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Prepared by U. S. Industrial Chemicals Co.
U.S.I. CHEMICAL NEWS June
*
A Series for Chemists and Executives of the Solvents and Chemical Consuming Industries
Growing Market Is Seen For Phosphoric Acid as Fertilizer Raw Material In a recent article in Farm Chemicals Maga zine, Lawrence Byck — U.S.I. Manager of Heavy Chemical Sales — discusses the value of wet-process phosphoric acid as an agricul tural chemical raw material. Phosphatic Fer tilizer Solution (PFS) has been an inter mediate in triple superphosphate production for many years, but its use as a raw material for fertilizer generally dates back only to 1957. According to Mr. Byck, the usefulness of P F S depends on these factors: (1) It is the only commercial source of P2O-. in liquid form. Dusting and massive solids handling problems are eliminated. (2) It is by far the most highly acid source of Ρ2Ο.Ί commercially available. (3) It is the most concentrated commercial source of P^Oo - 52-547e. (4) It may or may not be a markedly eco nomical source of PsOs, depending on con sumer location. Civen these factors, says Mr. Byck, here are some of the things P F S can do for the mixed fertilizer industry: • Neutralize large quantities of ammonia, because of high
New Commercial Route to Copper Strip Starts with Ammonia Leaching of Scrap Copper strip can now be made commercially from a powder which is derived from copper scrap by chemical means. Scrap is leached with ammonia, and reduced to copper pow der with hydrogen gas at 375° F and 1,200 psi. Via a specially developed process and re lated equipment, the powder is roll-compacted into strip that is sintered at oO-100°F below its m.p. under a hydrogen atmosphere. The strip is then rolled and annealed to speci fication.
Sodium Addition Properties of
Improves Alloy
Recent tests have indicated that metallic sodium, added in small quantities to alu minum 356, improves ductility and the al ready fine mechanical properties of this casting alloy. As little as 0.02 to 0.04% seems to do the job. Above about 0.04%, additional sodium causes fluidity loss and increased porosity, with an accompanying loss of mechanical properties. Al uminum 356, used extensively in indus trial, aircraft and missile service, contains about 7% silicon and 0.3% magnesium. The silicon crystals are large and needle-shaped, which tends to make the structure relatively brittle. Sodium refines the crystals to a small, finely dispersed form to improve alloy prop erties. In the tests, sodium bricks were added by immersing them in the molten alloy wrapped in aluminum foil. The foil gradually melts and allows the sodium below the surface of the molten alloy, to do its work.
1959
Missiles a n d Rockets, Fast Growing M a r k e t for Chemical Materials a n d Research Propellents, Lubricants, Plastics, Nonferrous Metals Among Materials Researched, Developed and Supplied by the CPI. It is e s t i m a t e d t h a t m o r e t h a n 2 5 % of t h e $ 4 - b i l l i o n - p l u s g o v e r n m e n t e x p e n d i t u r e f o r m i s s i l e s a n d r o c k e t s , in t h e fiscal y e a r j u s t e n d i n g , w e n t t o t h e c h e m i c a l industry for materials, research and develop ment. For the fiscal year starting July 1, total in this area is enormous. The reason: none of government expenditures for this program are the materials evaluated to date completely expected to be about 30% greater, with the answer the requirements of the ideal pro chemical industry's share possibly even higher pellent. than in 1958-1959. The U. S. space and Liquid systems, on the one hand, are com weapons program is becoming a larger and plex, and many of the component materials larger factor to chemical manufacturers. have the disadvantages of corrosiveness, toxi city, low density and, for ballistic purposes, Structural Materials Largest Market Where does the CPI fit into this vast un poor storage life. However, liquids are rela dertaking? Structural materials are of course tively easy to control and, most important, the greatest contribution in terms of tonnage have high specific impulse. Solid systems, on the other hand, present and of dollars. Practical materials must be found to withstand temperatures as high as problems of their own. Combustion control is 7,000° F. Strength must be high. Weight must difficult. Component materials need better be kept down. The chemical industry is work physical properties such as flexibility and ing on answers — evaluating nonferrous metals thermal expansion coefficients. Most impor and alloys, ceramics, organic and inorganic tant, they are low in specific impulse com polymers, graphites — developing new com pared to liquids. But solid systems are reli able, comparatively simple equipment-wise, pounds, new techniques, new combinations. and can be fired easily on short notice. In consequence, both types of systems are under intensive investigation, Nonferrous Metals Used or Proposed but with the emphasis on sol For Structures i n Missiles & Rockets ids growing. Aluminum Nickel Beryllium Cadmium Chromium Cobalt Columbium Copper Magnesium Molybdenum
Silver Tantalum Tin
Titanium Tungsten Zinc Zirconium
Non-Metal Materials Used or Proposed For Structures i n Missiles & Rockets Alkyds Aluminum Oxide Epoxies Glass Fluorocarbons Graphite Nickel Molybdate Phenolics Silicon Carbide Cpds. Polyamides Polybutadienes Thorium Oxide Zirconium Boride Polyesters Polysulfides Zirconium Oxide Other Ceramic Oxides Silicones Urethanes
Along with combinations of metals and ceramics (ceramets), researchers have re cently proposed metal-ceramic-plastic "alloys*' which, if practical, might make the ideal rocket materials. Propellents Greatest R & D Challenge Propellent procurement is rather small since, of course, propellents are actually used only during firings. But the research effort
Liquid Propellent Materials, Used or Under Consideration FUELS OXIDIZERS Alcohols Chlorine Trifluoride Alkyl Boranes Fluorine Amines Hydrogen Peroxide Aniline Liquid Oxygen Ammonia Nitric Acid Cyanogen Nitrogen Tetroxide Hydrazine Oxides of Nitrogen, Hydrogen Other Hydrogen Cyanide Oxygen Difluoride Kerosene Oxygen Fluoride Unsymmetrical Ozone Dimethyl MONOPROPELLENTS Hydrazine (UDMH) Ethylene Oxide \ Hydrogen Peroxide
Solid Propellent Materials, Used or Under Consideration FUELS Polyethylenes Boron-Based Polyurethanes Compounds Contain PolysulfideRubbers ing Metals Like OXIDIZERS Aluminum Ammonium Nitrate Beryllium Potassium Nitrate Magnesium Ammonium Resins such as Perchlorate Acrylics Potassium Butadiene-Vinyl Perchlorate Pyridine Lithium Cellulosics Perchlorate Epoxies DOUBLE-BASED Phenolics Nitrocellulose Polyamides Nitroglycerine Polyesters
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Prepared by U. S. Industrial Chemicals Co.
U.S.I. CHEMICAL NEWS
Juno
CONTINUED
Missiles
Many O t h e r T y p e s of M a t e r i a l s Needed The chemical industry also supplies to the missile field materials such as lubricants, hydraulic fluids, pressurizing gases, and plastics and rubbers for seals and gaskets and protective clothing. Of particular interest is the research work in progress on synthetic lubricants to supplement the mineral-based varieties. Among the compounds under investigation are included fluorine derivatives, diester derivatives, phosphorus-boron combinations, tin-silicon compounds, silicones and alkyl silanes. U . S . I . C o n t r i b u t e s in S e v e r a l Areas Because of its diversified interests in chemicals, plastics and nonferrous metals, U.S.I, contributes to the vital space and weapons program both directly and indirectly. Through Mi ownership of Mallory-Sharon Metals, U.S.I, supplies zirconium, titanium in commercial quantities, tantalum and columbium in pilot quantities. Polyethylene, made by U.S.I., is among the resins under investigation in solid propellent fuels. Another U.S.I, product, 1SOSEBACIC® acid, may be used as an intermediate for the polyurethanes studied for the same purpose, as well as for diester bases in synthetic lubricants. U.S.I, makes ethyl alcohol, long used in liquid propellent systems. AFN, Inc., 2 5 % owned by U.S.I., has a government research contract on boron-based fuels. And in a joint venture with Food Machinery, dimethylhydrazine-type fuels are being studied.
CONTINUED
Phosphoric
acidity — an important advantage. • Allow formulation of high-analysis grades — a strong trend in the industry — because of high concentration. • Granular goods are growing in popularity. PFS formulations generally give more rugged granules — better suited to subsequent handling—without adding granulation aids. In summation Mr. Byck notes that because of transportation costs, P F S will probably be uneconomical in many areas. But in many more of the important agricultural areas, it is becoming the product of choice for reasons of product quality, overall costs and adaptability to process needs.
Faster Analysis Developed For Halogens in Organics A researcher at the Texas Agricultural Experiment Station has worked out an improved method of the quantitative determination of halogens in organic materials. It is said to be faster, cheaper than previous techniques. In a typical analysis, the chemist would weigh a sample containing about one milliequivalent of chlorine into a beaker, add excess ammonia to dissolve and chill the sample, and ethyl ether to insure that the sample stays in solution. Chlorine is then reduced to chloride with about half a gram of metallic sodium. Appearance of a blue color indicates complete reduction, which takes only about two minutes. Ammonia and ether are evaporated, excess sodium combines with water vapor to yield sodium hydroxide, and the blue color disappears. Nitric acid is used for neutralization, and the chloride is titrated with silver nitrate. As little as ten minutes of the chemist's full attention is devoted to a single analysis, and several analyses can be conducted simultaneously. Error is rarely higher than 3 % .
New Extraction Process Purifies Many Elements A new extraction process for purifying a large number of elements, including many not usually subject to extraction processes, is described in USP 2,874,176 issued recently. By this technique, elements can be separated selectively from an aqueous solution containing a mixture of elements. Here is how it works. The various elements in the solution are reacted with an alkali metal salt of perfluorocarboxylic acid. From the resulting compounds in solution, the desired compound is selectively extracted with a substantially immiscible polar organic solvent such as an alcohol, ether, ketone or phosphate. Extraction is reported to depend on a number of variables: chain length of acid, valence of cation, organic solvent, molar ratio of cation to reagent, ion size, complexing ability of cation and p l l . For example, uranyl and vanadyl ions extract together at pH 2, but at pll 1.65, only uranyl ion extracts. After separation of the desired element, the reactions can be easily reversed so that the element is once more in aqueous phase and the reagents are recovered.
PRODUCTS Alcohols: Ethyl (pure and all specially denatured formulas); Anhydrous and Regular Proprietary Denatured Alcohol Solvents SOLOX®, FILMEX®, ANSOL® M, ANSOL PR. Organic Solvents and Intermediates: Normal Butyl Alcohol, Amyl Alcohol, Fusel O i l , Ethyl Acetate, Normal Butyl Acetate, Diethyl Carbonate, DIATOL®, Diethyl Oxalate, Ethyl Ether, Acetone, Acetoacetanilîde, Acetoacet-Ortho-Chloranilide, Acetoacet-Ortho-Toluîdide, Ethyl Acetoacetate. Ethyl Benioylacetate, Ethyl Chloroformate, Ethylene, Ethyl Sodium Oxalacetate, Sodium Ethylate, ISOSEBACIC® Acid, Sebacîc Acid, Urethan U.S.P. (Ethyl Carbamate), Riboflavin U.S.P. Pharmaceutical Products: Dl.-Methionine, Ν -Acetyl -DL- Methionine, Urethan USP, Riboflavin USP, Intermediates.
OF
TECHNICAL
1959
DEVELOPMENTS
Information about manufacturers of these items may be obtained by ivriting U.S.I. Identification reagent for synthetic fibers, as well as for animal and vegetable fibers, can now be obtained. Claimed to give reliable identification in minutes by imparting distinct colors to different fibers. No. 1480 New economical corrosion inhibitor for aqueous recirculating systems combines sodium molybdate with orthophosphate. Combination claimed to be synergistic—effective as the molybdate alone but at greatly lowered cost. No. 1481 Automatic recording titrator now on market is designed to make variable and constant pH measurements automatically. Simultaneously provides permanent record. Titrant delivery rate and chart speed are both variable. No. 1482 Corrosion and spotting preventive for all metals, recently developed, is added to hot water rinses. Said to promote spot-free drying, and to leave an invisible film which protects against tarnish and corrosion for months. No. 1483 Volume I of new series of publications on advances in inorganic and radiochemistry can now be purchased. 449-page book contains sections on boron hydrides, lattice energies, activation analysis, phosphonitrilic halides, etc. No. 1484 Commercially-pure titanium anode hooks and baskets, designed to meet need for high corrosion resistance in nickel and chrome plating operations, are now on market. Said to have indefinite life in highly corrosive mixtures. No. 1485 Selective reductions of organic compounds with complex metal hydrides are discussed in new brochure now available. This review of published literature covers types of reactions possible, includes bibliography. No. 1486 Polyethylene aspirator pump now on market cannot corrode; said to perform as capably as metal aspirators, operate efficiently on all water pressures from 11 pounds up. Recommended for highly corrosive filtrates. No. 1487 Physical and thermodynamic properties of many commonly-used elements and compounds are covered in new brochure offered by catalyst maker, to aid in catalyst selection when factors of equilibrium, heat exchange, etc. are vital. No. 1488
Thorium technology is discussed in series of papers now bound in 397-page volume and offered for sale. Topics include melting, refining, structure, properties, fabrication, corrosion, production of compounds. No. 1489
U.S.I.
Heavy Chemicals: Anhydrous Ammonia, Ammonium Nitrate, Nitric Acid, Nitrogen Fertilizer Solutions, Phosphatic Fertilizer Solution, Sulfuric Acid, Caustic Soda, Chlorine, Metallic Sodium, Sodium Peroxide, Sodium Sulfite, Sodium Sulfate. PETROTHENE® Polyethylene Resins Animal Feed Products: Antibiotic Feed Supplements, BHT Products (Anti oxidant), Calcium Pantothenate, Choline Chloride, CURBAY B-G®, Special Liquid CURBAY, VACATONE®, Menadione (Vitamin K 3 ), DL-Methiontne, MOREA® Premix, Niacin USP, Riboflavin Products, Special Mixes, U.S.I. Permadry, Vitamin ΒΊ2 Feed Supplements, Vitamin D3, Vitamin Ε Products, Vitamin Ε and BHT Products.
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