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By D. V. Doane, G. A. Timmons, W. G. Scholz

Molybdenum of high purity can be produced by direct dissociatiott of commercial molyhdenm disulfide in vacuo at 1600° to 1700°C (2910° to 3090°F). The Product is lower in oxygen than commercially available molybdenzdm powder. Analyses of ingots arc-cast from commercial molybdenum powder, hydrogen-re-cluced from animonium molybdate, and from thermally dissociated molybdenum disulfide indicate that the levels of chemical impurities in these ingots are similar. Equipment now in operation will produce 100-lb hatches of powder product. The paper describes development of processing equipment, control of processing varzahles, handling of the product, and evaluatiotl of the melal produced. MOLYBDENITE (molybdenum disulfide) can be decomposed by heat in the absence of oxygen to produce elemental molybdenum and sulfur, which is evolved as a gas. The temperatures required for the dissociation are above 1370°C (2500°F); the sulfur must be continuously withdrawn to permit the reaction to proceed to completion. This is accomplished by continuous evacuation of the thermal dissociation chamber and condensation of the gaseous sulfur in another part of the system. Cognizance of the fact that the dissociation takes place in two steps is important in controlling the process. Basically, the molybdenite dissociation process has two potential advantages as a method of produc- ing pure molybdenum: 1) The materials entering into the process contain little or no oxygen. Since the process is carried out in vacuum at high temperature, the quantities of interstitial oxygen, nitrogen, and hydrogen in the product should be very low. 2) The process is more direct than the commercia1 method of producing high-purity molybdenum. In the conventional process, molybdenite is roasted to molybdic oxide, the oxide is purified first by sublimation, then by conversion to ammonium molybdate, and finally, the molybdate is reduced in a hydrogen atmosphere (usually in two steps) to the metal lic molybdenum powder. This paper presents a description of the stages in scaling-up of the dissociation equipment and an account of attempts to evaluate the molybdenum produced by thermal dissociation, rather than a report of a fundamental study of the dissociation reaction. Since little has been written on the subject, it is appropriate, before detailing the development of the process, to review briefly the research that has been conducted over quite a period of years. LITERATURE SURVEY The first accounts of the possibility of thermal dissociation of the mineral molybdenite were re-

Jan 1, 1962

By S. K. Tarby, W. O. Philbrook

Limited experimental data and a critical review of the literature are given to indicate that the true equilibrium distribution of manganese between carbon-saturated iron and blast-furnace type slags has not yet been satisfactorily established as a function of the composition, temperature, and pressure of the system. THE distribution of manganese between carbon-saturated iron and blast-furnace type slags has been studied by a number of investigators.1-7 Generalization of the results of these works indicates that the weight percent distribution ratio, (%Mno)/[%Mn], decreases with increasing temperature and slag basicity, in accord with thermodynamic data and practical observation. However, where comparisons among these studies can be made for similar slag compositions and temperatures, the reported values of the manganese distribution ratio are discordant. The variations are attributed to failure of the experimenters to bring their systems completely to equilibrium with graphite and CO at 1 atm, as judged by departures from silicon equilibrium. Even in the most recent work,5-7 this problem was recognized but the authors made the questionable assumption that equilibrium could prevail for manganese distribution even though other reactions were still in progress. Manganese equilibrium values for three particular slag compositions were required incidental to a kinetic study8 and were determined experimentally. Special pains were taken to approach concurrent equilibrium with respect to silicon. Although the results were not completely definitive, they indicate that the true manganese equilibrium distribution ratios are lower than have heretofore been reported. The data are presented together with a brief commentary on the literature to suggest the need for further work in this area. EXPERIMENTAL METHOD Equilibrium runs were carried out in a stationary, induction-heated graphite crucible closed by a graphite lid and flushed continuously by a slow flow of carbon monoxide at 1 atm pressure. Temperature was controlled manually within ±3 deg C with the aid of immersed thermocouples in mullite tubes protected against slag attack by graphite sleeves. The desired temperature was established by a calibrated Pt vs Pt-10 pct Rh thermocouple and control was then maintained using a more stable W-Mo couple. Runs were made at 1500º and 1575ºC for durations of 7.5 to 10.5 hr. The charges were calculated to yield 400 g of metal and 100 g of slag. The primary slag compositions and designation numbers were as follows:

Jan 1, 1963

By C. F. Allen, G. B. Walker

K. F. TROMP*—In dealing with the question of the most suitable kind of solid media for heavy density suspension processes Walker and Allen point out that the particle size of the solid media should not be taken too fine, as the viscosity increases with the area of the solid media and a low viscosity is essential lor high tonnage and accurate separation. A coarser particle size of the solid media will, in their opinion, of necessity give rise to a differential density in the bath (higher gravity at the bottom of the bath than at the top) but they advocate acceptance of the differential density rather than a higher viscosity. Though I fully agree with the choice the authors have made, I cannot subscribe to their view that only by accepting a differential density in the bath a coarse particle size of the solid media can be used. There certainly is another alternative: stronger agitation. Applying sufficiently strong vertical currents, a uniform gravity can be obtained quite well in a suspension of a coarse solid media. Of course, this is not a very attractive solution, for it means a degradation of the true gravity separation and a step backwards to hydraulic classification, which makes the washing dependent on size and shape of the particles. However, to a greater or lesser extent, this is what actually takes place in all the heavy density suspension processes relying on a uniform gravity in the bath. The so-called "stable" suspension processes make no exception. They all "stabilize" their suspensions by introducing or creating vertical currents, be it upwards or downwards or both, be it by hydraulic or by mechanical means. In fact, there is no such thing as a "stable" suspension in gravity separation, as the very reason for the use of suspensions in this field is the property that the solid media is able to settle and so facilitate the recovery. I have been enlarging on this point because the characteristics of the various processes can only be well understood and viewed from the same angle (from Bar-voys up to Chance) when the fact is recognized that mechanical or hydraulic agitation is a condition sine qua non for obtaining a uniform density from top to bottom in a suspension. Is a Cone-slraped Vessel Essenlial? Of the two alternatives for getting a low viscosity Walker and Allen have preferred correctly the sacrifice of uniform gravity in the bath instead of increasing further their vertical current arid agitation. The resulting differential density of the bath brings the problem of bow to prevent accumulation of intermediate gravity products in the bath, an accumulation which, if not prevented, would ultimately plug their cone. According to the authors an open-top cone combined with a downdraft current of the bath liquid would he the only suitable way to cope with such suspensions and they assume as a fact that "in any vessel other than a cone, such a differential density could not be tolerated." My experience is quilt: different. In my process, which has been in successful operation for more than a decade, differ-ential density of the suspension is applied ranging from values below 0.1 up to differentials above 0.5, according to the prevailing requirements of the individual plant. In this process, which is charac-terized by the use of horizontal currents in a suspension of differential density, the form of the vessel is of secondary importance and different types are in operation. It so happens that none of these are in the, form of a cone. The fact that 24 washboxes on my process have been installed and 12 others are under construction may constitute sufficient proof against the opinion that only a cone-shaped separator would be suited for differential density separation. Horizontal Currents in Differentia1 Den-sity Sepparation I myself have some doubts as to the suitability of a cone with downdraft for dealing with differential density (or, for that matter, any other washbox relying on vertical currents for removing the intermediate gravity products). It ap-pears to me that it is restricted to feed of small size only and even then with watch-fulness. If we take, for example, a piece of 2 in., the draft necessary to pull such a piece down to a zone wherein the den-sity of the suspension is, say, 0.03 higher, is quite considerable. For a suspension of, say, 1.6 sp gr the downdraft will have to be in the region of 3 in. per second. Unfortunately. most of the differential in density is in the part immediately below the reach of the top current which transports the floats. Consequently, we need the downdraft where we like it least: in the upper part of the cone. This entails the risk that light float particles are carried away with the downward current. This current of, say again, 3 in. per second would carry particles up to 1.3 sp gr and 3/8 in. size into the 1.6 gravity zone. This is prohibitive. It is also prohibitive because a downdraft of 3 in. per second in the upper part of the cone would require a tremendous circulation of medium. IIalf way up a 20 ft diam cone, a downdraft of 3 in. per second would correspond with 8500 gpm. With the downward current following the way of least resistance, the strength of the downdraft will not be exactly the same at different places of a cross area. If, as I anticipate, the center of the cone is favored, the strength of the downdraft will fall below the critical value near the

Jan 1, 1950

By F. A. Forward, A. H. Ross, J. Halpern

IN treating carnotite ores by carbonate leaching it is often necessary to subject the ore to a prior roast. Among the advantages that may result from roasting are: 1) improvement in settling and filtering characteristics of the ore; 2) destruction of carbonaceous impurities that would otherwise contaminate the leach solution and consume carbonate reagent; and 3) substantial increase in extraction of vanadium, which is usually low when the un-roasted ore is leached. Recovery of vanadium may be an important factor in processing carnotite ores, and the fact that vanadium is usually recovered in good yield by acid leaching has often been an economic advantage over results obtained with carbonate leaching. It has been found that response of an ore to carbonate leaching, following roasting, depends primarily on its composition and on the conditions of the prior roast treatment, particularly with regard to the roasting temperature, the atmosphere maintained above the charge during roasting and cooling, and the presence of certain reagents. These factors, especially the last, virtually determine the extractions of uranium and vanadium attainable by carbonate leaching, as well as the reagent consumption on leaching, whereas adjustment of the leaching conditions has only a limited influence. These variables were examined systematically to elucidate roasting and carbonate leaching of carnotite ores and to establish a treatment yielding high recoveries of both uranium and vanadium. Tests were conducted on samples of four different Colorado Plateau ores, described in Table I. Roasting Procedure: The roasting tests were conducted in an electrically heated furnace in which the temperature was controlled to +15oC. The ore (usually a 500-g charge) was ground to —100 mesh, mixed with the desired reagent, and spread in a silica tray to a bed depth of about 1/2 in. During the roast the charge was rabbled at intervals of 15 min. To provide free access of air the furnace was usually ventilated; however, in a few experiments a controlled atmosphere such as carbon dioxide or hydrogen was maintained above the charge. Leaching Procedure: The pulp, generally comprising 500 g of ore and a 2000-cc solution containing 80 g per liter of Na2CO3 and 20 g per liter of NaHCO3, was agitated in an autoclave at 120°C, under 30 psi O2. Samples were withdrawn periodically, and the solution and ore residue were analyzed. Under the conditions employed, maximum attainable extractions were generally achieved in 4

Jan 1, 1958

Discussion of the paper of E. C. HARDER, presented at the Pittsburgh meeting, October, 1914, and printed in Bulletin No. 94, October, 1914, pp. 2573 to 2586. I. C. WHITE, Morgantown, W. Va.-I have seen some of the great iron-ore deposits described in this paper. -One of these in the State of Minas Geraes appears to be an immense mountain of iron ore about 2,000 ft. in height. All over its surface from bottom to top may be seen large masses of rich iron ore, varying in weight from a few pounds to several tons, and from all that one can judge without exploitation, the quantity of available ore is certainly very large in this particular mountain. Whether it will prove a mere surface deposit or shell, like the famous Iron Mountain of Missouri, is for future exploration to determine. The question of transportation is the main factor in determining the availability for exportation of these Brazilian iron ores. There is no coal in Brazil that can be manufactured into coke without expensive previous treatment, since the best of the raw coal in the States of Rio Grande do Sul, Santa Catharina, and Parana, contains about 35 per cent. of ash, of which about 6 per cent. is sulphur, and coal of this composition cannot be utilized in iron smelting without purification. When I was chief of the Brazilian Coal Commission in 1904 to 1906, I had a cargo of this coal shipped to Balk, Germany, and treated in the great coal-testing plant of the Humboldt Engineering Works, located just across the Rhine from Cologne. It was found that by crushing and washing the Brazilian coal, it yielded 33 per cent. of briquetting coal, containing only 10 to 12 per cent. of ash (of which 1 per cent. was sulphur), and 42 per cent. of slack coal, with 25 per cent. of ash and low in sulphur, so that about 33 per cent. of the Brazilian coal could be converted into coke of fair quality, as shown by the following average of three analyses, using air-dried coal, of briquets made from the Barro Branco coal bed, State of Santa Catharina: Moisture 1.56 Volatile matter 31.66 Fixed carbon 56.73 Ash : 10.05 Total 100.00 Sulphur 1.34 Phosphorus 0.003 B.t.u 13,395

Jan 4, 1915

By D. A. Lyon

Discussion of the paper of DORSEY A. LYON and ROBERT M. KEENEY, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 104, August, 1915, pp. 1707 to 1730. LAWRENCE ADDICKS, Douglas, Ariz.-I think papers of this character, while general in, nature, are of particular value and interest, because when we figure on competing with the East in electrometallurgical industries, on account of the cheap power on the Pacific Coast, we have to take two or three things into account. In the first place, power very rarely amounts to more than 20 per cent. of the total cost of an operation, even .though it be electrometallurgical, and I think it is the common opinion among those who are not familiar with those particular industries, that it amounts to more than 50 or 60 per cent. Take copper refining; we may say that it is 15 per cent. of the total cost. In the second place, around New York City, with 100 per cent. load factor and a reasonably large load, say 10,000 kw., we can generate from a certain class of coal 1 kw.-hr. for about 0.3c. I might say, however, that 0.3c. does not include overhead charges, interest on the investment, etc. The third factor we have to consider out here is that any product to be salable, must command a retail market. It would be useless to produce wire bars here on the Pacific Coast because there is no place to roll them. If we were going to establish a copper refinery, that part of its output which goes into wire bars would have to be taken care of by building a rolling mill alongside of it to turn it into wire and finally make a product that is salable. I do not think, however, that Mr. Lyon need have excluded copper refining from his industries. There are perhaps 50,000,000 lb. of copper a month refined in this country on a custom basis. I think the smelting companies would be very glad to build refineries here if conditions warranted it. The recent extensions of the Great Falls refinery and of the Tacoma refinery in the last few months give evidence of that.

Jan 12, 1915

By A. F. Taggart, Nathaniel Arbiter

The chemical reaction occurring in collection of nonmetallic minerals with amine-type collectors was early postulated by students of flotation phenomena to be metathesis between the mineral and the collector, involving exchange between the amine-bearing (aminium) ion and the cation of the mineral, and formation at the mineral surface of an oriented film of the amine salt of the mineral anion. Qualitative evidence of exchange has been obtained on several occasions at Columbia. Thus 1000 C.C. of a solution containing 495 mg of laurylamine hydrochloride was shaken 17 min. with 100 grams of barite and ground in a porcelain mill to pass a 200-mesh screen; the mixture was then set aside for 48 hr. Filtrate therefrom analyzed 476 mg. per liter of laurylamine hydrochloride. There was no substantial loss of chloride ion (78.4 mg. per liter in the original; 74 in the filtrate). No successful analyses were concluded for barium ion. Earlier, confessedly rough work with scheelite indicated a solution gain in Ca++ equivalent to about one-half the aminium ion lost. Real quantitative roof of the exchange, in the form of an established stoichiometric balance, is unknown to the authors. The data of the present paper, however, obtained from experiments designed on the basis of the exchange hypothesis, constitute strong evidence of its truth, and at the same time point the way to economic utilization of the expensive nitrogen-bearing collectors in concentration of the low-priced nonmetallic minerals. The basic postulate underlying the experiments performed was that, if the collecting reaction is of the type R+ + Y- + MX = RX + M+ + Y- where R = aminium ion, Y = the anion of the amine salt, and M and X are, respectively, the cation and anion of the mineral, the reaction should obey qualitatively the implications of the mass-action and solubility-product laws. This is to say that coating and collection should be aided by the addition to the solution of either ion (R+ or X-) of the collector-coating compound, and hindered by the addition of either of the ions M+ or y-. Experimental work comprised determination of (,) the relative solubilities of the laurylammonium salts of a variety of nonmetallic-mineral anions; and (21 the contact angles' of various minerals in solutions containing different concentrations of the postulated controlling ions. Semiquantitative flotation tests were run With barite as checks on the diagnostic character of the contact angles. The amine

Jan 1, 1947

By Nathaniel Arbiter, A. F. Taggart

The chemical reaction occurring in collection of nonmetallic minerals with amine-type collectors was early postulated by students of flotation phenomena to be metathesis between the mineral and the collector, involving exchange between the amine-bearing (aminium) ion and the cation of the mineral, and formation at the mineral surface of an oriented film of the amine salt of the mineral anion. Qualitative evidence of exchange has been obtained on several occasions at Columbia. Thus 1000 C.C. of a solution containing 495 mg of laurylamine hydrochloride was shaken 17 min. with 100 grams of barite and ground in a porcelain mill to pass a 200-mesh screen; the mixture was then set aside for 48 hr. Filtrate therefrom analyzed 476 mg. per liter of laurylamine hydrochloride. There was no substantial loss of chloride ion (78.4 mg. per liter in the original; 74 in the filtrate). No successful analyses were concluded for barium ion. Earlier, confessedly rough work with scheelite indicated a solution gain in Ca++ equivalent to about one-half the aminium ion lost. Real quantitative roof of the exchange, in the form of an established stoichiometric balance, is unknown to the authors. The data of the present paper, however, obtained from experiments designed on the basis of the exchange hypothesis, constitute strong evidence of its truth, and at the same time point the way to economic utilization of the expensive nitrogen-bearing collectors in concentration of the low-priced nonmetallic minerals. The basic postulate underlying the experiments performed was that, if the collecting reaction is of the type R+ + Y- + MX = RX + M+ + Y- where R = aminium ion, Y = the anion of the amine salt, and M and X are, respectively, the cation and anion of the mineral, the reaction should obey qualitatively the implications of the mass-action and solubility-product laws. This is to say that coating and collection should be aided by the addition to the solution of either ion (R+ or X-) of the collector-coating compound, and hindered by the addition of either of the ions M+ or y-. Experimental work comprised determination of (,) the relative solubilities of the laurylammonium salts of a variety of nonmetallic-mineral anions; and (21 the contact angles' of various minerals in solutions containing different concentrations of the postulated controlling ions. Semiquantitative flotation tests were run With barite as checks on the diagnostic character of the contact angles. The amine

Jan 1, 1947

By Samuel S. Adams

Potash, the generic term for a variety of potassium-bearing minerals, ores, and refined products (Table I), owes its importance as an industrial mineral to the potassium requirement of growing plants. The term "potash" originally referred to potassium carbonate produced by the leaching of wood ashes. This process, for which the first U.S. patent was issued in 1790, was the basis for the largest United States chemical industry in the early nineteenth century. The agricultural use of potash soon eclipsed the chemical applications following the German discovery in 1840 that potassium is essential to plant growth. The initial discoveries of large deposits of soluble potassium minerals, essential for agriculture applications, were made in 1857 in Germany and in 1914 in the United States. More than 90% of the 20.4 million short tons K2O produced in the world in 1970 (Eilertsen, 1971 ) was derived from marine evaporite deposits and approximately 90% was used in fertilizers. The potassium content of an ore, mineral, or product is customarily expressed as % K,O, a unit of measure which is neither a natural nor synthetic compound of potassium (1 .O% K is equivalent to 1.2046% K,O) . Geology Potassium, the seventh most abundant element in the earth's crust, is present in silicate minerals in igneous, sedimentary and meta- morphic rocks. Potassium is also a major constituent of many surface and subsurface brines (Table 2). Economic potash deposits are essentially restricted, however, to widespread, thick accumulations of marine chloride evaporite deposits. These deposits yield high grade, large tonnage ore bodies, many of which are amenable to low cost mining and beneficiation. The products from these deposits are, moreover, ideal for use in fertilizer because of the high relative solubility of the potassium chloride and sulfate evaporite minerals. World potash production and reserves for such de- posits so vastly overshadow other sources of potassium that the following discussion will be limited largely to potash deposits in marine evaporites with brief reference to certain potash-rich brines. Approximately 85% of current domestic production is from bedded salt deposits and much of the balance is from brines. Marine evaporite deposits are accumulations of salt minerals deposited in structural sedimentary basins through the evaporation of sea-water or mixtures of seawater and other brines. The salt minerals are precipitated in assemblages and sequences of assemblages as determined by the compositions of the brines and the solubility relations in the salt systems (D'Ans, 1933). The evaporation of seawater normally yields carbonate minerals as the first precipitates (Table 3). Further evaporation and concentration of the brine leads to the precipitation, in succession, of sulfate, chloride, and supersaline mineral assemblages including the salts of potassium and magnesium. The common minerals, ores, and products of potassium deposits are listed in [Table 1]. Many potash deposits contain accessory evaporite minerals together with a variety of detrital and authigenic silicates (Braitsch, 1971).

Jan 1, 1975

By E. Miller, J. M. Eldridge, K. L. Komarek

Activities of magnesium in liquid Mg-Sn alloys have been determined between 5 and 90 at. pct Sn and 990" and 1290°K by an improved isopiestic method wherein tin specimens, heated in a temperature gradient and contained in crucibles of special geometry, were equilibrated with magnesium vapor in a closed titanium system. The crucibles were designed so that the equilibrium compositions of the specimens were satisfactorily preserved on termination of the experimental runs by quenching. The activity values are in excellent agreement with those predicated on the phase diagram and allowed a delineation of the solidus curve of the compound Mg2Sn near its melting point. EQUATIONS have been recently derived relating the chemical potentials of the components to the liquidus and enthalpy data for binary systems exhibiting one congruently melting compound.' The liquidus curve of the Mg-Sn system between the eutectics was carefully redetermined and the thermodynamic properties thus calculated were in reasonably good agreement with values derived from electromotive-force measurements of an,' but differed greatly from the iso-piestically determined values of Ashtakala and Pid-geon.3 The present study was initiated: a) to resolve the discrepancies; b) to develop a method for measuring activities in systems having volatile (and possibly highly reactive) components; and c) to use the method in a general investigation of the thermodynamic properties of the homologous series of Mg-Group IVb systems, i.e., Mg-Pb, Mg-Sn, Mg-Ge, and Mg-Si. This paper describes the results for the Mg-Sn system. An isopiestic technique, originally developed by Herasymenko 4 and adapted for alloys having a component of high reactivity and low volatility,5-8 was modified in this study by using crucibles designed to preserve the equilibrium composition of highly volatile liquid specimens on quenching from high temperatures. Tin specimens, contained in tightly covered graphite crucibles and heated in a temperature gradient, were equilibrated with magnesium vapor of fixed pressure from a magnesium reservoir kept at constant temperature in a previously evacuated and sealed titanium tube. During equilibration magne-

Jan 1, 1967

By Joseph A. Holmes, Henry Kreisinger

At the Mining Experiment Station of the U. S. Geological Survey, in Pittsburg, an investigation of the process of combustion is being carried on in a specially-designed furnace having an unusually long combustion-chamber. This work is conducted by a con~mittee consisti~lg of 11. Kreisinger, mechanical engineer; Dr. J. C. W. Frazer, chemist; and Dr..J. K. Clement, physicist. The problem, essentially one of physical chemistry, is estremely interesting to all who are concerned in the burning of coal or the construction of furnaces. The main object of these experiments is to ascertain the relation between the amount of' the volatile combustible driven from the coal and the combustion-spaces necessary to burn it completely. Our best steam-coals vary from 15 to 45 per cent. in volatile matter and from 40 to 75 per cent. of fixed combtistible. The greater part of the latter is burned on the grate: but the volatile combustible leaves the freshly-charsed coal and must be burned in the combustion-space. If this space is not large enough, the volatile combustible mill leave the furnace only partly burnecl, and the result will be a considerable heat-loss and a smoky stack. Strictly speaking, the factor which determines the completeness of combustion of the volatile matter, after it has been mixed with a certain amount of air, is the length of time the mixture is allowed to remain in the combustion-space; but this length of time depends on the extent of the space itself. Let us suppose, for instance, that, when a given coal is burned at a certain standard rate, the volume of the volatile combustible driven oft' per second is 10 cu. ft. Adding, say, 10 cu. ft. of air, the volume of the resulting burning mixture is increased to 20 cu. ft. If the combustion-space is 30 cu. ft., the burning mixture will stay in it,

Jan 1, 1911

By J. L. Gregg, C. W. Kuttner

ReceNtly there has been considerable interest in the production and use of extra hard alloys composed primarily of tungsten and carbon. Dr. Hoyt's recent paper1 gives a good description of these alloys and describes their performance when used as tools. There are a number of these alloys on the market sold under various trade names, and it is the purpose of this paper to describe the results of an investigation of the structure of five of these alloys by means of microscopic and X-ray methods. The samples studied were in the form of small tools or wiredrawing dies, which were either purchased or supplied as samples. They were in some cases not supplied by the original makers but were furnished by the agents in this country, and we wish to call attention to the fact that they may not be truly representative of the materials supplied under the various trade names No performance data are given and no inference as to the inferiority of one alloy as against any other is made. K. Schröter2 recently described methods for polishing alloys of this type for microscopic examination and has presented photomicrographs of several alloys. However, he did not identify their constituents or describe methods for their identification. Constituents and Their Identification As far back as 1915 attempts were made to utilize tungsten carbides commercially, but the great brittleness of these carbides made these first attempts unsuccessful. Later, successful dies were made by sintering the powdered carbides with small amounts of iron, nickel, or cobalt. Due to the high melting points of the tungsten carbides (2600" to 2800" C.), it is difficult to melt the carbides without volatilizing almost quantitatively the added element of the iron group. Inasmuch as the added metal does not exceed 20 per cent. and is usually present in much smaller amounts, some understanding of the tungsten-carbon equilibrium dia-

Jan 1, 1929

By C. W. Kuttner, J. L. Gregg

ReceNtly there has been considerable interest in the production and use of extra hard alloys composed primarily of tungsten and carbon. Dr. Hoyt's recent paper1 gives a good description of these alloys and describes their performance when used as tools. There are a number of these alloys on the market sold under various trade names, and it is the purpose of this paper to describe the results of an investigation of the structure of five of these alloys by means of microscopic and X-ray methods. The samples studied were in the form of small tools or wiredrawing dies, which were either purchased or supplied as samples. They were in some cases not supplied by the original makers but were furnished by the agents in this country, and we wish to call attention to the fact that they may not be truly representative of the materials supplied under the various trade names No performance data are given and no inference as to the inferiority of one alloy as against any other is made. K. Schröter2 recently described methods for polishing alloys of this type for microscopic examination and has presented photomicrographs of several alloys. However, he did not identify their constituents or describe methods for their identification. Constituents and Their Identification As far back as 1915 attempts were made to utilize tungsten carbides commercially, but the great brittleness of these carbides made these first attempts unsuccessful. Later, successful dies were made by sintering the powdered carbides with small amounts of iron, nickel, or cobalt. Due to the high melting points of the tungsten carbides (2600" to 2800" C.), it is difficult to melt the carbides without volatilizing almost quantitatively the added element of the iron group. Inasmuch as the added metal does not exceed 20 per cent. and is usually present in much smaller amounts, some understanding of the tungsten-carbon equilibrium dia-

Jan 1, 1929

By J. Gordon Parr, A. J. Goldak

OgdEN et al.1 and Bumps et al.2 suggested that the solubility of aluminum in a titanium extended to 30 pct.* Sagcl,3 Clark and Terry,4 Anderko et al.,5 Ence and Margolin6 and Saulnier and croutzelles,7 subsequently proposed the existence of an intermetallic compound in the region of 25 pct Al. Although Anderko et al.5 suggested that the structure of this phase, Ti3Al, was of the DO,, (Ni3Sn) type, their conclusion was based only upon the results of a powder photograph that included reflections from ? = 0 to ?= 27° (CuK),some of which were reported to be indistinct. Ence and Margolin,6 referring to a 25 pct alloy (but without indicating whether the figure referred to weight or atomic pct) stated: "The structure of Ti2Al is isomorphous with Ti3Sn DO19, as pointed out by Pietrokowsky". But the point was not proven, because Ence and Margolin did not report values of calculated intensities of Ti2Al with the DO,, structure. In fact, the observed intensities they reported are in poor agreement with the values we calculate for DO19 (see Table I). Saulnier and croutzelle7 concluded, on the basis of electron micrography and microdiffraction studies, that the structure of the 25 pct A1 alloy was ordered hexagonal. Our purpose has been to unequivocally determine the Ti3Al structure. Alloys containing 25 pct Al were prepared from iodide titanium and spectrographic standard aluminum by levitation melting. The levitation chamber was evacuated to 10-6 mm Hg before filling with 99.999 + pct A. After casting, the alloy was chilled to liquid air temperature and crushed to -200 mesh in a percussion mortar. The powder, wrapped in molybdenum foil, was annealed (by induction heating) at 1000 "C for 2 hr in the argon atmosphere of the levitation chamber. No sublimate was seen on the foil or elsewhere, and therefore the assumption is

Jan 1, 1962

By Harry Roeser

Short cuts for determining the constants of oil decline curves, with the method of least squares as a starting point, are presented and applications made to practical examples. The nature of the raw data does not justify rigid adherence to the orthodox theory but does lend justification to convenient methods of approximation within reasonable limits. If the conventional form y = kxn were changed to y = k(x + c)', methods of determining the curves would be simplified and greater uniformity in calculated results would probably follow. As A result of the publication, several years ago, of some articles on determining the constants of empirical formulas, the determining the constant's of types of curves used for estimating the production decline of oil wells was brought to the writer for study. Methods requiring a minimum of time and labor and a maximum of rigor were sought, as it appeared that the nature of the data from which such curves are computed and the relative uncertainty of occurrence of the events predicted from them did not justify close adherence to the theory on which the solution of such problems is ordinarily based. The technical deficiencies of the solutions presented in this paper, from the standpoint of the method of least squares, are readily apparent to those familiar with that method, but their presentation in detail here is irrelevant to the subject matter. However, it is the author's conviction, after a rather exhaustive study of the problem, that the value of the solutions lose little by the approximate application of the conventional theory. It must be understood by those who use these formulas that the solutions herein given, and the formulas based on them, are merely facilities to aid the valuation engineer in forecasting future events. It is assumed, also, that before application is made of them, prescient judgment based on the circumstances in each case, shows that the forecast has some probability of realization. On this basis only will these formulas be found useful.

Jan 6, 1924

By H. R. Shidel

This paper summarizes the results obtained from the preliminary cementing of wells in an effort to cut off the bottom water. The object of this work was two-fold: (1) To prevent the oil sand from becoming flooded. (2) To plug off bottom water, thereby preserving the individual well and reclaiming production. Valuable suggestions and help have been given by the following named: Messrs. Kyle and La Velle, of the U. 8. Bureau of Mines; Magnolia Petroleum -Co.; Freed Oil and Gas Co. The cementing work was carried out under the personal supervision of L. J. Snyder. In an unpublished paper on the "Water Problem in the Augusta Field," 5. K. Clark reaches the following conclusions: (1) That the great amount of water present is bottom water, occurring in the Varner sand, the main producing or the 2500-ft. horizon, (2) That the only striking connection between structure and water is in .the area of the marked fault on the Ralston, E. C. Varner, and F. Varner leases in sections 8, 9, 16 and 17. (3) That the oil occurs in porous streaks, generally separated by finegrained, well cemented sand, which is barren. Possibly two or three such pay streaks may be found. That under a pay, fine-grained sand occurs, which is presumably barren at the time of drilling, but soon reveals water. The writer takes partial exception to the last point, because well defined shale, slate, lime, or hard sand breaks have been encountered in a great many cases, separating the pay streaks under which water is often found. This is not an invariable occurrence, as cases have been noted when the oil has been followed immediately by water in the same stratum. In an effort to overcome the water menace, the following methods of plugging were tried: (1) Plugging with wood, lead, and limit plugs. (2) Plugging with sand pumpings.

Jan 1, 1920

By H. R. Shidel

THIS paper summarizes the results obtained from the preliminary cementing of wells in an effort to cut off the bottom water. The object of this work was two-fold: (1) To prevent the oil sand from becoming flooded. (2) To plug off bottom water, thereby preserving the individual well and reclaiming production. Valuable suggestions and help have been given by the following named: Messrs. Kyle and La Velle, of the U. S. Bureau of Mines; Magnolia Petroleum Co.; Freed Oil and Gas Co. The cementing work was carried out under the personal supervision of L. J. Snyder. In an unpublished paper on the "Water Problem in the Augusta Field," S. K. Clark reaches the following conclusions: (1) That the great amount of water present is bottom water, occurring in the Varner sand, the main producing or the 2500-ft. horizon. (2) That the only striking connection between structure and water is in the area of the marked fault on the Ralston, E. C. Varner, and F. Varner leases in sections 8, 9, 16 and 17. (3) That the oil occurs in porous streaks, generally separated by fine-grained, well cemented sand, which is barren. Possibly two, or three such pay streaks may be found. That under a pay, fine-grained sand occurs, which is presumably barren at the time of drilling, but soon reveals water. The writer takes partial exception to the last point, because well defined shale, slate, lime, or hard sand breaks have been encountered in a great many cases, separating the pay streaks under which water is often found. This is not an invariable occurrence, as cases have been noted when the oil has been followed immediately by water in the same stratum. In an effort to overcome the water menace, the following methods of plugging were tried: (1) Plugging with wood, lead, and limit plugs. (2) Plugging with sand pumpings.

Jan 10, 1918

By D. J. DeLazaro, W. Rostoker, R. E. Riley, M. Hansen

KNOWLEDGE of the isothermal transformation behavior and the TTT chart method of graphically summarizing such information has been of invaluable aid to the ferrous metallurgist in understanding and developing heat treatments intended to provide specific mechanical properties. It is to be expected that similar lines of study directed to titanium-base alloys will be as profitable. This paper summarizes, on conventional TTT charts, the isothermal transformation products and pertinent reaction rate data for binary alloys of titanium containing 1, 3, 5, 7, 9, and 11 pct Mo, respectively. The results so presented were derived from metal-lographic examination. Some X-ray diffraction work was done to clarify certain points of question. Ti-Mo System To the authors' k.nowledge, TTT charts have only been used to describe the reaction rates of eutectoidal decompositions. It would seem that the kinetics of decomposition of any unstable solid solution might be conveniently described in this manner. The equilibrium diagram of the Ti-Mo system' is shown in Fig. 1. The similarity with the Fe-Ni system will be recognized. Additions of molybdenum serve to stabilize the /3 phase to increasingly lower temperatures. The solubility of molybdenum in the a phase is restricted to less than 1 pct at 600°C. Under normal conditions. a homogeneous ,8 structure quenched to a, temperature in the a f & field will reject a of invariant composition. The rate at which this occurs depends on the degree of undercooling and the degree of supersaturation of /3. The structural character of the rejected phase may also be expected to be related to the undercooling. Materials and Experimental Methods A sponge titanium was used which has a nominal impurity content as reported in Table I. The nominal composition of the molybdenum used is also included. The alloys were prepared in 150 g melts by arc melting in an evacuated water-cooled copper crucible of the type reported in an earlier paper.' The pancake-type ingots were forged to 1/4x1/4 in. bars and homogenized for 24 hr at 1000°C in evacuated Vycor bulbs. Specimens Vi in. thick were cut from these bars for heat treatment. The heat treatment cycles followed an invariant procedure. The specimens were soaked at 1000°C for 20 min under a helium protective atmosphere prior to quenching into a lead bath held at a temperature corresponding to a chosen degree of undercooling. After a prescribed period of time at this temperature, the specimen was removed and water quenched. A series of specimens so treated for progressively longer periods served to establish the times for initiation and completion of the decomposition of the /3 phase at a particular temperature. Although heat treatment of unprotected specimens in a lead bath does permit surface contamination by lead diffusion, this method is necessary to insure sufficiently rapid quenching rates. As long as the bath treatments were of less than 1 hr duration. the contaminated surface was not unduly deep and could be removed without excessive grinding. Metal-lographically, the contaminated zone could be readily distinguished from the pure binary alloy. Transformation Characteristics of Ti-Mo Alloys Metallographic examination showed that a supersaturated p phase may decompose by one of two processes. Alloys containing 1 to 9 pct Mo, when quenched in water from the homogeneous /3 field,

Jan 1, 1953

AN extremely successful meeting, under the joint auspices of the Ohio Section and the Iron and Steel Committee, was held at Cleveland on April 19 and 20, about one-half of those in attendance being from the Cleveland district and the other half from a distance. The morning session on April 19, C. K. Leith presiding, was opened by the presentation of the ad-dress of which an excerpt is printed on the opposite page. In the subsequent discussion R. A. Allen pointed out that the meeting had not been called "to blow the lid off the tariff" since that is only one of the many problems connected with the wisest utilization of man-ganese, and it was the purpose of this meeting to con-sider all those interdependent problems. The purpose of the tariff was to develop an adequate domestic sup-ply, and that result had not been accomplished. An-other important problem, linked with the tariff, is the need for assuring, while we are at peace, an adequate war supply of manganese, and at present this country has no such policy. D. F. Hewett said that his 3-months' trip in Europe last summer had impressed him with the fact that England had once been in the position United States now is in, of being the principal world's producer of all the more important minerals and with a declining reserve had gone on a free-trade basis. No one pointed out that, with the exception of tin, the present relative position of England is due more to an increase in pro-duction in other countries, rather than to a decrease of domestic production. J. Sharshall Grasty referred to recent development work-in Virginia where of 30 per cent easily concen-trated manganese ore about 300,000 tons has been blocked out and possible and probable ore amounting to 700,000 tons more is indicated.

Jan 5, 1927

By H. W. Immolz

The Palo Pinto limestone pools of Jones and Shackelford Counties were defined and almost fully developed during the year. A new Palo Pinto limestone pool was apparently discovered when the K. B. Nowels NO. 1 Pardue, S.F.I. and W. survey, south central Haskell County, was completed for a small well in Palo Pinto limestonc at 3395 to 3421 feet. In Haskell County, Amerada Petroleum Corporation's C. J. Kleiner, J. M. Cass survey, drilled to the Ellenburger with a total depth of 5607 ft., where it was abandoned. A Bluff Creek sand field of undetermined size was discovered by the Fain-McGaha No. 1 Dawson-Conway, P. G. Holcomb survey, which was chompleted for 37 bbl. at 1496 feet. The Cook field was extended by the Roeser-Pendleton B-113 Cook in sec. 113, E.T.R.R. Co. survey, the well being completed for 510 bbl. from Cook sand encountered at 1545 to 1568 feet. Several shallow pools of minor importancc mere also discovered in Shackelford County during the year. In Jones County the Lewis and the Steffens fields, in block 15, T. and P.R.R. Co. survey, were further developed during the year but the limits of the Steffens field were not definitely defined. The most, important discovery in Jones County was the Guitar field, where most of the wells that had been producing from the Cook sand were deepened to the Hope limestone, a new producing horizon. In Taylor County, the Bowles field, see. 28, B.A.L. survey, was defined arid proved to he of minor importance. The Goldsboro and Novice area, ill northwest Coleman County, continued to hold considerable interest because of the developments near the town of Novice, where new Ieases continued to be opened for production. Nolan County was placed in the ranks of the producing counties when the S. B. Owens No. 1 Tipton, sec. 43, block 19, T. and P.R.R. Co. survey,

Jan 1, 1940