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By Paul D. Merica, W. A. Mudge

One of the most prominent features of our present-day industrial development is the ever-increasing demand put upon materials of construction. Engineering ingenuity, within the past 25 years, has been unusually active, and in some fields at least engineers frankly say that engineering design has progressed as far as the limitations imposed by the properties of the present materials of construction will permit. Consequently, they are today demanding improvement in their working materials and seeking new ones, through the aid of which the present limitations of design may be overcome. The activity of this search is evident in all fields, but it is particularly so in that of structural materials required to be resistant to corrosion. The corrosion resistance of metals and alloys is never absolute and all-inclusive; a particular alloy will withstand some corrosive conditions well and fail utterly under others. Furthermore, other properties, physical and mechanical, required in conjunction with corrosion resistance vary considerably for different commercial applications. One wants a soft, ductile sheet metal resistant to atmospheric corrosion; another, a high-strength alloy resistant to sulfuric acid. The last decade has witnessed active and definite progress in the development of high-strength, corrosion-resisting alloys. In June, 1924, a symposium by the American Society for Testing Materials, on Corrosion-resistant, Heat-resistant and Electrical-resistance Alloys, disclosed no less than 60 commercial alloys the properties of which were described as being suitable for industrial service where corrosion resistance was a feature. Today the number of these alloys has been doubled, at least. In addition, economy in design and construction through decreased weight has given considerable impetus to the improvement of alloys of which the mechanical propprties may be improved by heat-treatment.

Jan 1, 1935

The following discussion was held on August 2.2, 1927, during the meeting of the Institute at Salt Lake City. It. IIIatch, Garfield, Utah.—The object of the meeting, I belicve, is to determine the proper chemical composition to insure long wear of a ball in a mill. This might also apply to rods. I feel that there is only one way of determining accurately the wearing qualitites of balls in mills, and that is by actually wearing out 400 or 500 tolls of different kinds of balls. Two things add to the wearing qualities of a ball: (1) the tenacity, with which the particular particles of iron or steel are cemented together; (2) the individual hardness of each partiele. My cxperience is that a ball that has a Brincll of 550 to 650 will give comparatively long life. There is considerable difference of opinion as to the best steel and iron alloys neressary to produce a satisfactory grinding ball. Some favor chrome, somr manganese and some nickel. Personally, I believe cast iron alloyed with chrome makes the best ball for small sizes; for large sizes (31/2 in. arid up) steel alloyed with mangancse is best. L. O. Howard, Pullman, Wash.—How would this method apply to hning? A. Kissock, New York, N. Y.—I do not subcrribe to that exactly. As I am connected with the Climax Molybdenum Co. you would hardly expeet me to. We have been much interested in trying to work out this grinding-ball problem and have spent a, great deal of thought and effort on it. As we are associated with the American Metal Co. and have a number of Proprrties of our own, we are in poaition to try our ideas on ourselves first. We have tried different compositions, but, have not done anything very remarkable with them yet,, except that we have been able to say that the combination of chrome and molybdenum has given the best, wearing ball. Mr. Hatch feels that iron is the best. medium for grinding, hut since toughtiess as well as hardness is a factor in wearability we feel that a well made steel is better for this purpose. Another difficulty with cast, or chilled, iron is lack of uniformity front day to day or from heat to heat, and the impossibility of protlucing balls free from blow or shrinkage holes which matcrially affect their life. If cast iron is made hard it becomes brittle and lacks strctc11 or toughness. This prevents its use in the larger sizes, aS break:lgc, is a sorious hantlic:~p to efficiency. We have trirtl hard and brittle balls and softer but very tough balls and have proved that maximum hardness, with sufficient toughuess to prevent hrcakagv, is the most important factor. in resistarnce of a steel to abrasion. It is well known that. chromium is one of the best hardening agencies for cither iron or. steel; and molybdenum is recognized as an clerment capable of introducing tonghness. In other words, the proper combination of chromium and molybdenum permits unusual hadness with still sufficient touglmess to stand up under severest impact. It is yet too early to give any actual mill results of this new Combination and though we are proving our ideas at our own properties we have to depend on others to help us make the data more general and more worth while and would like to get some testa 206

Jan 1, 1928

By E. R. Macgregor, J. Halpern

The kinetics of the reduction of cupric salts in aqueous solution by molecular hydrogen to metallic copper are described. The rate of reduction appears to be homogeneously determined and shows a marked inverse dependence on the hydrogen-ion concentration. Precipitation of copper is more rapid and complete in sulfate than in per-chlorate solution. A mechanism is proposed which accounts for this behavior. IN recent years a number of important hydro-metallurgical processes have been developed in which metallic salts in aqueous solution are reduced by gaseous hydrogen, usually at elevated temperatures and pressures, and thereby precipitated either in metallic form (e.g. Ni, Co, Cu) or as an oxide or salt of lower valence (e.g. VO, and VA).1 ; In connection with applications such as these, most of which involve heterogeneously catalyzed reactions, recent demonstrations"-" that salts of certain metals, e.g., Cu", Ag' , Hg" , and Hg,+ can activate molecular hydrogen homogeneously and thus catalyze hydrogenation reactions in aqueous solution, are of considerable interest. For example, cupric salts catalyze the otherwise slow homogeneous reduction of dichromate and ceric salts by hydrogen, i.e. Cr,O; + 3HL. + 8H1 ? 2Cr'- -- 7H,O [1] 2Ce ' ! H.. ? 2Ce" | 2H . [2] In perchloric-acid solution, where Cu" is not appreciably complexed, the kinetics have been found" " to be of the form -d [H,] _- k,[HJ [CU"]' dt -LCu+' l+ (k ,/k,) [H] [3] where, K = 1x10"' exp [—26,600/RT] 1, mole-' min-' ... [4] and (k ,/k,) - 0.25 at 110°C. This kinetic behavior suggests that the reaction proceeds by a mechanism involving the following sequence of steps kt Cu" +H1CuH' 4-HA [51 k., CUH + CU" ? + 2Cu f H' [GI 6Cu'+ Cr,07 + 14H'+ 2Cr- (¦ 7H,O + 6Cu" ['i] fast The catalytic activities of the undissociated cupric-sulphate and cupric-acetate complexes are somewhat greater (by factors of 6.5 and 120, respectively) than that of the simple hydrated Cu" ion.'" These considerations suggest that, in contrast to the other hydrometallurgical hydrogenation reactions, referred to previously, reduction of cupric salts in aqueous solutions by molecular hydrogen, should proceed homogeneously, and in the absence of an extraneous catalyst. This has already been demonstrated" for acetate-buffered solutions where the product of the reaction is a precipitate of cuprous oxide (Cu,O). In the present paper, an investigation of the reduction of cupric salts in perchloric-acid and sulphuric-acid solutions, leading to the precipitation of metallic copper, is described. Some results for the sulphate system, which is of considerable hydrometallurgical interest, have been reported previously by Ipatieff",' " and by Schaufel-berger' but these do not give a quantitative account, of the kinetics and mechanism of the reaction. Experimental The reduction experiments were conducted in the 1-gal, titanium-lined autoclave described in connection with earlier related investigations," " and using a similar procedure. The solutions were made up by dissolving known amounts of CP grade Cu(ClO,), and HC10, (or CuSO, and HISO,) in dis-tilled water. While in the autoclave, the solution was stirred and maintained at a constant temperature (±loc) and under a constant partial pressure of hydrogen gas. It was ascertained that the agitation (provided by two 3-in., four-bladed stirrers, rotating at 900 rpm) was adequate so that at no time was the rate of reaction limited by solution of hydrogen. During each experiment, samples of the solution were withdrawn periodically, allowed to cool, and the concentration of copper remaining in solution was then determined electrolytically. Some Cu' is formed during the reaction, but undergoes disproportionation when the solution is cooled to room temperature. For purposes of kinetic calcula-

Jan 1, 1959

By Frederick M. Becket, Russell Franks

WideSpread experimentation has been conducted in recent years to devise a means of preventing intergranular corrosion in austenitic chromium-nickel steels of the 18 per cent chromium-8 per cent nickel type. Additions of titanium to these steels have been used commercially to overcome this dificulty, as advocated by Krupp of Germany, and the latest literature reference concerning improved details of this method is the article by Bain, Aborn and Rutherford.' Extensive work by the present authors has shown columbium also to be a particularly valuable agent for inhibiting intergranular corrosion. This paper does not deal with steels that are largely or wholly austenitic; it is limited to a discussion of the results obtained through the use of titanium and columbium in plain high-chromium steels. For many years titanium has been used commercially by some steelmakers as a cleanser, and to a lesser extent as a hardener, but then in greater percentages. The results of the work to be described disclose that titanium and columbium in proper Proportions act as effective softeners in the high-chromium steels. It is well known that chromium intensifies the hardening effect of carbon in steel; it imparts pronounced air-hardening properties within a rather wide range of chromium content; it provides increased ductility in steels of given strength and hardness; and it enhances resistance to corrosion and oxidation at elevated temperatures to a marked degree. However, in applications requiring a combination of some of these valuable properties great hardness is frequently a detriment rather than a merit. When the objective is a soft and ductile steel having optimurn corrosion resistance, the producer strives for a carbon content as low as commercially practicable. Despite these efforts some of the commercial high-chromium steels low in carbon present considerable difficulties during production, owing to their air-hardening properties, and in consequence the economic result is not favorable. A good example is found in the 5 to 6 per cent chromium steels employed chiefly in the oil-cracking industry. Sleels

Jan 1, 1934

By H. C. Johnson, J. K. Elliott

One of the primary requirements for successful operation of an enriched gas-drive project is to control the composition of injection gas. This can become a serious and difficult problem, particularly in cases where the enrichment material is being furnished from a number of field -produced gas streams. It is possible to effect control of the injection gas composition through frequent or continuous sampling; however, this can be extremely costly and, in many cases, impractical due to laboratory requirements of time. Another alternative would be to provide a calculation technique which would be flexible and sufficiently accurate to predict composition of the liquid and gas streams of interest at any point in the system. The purpose of this paper is to discuss a technique that was used successfully on an operating enriched gas-drive project for developing information which could be used for controlling composition of the injected gas. FIELD OPERATIONS The particular field (hereafter called Example field) in the example operation being discussed is composed of four oil reservoirs (A. B, C and E) and one gas condensate reservoir (D). Casinghead gas from the oil reservoirs and gas from the gas condensate reservoir are gathered through a field gathering system as shown in Fig. I for injection into Reservoir C. The gas mixture which is recovered from the five reservoirs for injection purposes is composed of gases liberated in 19 individual separators, each operating at a separate temperature and pressure. PROPOSED CALCULATION TECHNIQUE It is well known that vapor-liquid equilibrium calculations in general use throughout the petroleum industry can be used to predict reliably the phase behavior of hydrocarbon mixtures, particularly at pressures less than 1,000 psig. It is then a simple matter to account for the material on a ComPonent basis by m''ing flash and material balance calculations at each separation point in a hydrocarbon system. Accordingly, it was proposed to use vapor-liquid equilibrium and material balance cal- culations with a medium-sized electronic digital computer as a basis for developing a control procedure for use in controlling injection gas composition in the enriched gas-drive project. Although the approach is a simple one, the numerous vapor-liquid equilibrium calculations involved make the problem laborious; in this particular case, it would have been impractical to make sutficiently complete analysis without the aid of digital computing equipment. SAMPLING AND VERIFICATION OF CALCULATION PROCEDURE To obtain representative gas and liquid stream samples and to provide a quantitative measure of overall system Performance for comDarative purpLses, a thorough test of the field and plant system was conducted in the summer of 1957. Oil production at each battery was sta-

By John Chipman, Theodore B. Winkler

IN order to understand more fully the complexities of the reactions occurring between the liquid steel and the slag in the basic open-hearth steelmaking furnace, investigations in this country and abroad have turned to laboratory equilibrium studies. This paper is one of a series of reports on investigations being conducted at the Massachusetts Institute of Technology. The experimental work was completed early in 1942. The slag systems found in the basic open hearth are very complex, being made up of at least eight major components and as many others whose effect might be classified as minor. The first two papers of the series, by Fetters and Chipman,l,2 as well as the paper by Taylor and Chipman,3 dealt with the simplest possible slag system that would resemble those found in the basic open hearth-the slag system consisting of CaO-MgO-SiO2-FeO. (Taylor's rotating induction furnace eliminated the necessity of contamination of the slag by MgO.) Having arrived at some reasonable conclusions regarding the physical chemistry of the reactions between molten iron and the simple slags at equilibrium, the next step was to investigate more complex slag systems. The major purpose of the present investigation was to determine what factors control the distribution of phosphorus between molten iron and the more complex basic slags at equilibrium, and to what extent these factors are influential. The slags used contained CaO, MgO, Si02, FeO, Fe203, P205, MnO, A1203 and CaF2, but not all of the slag samples contained all of these components at one time. REVIEW OF LITERATURE Although a number of interesting papers have been published on the subject of dephosphorization of an iron bath, there are as yet no results from laboratory studies that give thoroughly reliable information on the dephosphorization reaction. Even for the supposedly simple Fe-O-P system involving iron-phosphorus melts and iron oxide-iron phosphate slags, the experimental results are contradictory and no formulas have been established that adequately fit the equilibrium conditions. The Fe-O-P system has been studied by Schackmann and Brings4' von Samson-Himmelstjerna,5 Oelsen and Maetz,6 Bischof and Maurer,7 Diepschlag and Schürmann,8 and Herty,9 and the results of their investigations appear in Table I. A number of different equilibrium constants and distribution ratios

Jan 1, 1946

By Burt Hartmann

The nation's ever-expanding construction and mining activity has placed an increasing demand upon engineers and geologists to design and construct stable slopes in earth materials-soil and rock. Man's attempt to handle these slope stability problems has been based primarily on practical experience and the resulting theories formulated to explain the phenomena. Too many instances occur when man is faced with a slope stability problem that has not yet been experienced and doesn't lend itself to solution by any existing theory. At this point he must extend himself in using his engineering judgment to arrive at a reasonable and safe design. As past experience has shown, all of the "safe designs" are not really safe. Sometimes they result in embarrassing failures. Measurements provide the key to understanding and controlling natural phenomena. We cannot hope to gain control of the slope stability problem until we understand the causes of slope failure, their behavior with respect to time and their relative magnitudes. Measurements required for an adequate definition of any slope problem must be of the highest reliability because of the importance of decisions which must be based on them. For this reason, direct measurements of movement, shear strength, water pressure, etc. of the unstable mass are preferable to indirect measurements of other physical properties. Movement instruments which can be positioned inside of the slope mass (within boreholes) are among the most useful in diagnosis and/or monitoring of slope movements. The higher the sensitivity and il-measurement precision possible with borehole instruments, the quicker the required information can be obtained and the more exactly may hazardous conditions be observed. A high density of measuring points in a single drill hole is deemed essential for diagnostic purposes. Behavior gradients may thus be obtained. The Pressure Meter (Fig. 1) can be used to measure a relative strength

Jan 1, 1968

By Leonard D. Jaffe

In recent years, the advantages of tempered martensite as a microstructure for steel parts have been well established. For parts that must not fracture brittlely when loaded at high rates, at low temperatures, or under conditions of combined stress, tempered martensite is especially desirable. One of the factors that determine whether a steel part will have a martensitic structure after heat treatment is the hardenability of the steel. Despite the large amount of recent research, there are still many unsettled basic questions concerning hardenability and its relation to chemical composition, and, indeed, considerable disagreement among investigators in the field. Much of the uncertainty that beclouds the existing knowledge of hardenability arises from the fact that hardenability is still a wholly empirical concept, and has not been quantitatively related to the more fundamental knowledge of isothermal decomposition of austenite. Hardenability is, essentiaily, a measure of the time required for small percentages of austenite to decompose, during continuous cooling, to pearlite, bainite, proeutectoid ferrite, or proeutec-toid carbide. In the practical heat-treat- ment of steel, also, the decomposition of austenite is usually not isothermal but rather during cooling, or, in general, is not at a single constant temperature. Thus, both hardenability and practical heat treatment involve anisothermal decomposition of austenite. In a previous publication1 the author and his collaborators outlined the principles that govern the relations between isothermal and anisothermal decomposition of austenite, and reviewed the experimental information available in 1945. To avoid repetition, familiarity with that article (Paper I) will be assumed, and attention given primarily to work carried out or published since 1945. The method generally employed was explained in Paper I: anisothermal transformation is studied through investigation of the effect of holding austenite at one temperature upon its subsequent decomposition at another temperature. Both temperatures are below the stability range of the austenite. This paper is confined to studies in which only a small amount of transformation occurred at the first temperature. This is the only case of importance in practical heat treatment when an essentially martensitic structure is sought. Materials and Procedure It was necessary to use different steels for the studies involving proeutectoid ferrite and for those involving proeutectoid carbide, beeause the two constituents have not been found to form in the same steel. Several steels were tried and rejected

Jan 1, 1949

By Leonard D. Jaffe

In recent years, the advantages of tempered martensite as a microstructure for steel parts have been well established. For parts that must not fracture brittlely when loaded at high rates, at low temperatures, or under conditions of combined stress, tempered martensite is especially desirable. One of the factors that determine whether a steel part will have a martensitic structure after heat treatment is the hardenability of the steel. Despite the large amount of recent research, there are still many unsettled basic questions concerning hardenability and its relation to chemical composition, and, indeed, considerable disagreement among investigators in the field. Much of the uncertainty that beclouds the existing knowledge of hardenability arises from the fact that hardenability is still a wholly empirical concept, and has not been quantitatively related to the more fundamental knowledge of isothermal decomposition of austenite. Hardenability is, essentiaily, a measure of the time required for small percentages of austenite to decompose, during continuous cooling, to pearlite, bainite, proeutectoid ferrite, or proeutec-toid carbide. In the practical heat-treat- ment of steel, also, the decomposition of austenite is usually not isothermal but rather during cooling, or, in general, is not at a single constant temperature. Thus, both hardenability and practical heat treatment involve anisothermal decomposition of austenite. In a previous publication1 the author and his collaborators outlined the principles that govern the relations between isothermal and anisothermal decomposition of austenite, and reviewed the experimental information available in 1945. To avoid repetition, familiarity with that article (Paper I) will be assumed, and attention given primarily to work carried out or published since 1945. The method generally employed was explained in Paper I: anisothermal transformation is studied through investigation of the effect of holding austenite at one temperature upon its subsequent decomposition at another temperature. Both temperatures are below the stability range of the austenite. This paper is confined to studies in which only a small amount of transformation occurred at the first temperature. This is the only case of importance in practical heat treatment when an essentially martensitic structure is sought. Materials and Procedure It was necessary to use different steels for the studies involving proeutectoid ferrite and for those involving proeutectoid carbide, beeause the two constituents have not been found to form in the same steel. Several steels were tried and rejected

Jan 1, 1949

By Charles White Merrill

Mankind's progress is measured in minerals. Man's emergence from prehistory is marked by passage through a Stone Age and a Bronze Age and into the present era, sometimes called the Iron Age or the Age of Metals. With the evolution of civilization and the development of a modem industrial economy, minerals become more and more important. Structures, roads, and machines are built largely of minerals; the energy to heat the structures and to drive the machines is mostly mineral; agricultural fertility is maintained by mineral fertilizers and water; and military strength is provided by fortresses, armaments, and munitions, largely of mineral origin. Thus in the material world, in the productivity of the economy, access to minerals has paramount importance. Every evidence indicates increasing dependence on minerals in the modem economy, particularly on the mineral fuels as energy sources to provide the power base for advancing industrialization. Both the total and the per capita consumption of almost every mineral is increasing in the industrialized nations. Moreover, nations with predominantly agrarian economies call themselves underdeveloped and universally strive to industrialize. Most mineral consumption trends in the more advanced economies have been greatly exceeding population growth-which itself has been advancing at an accelerating rate--and sometimes have surpassed the growth in real income. Some minerals have only recently been adopted or grown to importance in use. Titanium as a metal appeared as a commercial product only in 1948, and even coal seriously displaced wood as a source of heat less than two centuries ago. On the other hand, minerals have always played an important role in construction. The prehistoric megaliths that form the dolmens of Salisbury Plain are stone; the pyramids are andesite faced with limestone; and many other ancient structures are built of mineral materials. In modem times the whole course of architecture has been redirected by new building materials, mostly mineral. Most conspicuous is the sky-

Jan 1, 1959

By M. Cohen, C. Wagner, J. E. Reynolds

If the total volume of a diffusion couple changes during the diffusion, the measurement of distance becomes ambiguous. Use of distance parameters as suggested by Hartley and Crank is discussed. For small concentration differences, the standard form of Fick's second law is retained with conventional length units and the in- terdiffusion coefficient D. It is shown how D can be calculated from experiments involving large concentration differences and analyzed in terms of distance parameters. 'The merits of incremental diffusion couples involving small concentration differences are emphasized. THE conventional form of Fick's second law for one-dimensional diffusion of component B in a binary solution of A and B is where c, is the concentration of component B; x, the distance; t, the time; and D, the interdiffusion coefficient which may depend on ca. Hartley and Crank' have pointed out that Eq. 1 applies only if the total volume of the diffusion couple does not change during the diffusion process; otherwise, the definition of x becomes ambiguous. No change in total volume takes place if the specific volume of the solution is a linear function of the weight fraction Wb, or if the molar volume is a linear function of the mol fraction N. In some alloys, however, these relationships do not hold, and then it is necessary to introduce a modified measure of distance, 4 in order to retain the general form of Eq. 1. The application of Hartley and Crank's suggestions to diffusion in alloys has been discussed by Wagner.' Relation Between Measure of Distance and Units of Concentration The definition of [ depends on the choice of units for the concentration c,, as follows: 1—If the concentration ca is measured as the weight fraction W, (or weight percent), [ = 5, has to be defined so that equal increments of contain equal increments of mass m of the solution, e.g., dm = pSdx = Sdw [2] where p is the local density of the solution, and S is the cross-sectional area in sq cm which is taken to be constant in this problem of one-dimensional diffusion." * da Silva and Mehla have demonstrated the constancy of the cross-sectional area in the usual type of diffusion couple. However, experiments involving diffusion into thin wires4, 5 may exhibit changes in cross-sectional area, and therefore are excluded from the present treatment. Thus and the unit of is gram per sq cm instead of cm. 2—If the concentration c, is the mol fraction N, must be defined so that equal increments of contain equal numbers of mols of solution, e.g., dn= (S/V)dx= Sd [41 where V is the local molar volume of the solution. Thus dt, = dx/V [51 and the unit of is mols per sq cm. 3—If, as may be advisable in the case of interstitial solutions, the concentration C is measured in terms of the molar ratio of components B and A (c,, = Y, = nH/nA, where n and nl are numbers of mols of B and A), = Y has to be defined so that equal increments of contain equal numbers of mols of A, e.g., dnA= (NAS/V)dx = Sdf [6]

Jan 1, 1954

By Immo H. Redeker

Through close cooperation with geophysical and geological test work by Texas Gulf Sulphur Co. in Beaufort County, the Asheville Minerals Research Laboratory assisted in the evaluation of North Carolina's most valuable mineral resource, the Pungo River phosphate deposit. After a core evaluation study, the flotation process for the concentration of North Carolina phosphate was demonstrated in a 500-lb per hr pilot plant in Asheville. Tonnage samples of phosphate concentrate were produced for customer evaluation in the United States, Europe, and the Far East. Plans for a larger pilot plant to be erected at the plant site at Lee Creek were prepared for TGS. The larger pilot plant was operated by TGS in conjunction with a test dredging operation which led to the adoption of a dragline dry mining method to move 90,000 tpd of material for the production of 10,000 tpd of phosphate concentrate in the all-flotation phosphate concentrator. Calcining, dry grinding, and byproduct studies complimented the construction of one of the world's largest and most modern fertilizer raw-feed complexes on the eastern North Carolina seaboard.

Jan 1, 1972

By R. S. Dean

THE commercial production of electrolytic manganese on a small scale commenced in 1939. The writer made a short report on the progress of production and utilization in MINING AND METALLURGY for January 1941. Progress during the last two years, naturally, has been more rapid. In June 1940, Congressman (now Senator) Scrugham presented a proposal to Congress for an appropriation authorizing erection of a pilot plant for "the production of metallic manganese by electrolytic or other means." As a result of this, a pilot plant, having a capacity of a few hundred pounds per day was built at Boulder City, Nev. Subsequent appropriations permitted expansion of the plant to about a ton per day. Much has been learned in this plant about electrolytic manganese, and the product even in its small way has found war uses of considerable importance. Meanwhile, the Knoxville plant of the Electro Manganese Corporation, the sole commercial producer, was expanded to about 4 tons per day to supply needed material for the war program. Other proposals for commercial plants have not been favorably received by the War Production Board. The Bureau reported on one such proposal by the American Alloys and Chemical Corporation. PRACTICE AT BOULDER CITY The present practice, as carried out at Boulder City, which is being described in more detail in a current paper by the Bureau staff at Boulder City, starts with a manganese dioxide ore containing about 20 per cent manganese. Currently this ore comes from the Three Kids deposit near Las Vegas. The steps for the production of electrolytic manganese, in general, are as follows: I. The manganese in the ore is reduced to MnO. 2. The MnO is dissolved from the ore in spent electrolyte, which contains about 38 to 47 grams per liter of free sulphuric acid, 135 grams per liter of ammonium sulphate, and 10 to 12 grams per liter of Mn as sulphate. In the leaching step the manganese is built back up to 32 to 36 grams per liter of Mn as sulphate; the pH is adjusted to neutral by means of gaseous ammonia and passed through thickeners. 3. The electrolyte is purified by adding H2S, which precipitates the heavy metals. After filtering, ferrous sulphate is added to the solution and oxidized with air and the solution is filtered and clarified on a precoat filter. 4. The purified catholyte is electrolyzed in a diaphragm cell using stainless-steel cathodes and lead-silver anodes. The current density is about 45 amp. per sq. ft. Current efficiencies of 60 to 65 per cent are regularly obtained.

Jan 1, 1944

By R. S. Dean

The commercial production of electrolytic manganese on a small scale commenced in 1939. The writer made a short report on the progress of production and utilization in Mining and Metallurgy for January 1941. Progress during the last two years, naturally, has been more rapid. In June 1940, Congressman (now Senator) Scrugham presented a proposal to Congress for an appropriation authorizing erection of a pilot plant for " the production of metallic manganese by electrolytic or other means." As a result of this, a pilot plant, having a capacity of a few hundred pounds per day was built at Boulder City, Nev. Subsequent appropriations permitted expansion of the plant to about a ton per day. Much has been learned in this plant about electrolytic manganese, and the product even in its small way has found war uses of considerable importance. Meanwhile, the Knoxville plant of the Electro Manganese Corporation, the sole commercial producer, was expanded to about 4 tons per day to supply needed material for the war program. Other proposals for commercial plants have not been favorably received by the War Production Board. The Bureau reported on one such proposal by the American Alloys and Chemical Corporation. Practice at BouldeR City The present practice, as carried out at Boulder City, which is being described in more detail in a current paper by the Bureau staff at Boulder City, starts with a manganese dioxide ore containing about 20 per cent manganese. Currently this ore comes from the Three Kids deposit near Las Vegas. The steps for the production of electrolytic manganese, in general, are as follows: 1. The manganese in the ore is reduced to MnO. 2. The MnO is dissolved from the ore in spent electrolyte, which contains about 38 to 47 grams per liter of free sulphuric acid, 135 grams per liter of ammonium sulphate, and 10 to 12 grams per liter of Mn as sulphate. In the leaching step the manganese is built back up to 32 to 36 grams per liter of Mn as sulphate; the pH is adjusted to neutral by means of gaseous ammonia and passed through thickeners. 3. The electrolyte is purified by adding H2S, which precipitates the heavy metals. After filtering, ferrous sulphate is added to the solution and oxidized with air and the solution is filtered and clarified on a precoat filter. 4. The purified catholyte is electrolyzed in a diaphragm cell using stainless-steel cathodes and lead-silver anodes. The current density is about 45 amp. per sq. ft. Current efficiencies of 60 to 65 per cent are regularly obtained.

Jan 1, 1944

By R. S. Dean

The commercial production of electrolytic manganese on a small scale commenced in 1939. The writer made a short report on the progress of production and utilization in Mining and Metallurgy for January 1941. Progress during the last two years, naturally, has been more rapid. In June 1940, Congressman (now Senator) Scrugham presented a proposal to Congress for an appropriation authorizing erection of a pilot plant for " the production of metallic manganese by electrolytic or other means." As a result of this, a pilot plant, having a capacity of a few hundred pounds per day was built at Boulder City, Nev. Subsequent appropriations permitted expansion of the plant to about a ton per day. Much has been learned in this plant about electrolytic manganese, and the product even in its small way has found war uses of considerable importance. Meanwhile, the Knoxville plant of the Electro Manganese Corporation, the sole commercial producer, was expanded to about 4 tons per day to supply needed material for the war program. Other proposals for commercial plants have not been favorably received by the War Production Board. The Bureau reported on one such proposal by the American Alloys and Chemical Corporation. Practice at BouldeR City The present practice, as carried out at Boulder City, which is being described in more detail in a current paper by the Bureau staff at Boulder City, starts with a manganese dioxide ore containing about 20 per cent manganese. Currently this ore comes from the Three Kids deposit near Las Vegas. The steps for the production of electrolytic manganese, in general, are as follows: 1. The manganese in the ore is reduced to MnO. 2. The MnO is dissolved from the ore in spent electrolyte, which contains about 38 to 47 grams per liter of free sulphuric acid, 135 grams per liter of ammonium sulphate, and 10 to 12 grams per liter of Mn as sulphate. In the leaching step the manganese is built back up to 32 to 36 grams per liter of Mn as sulphate; the pH is adjusted to neutral by means of gaseous ammonia and passed through thickeners. 3. The electrolyte is purified by adding H2S, which precipitates the heavy metals. After filtering, ferrous sulphate is added to the solution and oxidized with air and the solution is filtered and clarified on a precoat filter. 4. The purified catholyte is electrolyzed in a diaphragm cell using stainless-steel cathodes and lead-silver anodes. The current density is about 45 amp. per sq. ft. Current efficiencies of 60 to 65 per cent are regularly obtained.

Jan 1, 1944

By Frederick Laist

I. EXPERIMENTAL FLOTATION CONCENTRATION INTRODUCTION EARLY in 1914 it was decided to test, on a fairly large scale, the treatment by flotation of Anaconda slime and mill tailing. For this purpose a standard-type Minerals. Separation machine was installed at the Washoe Reduction Works during May and June, 1914. This was followed by the. installation of a full-size Callow pneumatic machine plant. Experiments were also made, on a smaller scale, with the Froment, the Towne, the Fields, and the Anaconda flotation machines. The last-named machine was developed at this plant. In addition to the tests made in the standard-type Minerals Separation machine some tests were made using a Minerals Separation machine of the sub-aeration type. During the series of experiments a large variety of oils was tested. Experiments were also conducted using both round-table feed and tailing to determine whether it would be better to displace the round tables by flotation for the treatment of the slime, or to supplement the round tables by flotation of the round-table tailing. A series of tests was also made on the treatment of the mill tailing by grinding followed by flotation to determine the relative merits of flotation and leaching for the treatment of this product. In addition, flotation tests were made on mixtures of mill tailing and slime. The round-table feed referred to above is the total slime from the mill. It contains about 35 per cent. colloidal solids and approximately 90 to 95 per cent. of the total solids will pass through 200 mesh (0.067 mm.). It assays from 2.3 to 2.6 per cent. Cu. The mill tailing referred to above is the total discard from the mill, exclusive of the slime. It is all finer than 2 mm. and about 90 to 95 per cent. will remain on 0.25 mm. It assays about 0.60 per cent. Cu. A brief summary of the experimental flotation results follows:

Jan 3, 1916

By J. B. Cheatham, R. B. Paslay

Rock stresses and steady-state flow rates induced by the pressure gradient associated with the flow of formation fluid into a borehole have been analytically determined for a permeable, elastic material saturated with an incompressible fluid. In this analysis, the material properties and loading are considered to be symmetric about the axis of the borehole and independent of axial position. For Case I the material is assumed to have uniform permeability in the radial direction, whereas for Case 11 the permeability is assumed to have been reduced in a localized region adjacent to the hole by either normal well completion and production operations or deliberate plugging during air drilling. Results of a numerical example indicate that, in the absence of plugging, the rock shear strength must be approximately two-thirds the formation fluid pressure in order to prevent rock failure. The required rock strength is high for small radial zones of plugging and decreases as the region of reduced permeability becomes larger; however, a depth of plugging can be reached beyond which there is no real gain in strength, although the flow rate can be further reduced. INTRODUCTION During normal production of oil from a well, it is often desirable to increase the production rate of the formation fluid by increasing the pressure gradient through the formation adjacent to the borehole. Depending upon the magnitude of this pressure gradient and strength of the rock material, this production-rate increase can cause sloughing of the hole wall. In many cases, the production - rate increase can result in excessive sand production, increased wear of production equipment, lost production time and expensive workover jobs. In addition, the phenomenon of increased rock bit penetration rate with the use of a gaseous instead of a liquid drilling fluid has been observed in oilfield drilling operations and experimentally demonstrated by various investigators for several years. The improvement obtained by employing this technique can be quite significant and offers apromising method for reducing drilling costs. However, air drilling is currently limited to geographical locations where high-capacity water-bearing formations are not encountered. This limitation has prevented widespread adoption of air-drilling techniques, because the water influx into the borehole interferes with efficient removal of the drilling cuttings and usually results in a condition such that the bit becomes "balled-up" or stuck in the hole. In an attempt to remove the water - intrusion limitation from air drilling, various chemical and mechanical water shut-off methods have been proposed. Goodwin and Teplitzl suggested one such proposal whereby the permeability of the water-bearing rock structure was reduced in the vicinity of the borehole. Although the development of a shut-off method based upon this approach would certainly be welcomed by the oil industry, it is conceivable that, under certain conditions of the pressure gradient, strength of the rock material and depth of the modified permeability zone, a stress field can be created that will result in an unstable hole. As part of their study, an analytical solution is given for stresses in an idealized model of a hole and the surrounding rock material. The purpose of the present study is to extend the analysis of Goodwin and Teplitz to gain more insight into the details and consequences of excessive production rates and formation water shut-off. In particular, simplified models of these problems have been analytically examined, which makes possible the evaluation of the type of stress fields that can be anticipated as a result of these production and drilling practices. Both problems solved concern the determination of the steady-state volume flow rate of the formation fluid and the resulting steady-state stress and displacement distribution in a hollow, cylindrical configuration. The cylinder of Case I, corresponding to the production-rate problem, consists of a material with a constant permeability from the inside surface to the outside surface; the cylinder of Case 11, corresponding to the water shut-off problem, consists of a material with a constant permeability from the inside surface to an intermediate concentric cylindrical surface and a second constant permeability from the intermediate surface to the outside surface-

By James F. Kemp

Discussion of the paper of JAMES F. KEMP, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 105, September, 1915, pp. 1801 to 1836. WALLACE E. PRATT, Manila, P. I.-I am glad that Professor hemp has referred to the Philippine ores in his paper, inasmuch as I have had the privilege of examining, in a preliminary way, the ores there. I must say, from the resume given us, that the Daiquiri ores seem to be similar in origin and character to the magnetite-hematite ores in Bulacan Province, Philippines. Professor Kemp has also referred to C. M. Weld's description of the magnetite-hematite ores at Hongkong and to the similarity of these ores to the ores at Daiquiri and to those in Bulacan. There is a minor feature of apparent difference in origin in the Hongkong and Bulacan ores. Mr. Weld believes the iron ores at Hongkong to have resulted from the intrusion of the Hongkong granite, a distinctive rock of wide distribution in the Orient, into sedimentaries which are probably of much greater age than those which have been replaced in part by the ores in Bulacan. Associated with some of the ores in Bulacan and elsewhere in the Philippines there is a granite which may be the equivalent of the Hongkong granite; but the Bulacan ores are not related in origin to the intrusion of this granite, which is clearly older than the ores, but to the later intrusion of dikes and small bodies of basic rocks into the granite and into associated tuffs, breccias, and sedimentaries, including limestone. I gather that the intrusives to which the mineralization is related at Daiquiri are also small in volume and later than larger bodies of associated igneous rocks, from which it would appear that the Bulacan ores are even more closely related to the Daiquiri type than are the Hongkong ores. The deposits in Bulacan are inaccessible and are not large, the largest one containing about 1,000,000 tons, according to an estimate based solely on its outcrop dimensions. Ores of similar character, however, occur in Camarines Province in apparently larger quantity and in a situation on the coast adjacent to deep water.

Jan 12, 1915

By L. L. Gray, D. W. Reed, F. Morgan

A flowMeter has been developed at Gulf Research and Development Co. and tested in the field for measuring the flow of gas in well bores. It has been used in a study of the injection capacity of different horizons in gas injection wells in Oklahoma. The flow sensitive element of the meter is a semi-conductor having a very high temperature coefficient of resistance. Advantages possessed by this meter are the result of that property and the high specific resistance of the element. The instrument possesses a sensitivity considerably higher than any reported previously. In the application described here the element is heated to a temperature considerably above ambient by an electric current, which is supplied by a voltage source at the surface. When fluid flows through the meter the rate of dissipation of heat is increased and the temperature of the element decreases. Because of the negative temperature characteristics of the resistance element such a decrease of temperature will be accompanied by an increase of resistance which, under flow conditions ordinarily found in wells, is of such a magnitude that it can be directly measured or recorded in terms of a change in voltage at the surface. In practice, rate of flow is measured in terms of the drop in voltage in the resistance element. All the metering and control apparatus remains at the surface while the thermal element is lowered into the well on a single conductor cable, consisting of an insulated wire and sheath. The meter is calibrated by passing known quantities of gas through it either at the surface or in the hole at a point immediately above the region in which gas is lost to the formation. In case calibration is made at the surface, the ambient temperature in the hole may readily be obtained by a second resistance element which is operated at a current so low that effectively no heating occurs. The instrument has been adapted to con-tinuous recording, but the velocity of the meter relative to that of the gas must be low unless corrections are made. Curves giving data obtained in actual field tests are shown' The meter can also be used to determine the distribution of flow capacity in a gas producing well. A differential form of the meter has been designed and built in which the local flow or injection capacity of the formation is obtained directly. Introduction When fluid is injected into a well in a secondary recovery or pressure-maintenance operation the question of its most effective use invariably arises. Although the core log, when available, will show the regions of good permeability and oil saturation, there is normally no assurance that the fluid actually enters the formation in zones where injection is deemed desirable. In view of the uncertainties involved in such programs, it is generally conceded that measurements of permeability for a formation in place are more significant than those obtained by the core-sampling technique. A subsurface meter has been developed at the Gulf Research and Development Co. for measuring flow of fluids at different horizons in a well bore, and field tests have been made on the instrument in Cooperation with the Tulsa Division of the Gulf Oil Corp. In this paper the meter is de-

Jan 1, 1948

By F. Morgan, L. L. Gray, D. W. Reed

A flowMeter has been developed at Gulf Research and Development Co. and tested in the field for measuring the flow of gas in well bores. It has been used in a study of the injection capacity of different horizons in gas injection wells in Oklahoma. The flow sensitive element of the meter is a semi-conductor having a very high temperature coefficient of resistance. Advantages possessed by this meter are the result of that property and the high specific resistance of the element. The instrument possesses a sensitivity considerably higher than any reported previously. In the application described here the element is heated to a temperature considerably above ambient by an electric current, which is supplied by a voltage source at the surface. When fluid flows through the meter the rate of dissipation of heat is increased and the temperature of the element decreases. Because of the negative temperature characteristics of the resistance element such a decrease of temperature will be accompanied by an increase of resistance which, under flow conditions ordinarily found in wells, is of such a magnitude that it can be directly measured or recorded in terms of a change in voltage at the surface. In practice, rate of flow is measured in terms of the drop in voltage in the resistance element. All the metering and control apparatus remains at the surface while the thermal element is lowered into the well on a single conductor cable, consisting of an insulated wire and sheath. The meter is calibrated by passing known quantities of gas through it either at the surface or in the hole at a point immediately above the region in which gas is lost to the formation. In case calibration is made at the surface, the ambient temperature in the hole may readily be obtained by a second resistance element which is operated at a current so low that effectively no heating occurs. The instrument has been adapted to con-tinuous recording, but the velocity of the meter relative to that of the gas must be low unless corrections are made. Curves giving data obtained in actual field tests are shown' The meter can also be used to determine the distribution of flow capacity in a gas producing well. A differential form of the meter has been designed and built in which the local flow or injection capacity of the formation is obtained directly. Introduction When fluid is injected into a well in a secondary recovery or pressure-maintenance operation the question of its most effective use invariably arises. Although the core log, when available, will show the regions of good permeability and oil saturation, there is normally no assurance that the fluid actually enters the formation in zones where injection is deemed desirable. In view of the uncertainties involved in such programs, it is generally conceded that measurements of permeability for a formation in place are more significant than those obtained by the core-sampling technique. A subsurface meter has been developed at the Gulf Research and Development Co. for measuring flow of fluids at different horizons in a well bore, and field tests have been made on the instrument in Cooperation with the Tulsa Division of the Gulf Oil Corp. In this paper the meter is de-

Jan 1, 1948