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By Frank Fahrenwald

INTRODUCTORY A COMPLETE list of the elements as given for 1915 includes 18 that melt above 1,700° C. There does not exist one complete thermal equilibrium diagram for any pair of these 18 elements. Several of these elements have been combined, in relatively small proportions, with metals of lower melting point: e.g., tungsten, molybdenum, and vanadium, in steels, or with nickel and cobalt; but of this refractory group, platinum is the only one that has been extensively studied in this connection. When one considers that, with few exceptions, the industries have made use of alloys to the exclusion of pure .metals, it is reasonable to expect that alloys of this refractory group will invade fields in which the pure metals have found little application. The past neglect of this class of metals has, no doubt, been partly due to the rarity of some of them, for even though alloys of very valuable properties should be developed, their cost, unless in exceptional applications, would be prohibitive. There is also a well-founded reluctance to undertake research involving very high temperatures which, in the case of most of these elements, must be accompanied by an inert atmosphere as well. This combination of high temperatures* and control of atmosphere within the heating chamber of any furnace of present design is a difficult problem. It is the purpose of this paper to give results,1 of an investigation of one binary series of this group, in which methods were employed that avoided the usual difficulties accompanying high-temperature alloy investigation.

Jan 6, 1916

By John W. Tieman

Coal is a term applied to vegetable matter (trees, grasses, etc.) which was subjected to heat and pressure through geologic ages. This resulted in a change in both the physical and chemical properties. Because its chemical composition is variable, geologists classify coal as a heterogeneous mineral rather than a homogeneous mineral. Peat represents the initial, unconsolidated stage in the development of coal. This coalification continues with time and the application of temperature and pressure to lignite, subbituminous, bituminous, and anthracite toward the theoretical graphite end member. PHYSICAL PROPERTIES OF COAL The physical properties are concerned with the characteristics of coal in its natural state, or prior to its end use as a fuel. For example, the hardness and grindability of coal determine the maintenance cost for coal mining, handling, and pulverizing equipment; the specific gravity of coal and its associated minerals determines the coal preparation technique used in a cleaning plant as well as the capacity of coal bins, boats and size of cargo, and other coal storage facilities. The physical properties are, of course, dependent on the chemical constituents of coal, and all properties are interrelated. Specific Gravity The specific gravity (sp gr) of a solid is the ratio of the weight of a cubic foot of the solid to the weight of a cubic foot of water. The specific gravity of pure coal has been reported to range between 1.23 to 1.72 and increases with the change in rank from lignite to anthracite. This means that it is 1.23 to 1.72 times heavier than water.

Jan 1, 1981

Discussion of the paper of J. V. EMMONS, presented at the Pittsburgh meeting, October, 1914. and printed in Bulletin No. 93, September, 1914, pp. 2233 to 2248. ALBERT SAUVEUR, Cambridge, Mass.-Mr. Emmons is to be congratulated for having placed before us in so forcible and satisfactory a manner a question of much importance-that of the surface decarbonization of steel. Of course, both manufacturers and consumers have known for many years that during the heat treatment of high-carbon steel, surface deca.rbonization is always likely to occur to a greater or less degree, but the subject does not seem to have been investigated with the method and thoroughness it deserves. I am in substantial agreement with Mr. Emmons's conclusions, and I have but little to add to what he has so well said. His statement that carbon dioxide is just as effective an oxidizing agent as pure oxygen is likely to cause surprise and some will wonder whether his investigation has been carried far enough to warrant so unexpected a conclusion. The reaction C + 0 = CO, expressing the oxidation of carbon by pure oxygen, is decidedly exothermic, whereas the reaction C + C02 = 2C0, expressing the oxidation of carbon by carbon dioxide, is endothermic. Decarburization by pure oxygen, therefore, should take place much more readily than by carbon dioxide. One cannot help regretting that the author does not mention' the best way of preventing in a practical manner surface decarbonization while treating tool steel and other high-carbon steels.

Jan 4, 1915

Economic Significance of High-grade Concentrates BY PAUL M TYLER AND CARLE R HAYWARD (Min & Met, Dec, 563 4000 words) Generally pyro¬mctallurgical methods yield a higher recovery but cost more per ton of ore treated Milling methods are inherently cheaper for the reason that they do not involve dissipa¬tion of heat energy in slag formation, ctc It is vaguely realized that the smelter man could do a better job if he were supplied with purer raw materials but hard¬headed mill men have been offered little inducement to do a really good job of cleaning concentrates To do this may involve some sacrifice in percentage yield and in mill capacity and unless there is a compensating saving in freight and smelter charges, it simply is not good business to go beyond a certain point in the way of making clean concentrate Opportunities exist for eliminating one or more steps in the expensive series of processes for recovering various metals, or at least reducing the volume of materials that has to be handled at the most costly steps The beneficiation of nonmetallic minerals likewise affords numerous examples of over-all economies obtainable through more refined methods of mechanical improvement All this leads to the conclusion that perfecting selective processes for isolating pure minerals (e g, galena) virtually free from other sulfides as well as gangue may be productive of industrial economies Conversely, cheapening smelting methods may invade the field of mechanical improvement of ores but, as Kiphng said, that is another story

Jan 1, 1937

By J. C. Mertz

ACCURATE knowledge of the solid solubilities of the elements that dissolve in the important base metals is needed for guidance in the preparation and heat-treatment of the alloys derived from these compo-nents. While there is still difference of opinion concerning the merits of the X-ray and microscopic methods of determining such solubilities, it is certainly true that the recent extensive use of X-ray diffraction to review the existing constitutional data has revealed many glaring inaccu-racies and has brought about a much improved knowledge of phase-boundary locations, which will inevitably come to include all of the important alloy systems. When the work is done with all necessary precautions it appears that in the majority of cases where the solubilities extend beyond a few tenths of a per cent the X-ray back-reflection technique is capable of furnishing the best of information in this field. For the most prolonged and thorough studies it is obviously advisable to combine the results of several methods, in particular, to obtain an agreement between X-ray and microscopic data. This paper reviews the work previously done on the solubilities of phosphorus, arsenic, antimony and bismuth in copper and, in considera-tion of the uncertainties thus made apparent, presents, new X-ray data obtained with the first three members of this group.

Jan 1, 1936

By Eric L. Christiansen

A dynamic simulation model for the iron blast furnace has been developed which predicts flow rates, compositions, and temperatures of the top gas, slag, and hot metal exit streams as a function of time from specification of the time-dependent tuyere inputs and raw material charges. As a matter of convenience, a previously developed steady- state model is employed to fix furnace-dependent parameters. It also provides initial conditions for the internal states of the furnace for subsequent dynamic solution of the simultaneous differential equations which describe the local rates of chemical reaction, heat transfer, and mass transfer in the stack, bosh, combustion zone, and hearth of the furnace. The dynamic model was tested by a demonstration of its ability to relax to steady-state representations of the time-averaged data from two separate industrial blast furnaces and of its ability to follow eight days of time-dependent operating data for one of them. Simulated responses to step changes in tuyere input and burden variables have been shown to be of the correct magnitude and duration. Although complex functions of many variables, a proper description of these responses is needed for the development of optimization and control strategies . The model correctly predicts the non-minimum-phase type dynamic response observed in real furnaces in which the output variables proceed through local minima or maxima, often including inverse responses (i.e., opposite signs from their final steady-state values ) .

Jan 1, 1984

By S. W. Parr

THE low-temperature carbonization of coal involves the carrying out of the coking process under conditions wherein neither the coal mass nor any of the passageways through which the volatile products pass are heated above 700° or 800° C. For convenience in this discussion, the single number 750° will be used to designate the maximum range. This temperature is not selected arbitrarily; it is the result of certain natural conditions that are inherent in the substances involved. Two of these conditions arc sufficiently pronounced to suggest a line of demarcation at this point as follows: (1) Below 750°, all the heavy hydrocarbons are expelled, which means that, at these lower temperatures, the illuminants, the gases of high calorific value, and the condensible oils are discharged; above 750°, there are given off the lean, non-illuminating gases consisting for the most part of hydrogen and marsh gas and having no condensible constituents present. (2) Below 750°, there is substantially no secondary decomposition; above 750°, the volatile products are readily decomposed, forming tars, naphthalene, free carbon, etc. It is not intended to maintain that no secondary decompositions occur below 750°. Many recent studies have demonstrated the practicability, especially in the presence of catalytic substances, of cracking certain of the hydrocarbon compounds; but at these lower temperatures the step is a moderate one, as, for example, from xylene to toluene or from toluene to an anthracene. These changes are moderate in amount. Not only do the reactions proceed slowly but they are subjected to the decomposing conditions for only a short time. This is evident when it is recalled that at these initial temperatures the decomposition, of the coal is very rapid and, if anywhere near a neutral pressure is maintained, the movement

Jan 2, 1920

By Robert C. Berggren

THE hot-milling process for reconditioning rock-drill bits is not new. It has been employed by a few mines for years and in the past decade it has been widely adopted, as its advantages have become better known. Because of the extensive commercial development in England and Canada of machines to operate on this principle, general acceptance has been largely in the British possessions and until recently has been chiefly in the field of conventional steel. In the past two years there has been a definite trend toward hot-milling of detachable bits in Canada, [t] but only in the past year has any considerable attempt been made to build special machines for this type of work. Generally a machine designed for conventional steel has been used and special holders employed to manipulate the bit. As early as 1934 at least one operator in the United States had adapted hot-milling to conventional steel with a substantial saving in resharpening costs.1 Several other operators have taken it up but there has been no widespread adoption of the method in this country by users of conventional steel. This may be partly explained by the fact that until recently no American manufacturer produced this equipment and operators have been obliged to build their own hot-millers or import them. Several years ago a few machines were built in Seattle, Washington, and operated in some mines in the northwest, but, for reasons not generally known, the effort was abandoned. THE PROCESS Hot-milling performs the function of re-dressing the bit at a forging temperature of about 1650°F., by the removal of metal from the flutes with a milling cutter, followed by a similar cut from the bit gauge. Conventional bits are thus treated following the usual forging operation in a sharpener, and usually in the same heat.

Jan 1, 1940

By T. Sterry Hunt

THE essential principle of this new process, now in operation in Chili and in North Carolina, for the extraction of copper from its ores, is the dissolving of the oxides of copper by a hot solution of protochloride of iron and common salt. In the action which takes place, the protochloride of iron is converted into peroxide, while the oxides of copper are changed into protochloride and dichloride, the latter of which, though insoluble in water, is readily soluble in a hot strong brine. From the solution thus obtained, metallic iron throws down the copper in a metallic state, regenerating the protochloride of iron; which is then ready for the treatment of a fresh portion of oxidized copper ore. In the case of slimy ores, the contact of the bath with the ore is effected by agitation in tubs ; but when the ores are granular, lixiviation in large vats is equally efficient and simpler. The hot solutions, charged with chlorides of copper, are digested in tanks with scrap-iron, or better, are made to flow through covered channels containing the scrap-iron, and in their passage lose the whole of their copper; the reaction at the same time evolving so much heat as to keep up the temperature of the liquid. In order to prevent a certain loss of chlorine, which otherwise takes place from the production of some basic ferric chloride in the reaction between the ferrous chloride and the oxides of copper (both protoxide and dinoxide being generally present in calcined ores), a portion of sulphurous fumes from the roasting is made to pass through the regenerated bath before adding it to fresh ore. This has hitherto been effected by injection, with the aid of a jet of steam.

Jan 1, 1873

By R. F. Mehl, J. T. Ransom

For many years the Metals Research Laboratory of Carnegie Institute of Technology has been concerned with the statistical nature of the engineering properties of steel from an experimental viewpoint, particularly those properties representing ductility.' In the past three years new work has been directed toward evaluating the statistical nature of the endurance properties. It has been shown that both the fracture curve and the endurance limit in fatigue are markedly statistical in nature. The S-N curve (and the endurance limit) of ferrous materials is often determined with specimens which number as few as ten. The common procedure is to test the first specimen at a stress well above the expected endurance hmit. Each succeeding specimen is then tested at a progressively lower stress, until, after five or six tests, a specimen runs ten million or so cycles without failing. Two or three more specimens are then used to find the highest stress at which failure will not occur; the limiting stress determined in this way is called the endurance limit. It has now been found, however, that the variability in the fracture curve and in the endurance limit in heat-treated alloy forging steels is so great that S-N curves must be drawn on the basis of distribution curves which can be appraised only by statistical methods. Two methods have been adopted in this study: (1) straightforward statistical studies of cycles to fracture of a number of specimens at each of a series of stress levels, and (2) a new abbreviated statistical method, known as "staircase testing."2 The latter corisists in testing a series of specimens, one by one, with the test stress for any given specimen automatically

Jan 1, 1950

By E. F. Northrup

THESE brief notes respecting the properties of pure tin that make it useful as a pyrometric substance summarize information gathered by the writer In an extensive experimental investigation on the electrical properties of metals in the molten state. Tin in quantities sufficient for pyrometric purposes may be obtained at relatively low cost and in a state of high purity. The metal melts at 232° C. and, according to determinations made by Greenwood,. 1909, does not begin to boil until a temperature of 2270° C. is reached. The writer can assert, from personal observations carefully made, that tin shows no tendency to boil at a temperature of 1680° C. If Greenwood's observations are correct the temperature interval, 2038° C., in which tin exists as a liquid under atmospheric pressure, exceeds that of any other substance. It has never been observed, as far as the writer is aware, that tin forms any chemical union, as carbide, with carbon at the highest temperatures at which it can exist as a liquid. It is quite certain from the writer's personal observation that tin heated in Acheson graphite to 1680° C. remains chemically uncontaminated. Wires of pure tungsten do not dissolve in molten tin at temperatures at least as high as 1680° C. Tungsten wires or rods may, therefore, be used as electrodes dipping into molten tin when required for measuring the resistance of the molten metal at very high temperatures. When tin is raised to a high temperature in a covered graphite container, the CO atmosphere that exists above its surface has a reducing action, which maintains this surface of mirror brightness. Incidentally, tin maintained molten in a crucible of Acheson graphite makes a most excellent bath into which may be inserted several pyrometers that are to be intercompared at the same temperature.

Jan 8, 1919

By Walter Harvey Weed

THE enrichment of mineral-veins as a result of the migration of material from an upper oxidized or disintegrated part of a vein to a lower level, where it is redeposited, is now, I believe, quite generally accepted as one explanation of the occurrence of bonanzas in gold- and silver-veins, as well as that of bodies of high-grade ores in cupriferous deposits.* Vogt has called attention to the fact that there are numerous examples of such rich shoots which are " of exclusively primary character, and dependent upon the laws which governed the original ore-deposition." To this I would add that there are also other examples which are neither of primary origin nor clue to descending waters, but result from a reopening of the veins and their penetration by ascending heated waters whose metallic contents are deposited by reaction with the primary pyrite (and possibly other minerals), forming "secondary" enrichments. My studies of the copper-veins of Butte, Montana, show: That the veins there are of several ages and systems; that the older primary quartz-pyrite veins were reopened by later movements, correlated with a period of volcanic activity; and that they were penetrated by hot alkaline waters carrying copper and arsenic in solution, which were deposited presumably by reaction with the pyrite of the original vein. The enormous development of the Butte deposits, attendant upon the extraction of nearly 10,000 tons of ore a day, has revealed many facts concerning the nature and distribution of the ores. Enargite, the copper sulpharsenate, formerly a relatively rare mineral, is now found to be the chief ore of some veins,

Jan 1, 1913

By I. N. Zavarine

THE present paper is a continuation of the work on the relationship between the magnetic and the phase transformations in carbon steels during quenching. An account was given by the author in a previous paper It of an investigation of this relationship during a continuous quench. The experimental difficulties then encountered prevented a conclusive proof of the existence or absence of such a relationship. The conclusions of the previous paper were derived indirectly. The present paper deals with the same problem, but the method of attack is modified. The technique developed by Davenport and Bain2 in their well-known study of austenite transformation at subcritical temperature was adopted in the present investigation. They have shown that the austenite to martensite transformation can be caused to proceed at a relatively slow rate by quenching steels into a hot metal bath. Slowing down of the rate of transformation, together with an observation by Lewis3 that a eutectoid steel can be preserved in the nonmagnetic state by such quench-ing, pointed out a possibility of a study of both transformations under more favorable conditions than previously described. The preliminary steps were connected with the technique of the hot bath quench. To study this phase of the present work a modification of the apparatus previously describe1 was used. The modification con-sisted in the use of a hot quenching bath instead of brine, and in fixing the secondary and the primary coils of the apparatus in a stationary position in and around the bath. Tubular specimens, as in the previous investiga-tion, were heated in a suitable furnace to a temperature in the austenitic.

Jan 1, 1935

By R. Taggart, R. H. Ericksen, D. H. Polonis

MarTENSITIC a has been observed to form spontaneously from the retained ß phase during the preparation of thin foil specimens of metastable Ti-Cr alloys containing from 6.9 to 20 wt pet Cr. Similar spontaneous martensite reactions have been reported in thin foils of 0 brass' and other alloys.2 4 The absence of retained austenite in iron-based alloys has also been attributed to spontaneous decomposition during thinning.5 The present work indicates that a unique situation occurs during which the spontaneous transformation takes place when the transitional ? phase is present in the as-quenched or partially aged ß phase. Alloys containing 6.9, 7.0, 8.0, 12.0, and 20.0 wt pet Cr were prepared by the levitation melting of "io-chrome" chromium and iodide titanium. The 0.5-in.-diam ingots were vacuum-annealed at 1000oC, and wafers 0.020 in. thick were then cut from the ingots. These wafers were wrapped in molybdenum foil, encapsulated in Vycor under a reduced pressure of purified helium, and then held for 30 min at 1000°C. The specimens were quenched in water to retain the metastable high-temperature ß phase. The quenched alloys were thinned by mechanical grinding to about 0.005 in. thick, then electropolished in a solution of 300 ml methyl alcohol, 175 ml n-butyl alcohol, and 30 ml perchloric acid at a temperature of -40°C. Needle specimens 0.005 to 0.010 in. diam were taken from each ingot and heat-treated with the foil specimens. X-ray diffraction patterns indicated the structure of the 6.9, 7.0, and 8 wt pet alloys to be a

Jan 1, 1968

By I. N. Zavarine

THE present paper is a continuation of the work on the relationship between the magnetic and the phase transformations in carbon steels during quenching. An account was given by the author in a previous paper1 of an investigation of this relationship during a continuous quench. The experimental difficulties then encountered prevented a conclusive proof of the existence or absence of such a relationship. The conclusions of the previous paper were derived indirectly. The present paper deals with the same problem, but the method of attack is modified. The technique developed by Davenport and Bain2 in their well-known study of austenite transformation at subcritical temperature was adopted in the present investigation.. They have shown that the austenite to martensite transformation can be caused to proceed at a relatively slow rate by quenching steels into a hot metal bath. Slowing down of the rate of transformation, together with an observation by Lewis3 that a eutectoid steel can be preserved in the nonmagnetic state by such quenching, pointed out a possibility of a study of both transformations .under more favorable conditions than previously described. The preliminary steps were connected with the technique of the hot bath quench. To study this phase of the present work a modification of the apparatus previously described1 was used. The modification consisted in the use of a hot quenching bath instead of brine, and in fixing the secondary and the primary coils of the apparatus in a stationary position in and around the bath. Tubular specimens, as in the previous investigation, were heated in a suitable furnace to a temperature in the austenitic

Jan 1, 1935

By Reginald S. Dean

THE commercial availability of electrolytic manganese has greatly changed the position of manganese as a nonferrous alloying metal. Manganese metal commercially available up to about ten years ago was reduced with either silicon or aluminum and contained substantial amounts of the oxides of these metals and other impurities. Manganese was accordingly not available as an alloy base and its addition to copper-base and nickel-base alloys was generally limited to a manganese content of a few per cent. Several special alloys like manganin contained up to 12 pct of manganese. A method for the production of electrolytic manganese was developed by the Bureau of Mines in 1936 and commercial production was begun in 1938. At the present time (June 1951), production is about 12 tons per day but appears likely to be substantially increased. Electrolytic manganese is deposited from an aqueous electrolyte containing manganese and ammonium sulphates and is marketed as cathode fragments about 1/8 in. thick. The impurities in its composition are as follows: iron, 0.0015 pct; copper, 0.001; arsenic, 0.0005; cobalt, 0.0025; lead, 0.0025; molybdenum, 0.001; sulfide sulfur, 0.017; sulfate sulfur, 0.014; insoluble, 0.002; carbon, 0.002; hydrogen, 0.015. These figures are from Bulletin 463, U. S. Bureau of Mines. From an alloying standpoint, the most important impurity is hydrogen. This can be removed by heating; 95 pct of the hydrogen can be removed in this way without introducing significant amounts of oxygen or nitrogen. Much of the commercial electrolytic manganese used in alloys is dehydrogenited by the producer, since the amount

Jan 1, 1953

By Porter W. Shimer

Ox completing the filtration of a solution of pig-iron in hydrochloric acid, and after apparently everything had been transferred to the paper, a minute residue was observed remaining in the angle of the beaker in which the solution had been made. This residue had a steel-gray color and metallic luster and was hard and gritty when touched with a glass rod. Placed under a microscope and magnified 400 diameters, the substance was found to be made up almost entirely of opaque cubical crystals with some fragments having the same color and luster as the cubes. The appearance was strikingly like that of a collection of crystals of iron pyrites. The amount of material obtained from ten to twenty grams of borings by solution in dilute hydrochloric acid, and careful decantation from graphite, was barely sufficient for a microscopic slide. A qualitative test of the minute amount of material obtained in this way, showed the presence of considerable titanium. After many fruitless trials by decantation and other methods, sufficient material for quantitative analysis was finally obtained in the following manner: Two hundred and fifty grams of the coarsest possible borings were dissolved in seven liters of hydrochloric acid of sp. gr. 1.03. A solution by the aid of heat took four to five hours. It was allowed to settle, and the clear solution poured off. Great care was taken that none of the material which had settled to the bottom was lost. The graphitic residue was then completely transferred upon fine bolting-cloth, previously Stretched and fastened over the top of a beaker. All graphitic lumps were broken up by the finger while

Jan 1, 1887

By Charles R. Keyes

During the past decade the genesis of the lead- and zincdeposits of the Mississippi valley has received special attention from many distinguished observers. But their united egorts, instead of settling all disputed questions, have, in many respects, involl-ed the general problem in greater uncertainty than would be thought possible under the circumstances. In place of the harmony of opinion that might be expected, there is unexpected disagreement, largely due to the fact that, instead of giving attention to a possible multiplicity of ore-producing conditions among the different deposits, the attempt has been made to bring all deposits under a single genetic head. To a new observer of the lead- and zinc-deposits of the Mississippi valley, it appears at the outset that all the deposits cannot possibly have had the same genesis. In fact, different modes of origin have been often asserted for the ore-bodies, but the difficulty has been that each writer has referred them either all to one category or all to another, and no intermediate ground has been considered possible. Such a position now appears to be clearly untenable. The opinion that, in the deposits of the region under consideration, the ore-materials represent original depositions, made at the time the rocks themselves were formed, is no longer held by any authority, and therefore need not be considered here. Of late years, a number of writers have attempted to account for the presence of the lead- and zinc-ores on the hypothesis that the metallic materials arose in heated solutions from the

Jan 1, 1902

By R. J. Borg, C. E. Birchenall

The self-diffusion coefficients for a iron have been deternzined between 980° and 1167° K using Fe55 as the tracer. With decreasing temperature the diffusivity was found to decrease more rapidly than predicted by the Arrhenius equation in the region of the Curie temperature. The diffusion coefficients obtained well above the temperature of the magnetic transformation are more precise ard differ substantially from all the previously reported values. In the temperature region beginning at least 50" above T,, the diffusion coefficient is given by D = 118 (±2) exp 1 HE self-diffusion coefficients for a iron have been reported previously as the result of four independent investigations The general lack of agreement and the poor precision of most of the previous work prompted the redetermination by the present authors. The possible effect of the onset of ferromagnetism upon the diffusivity5 provided an additional impetus for this investigation. The earlier measurements of Birchenall and Mehl1 gave low values for the diffusion coefficient at temperatures below the Curie temperature, Tc. However, the precision of these measurements is not sufficient to establish an indisputable correlation between the low values and the magnetic transformation. The results of this investigation along with all the previous ones are shown in Fig. 1. EXPERIMENTAL Small rectangular samples, approximately 1 by 0.5 by 0.3 cm, of high-purity iron (Vacuum Metals Corp., "Ferrovac") are first heated in hydrogen at 900°C for24hr in order to remove possible trace amounts of dissolved carbon and oxygen. The small

Jan 1, 1961

By H. U. Schutt, J. M. Toguri

REGARDLESS of the degree of purification effected during the electrorefining of copper, a danger of re-introducing impurities exists in the operation of melting and casting of the refined copper. Logically only a combination of the purification and casting operation would remedy the situation. A well-known method of metal purification is the "Gross"-type process, whereby a volatile halide is produced, purified, and decomposed.' In the present case, this concept was used to remove the impurities rather than to form possible volatile copper halides. The object was to produce volatile halides of the impurities present and distill these away, leaving high-purity copper. It is interesting to note that such techniques are used in spectrographic procedures in order to shorten exposure time and enhance the density of impurity lines.' In the present investigation, copper hydroxy fluoride was used, since the temperature of decomposition of copper hydroxy fluoride and the melting point of copper nearly coincide. The fluorine released by the thermal decomposition of copper hydroxy fluoride purges the molten copper. Copper hydroxy fluoride was prepared by dissolving high-purity copper in nitric acid and adding hydrofluoric acid and ammonium hydroxide in the required proportions. The melt was made in a high-purity graphite crucible heated by an induction furnace. Trial experiments showed that impurities can be introduced from the crucible material. Therefore, preceding each cast, the crucible itself was cleaned by decomposing copper hydroxy fluoride and discarding the residual copper. Best experimental conditions were obtained by adding 30 g of copper hydroxy fluoride to 500 g of nor-

Jan 1, 1967