continue indefinitely, the National Production Authority advised the news­ p a p e r industry advisory committee, meet­ ing in Washington April 2 7 . United States and C a n a d i a n mills p r o d u c e d 1,665,670 tons of newsprint for t h e first t h r e e months of 1953 against a rated ca­ pacity of 1,698,936 tons. It is estimated that consumption of newsprint in t h e U. S. now exceeds 6,000,000 tons annually.

Aluminum Stockpiling Discontinued Continued high demand for military and atomic energy needs, has led the Prime Aluminum Products Industry Advisory C o m m i t t e e to r e c o m m e n d discontinuance of government stockpiling of p r i m a r y a l u m i n u m during the second half of this year. T h e publication of statistics on ship­ ments of aluminum products, either b y t h e

Titanium Extraction Certificate Largest f o r Period In the two week period from April 9 t h r o u g h April 22, O D M issued 202 n e w cer­ tificates of necessity amounting to $227,874,894. In addition, 44 applications were denied. With these new certificates, amortization a m o u n t i n g to $26,219,468,000 has been granted for 16.619 new or expanded facilities. T h e largest certificate granted in this period went to Cramet, Inc., Nashville, T e n n . , for titanium, $25,740,500, 90'4allowed. Certificates of chemical interest are listed below. N A M E OF C O M P A N Y AND LOCATION O F F A C I L I T I E S

P R O D U C T OR S E R V I C E

American Mineral Spirits Co. Toledo. Ohio The M il white Company Inc. .Harvey, La. Brunswick Pulp & Paper Co. Brunswick, Ga. Champion Paper & Fibre Co. Pasadena, Tex. Copper Creek Cons. Mining Co Pinal County. Ariz. First Uranium Corp. of Nevada, Inc. Imlay, Nev. Jones & Laughlin Steel Corp. Pittsburgh, Pa. General Electric Co. Schenectady, Ν. Υ. International Nickel Co., Inc. Huntington, W. V; American Enka Corp. Enka, N. C. The Burdette Oxygen Co., of Cleveland. Inc. Huntington Park. Calif. Ashland Oil & Refining Co. Catlettsburg, Ky. Pan American Refining Corp. Texas City, Tex. Shell Oil Company Wood River, 111. Loven Chemical of Calif. Newhall, Calif. Lehigh Warehouse & Trans. Co. Bayonne, N. J. Mathieson Chemical Corp. Pasadena, Tex. Radiation Counter Laboratories Inc. Skokie, 111. G. M. Giannini & Co., Inc. Springfield, N. J. Cramet Inc. Nashville, Tenn. Minerals Engineering Co. Salt Lake City, Utah Wah Chang Corp. Glen Cove, Ν. Υ.

Aviation alkylate facilities Barito ore

AMOUNT CERTIFIED

PERCENTAGE ALLOWED

$ 3,679,200

100

13,422

25

Bleached sulfate wood pulp

5,415.820

55

Bleached sulfate wood pulp

1,351,200

55

Copper

149,000

75

Copper-tin concentrates

160,709

75

5,135,000

65

547,000

40

Mick el & nickel alloys

280,000

50

NVlon-6 filament yarn

1,000,000

40

176,700 72,500

60 45

1,000,000 2,250,000 185,000 110,000

100 65 40 50

850,000

20

Iron ore Metallurgy· and electronic research

Oxygen

Petroleum refining facilities Petroleum refining facilities Petroleum refining facilities Phenol

3,670,000

50

Public storage facilities for chemi­ cals Sulfuric acid

1,450,000

40

380,000

45

Scientific & technical equipment for defense industries Technical & scientific equipment for defense Titanium

42,500

45

Tungsten Txingsten products

CHEMICAL

AND

3,681

70

25,740,500

90

197,381

70

12,913

50

ENGINEERING

NEWS

This effective plasticizer also serves as a coupling agent, intermediate and solvent in many other industries

Cork gaskets and other important products of cork sheet are made more flexible, more durable by the effective plasticizing action of diethylene glycol. Many industries are utilizing diethylene glycol today for other valuable properties—it mixes easily with water, yet dissolves many organic chemicals. It is odorless, tasteless and colorless. Diethylene glycol also has a high boiling point, low volatility, and is compatible with many substances. Diethylene glycol has proved to be " t h e better way"—

you can depend

V O L U M E

3 1,

NO.

19

M A Y

11,

often the most economical—in gas dehydration, as a solvent in vapor-set inks, as an intermediate in resin manufacture, as a coupling agent in textile soaps and as an humectant in tobacco. Perhaps these successful applications have pin-pointed your problem or suggested a similar use. In any case, we'll be glad to supply you with a n experimental sample and information on the properties of Dow diethylene glycol. W r i t e to THE DOW CHEMICAL COMPANY, Midland, Michigan. Dept. OC 3-9.

on DOW

1953

CHEMICALS

1989

THE CHEMICAL WORLD THIS WEEK G o v e r n m e n t or b y a private association, w a s also r e c o m m e n d e d by t h e committee. T h e new aluminum order, \ i - 5 a , which controls production and distribution of a l u m i n u m u n d e r the defense materials system after J u n e 30, 195-3, is expected t o be issued shortly, N P A officials advised. O n e bright spot in t h e aluminum picture is the improved water and power supply situation in t h e Pacific Northwest. T h e improvement has b e e n sufficient to warrant revocation of t h e Defense Electric P o w e r Administration orders limiting use of electric power in this area.

Use of Cobalt Residues Amended Cobalt salts and c o m p o u n d s made from residues not suitable for metallurgical applications have been released by the National Production Authority for certain uses which w e r e formerly prohibited. A m e n d m e n t of Schedule 2, Order M-80, now allows t h e use of cobalt compounds in coloring glazes, glass batches, p o r c e lain enamels, and paint or plastic p i g ments, effective immediately. T h e relaxation of controls is m a d e possible by a recent increase in imports of cobalt salts a n d compounds. It was e m phasized that there has been no increase in t h e available supply of other forms of cobalt for the United States, in relation t o present over-all requirements.

long and 18 inches in diameter could produce 5 million pounds of acid a year b y operating continuously for 340 days. A total fermentation capacity of 100,000 gallons would be required for the same annual production. T h e final crude lactic acid contains 50 to 60 r/ r of the theoretical amount of lactic acid and 20 to 2 5 % of this amount of other acids, excluding hydrochloric, formic, and acetic. Pure methyl lactate can b e obtained from the esterified acids by fractional distillation, b u t any development which could use t h e admixture of acidic products would m a k e t h e process promising. A potential application seems to be in the plastics field in alkyd resins and plasticizers. Methods of purifying t h e crude mixture were also studied. T h e best procedure for obtaining p u r e acid appears to be solvent extraction to remove inorganic materials in the crude liquor, followed b y esterification and fractional distillation. T h e work was reported in t h e May issue of Industrial and Engineering Chemistry, p a g e 1136.

Heat Treatment Increases Strength of 4340 Steel

Heat treating a n d processing procedures a r e enabling the aircraft industry to use effectively standard, deep-hardening 4340 steel with a pounds-per-square-inch t e n sile r a n g e of 260,000 to 280,000. T h e TECHNOLOGY m e t h o d , developed by Lockheed Aircraft Corp., means that aircraft parts, such as t h e landing gear, will have 4 0 % more Chemical Production of Lactic Acid Could Save Time and Space strength with a 2 3 % saving in weight. The first phase of t h e s t a n d a r d h e a t T h e alkaline degradation of molasses treating cycle includes normalizing of t h e offers possibilities for continuous p r o d u c - material at about 1600° F. t o produce a tion of lactic acid with saving in time a n d homogeneous structure with complete soluspace, according to work done at t h e E a s t - tion of carbides. Austenitizing is accomern Regional Research Laboratory, Phila- plished by heating to 1500° F . T h e reladelphia, Pa., b y Rex Montgomery a n d R. A. * rstiyéîx low t e m p e r a t u r e was selected to Ronca. All commercial lactic acid is I c e é ^ t o a m i n i m u m t h e retained austenite p r e p a r e d by the fermentation process, b u t upon ^quenching in oil. D r a w i n g is pert h e disadvantages of t h e method—need for formed at 400° t o 500° F. a n d as a final a large amount of space and operational therrrial operation all parts are h e a t e d to time, m a i n t e n a n c e of p u r e culture, a n d about 250° F. for 24 hours to stabilize addition of nutrients, increasing the alany residual austenite. Special machining, r e a d y high solids content in the final c r u d e grinding, welding, and finishing operations lactic acid—have aroused interest in other follow the h e a t i n g treatment. methods. T h e s e disadvantages are absent or at Process Yields Finely Divided least reduced in the chemical method. Particles for Uniform Dispersions Reaction time can b e only a few minutes a n d t h e reaction can b e carried out in more A process for converting solid substances c o n c e n t r a t e d solutions t h a n are possible by into dry, free-flowing, finely divided fermentation, resulting in lower evaporapowders has b e e n developed b y I. E. tion costs. Also, a continuous process is Puddington, director of t h e division of feasible. applied chemistry of t h e National Research E R R L studied t h e extent to which lactic Council of Canada. T h e solid is dissolved acid a n d various other acids are formed in a solvent w i t h a critical temperature from t h e action of calcium oxide and calbelow the melting point of t h e solid. T h e c i u m hydroxide on C u b a n blackstrap mosolution is h e a t e d in a closed vessel to a lasses, refiner's blackstrap molasses, beet temperature higher t h a n t h e critical point molasses, a n d r a w cane sugar. C u b a n of t h e solvent b u t lower t h a n t h e melting blackstrap h e a t e d to 230° to 240° C. for point of the solid. This vaporizes the 3 0 minutes gave a yield of 1.2 equivalents solvent a n d leaves t h e solid in a finely of esterified acid p e r mole of molasses. At divided, free-flowing powder. 90 r / r of this vield, a tubular reactor 10 feet T h e process should be of importance in

1990

CHEMICAL

many chemical reactions in which surface areas are important for ready uniform dispersions in other materials with which the particles are to react or t o remain in suspension. It is available for licensing through Canadian Patents a n d Development, Ltd., National Research Bldg., Sussex St., Ottawa, Ont., C a n a d a .

Ketone Derivatives of Rhodanine Show Mildewproofing A c t i v i t y Cotton cloth impregnated with 2Pfc of either of three compounds of the general tvpe R'N — 0 = 0 loses no m o r e t h a n

I

!

C

s

|C=R

s

2 0 % of its tensile strength after four weeks' burial in composted greenhouse soil, according to a group of D u k e Universitv researchers. When R = C—C.-,Hu a n d

c aI "

R' =

H, the strength loss is 209ir; w h e n CH2—CH2

/

X

R = C

CH2

\

/

C H3— C H 2 CH a n d R' = H, t h e loss is 6 % ; , w h e n CH2—CrÏ2 CHCH3

R = C

\

CH2—CH2 a n d R' = H, t h e loss is 9 % . T h e D u k e study started from t h e observation that many common organic sulfur compounds used as fungicides contain S

II

t h e structure — N ' ^ - C — S — . R h o d a n i n e , which contains this group, has been p a t ented as a fungicide, b u t t h e Duke r e search t e a m found t h e m a t e r i a l to b e ineffective in protecting cotton cloth against mildew and rot, which are caused largely from the action of cellulolytic fungi a n d bacteria. T h e y t h e n set out to change the rhodanine structure to increase t h e mildewproofing and fungicidal activity. By condensation w i t h m e t h y l a n d alicyclic ketones, c o m p o u n d s w e r e p r e p a r e d which retain the toxiphoric group and in addition h a v e a carbonyl g r o r p conjugated with a d o u b l e bond, a feature present in t h e fungicidal chalcones a n d acrylophenones. W h e n R' = CH 3 and R is limited to normal alkyl groups, a graph of the n u m b e r of carbon atoms in R -vs. residual strength after four w e e k s ' burial shows that t h e lower members of t h e series are not effective; starting at t h e propyl group there is a marked increase in activity. W h e n more than five c a r b o n atoms are present in t h e normal alkyl group, t h e activity drops markedly; a n d a t 9 carbons, it disappears almost completely. This parallels w h a t has been observed in the (Continued

AND

on page

1995)

ENGINEERING

NEWS

THE CHEMICAL WORLD THIS WEEK biological activity of other Homologous series. Another series of compounds were studied—31 simple benzylidenerhodanines as well as four products from t l i e conden­ sation of acetophenones with rhodanine. T h e most active of the benzylidenerhoda­ nines were t h e alkyl a n d halogen deriva­ tives. Five of them w e r e sufficiently ac­ tive to prevent more than 3 0 % l o s s in tensile strength after four w e e k s ' b u r i a l . T h e D u k e research team, F . C; Brown, C. K. Bradsher, E . L. Lavvton, and S . M. Bond reported their work in t h e May issue of Industrial and Engineering Chemistry, page 1027.

SCIENCE

P e r f e c t C r y s t a l s Point W a y To I n c r e a s i n g M e t a l S t r e n g t h Microscopic crystals of zinc, zinc sulfide, and mercury without the defects which are usually present a r e far stronger than ordinary crystals, according t o J . Η. Ήοΐΐοmon, manager of General Electrics metal­ lurgical research department. Dr. TTollomon, speaking before the annual New England regional conference o>f the insti­ tute of metals division of t h e American Institute of Mining and Metallurgical Engineers, said that if defects i n the regular arrangement of the a t o m s of metal crystals can b e eliminated, theory indi­ cates that metal strength m i g h t b e in­ creased as m u c h as a thousand times. T h e question of h o w , w h e n one layer has been laid down, t h e crystal i s able to start another has been clarified, h e said. GE research shows t h a t crystal growth takes place in a helical direction. When a crystal forms, successive l a y e r s of atoms are built u p , b u t a layer i s ordinarily never entirely completed. Instead, i t ad­ vances in a spiral, continually getting higher. Vinyl Ether Derivative Shows Promise a s A n e s t h e t i c Tests on trifluoroethyl v i n y l ether by John C. Krantz, University o f Maryland medical school, and Max S. Sadove, Uni­ versity of Illinois, indicate t H e material may b e useful as a n anesthetic. Dr. Krantz, w h o is well known f o r his studies on derivatives of vinyl e t h e r , says tri­ fluoroethyl vinyl ether is t h e result of a trial of about 4 0 different compounds. Now that preliminary tests h a v e been suc­ cessful, further clinical testing i s scheduled by Dr. Sadove, who w a s one of t h e test "patients" himself. Contrary t o newspaper stories, t h e an­ esthetic does not necessarily c u t d o w n on operating time—in fact, so l i t t l e is known about t h e compound's action that i t isn't possible to specify the types o f operations for which it m a y be especially suitable. Although several firms are s a i d to b e in­ terested in commercial production o f the V O L U M E

3 1,

N O .

1 9

•••to he available in substantial quantities a t lower prices! By mid-1953, you can take full ad1

Emery Azelaic Acid

Α^?ώ*ΡβΚ!ίώ ! Ώ^ Νο^

Α

ieal intPrmpdiflrpc, e«n hopvnlrnfpd £ ίv£ ÏÏ]uw ~SL+ J£L ^ ™ i l t to the iullest extent, with a potential virtually unlimited. y U ο/ , """"W3^Start an evaluation program today, to plan for your production tomorrow. Emery Pelargonic Acid ._, . . ., . .Λ „ 1 his unique acid is a mixture or saturated, monobasic liquid acids, predominantly C9 pelargonic acid. Its esters have widespread use as vinyl plasticizers and synthetic lubricants. A s a fatty modifier for n o n - d r y i n g alkyd resins, the saturated structure of Emery Pelargonic Acid resuits in excellent color-jretention properties. The solubility and surface activity of the acid itself have proved very effective in the flotation of various minerals.

reactions typical of dibasic acids, including esterification and conden„ Λ4 .· _ „„·+ι ι„ΛΛι„ „^Λ Λ,·«~,·~ Λ ~ ??. tlo + n with glycols and diamines. Diesters of Azelaic Acid have wides p r e a d use as plasticizers for vinyls, cellulosics and synthetic rubbers, a n c | a s synthetic lubricants. Azelaic Acid is used also as a modifier of alkyd resins to produce *