Search Documents

By F. V. Lenel, G. S. Ansell, M. J. Salkind

An experiment is described in which the growth of interparticle necks in an array of loose spherical silver powder at temperatures near 300°C was determined by measuring changes in the electrical resistance of the array. The activation energy for neck growth of contacts was derived by abruptly changing temperature and noting the change in the rate of neck growth. Since the experiments were run under an external load, the changes in activation energy with stress could he determined. The activation energy was found to decrease rapidly with increasing stress. It is concluded that the material transport in the experiments is one of plastic flow by dislocation motion. The variation of activation energy with stress is typical for cross slip of dislocations, an important material transport mechanism in the temperature range investigated. THE process in which powder compacts or aggregates of loose powder are held at an elevated temperature under an external load is called hot pressing or sintering under pressure by powder metallurgists. In this investigation the early stages of this process as applied to loose spherical silver- powder aggregates were studied. The powder particles were approximately 100µ in diameter and the temperature was near 300°C, i.e., below one half of the melting point of silver in degrees Kelvin, where volume diffusion is not expected to contribute to sintering. In the process, the contact or neck areas between powder particles grow. Since this involves plastic deformation of the particles under a constant external load (even though not under constant stress) it would be termed creep by mechanical metallurgists. On the other hand, the growth in neck area observed in compacts or loose-powder aggregates held at elevated temperature without the application of an external load is termed sintering by powder metallurgists. During sintering the major driving force is the stress due to surface tension. However, even when no load is placed on the compact or powder aggregate, an external stress, i.e., gravity, plays an important role in sintering in addition to those stresses arising from surface tension, as was shown in two previous investigations.'" It is therefore postulated that no sharp dividing line can be drawn between the phenomena of "creep" and "sintering". Different material transport mechanisms may be involved in either of these phenomena, but they will depend upon the temperature and the level of stress, but not necessarily upon the nature of the driving force: surface tension or external load. At the low temperatures of this investigation, an external stress much higher than the stress due to surface tension is necessary to obtain measurable rates of neck growth. In order to avoid misunderstanding this phenomenon will be called "creep". The rate of growth in contact area in the loose silver-powder aggregates was determined by meas-

Jan 1, 1965

By T. E. Leontis, D. H. Feisel

MAGNESIUM alloys containing rare earth metals have received considerable attention during the past several years because of the need for light alloys having high strength and creep resistance at elevated temperatures. Although much of the work reported earlier has dealt with alloys containing Mischmetal, it has been shown in two previous papersl, V hat distinctly different effects are produced by various rare earth metals and rare earth metal mixtures on the properties of magnesium. For example, much higher strengths are obtained in magnesium alloys containing didym-ium (essentially neodymium plus praseodymium) than in alloys made with Mischmetal, which contains all the rare earth metals in the proportions in which they occur naturally in the monazite ore. Mg-rare earth metal alloys are characterized by a relatively coarse grain size, which greatly impairs castability. The addition of zirconium as a second alloying ingredient has been shown8,7 to refine the grain size, which also produces a distinct improvement in the strength properties. Certain Mg-Mischmetal-Zr and Mg-Mischmetal-Zn-Zr alloy compositions which are currently being produced commercially have been discussed in dytail by Nelson and Strieter,8,4 who also present some in- formation on a Mg-low Ce-Mischmetal-Zr alloy, and by Nelson.8 A patent issued to Jessup, Emley, and Fisher9 emphasizes the superiority of Mg-didymium-Zn-Zr alloys over the corresponding alloys made with Mischmetal. The purpose of this paper is to present the results of an extensive investigation concerned with the effect of increasing amounts of zirconium on magnesium sand casting alloys containing several different rare earth metal mixtures in varying amounts. The effect of the addition of zinc to some of these alloys is also being reported. Preparation and Testing of Alloys The alloys studied in this investigation were prepared in small laboratory melts according to the melting procedures described by Nelson1" as the Crucible Method. Electrolytic magnesium having the composition shown in Table I was used as the starting material. The rare earth metal alloying ingredients used in preparing these alloys were essentially of the compositions listed in Table 11. Some of the didymium-containing alloys were prepared using a Mg-didymium hardener. The rare earth metal content of this hardener analyzed 1.2 pct Ce, 10.4 pct Pr, 80.8 pct Nd, and 7.6 pct La. The zirconium was added in one of three forms: 1) as sponge zirconium obtained from the Bureau of Mines; 2) as a fused salt consisting of 50 pct ZrCl, and 50 pct alkali chlorides from which the zirconium is reduced by the magnesium; or 3) as a Mg-Zr hardener. The alloying procedures and melt hand-

Jan 1, 1958

By J. B. Bassett, E. S. Rowland

The experimental work reported herein firas inspired by the publication of a paper by Grange and stewart, in which it was suggested that at low chromium contents the effect of this element on the Ma point was greater than at higher chromium contents, It was argued that, if a small increase of chromium in solution in austenite caused a sharp lowering of the M, point, it might lead to an explanation of occasional unsolved stress cracking of SAE 52100 during heat treatment. Commercial hardening is carried out at temperatures of incomplete solution, leaving carbides available to enrich the austenite during any inadvertent increase in temperature, such enrichment of the austenite in chromium content would lower the M, point nearer room temperature where cracking is more likely to occur. According, it was decided to investigate the effect of chromium, in quantities between o and 2 pet, on the M, point of commercial steels. Fig I summarizes the data available on chromium steels. For purposes of comparison, the M, temperature values were corrected by means of the Grange and Stewart formulas to (I) Hypoeutectoid compositions: 0.50 pct carbon and 0.80 pct manganese (z) Hsereutectoid compos-sition': 1." pet carbon and O.35 pct manganese. Only the steels having compositions reasonably close to these corrected values were included, because large adjustments inevitably introduce increased error such as are experienced in using the formula. The straight lines of Fig I were drawn by the authors. These data obviously do not settle the question Of the effect Of chromium On the Md Oint, particularly at low chromium contents. While it is fairly well established that chromium causes the M, to be lowered when present in quantities of I pet Or more, Grange and Stewart1 have suggested that in small amounts (less than 1 pet) it is more effective in lowering the Ma point, while Klier and Troiano2 have suggested that in small amounts it is less effective in lowering the Ma point. Payson and Savage3 concur with Klier and Troiano and further suggest that the effect is not linear at these concentrations. Rose and Fischer4 report that small amounts of chromium actually raise the Ma point of a 0.20 carbon steel. Material Two series of 35 Ib induction heats were melted for this work, the analyses of which are given in Table I. One series was aimed at 0.50 pct carbon and 0.80 pct manganese with chromium additions in 0,25 pet increments from o to 1.5 pct with a single heat at 2.0 pct Cr. This series was considered necessary because the commercial heat treatment of SAE 52100 does not generally introduce more than about 0.60 pct carbon in solution in the austenite. The high

Jan 1, 1949

By L. G. Graper, E. L. Ramsey

THE present program of increased production of armament and lend-lease material for mechanized war has created a problem for the shops that must do the machining. They have naturally turned to the steel producers to provide them with a steel that can be accurately machined with the greatest possible speed. The adding of sulphur to steel as an aid to machinability has long been practiced; however, it may cause red shortness in rolling and may result in billets with seams and cracks, which must be removed before rolling can be continued. This conditioning of billets slows down production and' adds to the cost of making steel. Experience with various grades of sulphur steel made to different specifications has shown that Bessemer sulphur steels roll better than similar grades made in the open hearth, and also that low-carbon steels that are open or semikilled .as tapped roll better than completely deoxidized or killed steels. This has led to the belief that oxygen plays an important part in the rolling qualities of sulphur-bearing steels. It is generally held that the red shortness of sulphur steels is due to the low melting point of the sulphide compounds that separate out at the grain boundaries when the steel solidifies. At the rolling temperature of steel these sulphide compounds melt and cause cracking. ADDING SULPHUR AS A SULPHITE These difficulties can be avoided if sulphur is introduced into the steel by means of an anhydrous sulphite, such as sodium sulphite or sodium bisulphite, which-upon decomposition-forms sulphur dioxide. It is assumed that, in this case, the oxygen of the sulphur dioxide forms part of the sulphide inclusions in the steel, and raises their solidification temperature enough so that the formation in the steel of a low-melting eutectic is prevented. The result is the prevention of hot shortness and a more uniform distribution of inclusions. Fig. I shows photomicrographs of steels made with sulphur, while Fig. 2 illustrates the structure of steels made with sodium . bisulphite. These samples were cut from the steels as cast-that is, before rollingand were polished and lightly etched to bring out the grain boundaries. Fig. I shows that sulphide -inclusions segregate more or less at the grain boundaries, and it can be seen how the continuity of these low-melting inclusions would cause red shortness. Fig. z shows that the sulphide inclusions are more or less uniformly distributed throughout the matrix. This arrangement of inclusions has no apparent effect on the rolling qualities of a steel. This statement has been substantiated by the observation of the rolling of over 6000 tons of steel made with a sulphite addition. RESULTS As stated before, the sulphur dioxide-is added to steel by means of the decomposi-

Jan 1, 1942

By R. S. Handy

Does hand-sorting of mill feed pay? The fact that the practice is so general would seem to indicate that there must be good reasons for following it; yet, to my mind, the advantage in many cases is doubtful enough to invite a thorough discussion of the subject, in an effort to determine under what conditions hand-sorting does pay. A typical sorting plant in the Cœur d'Alene district handles about 800 tons of mine-run ore per day. The material is run over a grizzly with about 4-in. opening; the oversize is crushed to about 4-in. size and joins the undersize, and the whole product is washed and screened on trommels with about 11/2-in. openings. The oversize from these trommels is spread on a belt and the waste and first-class ore are sorted out by hand, the residue being further crushed, and passes, together with the trommel undersize, into the mill feed bins. About 50 tons of shipping ore and 150 tons of waste are sorted out per day, leaving about 600 tons of mill feed. To sort out this material requires 20 ore sorters and five bosses and repairmen. The normal cost of hand-sorting is about 16 c. per ton of run-of-mine ore, or 65 c. per ton of material sorted out. I believe that straight crushing and milling of the run-of-mine ore, in this case, is not only cheaper, but is metallurgi-cally more economical and efficient than hand-sorting followed by milling of the residue. At one of the Bunker Hill rock-houses, 1250 tons of run-of-mine ore are reduced to pass 30-mm., or about 11/4-in., opening in six hours, requiring five men. The equipment and the power consumed are not greatly different from that required in a sorting plant of the same capacity, and the normal cost of thus preparing the feed for milling is under 3 c. per ton of mine product. The relative cheapness of this method as against hand-sorting is thus clearly established, the saving being about 13 c. per ton. If there is any virtue in, hand-sorting, then, it must lie in the metallurgical results achieved. Possibly the favor that hand-sorting has found is due to a misconception as to what happens to the clean shipping ore if it is sent to the mill. If a mill makes, say, an 80 per cent. recovery on its feed, the hand-sorting advocate may assume that if the hand-sorted product be sent to the mill, 20 per cent. of the metals contained in it will be lost. This, I believe,

Jan 1, 1920

By Blake M. Loring, Robert A. Colton

MELTING procedures for most metals and alloys usually include some provision for the control of oxygen, since this element frequently has some undesirable effect on the properties of the metal or alloy concerned. In the melting of the various bronzes, this is especially true, since oxygen can be introduced into the melt in a number of ways, most of which are difficult to control. In making bronzes from virgin materials, oxygen is usually present in the commercial grades of copper used; electrolytic he refined copper ingots usually contain from 0.02 to 0.05 per cent oxygen. When ingot metal or scrap bronze is used in the charge, oxides are almost always present to some degree. Under certain melting conditions and in certain types of melting equipment the atmosphere over the metal may be highly oxidizing. This, of course, may be desirable in the melting practice used, but is certain to introduce appreciable amounts of oxygen into the melt, and that may not be entirely desirable. From the foundry viewpoint oxygen may have several harmful effects on bronzes. The formation of excessive amounts of oxides may produce drossy metal, which, in turn, means dirty castings and a potentially high rejection rate. It is claimed, too, that oxides in the metal may combine with hydrogen to form steam and thereby produce porosity in certain of the bronzes. The presence of certain refractory oxides, such as SnO2, may be undesirable from the viewpoint of making machining difficult, or as possible stress-raisers in the metal matrix. It is often said that excessive oxide present in the liquid metal makes the metal run sluggishly. Since it appears impractical to try to control the amount of oxygen introduced into the metal beyond taking the economical limit of precaution about charging dirty scrap, it would seem that control of the oxygen content of the liquid metal offers the most promising approach to this problem. This might be done by using slags, or covers, or by the use of some element or compound added to the melt to remove oxygen preferentially. Most aspects of this problem have been considered and considerable work has been done along these lines. A reconsideration of the problem is indicated, however, by the controversial nature of the evidence at hand, especially on the possibility of using a chemical deoxidizer to control the oxygen content of bronzes. CHOICE OF DEOXIDIZER The choice of the chemical agent selected as a deoxidizer would naturally depend first on the alloy in which it is to be used; in this particular case the alloy is Navy gun metal. In Table I are listed a group of elements that might be considered as

Jan 1, 1946

By C. V. Millikan, Herbert F. Beardmore

Declining Productivity Index, as considered herein, is a productivity index that has a substantially and consistently decreasing value when measured over a period of a few hours. If not recognized, it may be interpreted as representing an unsettled or unstable condition in a producing well. It forms the basis of a number of predictions as to future performance compared with the performance of wells in which the productivity index does not decline. The nost important of these are that: (I) the rate of oil production will decline more rapidly, (2) the gas-oil ratio will usually increase abnormally, (3) the amount of water ultimately produced will be negligible, if any, (4) stop-cocking will increase current production and decrease gas-oil ratio. When such relative well performance is indicated, it follows that certain reservoir performance and operating practices may be anticipated: (I) disappointing recovery, (2) longer natural flow, (3) no active water drive, (4) better evaluation of acidizing, shooting and reworking, (5) intermittent operation of wells, (6) smaller pumping equipment required. It is significant that the basis of these important predictions is bottom-hole pressure tests that can be made immediately after completion of the wells. Introduction "'Productivity index" is the number of barrels of oil produced per day per pound per square inch of differential pressure between the reservoir and the bottom of the well. "Declining Productivity Index," as considered herein, is a productivity index that has a substantially and consistently decreasing value when measured over a period of a few hours. Productivity index can be determined only when the rate of production can be stabilized. In most wells the rate of production and bottom-hole pressure are easily stabilized to give a constant productivity index for a period of many hours. A few produce so erratically as to preclude probability of an acceptable test in the usual sense. A satisfactory productivity index can be determined in some wells only by gauging the production accurately by hours, measuring the bottom-hole pressure continuously, and from these data calculating the productivity index for successive hours. Such figures frequently will have a decreasing value—that is, a declining productivity index—and when plotted on double. logarithmic cross-section paper with productivity index as ordinate and time as abscissa will be a straight-line curve. The angle between the curve and the abscissa is referred to as the rate of decline. Declining productivity index may appear to be the result of change in permeability to oil due to decreasing saturation of oil and increasing saturation of gas in the reservoir. It is possible that such is in fact the cause, but if so, more is involved than merely relative saturation of oil and gas. This seems evident because the rate of decline in productivity index is substantially the same regardless of the pro-

Jan 1, 1945

By A. H. Daane, B. J. Beaudry

The uranium-antimony system has been investigated by metal-lographic, therma1, and X-ray methods. There are four intermediate phases present: USbz and U,Sb, which undergo peritectic decomposition at 1355°and 1695OC, respectively, and USb and UPSbs which melt congruently at 1850"and 1800°C, respectively. There is a eutectic between U4Sbs and USb which melts at 1770°C. USb,, UsSb4, and USb are line compounds while U4Sbs has a solubility range of approximately 1.5 at. pct at 1770°C. Single crystal studies of the cmpo,und U.,SbS show it to have a hexagonal unit cell with a, = 9.268A and c, = 6.201b;. The solubility of uranium in liquid antimony increases from 0.1 at. pct at 650°C to 1.5 at. pct at 900°C. The solubility of antimony in a, P, and y uranium is approximately 0.02, 0.1, and 0.05 at. pct respectively. IN nuclear reactors, uranium has been used mainly in the form of solid-fuel elements of the pure-metal or uranium-rich alloys. However, in attempts to overcome some of the difficulties inherent in solid-fueled reactors, reactor concepts hive been proposed in which the fuel would be a liquid metal, such as a solution of uranium in another metal. The liquid-metal fueled reactor (LMFR) designed by the Brook-haven National Laboratory of the U.S. Atomic Energy Commission is an example. Fuel for this reactor is a solution of approximately 800 ppm enriched uranium in bismuth.' To design such liquid-fueled reactors, a background of information on the solubility of uranium in various metals is obviously necessary. The present study was undertaken to pro- vide information for such purposes, and in addition, to study the uranium-antimony system as a whole. A preliminary literature search showed that some work had been done previously on uranium-antimony alloys, but no attempts had been made to make a complete study of this system. The solubility of uranium in antimony was studied by Cammack and Bridger' up to 950°C and by Hayes and Gordon up to 900'-C. Their data are plotted in Fig. 1. Ferro, in an X-ray structure study of some uranium-antimony compounds, found USg to be tetragonal with a, = 4.2724 and c, = 8.471A, U3S4 to be b.c.c. with aO = 9.095A and USb to be f.c.c. with a,= 6.191A. Colani reported the compound UsSba; however, work by Ferro and by this Laboratory showed that this compound does not exist. foote' reported several intermediate phases in the uranium-antimony system, but did not identify them. Greninger' re-ported finding an intermediate phase in a 5 at. pct Sb

Jan 1, 1960

By R. I. Jaffee, J. G. Dunleavy, W. Hodge, H. R. Ogden

Early in 1946, at the instigation of the U. S. Army Signal Corps, the authors made an extensive survey of the available literature covering high-strength, high-conductivity alloys. For the purposes of the Signal Corps, the minimum tensile strength to be considered was 150,000 psi, together with at least 50 pct IACS conductivity. No single alloy was found to be in production, or mentioned in the literature, which had this combination of properties. The constitution diagram for the iron-copper alloys is not well established in the respect to the two-liquid region. Fig I, taken from the 1939 Ed. of the ASM Metals Handbook, shows a two-liquid system existing above the liquidus temperature, but disconnected from it. Although Ruer and Fickl and Ruer and Goerensz definitely established the fact that two liquid layers could occur in the system, Ruer3 was not convinced that the line of immiscibility was closed in the center. Maddocks and Claussen4 found no liquid immiscibility at temperatures up to 157oOC in alloys containing almost no carbon. Although the diagram would indicate age hardening of the copper-iron alloys is possible, Hanson and Fords found that little hardening effect could be obtained. However, Gordon and Cohen6 reported that the response is better if the quenching is very efficient. Although iron has a potent effect on the conductivity of copper, Hanson and Fords have shown that, when hot-rolled copper-iron alloys are aged at 1200°F, the electrical conductivity decreases sharply with iron contents up to 0.2 pct Fe, and then levels off at conductivities between 60 to 70 pct IACS with compositions to 2.1 pct Fe. They also found that aging did not increase the tensile strength, although increasing iron content gave a moderate improvement in strength. High-strength copper-iron alloys, usually containing about 60 pct iron, had been reported by Smith and Palmer.7 They found that an alloy containing 56.4 pct copper, 0.21 pct magnesium, balance iron, would give a maximum tensile strength of 170,000 psi and an electrical conductivity of slightly over 35 pct IACS. The alloy could also be processed to have I50,000 psi tensile strength, and about 41 pct I.\CS conductivity. Decreasing the iron content increased the electrical conductivity, but the long mushy range during freezing of the alloy containing 10 to 20 pct iron made the production of good castings difficult. In spite of the difficulty encountered by Smith and Palmer with alloys of around 20 pct iron, it was decided to make a rather complete investigation of this type of alloy. As a result of this investigation, a method of alloying and fabricating copper alloys containing 10 to 15 pct iron was developed

Jan 1, 1949

By E. J. Duggan

THE mine and mill of the Climax Molybdenum Co. are at Climax, Colorado. Climax is on Fremont pass directly on the Continental Divide, at an elevation of 11,400 feet. DESCRIPTION OF ORE The Climax ore-bearing rock is essentially an altered and highly silicified granite, fully half of the gangue being quartz. Molybdenite is the only mineral of economic consequence and most of it is intimately associated with quartz in the form of fine veinlets and stringers. Other minerals are molybdite, pyrite, and chalcopyrite. While the molybdite may be readily extracted by hydrometallurgical methods, its content is too low to make such operations profitable. The pyrite content ranges from 2 to 5 per cent and that of the chalcopyrite from 0.03 to 0.05 per cent. There is not enough copper to make its recovery attractive and one of the metallurgical problems is the elimination of it and the pyrite from the product. On account of the dose association of the molybdenite with the quartz and the necessity of eliminating the pyrite and chalcopyrite from the final product, fine grinding followed by flotation is the only feasible method of concentration. HISTORY Construction of the first milling unit was started in 1917 and it was operated during parts of 1918 and 1919. In the postwar years, there was almost no demand for the product and production was at a standstill until 1924. The Company's research campaign to develop the use of the metal began to show results in that year. From 1926 to 1932 production ranged from 500 to 1200 tons per day. In 1931 an additional mill section was built and production was gradually increased until in 1934 and' 1935 about 3000 to 4000 tons was milled per day. This tonnage overtaxed the milling facilities, and as the demand for molybdenum was growing constantly, additional milling equipment was needed. In 1936 and 1937 another crushing plant, six additional mill sections and the necessary auxiliary plants were constructed and brought into operation. This plant was designed to mill 10,000 tons per day, but it was not long before 12,500 tons was being treated during periods of peak demands. During the summer of 1941, to meet defense needs, the mill has been required to treat 15,500 tons per day. This has been accomplished with little plant expansion and at no loss in recovery, as will be described later. To increase capacity still further, one more primary section is now being built. This will bring capacity to 18,000 tons per day, which can be stretched to 20,000 tons at a small sacrifice in recovery. CRUSHING There are two crushing plants: No. I, of 5000 tons capacity (flowsheet in Fig. 1) and No. 2, of 15,000 tons capacity (Fig. 2).

Jan 1, 1942

By E. J. Duggan

THE mine and mill of the Climax Molybdenum Co. are at Climax, Colorado. Climax is on Fremont pass directly on the Continental Divide, at an elevation of 11,400 feet. DESCRIPTION OF ORE The Climax ore-bearing rock is essentially an altered and highly silicified granite, fully half of the gangue being quartz. Molybdenite is the only mineral of economic consequence and most of it is intimately associated with quartz in the form of fine veinlets and stringers. Other minerals are molybdite, pyrite, and chalcopyrite. While the molybdite may be readily extracted by hydrometallurgical methods, its content is too low to make such operations profitable. The pyrite content ranges from 2 to 5 per cent and that of the chalcopyrite from 0.03 to 0.05 per cent. There is not enough copper to make its recovery attractive and one of the metallurgical problems is the elimination of it and the pyrite from the product. On account of the close association of the molybdenite with the quartz and the necessity of eliminating the pyrite and chalcopyrite from the final product, fine grinding followed by flotation is the only feasible method of concentration. HISTORY Construction of the first milling unit was started in 1017 and it was operated during parts of 1918 and 1910. In the postwar years, there was almost no demand for the product and production was at a standstill until 1024. The Company's research campaign to develop the use of the metal began to show results in that year. From 1926 to 1932 production ranged from 500 to 1200 tons per day. In 1931 an additional mill section was built and production was gradually increased until in 1934 and 1935 about 3000 to 4000 tons was milled per day. This tonnage overtaxed the milling facilities, and as the demand for molybdenum was growing constantly, additional milling equipment was needed. In 1936 and 1937 another crushing plant, six additional mill sections and the necessary auxiliary plants were constructed and brought into operation. This plant was designed to mill I0,000 tons per day, but it was not long before 12,500 tons was being treated during periods of peak demands. During the summer of 1941, to meet defense needs, the mill has been required to treat 15,500 tons per day. This has been accomplished with little plant expansion and at no loss in recovery, as will be described later. To increase capacity still further, one more primary section is now being built. This will bring capacity to 18,000 tons per day, which can be stretched to 20,000 tons at a small sacrifice in recovery. CRUSHING There are two crushing plants: No. I, of 5000 tons capacity (flowsheet in Fig. I) and No. 2, of 15,000 tons capacity (Fig. 2).

Jan 1, 1942

By William M. Newton, John E. Sherborne

The relation between the properties of electric logs and the fluid used in drilling a well is briefly discussed in this paper, and the fact that the resistivity of the drilling mud and its filtrate can appreciably affect such logs is shown. Apparatus was designed and a procedure established to determine the effect of various factors on the resistivity of drilling mud. Five muds commonly employed in California were tested and the following observations were made: I. The effect of raising the temperature from 80°F. to 180°F. is to decrease the resis-tiviiy of the mud or filtrate approximately 50 per cent. 2. The resistivity of the mud in most cases closely approximates that of its filtrate. 3, The change in the resistivities of muds caused by the addition of chemical is not the same function of the amount of chemical added for each mud. 4. The effect produced by increased sodium chloride content is to reduce markedly the resistivity of the mud and its filtrate. 5. Weighting materials, such as Baroid and limestone, tend to increase the resistivity of drilling mud. 6, Cement and counteracting reagents reduce mud resistivity. Introduction During recent years, the practice of "electrically logging9' a geologic formation by means of a system of electrodes lowered in a well bore has provided data of inestimable value concerning the nature of the sediments penetrated. Thus, it is generally possible, by means of electric logs, to distinguish readily the differences between shales, sandstones, cherts, limestones, and other rock forms. The distinguishing characteristics recorded in this manner have made possible long-range and closely detailed mapping and visualization of deeply buried structures1-5 to a degree not to be obtained with a reasonable expenditure of money by any other means at present in use. Besides being of value in correlation work, electric logs have been found, in some instances, to be useful in estimating the nature of fluid contained within the pores of a rock. In special cases, even the relative permeabilities at different horizons have been determined.6 That electric logs should reflect in some measure such physical properties of rocks as porosity and permeability and, in addition, give rise to data pertaining to the fluid content of rock interstices, becomes evident when the conditions giving rise to the electrical phenomena measured are known. However, it is not the purpose of this paper to review the present status of electric logging; rather, the reader is referred to the papers cited on page 220 for the principles and practice involved. Importance of Drilling FLuid in Electric Logging Because the drilling fluid must be the medium through which the electric logging device is made to traverse the formations penetrated by a borehole, and since, in general, the drilling mud completely surrounds

Jan 1, 1942

By E. J. Duggan

The mine and mill of the Climax Molybdenum Co. are at Climax, Colorado. Climax is on Fremont pass directly on the Continental Divide, at an elevation of 11,400 feet. Description of Ore The Climax ore-bearing rock is essentially an altered and highly silicified granite, fully half of the gangue being quartz. Molybdenite is the only mineral of economic consequence and most of it is intimately associated with quartz in the form of fine veinlets and stringers. Other minerals are molybdite, pyrite, and chal-copyrite. While the molybdite may be readily extracted by hydrometallurgical methods, its content is too low to make such operations profitable. The pyrite content ranges from 2 to 5 per cent and that of the chalcopyrite from 0.03 to 0.05 per cent. There is not enough copper to make its recovery attractive and one of the metallurgical problems is the elimination of it and the pyrite from the product. On account of the close association of the molybdenite with the quartz and the necessity of eliminating the pyrite and chalcopyrite from the final product, fine grinding followed by flotation is the only feasible method of concentration. History Construction of the first milling unit was started in 1917 and it was operated during parts of 1918 and 1919. In the postwar years, there was almost no demand for the product and production was at a standstill until 1924. The Company's research campaign to develop the use of the metal began to show results in that year. From r926 to 1932 production ranged from 500 to 1200 tons per day. In 1931 an additional mill section was built and production was gradually increased until in 1934 and 1935 about 3000 to 4000 tons was milled per day. This tonnage overtaxed the milling facilities, and as the demand for inolybdenum was growing constantly, additional milling equipment was needed. In 1936 and 1937 another crushing plant, six additional mill sections and the necessary auxiliary plants were constructed and brought into operation. This plant was designed to mill I0,000 tons per day, but it was not long before 12.500 tons was being treated during periods of peak demands. During the summer of 1941, to meet defense needs, the mill has been required to treat 15,500 tons per day. This has been accomplished with little plant expansion and at no loss in recovery, as will be described later. TO increase capacity still further, one more primary section is now being built. This will bring capacity to 18,000 tons per day, which can be stretched to 20,000 tons at a small sacrifice in recovery. Crushing There are two crushing plants: No. I, of 5000 tons capacity (flowsheet in Fig. I) and No. 2, of 15,000 tons capacity (Fig. a).

Jan 1, 1943

By Karl Fetters, John Chipman

The relationship between the composition of the slag and that of the underlying metal during the refining of a heat of liquid steel may best be studied in the light of the two broad physicochemical concepts of equilibrium and reaction rate. Actual steel-making processes, typified by basic open-hearth practice, involve such complexities of operating variables that it is impossible to distinguish with any degree of certainty between the general limiting conditions imposed by chemical equilibrium and the effects associated with rates of diffusion or of chemical reaction. Further advances in the physical chemistry of steelmaking will depend upon our ability to distinguish clearly between these two kinds of effects, and the experimental work that must be done falls naturally into two classifications. The first is the study of chemical equilibrium that cannot be carried out with assurance under operating conditions but must be done in the laboratory. The second is the -subject of rates of reaction and diffusion and the mechanism of the process as a whole, which can best be studied under operating conditions. The latter is not entirely independent of the former, since its interpretation often requires a knowledge of the equilibrium state. It is the purpose of this and of several papers that will follow to present the results of labora- tory investigations of equilibria involving liquid steel and slag. Open-hearth slag is a complex mixture containing at least eight major components and perhaps twice as many whose influence may be classified as probably minor. It is not surprising that progress toward a complete understanding of such a material at high temperatures has been slow. Attempts to apply the established principles of physical chemistry to the behavior of the individual components of this mixture have been beset by an almost complete lack of data on its chemical properties in the liquid state. This has necessitated the adoption of various methods of approximation based upon such assumptions as, for example, that for a given component the ratio of its mol fraction in the slag to that in the metal is a constant, or that the molecular composition of the liquid slag is the same as its crystalline constitution after solidification. From the thermo-dynamic viewpoint, such assumptions are merely useful dodges, which enable one to hazard a guess as to the magnitude of the more fundamental quantities, the chemical potentials and activities of the components of slag. The problem of determining the activity of each substance in an eight-component svstem seems too complex to be undertaken without the aid of generalizations derived from experimental data on similar systems containing a smaller number of components. Accordingly, it was planned in the present investigation to study the equilibrium of molten iron with the simplest

Jan 1, 1941

By W. A. Johnson, F. N. Rhines, W. A. Anderson

The rate of the high-temperature oxidation of pure copper has been measured repeatedly by numerous investigators. It appears to be generally agreed: (I) that at constant temperature, after the initial stages of oxidation have been passed and the scale has attained a substantial depth, the film thickness increases in proportion to the square root of the time of oxidation; and (2) that for any given period of oxidation the logarithm of the square of the film thickness is proportional to the reciprocal of the absolute temperature of oxidation.' These relationships are explained upon the basis that the rate of diffusion of copper to the external surface of the film is the controlling factor in establishing the rate of growth. Extensive studies have been devoted also to the mechanism and rates of the early stages of oxidation. There is thus available a reasonably well established theory of the oxidation of pure copper upon which to construct an explanation of the more complex oxidation of copper alloys. Few general principles have as yet emerged from the chaos of observations that have been reported in the field of the oxidation of alloys.2 It is evident, however, that the copper alloys may be divided into two main groups, whose oxidation characteristics are distinguish- able. The first group, composed of the alloys with the noble metals, forms substantially pure copper oxide scales; the alloying element is concentrated within the residual metal, and sometimes particles of almost pure noble metal are found in the scales completely surrounded by copper oxide. In the second group, composed of the alloys of copper with the baser metals, the alloying element appears as an oxide in the scale, often in greater concentration than in the alloy itself and sometimes to the exclusion of copper oxide. The oxide scales of the latter class have been found to be made up of one, two, and sometimes more distinguishable layers of which the innermost is often metallic in character, composed of particles of the oxide of the alloying element embedded in essentially pure copper and known as the subscale or zone of internal oxidation. The need for a thorough quantitative study of these modes of oxidation is evident. Since it is apparent that several mechanisms must be cooperating to produce the complex oxide scales found on copper alloys, the analysis of the process into its several simple operations should prove instructive. Fortunately, it is possible experimentally to produce internal oxidation in the absence of an external scale; this permits the isolation and intensive study of one of the steps in the oxidation process. In the present research the rates of internal oxidation of an extensive series of dilute solid solution alloys of copper have been measured and a theory has been developed to predict the observed

Jan 1, 1942

By Walter Knox, Charles H. Sawyer

All of the coals commonly used in domestic bituminous stokers form coke, and satisfactory operation depends upon the fact that the coke formed is so weakly bound together that it breaks readily in the normal operation of the stoker and automatically maintains a good fuel bed. Some coals, because of their tendency to form solid, blocky coke, are practically excluded from use in small domestic stokers as now built. Other coals, some among the best stoker coals available, can form this troublesome coke under certain conditions. Many contradictory methods have been offered as cures for coke formation. Generally the procedure has been to try various adjustments until a combination was found that seemed to give better results. Such random methods of treatment have not provided any reliable information as to causes. The present paper covers a comprehensive test program undertaken by the Koppers Company's Stoker Coal Research Laboratory at Kearny, N. J. The program had two main objectives; first, to discover what factors affected coke formation, and second; to define corrective steps that could be applied in stoker service work. Conclusions and Results i. The design of the stoker outweighs in importance all other factors capable of improving coke formation. 2. Insufficient air supply aggravates the formation of large blocky coke, although raising the air above 30 to 40 per cent excess (as determined during steady running) does not further improve the character of the coke formed and only reduces its accumulation at the expense of efficiency, increased fly ash, poorer clinker-ing, and other disadvantages. 3. Increasing the coal feed results in a somewhat more friable coke structure and is recommended for persistently troublesome jobs. 4. Increasing over-fire draft improves the character of the coke formed and reduces troublesome accumulations by accelerating off-period burning, although at some expense in efficiency and some increase in fly-ash accumulation. 5. Coke structure was not substantially improved by blocking some of 'the retort tuyeres, although the blocking of tuyeres at the feed-screw end of a rectangular retort did lead to somewhat improved performance, possibly because of considerably better distribution of coke in the fuel bed. 6. With the equipment tested no difference was shown between installation of the same stoker in a steam boiler and a warm-air furnace, or between a sand-filled and a ventilated type of hearth. 7. The following design features had no noticeable effect on coke formation: a. Presence or absence of coal-tube air as provided by many manufacturers to eliminate smoke-back. B. Presence or absence of a flap damper ill the air duct to minimize off-period burning. c. Continuous or intermittent (ratchet and pawl driven) movement of fuel feed screw.

Jan 1, 1944

By Parke A. Dickey

Potential differences between strata of shale and sandstone have been recognized for about 15 years, and they form the basis of the electrical logging of oil wells. Hitherto these potentials have been ascribed solely to electro-¦ chemical reactions caused by the disturbing effects of the water in the drill hole through which they are generally measured. Observations by the author in wells empty of water and in a mine shaft suggest that potential differences between sandstones and shales are natural and specific properties of the rocks, although they are moditied in measurement by the disturbing effects of the water in the drill hole. The cause of these potentials probably is to be sought in the relative polar adsorptive capacities of quartz and clay particles. Introduction The existence of potential differences in the surface of the earth has been known for some time, and their measurement has facilitated the discovery of geological discontinuities such as ore bodies. The technique of measurement has been well established.1-3 In measurements in oil wells, it has been found that the potential of shales with respect to some arbitrary reference is very nearly constant in any one well, at least below the zone to which meteoric water has gained access. Sandstones and some other types of sedimentary rocks have a difference of potential with respect to shale that is negative arid may attain a value of 200 millivolts or more. The difference of potential, as usually measured commercially with water in the hole, is distributed over about one foot vertically at the top and bottom contacts of the sandstones. The sharpness of the curve at the formation contacts can be improved by using a short electrode that is close to the wall of the hole' These potentials generally have been ascribed to the disturbing effects of the water in the drill hole. Potentials have been found, however, in wells in which no water was present. In the course of experiments in electrical logging in pennsylvania, carried out by the pennsylvania Geological Survey, observations were made of several phenomena that hitherto have not been described, to the author's knowledge, ill the published literature. The potential differences across the contacts of sandstone and shale are called ill this paper "natural potentials," as distinguished from the potentials caused by electroendosmosis (electrofiltration) and concentration differences, which will be discussed subsequently. Potentials in Cored WeLl In the spring of 1942, the author measured the potentials in an exploratory well (Day 13, near Grand Valley, Pa.) which had been cored With diamond tools. The potentials were first measured with fresh water in the hole. * null balance potentiometer was used in this and all the other measurements described in this paper. One nonpolarizing porous pot electrode, containing copper sulphate solution and

Jan 1, 1946

By R. Casting, J. Philibert, and C. Crussard

APPARATUS described in this paper uses the properties of X-radiation, emitted by substances under electron bombardment, as a means of rapid chemical point analysis. The method is based upon the principles of emission X-ray spectrography pioneered by Moseley in 1913. A very finely focused beam of electrons—the electron probe—is projected on the surface of a sample, which has a very large area compared with the beam diameter, at the point where it is desired to know the chemical composition. The minute volume of the sample which is thus irradiated emits a complex X-ray spectrum consisting principally of the characteristic radiations of the elements present in the volume. Measurement of the wavelength and intensity of each component of this spectrum thus affords a simple method of determining the chemical identity and concentration of these elements. The volume of sample which is analyzed at each position of the beam is limited by the diffusion of electrons in the sample. For an accelerating potential of the electron beam of about 30 kv, which is a convenient value for producing the characteristic radiation, this diffusion extends over a diameter of about 1 µ normal to the beam, and about 2 µ in the direction of the beam. Thus a beam of 1 µ in diameter leads to a volume of about 2 µ in diameter being irradiated. The limits of the analyzed region are thus considerably smaller than those obtained by using spark or arc emission spectrometry, which must extend to about 50 µ at right angles to the beam, and those obtained in X-ray fluorescence analysis, where the penetration of the specimen is considerably greater. The apparatus itself consists of three main parts: an electron optical system. an X-ray spectrograph and an optical microscope. The electron opticai system consists of a tungsten cathode emitting the electrow and a pair of magnetic lenses which focus the electron beam on the specimen to be analyzed. The specimen is prepared in the usual way, as in optical micrography. The X-radiation, emitted at the focal spot where the electrons strike the sample, is analyzed with a curved crystal, Geiger-Müller counter, vacuum spectrograph. The light microscope, designed to observe the surface of the sample in the region to be analyzed, is provided with a reflecting objective placed on the axis of the second magnetic lens. Its magnification is X450. The quantitative determination of an element A in the analyzed region is made by measuring the intensity I, of a strong characteristic line of the element, as emitted from the sample, and then the intensity I (A) of this same line as emitted from a

Jan 1, 1958

By Donald B. Hunter

The Ti-Be system up lo 10 wt pct Be with cortlmercialll' pure titanium has been determined using metal-lographic techniques. Beryllium forms the p eutec-toid type of dinqarz with titanium; the eutectoid occurs at 0.5 xt pct Be azd 1500 F, while an eutectic is foritled at 1887°F containing between 5 and 7.5 rt pct Be. The solubility of beryllium in a titanium does not exceed 0.05 zvt pct and the maximum solubility of Beryllim in 0 titanium is 1 wt pet. PREVIOUS work on the Ti-Be phase diagram indicated that additions of beryllium to titanium resulted in a marked lowering of the melting point,''' and it was also observed that the solubility of beryllium in both a and p titanium was retricted.- With the limited data available, McQuillan and McQuillan constructed a partial hypothetical diagram of the Ti-Be system,= assuming that beryllium formed the 0 eutectoid type of system with titanium. Subsequently Bedford published a tentative diagram of the entire Ti-Be system: although he did not investigate alloys containing less than 10 wt pct Be. This diagram included several compounds described by other authorities.'-l3 The following account describes work directed toward determining the form of the titanium-rich portion of the phase diagram up to 10 wt pct Be. MATERIALS AND METHODS Titanium sponge and a master alloy containing 25 wt pct Be were used in the formulation of the alloys; the chemistry of these materials is detailed in Table I. The alloys were prepared as 250-g compacts which were melted into buttons by arc melting under purified argon on a water-cooled copper hearth. Results of analyses for beryllium are shown in Table I but no determination of other elements was made at this stage. The alloys were hot-rolled at 1650°F to produce 0.1-in.-thick sheet. Alloys containing up to 1.5 pct Be were fabricated without trouble; samples containing 2 pct cracked initially upon hot rolling, but thereafter rolled satisfactorily to sheet. The 5, 7.5, and 10 pct were hot short and could not be rolled. Surface contamination was removed from samples by sandblasting and pickling in a 5 pct HF-35 pct HNOs solution. For metal log raphic examination, heat-treated specimens were mounted transverse to the rolling direction, ground on silicon carbide papers of increasing fineness to 600 grit, and electropolished at 20 v using a solution containing 600 ml of methanol, 60 ml of perchloric acid, 360 ml of butyl cellosolve, and 2 ml of Solvent "X". Difficulty was experienced in obtaining good electropolished surfaces with samples containing more than 1 pct Be, the degree of difficulty in-

Jan 1, 1967

By W. A. Anderson, F. N. Rhines, W. A. Johnson

THE rate of the high-temperature oxidation of pure copper has been measured repeatedly by numerous investigators. It appears to be generally agreed: (I) that at constant temperature, after the initial stages of oxidation have been passed and the scale has attained a substantial depth, the film thickness increases in proportion to the square root of the time of oxidation; and (2) that for any given period of oxidation the logarithm of the square of the film thickness is proportional to the reciprocal of the absolute temperature of oxidation.' These relationships are explained upon the basis that the rate of diffusion of copper to the external surface of the film is the controlling factor in establishing the rate of growth. Extensive studies have been devoted also to the mechanism and rates of the early stages of oxidation. There is thus available a reasonably well established theory of the oxidation of pure copper upon which to construct an explanation of the more complex oxidation of copper alloys. Few general principles have as yet emerged from the chaos of observations that have been reported in the field of the oxidation of alloys.2 It is evident, however, that the copper alloys may be divided into two main groups, whose oxidation characteristics are distinguish able. The first group, composed of the alloys with the noble metals, forms substantially pure copper oxide scales; the alloying element is concentrated within the residual metal, and sometimes particles of almost pure noble metal are found in the scales completely surrounded by copper oxide. In the second group, composed of the alloys of copper with the baser metals, the alloying element appears as an oxide in the scale, often in greater concentration than in the alloy itself and sometimes to the exclusion of copper oxide. The oxide scales of the latter class have been found to be made up of one, two, and sometimes more distinguishable layers of which the innermost is often metallic in character, composed of particles of the oxide of the alloying element embedded in essentially pure copper and known as the subscale or zone of internal oxidation. The need for a thorough quantitative study of these modes of oxidation is evident. Since it is apparent that several mechanisms must be cooperating to produce the complex oxide scales found on copper alloys, the analysis of the process into its several simple operations should prove instructive. Fortunately, it is possible experimentally to produce internal oxidation in the absence of an external scale; this permits the isolation and intensive study of one of the steps in the oxidation process. In the present research the rates of internal oxidation of an extensive series of dilute solid solution alloys of copper have been measured and a theory has been developed to predict the observed

Jan 1, 1941