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Inorganic Moves Info Limelight.. · . . . as chemists look for materials for high tempera ture service and plunge into chemistry of the solid state X HE YEAR 1956 for "inorganic" chem istry has been largely one of progress in borderline fields. For instance, lying between organic and inorganic chemis try are metallorganics, which come in for their share of scrutiny. These compounds have been studied chiefly as catalysts, but they have been dis cussed as a way to form polymers that can stand high temperatures. As yet, however, no really big use has been found for them. Maybe this year will bring the breakthrough. The armed forces lead the search for compounds that will remain stable and plastic up to, say, 700° C. For aircraft uses they want materials that are plastic for tubing, shock absorbing blocks, tires, gaskets, and the like. However, major problem is to find materials that are not only stable and plastic at 700° C , b u t also plastic at - 4 0 ° C , this being the possible range between planes in use and ones on the ground in the Arctic.
This h o t motor has run for 50 hours at 500° C , showing how new high temperature service materials work 38
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fusion lies in teaching. Borders are set up—organic, inorganic, biological, and so on—and students are taught these Enter gallium? subjects, with very little being said about the areas that he between. This Gallium may b e the next element I same professor feels that inorganic has to enter the industrial scene. Here- I been neglected because of this method tofore Jtoo expensive to warrant I of instruction. He feels that inorganic consideration as much more than a I is wasted on the young. Freshmen are laboratory curiosity, this metal can I not able to appreciate the niceties, yet now be recovered electrolytically I with more maturity in chemical think from t h e liquors of Bayer alumina I ing after two or three years, they get plants; the electrolytic recovery I organic and physical chemistry, see the process may lead to plentiful, less I subtleties, and focus their interest there. Another borderline field in for a look expensive gallium. j in 1956 was application of magnetism Gallium already has some spe- I Measuring magnetic cialty applications, and its increased I to chemistry. availability may spur further use I properties of catalysts helps unravel research. Price in pilot plant quan- I catalytic mechanisms. For example, titles h a s been dropped from $3.00 I finely divided nickel on an alumina a gram to 90 cents a gram by I carrier is used for catalyzing various Aluminum Industrie Aktien Gesell- j schaft of Lausanne, Switzerland, I owner of the rights to the electro- I lytic process. I If it were to b e recovered from I Lithium... Bayer process liquors, gallium could I be produced in this country at a Lithium lost none of its glamour rate of several hundred pounds per I during 1956, but many of the pre day. I sumed facts behind that glamour re main classified. Commercially, all four basic producers—American Pot ash (American Lithium Chemicals), Foote Mineral, Lithium Corp. of America, and Maywood ChemicalDuring the year a variety of com report satisfactory growth. "About ι pounds were studied, mostly coordina as predicted" is one way it was put. tion compounds in which the organic This applied chiefly to Hthium com part of tJhe molecule is stabilized by pounds used in ceramics, all-purpose the presence of metal ions. In some greases, and the like (C&EN, June I cases, polymerization is brought about 11, 1956, 2850). by the actual coordination with the Industry-wide, specific items of in metal ion. In others, a monomeric unit terest this year include: is built, metal with organic material around it, and then these units are poly • Use of Hthium and hthium deriv merized. So far, only low molecular atives in high energy fuels. weights bave been obtained, b u t it is • Development of techniques for clear that polymerization takes place. making hthium metal dispersions. And, apart from coordination com • Use of such dispersions as cata pounds, quite a number of others, not lysts, particularly to make Firestone's ably those of boron and phosphorussynthetic "natural" rubber (all cis, all nitrogen, are coming in for study. They 1,4-polyisoprene). are almost all substances that contain both organic and inorganic groups—the • First known production of pilot organic part t o give elasticity, the inor plant amounts (50 to 100 pounds) of ganic to give stability. lithium hydride dispersions in hydro carbons. Not o n the borderline but getting into a field long exclusively organic, are Also noteworthy was formation of inorganic fuels, particularly for rockets. the American Lithium Institute at Both very powerful oxidizing agents Princeton, N. J. Backed by American and combustible materials are needed. Potash, Foote Mineral, and Lithium Among combustible materials are the Corp., it will handle industry-wide boron hydrides and hydrazine; among research problems. Seven major re oxidizing materials are concentrated search programs are being con nitric acid, liquid oxygen, perchlorates, sidered, and the annual budget may perchloric acid, and hydrogen peroxide. reach six figures. The institute will During 1956 boron and its compounds ι support projects at colleges and other came in for the largest public attention. I research institutions and will gather If this seems t o be a lot of over and disseminate technical informalapping of organic and inorganic, re I tion on hthium. member it is still chemistry. As one professor points out, the source of con
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kinds of organic reactions. But what state is t h e .nick:el in? Typically, a nickel sulfate solvation i s used t o saturate t h e support· This is h e a t e d to form nickel oxide which is then reduced to metallic niclcel w i t h hydrogen. Nickel in bulk i s known to be ferromagnetic; single atoms never are. T h u s if the catabyst is extremely magnetic, it indicates that the nickel has formed in "islands" rather t h a n being uniformly distributed. Also, paramagnetism measurements indicate where t h e electrons are. This gives a measure of t h e nature of t h e surface that may make it possible f o r chemical reactions to occur. T h e r e is a rather general expectation that w e will understand catalytic strength w h e n w e learn more .about imperfections t h a t cause unbalanced forces a r o u n d atouis slightly o u t of position i n the lattice. Some surface chemistry work a t Bell Labs indicates that atoms several thousand diameters away from those that a r e actually out of place a r e affected. Bell researchers theorize t h a t with polarized infrared techniques they c a n determine t h e total strained content o f the crystal a n d learn something about i t s catalytic activity. Using similar solid state techniques, researchers are learning more about aqueous solutions. Working with dilute solid solutiorjLS, they are finding out a good deal aboxit interaction of ions and coulombic Forces. For instance, researchers a t Ball Labs feel that they know more about solutions of lithium in silicon—degree oF ionization, solubility, degrees of association—than is known about aqueous solutions. In water, local dielectric constants due to orientation of the water molecules a r e unknown, but in silicon the position of the atoms a r e known. With addition of a "solute/' t h e surroundings are k n o w n both geometrically a n d electrically a n d t h e ionization c a n be measured precisely. Using oxides, a good deal c a n be learned about the; formation of hydroxyl ions. Their formation on t h e surface of zinc oxide crystals c a n b e measured electrically at room t e m p e r a t u r e by varying the partia.1 pressure of hydrogen in t h e atmosphere. This, b y analogy, gives more information than c a n b e obtained w i t h liquid solutions themselves. T h e field of solid state science has not been static. One of the more dramatic advances "was discovery of two n e w families of ferroelectrics—guanidinium aluminuraa sulfate hexahydrate a n d t h e glycine sulfate series. I n the latter, three glycines are associated with one sulfate, rather than two glycines as >expected; this opens new views of electron b o n d i n g of a_mino acids. Discovery of a solid state analog of t h e water molecule has been m a d e by
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establishing existence of e+e~ where trie e+, is the solid state analog of t h e hydrogen ion a n d e" corresponds to hydroxy1. The measurement of formation of t h e e"e~ compound has permitted a prediction of the solubility of lithium i n boron-doped silicon and germanium over a concentration range of 10 5 . T h e real news of semiconductors i n 1956 was widespread commercial a p plication. In fact, starting about midyear, much of the potential seen over the past five or so years started to b e realized. This increased application brought about higher production, which coupled with better production equipment and newer processing innovations, has dropped prices 3 5 to 5 0 % . Efforts toward making semiconducting devices that operate at higher temperatures has swung commercial interest from germanium to silicon. As y e t no truly high temperature transistors have been made. However, t h e upper limit for temperature is being raised from time to time. A t present the practical limit for silicon is around 200° C . Germanium transistors, once thought to be limited to 85° C , are now found to operate a t 100° C , and can b e stored at 135° C. Giant strides are being made toward development of more high temperature materials. During t h e year Union C a r bide jumped into t h e field in a big w a y with the opening of National Carbon's research lab in Parma, Ohio. Primary function of this lab is research i n t o solid state arid refractory materials. Among refractories coming in for study a t the National Carbon labs a r e titanium diboride (called the hardest material that does not exist in nature ever m a d e b y m a n ) , titanium carbide (not only hard b u t resistant to corrosion), a n d cerium monosulfide (which has potential uses in production of titanium and zirconium). In general, refractory hard metals involve combinations of metallic transition elements with carbon, nitrogen, boron, or silicon. Besides their practical interest, they also offer opportunities for studying fundamental relationships between physical properties of solids and their atomic structure. One characteristic of hard metal refracrories is a large difference between atomic sizes of t h e two constitutents. At present there is some controversy as to the type of bonding present in t h e materials. Some of these compounds may exist over a wide range of compositions, leading to the assumption that some compromise between various types of atomic bonds exists. Where "inorganic chemistry" will go in 1957 is anyone's guess, b u t there is a rather widely held opinion that t h e s e fields hold economic promise that m a y equal t h e petrochemical boom of the past 2 0 to 3 0 years. 40
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Pesticides Up
25% in 1956 . . . . . . and the fertilizer industry gets more ammonia capacity. Big push coming up for moving fertilizers into new markets IN
COMMON with the balance of t h e
economy, the nation's pesticide industry had a good year in 1956. Basic producer sales reached $250 million, u p 2 5 % over 1955 and a new high for t h e industry. Aside from 2,4-D, here's how some of the basic insecticides stacked u p in sales for the first 11 months: •Benzene hexachloride basis) u p 6 6 % . • DDT up 25%. • 2,4,5-T u p 7 4 % .
(gamma
control on non-food crops, a n d Stauffer has data for applying for food crop registration. One advance during the year was a n e w injection rig that Contributing to the record was grow- permits injection in previously prepared ing farmer use of pesticides plus seed beds. several heavy insect outbreaks. Boll • Thimet ( American Cyanamid sysweevils in t h e South and grasshoppers in t h e West were two particularly temic) was out on test for cotton seed troublesome pests. Added to these treatment in the West and for a variety older pests, however, were t w o other of applications in the East. infestations of serious size: Mediter• Simazin (Geigy herbicide) was reranean fruit fly and spotted alfalfa ported by Cornell to show promise for aphid. controlling broad-leaved and grassy anBy year's end, t h e Medfly war in nual weeds. Florida looked like it might r u n a n • E P T C (Stauffer herbicide) has other six months before being completed. Cost—about $8 million to date, gone through t w o years of testing for with several million more to finish t h e grassy and broad-leaf weeds, is to move job. Outlook for spotted alfalfa aphid out into extensive field testing this year. control wasn't so good. Since t h e Feb- In contrast t o presently established carruary 1954 outbreak in California, t h e bamates, E P T C is a thiolcarbamate. pest has spread into the Southwest, u p • Phosdrin ( Shell Chemical systemic) into t h e Intermountain region, and o u t was introduced experimentally last year into the Midwest. Chemicals give and used on a trial basis on 23 fruit and good control, b u t reinfestation is rapid. vegetable crops. A major advantage: While old chemicals were doing well rapid disappearance (to 1 p.p.m. in 24 in 1956, a spate of n e w ones were in hours). Shell plans to file a petition various stages of test or commercial for permanent tolerance early this year. development: • Fertilizers. Pesticides may have .f'Nemagon (Shell Chemical nema- scored a record year, but t h e situation tocide) finished its first full year of for the other side of chemicals for agri.commercial sales. Worth noting in culture— fertilizers—was less clear. For 1956 was its granular formulation t h a t one of t h e first times in recent years, led t o greater sales, particularly on cot- supplies of all grades and types were ton i n the Southwest. adequate in all areas. This stems in • Vapam (Stauffer soil sterilant) part from recent fertilizer industry exmoved well for weed a n d soil disease pansions, in part from declining sales
