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By P. H. Metzger, D. W. Fuerstenau

The activation of sphalerite was found to occur at a much lower rate with Pb++ then with Cut++ or Ag+. To prevent activation with Pb++, the ratio [m in solution must approximate 103. An example is given illustrating how this condition is met in practice through the addition of zinc sulfate and soda ash. In selective lead-zinc flotation, the mill operator, especially the one who is concentrating a partially oxidized ore, often must add zinc sulfate and/or soda ash for effective depression of the sphalerite. In the present paper the authors show how this practice prevents the activation of sphalerite in the presence of Pb++. A number of years ago Gaudin (1) postulated that Zn++ might control the activation of sphalerite with Pb++ through competitive adsorption. However, recent experimentation has shown the activation of sphalerite with Ag+ and Cut++ to be a chemical reaction in which silver or copper ions replace zinc in the sphalerite lattice through the formation of a more insoluble sul-fide (2,3,4) Thus, if activation with Pb++ is similar to that with Ag+ or Cu t+, zinc salts should control the activation of sphalerite not through competitive adsorption but because the ratio of [zn++/Pb++] in solution regulates the extent of the chemical exchange between Zn++ and Pb++ in the solid phase. The objective of this investigation has been to study the kinetics and equilibrium conditions for the uptake of Pb++ by sphalerite and to investigate the prevention of lead activation with zinc salts. BASIC PRINCIPLES Sphalerite activation has been shown to be a replacement reaction wherein a less soluble compound is formed at the expense of the more soluble zinc sul-fide (2,3,4) For example, if sphalerite is placed in an aqueous silver nitrate solution, ZnS gives to the solution more S= than can exist together with Ag+, and hence the following reaction takes place: ZnS + 2 Ag+? Ag2 S + Zn ++; k = [zn ++]/[Ag ++]2 = 10 26 (1) Therefore, ZnS will dissolve in the presence of Ag+ and activation of sphalerite with Ag+ will proceed after monolayer coverage by solid state diffusion until equilibrium conditions are reached in the system (2, 4) Because of the large difference in the solubility of ZnS and Ag2S, zinc salts cannot affect the reaction unless a complexing agent, such as cyanide ions, is present to complex Ag+ more tightly than Zn++ . By complexing Ag+ and Zn++ in solution, the uptake of Ag+ by sphalerite can be regulated by controlling the ratio m. . Experimentally (2) it was found that the activation of sphalerite by Ag+ could be prevented through the addition of NaCN if this ratio reached a value of approximately 10 26. The mechanism of sphalerite activation with copper salts is given by the following reactions: ZnS + Cu ++ ? CuS + Zn + + ; (2) k = [Zn++]/[Cu++] = 10 11 ZnS + Cu + ? Cu2S+ Zn++; (3) Experimentally Mao (3) found that the activation of sphalerite with Cu++ or Cu + was prevented if the ratios expressed in Equations 2 and 3 were approximately l09 and l022, respectively, with cyanide ions as the deactivator. Although zinc salts do not affect the activation of sphalerite with silver or copper ions in the absence of a complexing agent, activation with lead ions theoretically can be controlled by the addition of zinc salts because of the relatively small differences between the solubility of ZnS and PbS (5). Equilibrium

Jan 1, 1961

By Enrique Hauser

Discussion of the paper of ENRIQUE HAUSER, presented at the New York meeting, February, 1916, and printed in Bulletin No. 110, February, 1916, pp. 521 to 534. GEORGE A. BURRELL, Pittsburgh, Pa. Mr. Hauser determined the influence of inert gases on the properties of fire-damp mixtures, and one might take some issue with his work on the effect of hydrogen, on those mixtures. It is valuable information to have, but as far as the practical application of it goes, it is not of much significance, because one does not find it in mines, at least not in any appreciable amount. The same Fig. 1.-APPARATUS FUR DETECTING COMBUSTIBLE GASES IN AIR. thing can be said of ethylene. Ethylene is formed in considerable quantities as a product of heat reaction, but normally, in the coal mines, as a result of a great many analyses we have made at the Bureau of Mines, we cannot say that ethylene is a combustible gas found in the fire-damp in coal mines.

Jan 5, 1916

By William E. Ford, Edward Salisbury Dana

URANINITE. Cleveite. Broggerite. Nivenite. Pitchblende. Isometric. In octahedrons (o), also with dodecahedra1 faces (d) ; less often in cubes with o and d. Crystals rare. Usually massive and botryoidal; also in grains; structure sometimes columnar, or curved lamellar. Fracture conchoidal to uneven. Brittle. H. = 5'5. G. = 9'0 to 9'7 of crystals; of massive altered forms from 6'4 upwards. Luster submetallic, to greasy or pitch-like, and dull. Color grayish, greenish, brownish, velvet- black. Streak brownish black, grayish, olive-green, a little shining. Opaque. Comp. -A uranate of uranyl, lead, usually thorium (or zirconium), often the metals of the lanthanum and yttrium groups; also containing the gases nitrogen, helium and argon, in varying amounts up to 2'6 p. c. Calcium and water (essential?) are present in small quantities; iron also, but only as an impurity. The relation between the bases varies widely and no definite for- mula can be given. Radium was first discovered in this mineral and it has been shown that it and the helium present are products of the breaking down of the uranium.

Jan 1, 1922

By Fred H. Perfect

The thermite process, now approximately 80 years old, has heretofore been practiced in ceramic vessels. This paper outlines the successful production of several million pounds of alloy produced in zuater-cooled copper vessels. THE high temperatures necessary to produce fluid high-alumina slags have probably discouraged earlier workers from attempting to utilize water-cooled vessels. The following is a report of the successful application of this method, together with a report of the physical and chemical problems which had to be solved to make the process practical. About 1955, when Reading Alloys was more concerned with the production of ferrotungsten than with most other types of alloys, it was found to be exceedingly difficult to predict the reaction rate that one would experience from one tungsten ore to another . This difficulty was increased for two reasons: the physical state of the ore as received was seldom uniform, and the size of the mass to be reduced is a very important factor in developing the proper mix for the final reaction rate and temperature. For example, the reduction of ferric oxide with aluminum would theoretically produce temperatures of about 2600°C, and, in spite of the losses due to radiation, the energy is quite sufficient to produce a very fluid slag and iron effecting a very clean separation. On the other hand, the reduction of ferrous oxide with aluminum, while it is not as energetic as the first reaction, nevertheless should give temperatures above 2000"C, which should cause separation of alumina and iron, but, in practice, this is not the case and good fluid slag is not obtained. The heat of reaction, calculated from the thermo-dynamic heats of formation of the constituents of the reaction, offers a convenient guide to the feasibility of a thermite reaction. Thus, the values listed in Table I can be used as an approximate guide for estimating the results which may be expected in the reduction of various oxides and combinations of oxides using aluminum as the reducing agent. As a generalization, those reactions releasing approximately 600 cal per g of total mass represent the lower limit at which to expect separation of slag and metal. On the other hand, those reactions which release 1100 to 1200 cal per g are too violent to be used successfully without the addition of considerable inert material, such as lime, fluorspar, and so forth. Reaction rate is also a very important factor. This, of course, is governed very largely by the sizing and intermingling of the oxidant and reductant and by the starting temperature of the reactants. This is why those figures shown in Table I can only be a general guide. Further, it must be understood, that by adding powerful oxidizing agents, such as nitrates, chlorates or metallic oxides, such as molybdenum trioxide or chromium trioxide, certain problems respecting low temperatures are not necessarily solved. This is true in the addition of oxidants, such as sodium chlorate. By adding too high a concentration of sodium chlorate as a booster for a particular reduction, explosions are generated. Generally, they are of an intermittent type so as to give a Roman Candle effect to the reduction itself; with each surge resulting from a minor explosion more and more material is thrown

Jan 1, 1968

By Carroll Forbes

INTRODUCTION MANY different shapes of drill bits are in use with hammer drills, but little definite information is available whereby to judge which one of these shapes is the best. The following investigation was undertaken in order to determine what effect, if any, the shape of the cutting edge has on the cutting speed and wearing qualities of drill bits. The bits tested were those in common use, namely, the 4-point or cross bit, the 6-point bit, the Z bit and the "Carr" bit. The rock in which the tests were made was the red granite from southeast Missouri. It is a coarse crystalline granite containing an unusually large amount of quartz and is extremely hard, and on account of its uniform texture is admirably adapted to this work. While tests in other rocks might show somewhat different results, nevertheless it is the opinion of the authors that the relative cutting quality inherent in the shape of the bits would be the same in all rocks. Other qualities, such as mudding freely, freedom from fitchering, etc., might make one bit more desirable than another in softer rocks. DESCRIPTION OF BITS TESTED The 4-point bits were the usual shaped bits commonly made on the Leyner sharpener with 14° taper on the wings and a 90° angle between cutting edges. Some tests were run at 85 lb. pressure with a 4-point bit made with a 5° taper on the wings. This was made by using the Carr bit die. The 6-point bits were the usual shaped hits made on, the Leyner sharpener. The Carr bits were made with a 5° taper and an angle of 100° between cutting edges.

Jan 8, 1917

By W. A. Scheuch

ORDINARILY secondary copper, unless electrolytically refined, is reclaimed directly as foundry ingots used in the manufacture of copper-rich alloy castings. This use does not require the elimination of the impurities to the degree required if the recovered metal is to be used for electrical purposes where a high electrical conductivity is of prime importance. However, as a part of the general policy of reusing its own scrap and by-products wherever possible, the Western Electric Co. at its Hawthorne Works is recovering its secondary copper as wire bars which are delivered to its own rod and wire mill and there processed into wire of high electrical conductivity. This departure from the usual recovery scheme has been accomplished through the careful classification and sorting of the material entering the furnace charges and the careful control of the subsequent melting and refining in a reverberatory furnace. Tests conducted over a period of approximately four years have shown that the quality of wire bars produced from selected secondary copper is equal to that of wire bars produced by the electrolytic refineries. The interest which has been exhibited in the process by those who have seen it has prompted the following general description. It is the authors' opinion that the recovery of secondary copper will become more and more an important factor in the copper production industry. The description is largely of the refining furnace and its operation, but it must be remembered that careful classification and sorting of the scrap materials to eliminate impurities are just as important as the furnace operation toward obtaining a satisfactory final product. Classification and sorting do not lend themselves easily to description; they must just be done. It should also be recognized at the outset that constant intelligent supervision is requisite to the success of the process because there are so many ways in which impurities can find their way into the final product.

Jan 1, 1929

By A. Alonso, J. Daubenspeck

In the nickel extraction process at Nicaro, Cuba, dried and ground nickel bearing laterites are reduced at 1300-1400F in multiple-hearth furnaces. Nickel is leached from the reduced ore by aeration in an aqueous solution of ammonium carbonate. Nickel carbonate is precipitated from the liquor and calcined to yield nickel oxide. The following are the more important modifications of the Nicaro process since plant rehabilitation and expansion. Ten percent increase in tonnage was achieved without decreasing the fineness of the ore by minor mechanical modifications of the grinding plant. Another five percent increase in tonnage was attained by intentionally overloading the ore prepration and leaching circuits in an effort to control cobalt extraction. Modifications at the sintering plant allowed it to handle the entire output of the expanded plant. A fifty percent increase in leach liquor cooling facilities alone provided an increase in nickel production of five percent. Stronger fresh leach liquor for increased nickel washing efficiency was obtained through improved distribution of water to the ammonia absorption towers. Advantage was taken of the reduced calcine's capability to precipitate cobalt, and modifications in the leach liquor circulation provided controlled cobalt solubility with minimum harm to nickel extraction. Several process changes at the drying plant brought about a ten percent reduction in the fuel oil consumption at this pint. Controlled air addition to the reduction furnaces' upper hearths burned formerly wasted combustibles thereby reducing oil consumption by twenty percent. The nickel extraction process successfully emplayed on the extensive but lowgrade lateritic ores of Eastern Cuba at the U. S. Government owned Nicaro plant, has been previously described in various publications. The large mine and plant operated by the Nickel Processing Corporation, located on the northeastern shore of Oriente Province, have been recently expanded to a yearly capacity of about 50 million pounds of nickel. Essentially, the operation involves open pit mining of a limonite-serpentine ore mixture containing 1.3 to 1.4 percent nickel and 34 to 38 percent iron. The comparatively lumpy, wet (25 to 30 percent moisture) ore is first dried and ground prior to chemical treatment, to which the entire 7,000 tons per day feed must be subjected. In the initial chemical action the dried and ground ore is reduced with carbon manoxide and hydrogen at 1300-1400° in multiple-hearth furnaces. The resulting metallic nickel is selectively leached from the reduced calcine by aeration in an

Jan 1, 1961

By P. B. Baxendell

The appraial of producing properties and profitability ntzalysis of a proposed capital expenditure are based on the same principles. In both problems a projection of future cash income is. cornpared to one or more capital expenditures. Several different methods have been in use either to compute a price to obtain a given earning power on the investment or to compute the earning power which will result from a given capital expenditure. One of these, the "Average Annual Rate of Return" method, computes in a simple manner the ratio of the present value of the future earnings after amortization to the present value of the undepreciated balances of the investment over the life of a project. This method, not well known generally, appears to have some rather unique advantages in reducing the computation work required, eliminating trial-and-error solutions, and providing a more accurate answer when applied to oil industry investments subject to the unit-of-production basis of amortization. Its derivation is given and its versatility demonstrated in the solution of certain everyday investment problems. A number of charts, useful in applying this method to profitability analysis and appraisal work, are provided. The current trend in the market values of producing properties is shown. INTRODUCTION Making sound capital expenditure decisions requires an objective means of measuring the productivity of individual investment proposals. Since the best measure of the economic worth of such proposals is their ability to produce profits, it is common practice to grade proposed capital expenditures according to their annual earning power as a percentage of the outstanding capital. The same principles which govern the determination of the rate of return of proposed capital expenditures also apply generally to the problem of determining the appraisal value or purchase price of income-producing oil and gas properties. Both problems are of prime importance in the producing phase of the oil business, where management is faced daily with decisions to drill or not to drill certain development wells, or with the determination of the appraisal value of producing properties. The common feature in both problems is that a projection of future cash income is compared with a known or estimated capital investment to determine itsiearning power or annual rate of return. In the case of development drilling, the cost of the proposed well can usually be estimated with a fair degree of accuracy and the problem consists of finding the rate of return on the invested capital. In the case of appraising producing properties, on the other hand, the desired rate of return is usually known in advance and the problem consists of determining the purchase price which, for the given income projection, results in the fequired rate of return. Certain accounting procedures common to the oil and gas producing business make these two problems and their solutions somewhat different from corresponding problems in other industries, and, in certain ways, simpler. The main difference is in the amortization policy which, for oil and gas production, is frequently on a unit-of-production basis, compared to the amortization on a time basis used in many other industries. The purpose of this paper is to discuss briefly the various methods currently in use for the measurement of productivity of invested capital in producing properties and, in more detail, the derivation and application of what will be called the "Average Annual Rate of Return Method". This rather interesting and not too well known method has some very definite advantages in the solution of many problems common to the oil industry. For the sake of simplicity, federal income tax considerations have been disregarded in the examples used, since they do not affect the principles involved. The use of the production payment route in the sale or purchase of producing properties, which has been amply covered in many other publications, has also not been included in this analysis. METHODS FOK MEASUKING THE EARNING POWER OF INVESTED CAPITAL, Of the many different methods used to measure the earning power of invested capital, four are applicable to oil or gas production ventures. Depending on whether these four methods utilize one or two interest rates, and whether a fixed amortization pattern is used, they may be classified as follows.

The regular activities of the Institute are financed mainly by income derived from members' dues, from advertising in MINING AND METALLURGY, and from the sale of publications to the public. In addition, collateral activities and special projects are financed each year by means of income from endowed funds controlled and administered by the Institute. In the aggregate, the principal sums of these endowments amount to more than $530,000. An active effort is being made to increase the endowment funds of the Institute through a standing committee, of which H. T. Hamilton is chairman, and of which the other members are: W. H. Aldridge, George D. Barron, Cleveland E. Dodge, D. C. Jackling, Henry Krumb and J. V. W. Reynders. This committee feels that there exists a tremendous opportunity for the Institute to be of ever-growing service to the public, to the mineral industries, and to the profession. It welcomes suggestions as to names of men of means who are vitally interested in the mineral industries, and to whom the opportunity to make a contribution or bequest might appeal favorably if presented in the proper light by the committee.

Jan 1, 1941

By Charles H. Jacoby

The solution mining of evaporites has a history of approximately 5,000 years. The insitu leaching of metalliferous ore will have many of the same characteristic problems which have confronted industry for years in the production of evaporite minerals. Basically we will be converting the less soluble forms of valuable metals into their more soluble salts and producing these in much the same manner as, for example, sodium chloride. There are a number of problems which we are faced with that are more complex and complicated and, therefore, will require a higher degree of sophistication than previously employed. One of our most important undertakings will be the clearcut definition of the problems involved. While a great deal of expertise can be drawn from the solution mining of evaporites and the oil industry, problems peculiar to the hydrometallurgical field will need to be solved. One of these is the introduction of permeability into an impermeable rock so as to expose the sought after values of metals which by volume are infinitesimal when compared with sodium chloride, potash or other type water soluble mineralization. After establishing this permeability which will be miniscule when compared to a solution cavity, there will be the maintenance of this permeability. In general, salt deposits are of a somewhat uniform chemical composition and thus their chemistry was relatively simple. Each metalliferous ore body is somewhat unique in its chemistry and will need to be treated accordingly.

Jan 1, 1974

By J. F. Wilson

An experimental investigation has been made of gas-driven slug displacements in a system of high gas saturation to evaluate the process for use in a California reservoir. Fluid compositions, temperature, pressure and core permeability duplicated reservoir conditions as closely as possible. The temperature was above the critical of the slug materials. The slug composition required for 100 per cent oil recovery in the linear flow systems was found to agree with that determined from equilibrium phase studies. A qualitative theory for the slug displacement of two-phase systems is proposed and found to be in general agreement with the observed flow behavior. The theory predicts that the length of the reservoir fluid-slug transition Zone will increase with increased initial gas saturation and decrease with increased oil swelling accompanying the composition change from reservoir oil to the critical composition. The precipitation of small amounts of an asphaltic phase during the formation of the transition zone had no adverse effects on the flow behavior of otherwise miscible systems. INTRODUCTION Despite the large number of recent publications relating to oil recovery by miscible displacement, little information is available concerning the behavior of crude oil-natural gas systems at conditions likely to be encountered in field application. The laboratory data reported here were obtained during an investigation of the possibility of using a gas-driven LPG slug in a partially depleted California reservoir. Seven gas-driven slug displacements employing slugs of different compositions and sizes were made in 26- to 27-ft long sandstone cores. The equilibrium phase behavior of the systems was also determined. The features of primary interest in this study are the following. 1. Data were obtained on the displacement of reservoir fluids at reservoir conditions. 2. A high gas saturation existed in the long cores at the start of the displacements. 3. The temperature of the studies was above the critical of the slug materials. 4. A comparison between the flow behavior and equilibrium phase behavior, as illustrated by a pseudo-ternary phase diagram, is afforded for a system of considerable complexity. THEORY Phase Behavior The use of the pseudo-ternary phase diagram to illustrate the phase behavior in miscible displacements has been discussed by Clark, Schultz and Shearin. Sie-vert, Dew and Conley and Arnold, Stone and Luffel' have presented both phase equilibrium and flow data for true ternary systems. For the true ternary, the application of the theory is straight-forward; for a reservoir system represented as a ternary, the theory undoubtedly gives a qualitatively correct picture. One purpose of this investigation was to see if the pseudo-ternary phase diagram could be used to predict with reasonable accuracy the conditions necessary for miscible displacements with actual reservoir systems. MiscIBLE Displacement of Two-Phase System A large number of papers "I3 have treated the miscible displacement of a single-phase fluid from both an experimental and a theoretical viewpoint. However, the normal field application of the process will be in a partially depleted reservoir. Often the state of the system will be such that the mobility of the gas phase is greater

By Fulton Flick

THE micrography and macrography of aluminum and its alloys present certain difficulties. Many of the difficulties attendant on the micrography have been removed by methods developed during the past few years, notably those of E. H. Dix, Jr.1 The development of grain size in aluminum and its alloys may be equally troublesome, yet comparatively little detailed attention appears to have been given to it. Satisfactory reagents. are available for the development of such structures in ferrous and most non-ferrous metals, but those applied to aluminum and its alloys, i. e., alcoholic or aqueous solutions of sodium hydroxide or hydrofluoric acid are not entirely satisfactory. Hanson and Archbutt,2 in speaking of these two reagents, state that "These two reagents give fairly satisfactory results, but they sometimes produce badly tarnished surfaces from which the surface deposit is difficult to remove." It has been our experience that neither of these reagents is to be entirely relied on for developing structures suitable for study or photography. This means that when the etch fails to produce satisfactory results the, specimen must be repolished, through the 000-paper at least, and then etched with another reagent. This procedure entails a con¬siderable loss of time, and the final results may not be all that might be desired. However, the reagent to be described, although not a panacea for all etching troubles, has improved results so markedly that it is felt that it is worth offering as a grain-size etch generally applicable to aluminum and aluminum alloys. Czochralski3 in 1915 mentioned the application of a solution of 10 to 20 c. c. concentrated hydrofluoric acid in 100 c.c. absolute alcohol, etching in this reagent being followed by dipping in concentrated hydrochloric-acid solution.

Jan 2, 1925

By Richard Rice

TURBO blowers for blast-furnace blowing have now been in use for some years, and a review of the experience gained and the present state of progress may be interesting. FIG. 1.-STEAM TURBINE DIRECT CONNECTED TO AIR COMPRESSOR. The first blast-furnace blowing engine of this type to be installed in America was built by the General Electric Co. and is installed at the oxford Furnace of the Empire Iron & Steel Co. This machine was put into operation March 8, 191.0. A duplicate unit is situated at the furnace of the Northern Iron Co. at Port Henry, N. Y., which unit was put into opera ion June 30, 1910 (Fig. 1).

Jan 5, 1914

By A. C. Fraker, H. H. Stadelmaier

In the systems Mo-Fe-C, Mo-Co-C, and Mo-Ni-C the phase boumdaries of the cubic Ij carbides were determined at 1000°C and the variation of the lattice parameter with composition was measured. In the system Mo-Fe-C a single ternary carbide, Mo3Fe3C, was observed. In Mo-Co-C and Mo-Ni-C two new n phases of the type M12C were found: Mo6C06C and Mo6Ni6C. At 1000°C they coexist with the M6C phases MO3-4,CO3-2C and Mo3-4Ni3-2C, respectively. Mo3C03C and Mo4C02C are not separate phases but parts of a single M6C phase region, and the same is true of Mo3Ni3C and Mo4Ni2C. THE n carbide structure type has been known since it was determined by westgren' in 1933, yet reliable information on phase compositions of this type is ap-parently scarce. The following selection of suggested formulas illustrates the extent of the confusion con-cerning compositions: W2-3Fe4-3C,1W6Fe6C,2 W2_4Fe4-2C,3 (W,Fe)6C,4 Tj.-W4Co2C and nz-W6Co6C,5 n1-W3Co3C and n2-w4Co2C,5 W3C03C and w6Co3C2,7 MO3Fe3C,8n2-M04Fe2C,9 (MO,Fe)6C,4 MO3CO3C,8 n2-MO4CO2C.9 Many of these compositions obviously overlap, some disagree in carbon content. The use of the designations 77, and n2 is not consistent. There is uncertainty whether two carbides M6C coexist or whether there is only one M6C with a wide range of substitution of one metal for the other. The existence of M12C seems questionable altogether if one ignores the results of a neutron diffraction study of W6Fe6C supporting that particular metal to carbon ratio.'' More reliable information is available for the iso-typic oxides studied by Nevitt,11 Nevitt, Downey, and orris," and Meussner and carpenter.l3 That n car-bides and oxides are structurally identical, particularly with respect to the location of the metalloid atom, has been demonstrated clearly by Stadelmaier and Meussner14 and also by Parthe, Jeitschko, and sadagopan.15 Therefore the present paper, which attempts to establish the phase boundaries of n defini-tively for three carbon systems, has implications for the whole family of filled Ti2Ni types. EXPERIMENTAL PROCEDURE The samples were prepared in two stages. Pellets weighing 3 g were compacted from powders of the elements and presintered in a closed tube of fused silica that had been evacuated to lO-4 mm Hg. This was fol- lowed by arc melting the sintered samples under argon. Remelting the button once was sufficient to produce homogeneous specimens. The metal powders had the following minimum purities in wt pct: molybdenum 99.5, iron 99.0, cobalt 99.7, nickel 99.9, graphite 99.94. Carbon determinations by the gas volumetric method were obtained from thirty-one of the one hundred samples in the annealed condition. They were limited to compositions that were critical to placing a boundary line in the isothermal sections. The carbon losses were comparatively low and averaged less than 1.5 at. pct. For annealing, the samples were sealed in tubes of fused silica evacuated to 10-4 mm Hg. The annealing schedule was 20 hr at 1250°C followed by 150 hr at 1000" ±10°C. For the water quench the silica glass tubes were broken mechanically to speed the quench. The specimens were examined in the as-cast and annealed condition by standard metallographic techniques. Some of the as-cast and all annealed samples were studied by X-ray diffraction using a 114.6-mm powder camera with filtered Co radiation. The lattice parameters of the n phases were determined by graphic extrapolation to 8 = 90 deg on a plot against sin2 8. It is estimated that the maximum error in the lattice parameters is ±0.002A.. The phase fields were determined by the disappearing phase method, relying on X-rays for phase identification and on microscopy to detect small amounts of a phase. RESULTS Pertinent information on the binary side diagrams has been summarized by Hansen and Anderko16 and Elliott17 and will not be discussed further. Photomicrographs documenting the equilibria at 1000°C have been selected to avoid redundancy due to the similarity of the three systems. Thus there will be only one picture showing an equilibrium with Mo2C, and so forth. Molybdenum-Iron-Carbon. An isothermal section of most of the Mo-Fe-C system at 1000°C is shown in Fig. 1. No attempt has been made to distinguish between a and y iron or to determine their phase boundaries. A conspicuous absence is the phase Fe2 1Mo2C6 with the Cr23C6 structure, supporting the suggestion by Krainer4 that it decomposes by annealing at high temperatures. The only ternary phase is found in a narrow range around Mo3Fe3C (MO43Fe43C14). A microstructure with a two-phase mixture of Mo + n is seen in Fig. 2. The variation of the lattice parameter of n with the estimated composition is shown in in Table IA. The phase diagram does not agree with the results of Kuo9 who reported n2-Mo4Fe2C. Our lattice parameter Varies from 11.095A at the iron-rich end to 11.140Å at the molybdenum-richoend of the phase field whereas Kuo9reported 11.26Å for Mo4Fe2C. We are in agreement with the older work

Jan 1, 1970

By William Paxton Hewitt

In the Santa Eulalia mining district, Chihuahua, Mexico, the main mineral zone occurs in a gently warped dome with simple associated structures and contains orebodies distributed through a vertical range of over 900 m. The stratigraphy of 1945 m of geologic column is described and an abrupt shrinkage is documented in the volume of limestones immediately associated with large orebodies. Termed collapse, this shrinkage occurred during the course of mineralization. Contacts of limestone with igneous sills, and 366 m of fossiliferous limestone beds, particularly the main fossil bed, have been important localizers of ore-bodies. Up-dip gravitational controls may have been important. Fractures have exerted only local controls and over short distances. Thrust zones have displaced diabase sills and in turn have been intruded by upper members of a group of rhyolite porphyry sills. Mineralizers were related to the rhyolite porphyry, and ore has been introduced to the limestone where certain sills lie between the displaced segments of diabase and have been cut by north-south fissures. Speculations are raised that fields of unreleased strain may have influenced orebody locations; the district's zoning pattern may be a reflection of the filtering effects of large volumes of limestone; and that metal-rich brines mobilized by or incorporated within the invading porphyry might be the source of the mineralizers. PRODUCTION AND LOCATION The Santa Eulalia district has a production record approaching or exceeding 35 million tons of silver-lead-zinc ore from replacement bodies in limestone. In operation since the first years of the 17001s, production has been confined to two intensely mineralized areas separated by 2 km of barren limestone, the West Camp and the East Camp. Probably 50% has been mined since 1908, with over 90% from the West Camp. The West Camp, exploited through a vertical depth of 1945 m and now approaching exhaustion, is the subject of this paper. The district lies in the northern part of the Santa Eulalia Mountains in central Chihuahua in northern Mexico, 400 km south of El Paso, Texas, and 22 km southeast of Chihuahua City. Dominating the northern part of the range is the Cerro de Santa Eulalia, a broad rolling upland which contains the district's West and East Camps. The West Camp, on the west side of the range, centers around the village of Santo Domingo, which is 2 km northeast of the Real de Santa Eulalia (Fig. 1). REGIONAL GEOLOGY Thick-bedded middle Cretaceous limestones, probably Aurora, form the great bulk of the Cerro de Santa Eulalia. These beds, warped into a gentle dome, are severed on the west by a faultline scarp and truncated on the north by the Dolores Pass, a wind gap that

Jan 1, 1969

By L. F. Pease, J. H. Brophy

A phase diagram for the Ta-Zr system is presented. The system is of the minimum-melting point type with the 0-zirconium phase decomposing monotectoidally at 785°C and 95.5 at. pct Zr. The minimum solidus temperature is 1875°C and the temperature of the top of the monotectoid loop is 1775°C. Techniques employed included X-ray diffraction and fluorescmce, electron microprobe analyses, diffusion couples, metallography, and melting-point measurements. Errors due to interstitial solutes and in melting observations are particularly common in this system, and their occurrence is discussed. SEVERAL versions of the Ta-Zr phase diagram have been reported in the literature.lm7 Williams et al.' report a diagram of the minimum-melting point type with a monotectoid reaction at 800°C and 12 wt pct Ta. The minimum in the solidus occurs at 1820°C and 25 wt pct Ta, while the top of the monotectoid gap is located at 1780°C and 80 wt pct Ta. The experimental techniques employed were metallography, electrical resistance variation with temperature, dilatometry, X-ray diffraction, and direct observation of melting by the technique of Pirani and ~lterthum.' Experience in the Nb-Zr phase diagram has shown that small changes in the interstitial content can cause large shifts in the positions of the phase boundaries. Small amounts of inter -stitials can cause similar changes in the Ta-Zr system and may be responsible for the wide variations in the phase diagrams previously reported.'-' The authors15 have found that alloys containing 0.75 wt pct 0 and 1.0 wt pct Ni with tantalum contents from 19 to 85 at. pct often contain a lamellar or cellular precipitate after annealing above 1400°C. This precipitate is very similar to that reported by pollack,12 Ralls," and Donlevy17 for the Ni-Zr system. In the present investigation, a wider variety of experimental techniques and improved alloy purity were applied to the resolution of errors in diagrams for this system as they now appear in the literature. New results have been obtained in the areas of alloy homogeneity and purity. Errors in the common techniques of direct melting observation in binary alloys have been demonstrated. In the commercially important high-tantalum region, the more accurate metallographic method of solidus determination has been employed. EXPERIMENTAL PROCEDURE Nominal analyses of the materials employed are given in Table I. The zirconium was low hafnium reactor grade iodide crystal bar, and the tantalum was in the form of high-purity sheet. Powders were impossible to use because of gas content. Alloys were melted on a water-cooled copper hearth, with a thoriated tungsten-tipped nonconsumable electrode in 2/3 atm of Zr "gettered" argon. Alloys were

Jan 1, 1963

By Thomas C. Wilder

Jan 1, 1965

By J. Geertsma, F. de Klerk

During the hydraulic fracturing treatment of an oil or gas well the liquid pressure in the borehole is increased until tensile stress in the surrounding rock exceeds tensile strength. Once a tensile fracture is initiated, it is penetrated by liquid from the borehole and fracture propagation under continuous hydraulic action takes place. The fracturing liquid carries a propping agent to ensure a highly permeable flow channel after pressure release. Field results range from failure to obtain increased production to outstanding success. In all cases, however, it unfortunately remains uncertain whether the values chosen for the operational parameters, such as injection rate, pumping time and fluid viscosity, were in fact the ideal ones. Though experience provides a lead, a more satisfactory way to predict results would seem to be to subject the fracture propagation process to a theoretical analysis that (1) makes the maximum use of the relevant physical information and (2) so simplifies the resulting calculations that the field engineer gets practical data that he can handle comfortably. We are attempting here to do this in connection with the prediction of fracture width and areal extent before pressure release. What remains of the fracture afterwards depends on the distribution of the propping agent between the fracture walls, and that is a separate story. Idealization of the Problem To keep the problem tractable, a number of simplify- ing assumptions have had to be made: 1. The formation is homogeneous and isotropic as regards those of its properties that influence the fracture-propagation process. 2. The deformations of the formation during fracture propagation can be derived from linear elastic stress-strain relations. 3. The fracturing fluid behaves like a purely viscous liquid; i.e., any peculiar flow behavior due to the addition of gelling agents or other additives is neglected. Moreover, the effect of the propping agent distribution on the distribution of fluid viscosity in the fracture is not taken into account. 4. Fluid flow in the fracture is everywhere laminar. 5. Simple geometric fracture-extension patterns are assumed — either radially symmetrical propagation from a point source (Fig. 1A) or rectilinear propagation originating from a line source (Fig. 1B). In the first case the periphery of the fracture is circular, in the second case it is rectangular. 6. A rectilinear propagation mode can be accomplished only by injection over a large perforated interval, thus forming a line source. Such a rectilinear fracture must therefore be located in the vertical plane. A circular propagation mode might be expected from injection through a narrow band of perforations. This forms a point source. Because gravity effects are excluded from our considerations, the fracture propagation plane may in this case assume any angle with respect to the wellbore as far as the

Jan 1, 1970

By C. O. Tarr, G. V. Smith, R. F. Miller

METALLURGISTS have long recognized that the Fe3C type of carbide is not a stable phase in steel and that, given sufficient time, it will decompose with formation of graphite, at least at temperatures below about 2050°F.1 This slow graphitization has never been of much concern to users of hypoeutectoid steels, for in such steels it occurs only during prolonged exposure at elevated temperature. In 1935, Kinzel and Moore2 reported complete graphitization of the carbide of a 0.1 5 per cent carbon steel that had been in senrice for about 26,000 hr. at a temperature of about 1100° to 1200°F. In discussing this paper, both Mathews and Sauveur reported graphitization of slightly hypereutectoid steels. In an extensive investigation of graphitization of high-purity iron-carbon alloys, Wells1 produced graphite at 7o0°C. (1290°F.) in an alloy containing as little as 0.13 per cent carbon, and showed that graphite may precipitate either directly from austenite or from decomposition of Fe3C, also that the rate of graphitization tends to increase with increase of temperature, at least up to a certain point, and with the presence of graphite nuclei. Jenkins, Mellor and Jenkinson,3 studying the structural changes in carbon steels ranging from 0.17 to 1.14 per cent carbon during stress-rupture tests at elevated temperature, obsenred graphite in an aluminum-killed 0.40 per cent carbon steel after fracture in 4340 hr. under a stress of 17,900 lb. per sq. in. at 840°F. and in many of the steels after stress-rupture test at 1200°F. Unstressed samples of 0.60, 0.86 and 1.14 per cent carbon steels graphitized almost completely in 360 hr. at 1200°F., while samples of 0.90 and 1.10 per cent carbon steels were somewhat graphitized, and steels containing 0.24, 0.40 and 0.57 per cent carbon showed no sign of graphite. Their results indicate that graphite precipitates the more readily the higher the carbon content, though this tendency is influenced to some extent by deoxidation practice, and that graphitization is accelerated by plastic deformation. In a recent study of the graphitization of 0.4 and 0.6 per cent carbon steel strip, made by M. A. Hughes,4 it was found that at 1200°F. graphite appeared after 72 hr. in aluminum-killed but not in silicon-killed steel, and that the rate of graphitization was increased by slow cooling from 1600°F. and by cold-working prior to annealing. In creep tests of normalized o. I 5 per cent carbon steel killed with 2.5 lb. of aluminum per ton, at the U. S. Steel Corporation laboratory at Kearny, spheroidization and some graphitization were found after 3000 hr. at 1000°F. under a stress as low as 15m lb. per sq. inch.

Jan 1, 1944

By R. Ruka, E. A. Gulbransen

ONE of the interesting questions in the understanding of the reaction of iron with oxygen is the kinetics and the mechanism of the crystal structure changes occurring in the formation and breakdown of the oxide film. In a recent work' the electron diffraction method was applied to the study of the solid phase reactions occurring internally in the oxide film on iron above 570°C and under vacuum conditions. The higher oxides which form under oxidizing conditions are reduced internally by the diffusion of iron into the oxide leaving the bulk of the oxide FeO (wüstite). This paper will ask and consider three questions. These are: (1) What is the nature of the depressed transformation temperature for the Fe3O4 + Fe ? 4Fe0 reaction in very thin oxide films?; (2) What is the mechanism of the forward transformation of Fe3O4 to FeO at or near 570°C?; and (3) What is the nature and mechanism of the slow reverse transformation of FeO to Fe3O4 and Fe below 570°C?. The composition of the oxide as well as its electrical, magnetic, mechanical, and chemical properties depends upon the kinetics of these reactions. Literature Survey The composition of the oxide film on pure iron at temperatures up to 570°C has been studied extensively by the electron diffraction method. Nelson,' Jackson and Quarrell,3 and Gulbransen and Hick-man4 have shown that Fe3O4 and a-Fe2O8 are formed in the temperature range of 225" to 570°C, while y-Fe,O, is most likely formed below 225°C for long oxidation times. In very thin films FeO (wüstite) is found to form at temperatures as low as 400°C, and its existence depends essentially upon the extent of initial oxidation. FeO is not found in the formation of thick films below 570°C. On the other hand X-ray5 and micrographic8 studies show that Fe3O4 may exist as the main com-ponent in thick films up to 650°C, well above the equilibrium temperature for the reaction Fe3O4 + Fe ? 4FeO. The kinetics of the forward and reverse trans-formations of the reaction Fe3O4 + Fe ? 4FeO have not been studied in oxide films. However, analysis of the data of Gulbransen and Hickman4 on the heat-ing and cooling of iron oxide films of known thick-nesses in high vacua shows that the forward reac-tion proceeds rapidly even for a 4000 A film at temperatures of 575" to 600°C. The reverse reaction or decomposition of wüstite (FeO) occurs at tem-peratures below 450°C. Thus, there appears to be a slow process in the decomposition which is in marked contrast to the rapid forward reaction. The decomposition of a bulk sample of FeO free from the metal has been studied extensively by Chaudron, Benard and coworkers using the micro-graphic, X-ray diffraction, and thermomagnetic methods. Chaudron7,8 first observed that the de-composition of FeO (wüstite) below 570°C occurs by the reaction 4FeO ? Fe3O4 + Fe. Later work by Chaudron and Forestier5 showed that the rate of de-

Jan 1, 1951