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By Clarence Balke

SMALL buttons of fused tantalum have been produced by are fusion in a vacuum, by drawing an arc between sticks of pressed tantalum and a tantalum-faced water-cooled copper block. However, ingots of appreci-able size can be produced only by the heat-treatment of bars pressed from powder. The following outline covering the production of finished bars of tantalum by the methods of powder metallurgy is also used for the production of columbium, taking into account the difference in the melting points of these two metals. PRESSING THE POWDER With possibly a few exceptions, a pressing operation is one of the essential steps in the practice of powder metallurgy. In fact, the author's experience with a number of high-melting-point metals and with numer-ous types of hard carbide compositions has led him to believe that this operation is often one of the most important in the- entire process, and frequently one of the most difficult to carry out in a satisfactory manner. Defects clue to improper pressing can readily lead to a defective finished product. It is the author's opinion that rarely is a bar or other article pressed from metal powder in such a way that all parts of the piece are uniformly pressed. The nearest approach to uniformity of pressing is possibly attained when the powder is contained in a flexible receptacle, such as rubber, and is pressed under a liquid by hydrostatic pressure. However, this method is not generally applicable. Hydraulic pressing in steel dies where one or two punches are forced into the die must usually be resorted to. As the pressure in such a die is built up, the powder begins to cling to the walls of the die with a tenacity dependent upon the nature of the powder, and this results in a bridging action, so that the layers of powder adjacent to the moving punch are pressed more heavily than those further removed in the mass. Frequently, as the pressure is carried higher, there may be a mass slippage of the powder upon itself, with the result that slip cracks are formed within the pressed

Jan 1, 1938

By Gerald Edmunds, M. L. Fuller

The development of "fiber" or preferred orientations, during the plastic deformation of metals, and the relation of such structures to the anisotropic characteristics of worked metals has become a subject of common knowledge among metallurgists. Very little has been published, however, relative to variations existent throughout the cross-sections of rolled strips,1 and the influence that such variations may have. This paper presents such a study on a rolled zinc alloy.2 The significance of small differences in surface structure is shown in relation to bending properties. Experience with zinc and its alloys has shown that the outer radius of the bend, which is subject to tensile deformation, is the common region of failure. In considering relations of structural characteristics to bending properties it will suffice, therefore, to consider the ease and possible extent of tensile deformation resulting from various orientations. It is necessary in this connection to assume that on the average the individual crystals of a polycrystalline material act substantially as if their movements were unobstructed by the surrounding grains. This assumption is not strictly valid, but the error involved is unlikely to affect seriously the qualitative conclusions derived from its use. The mechanism of the plastic deformation of zinc crystals has been described by Mark, Polanyi and Schmid3 and by Mathewson and Phillips14 and is regarded as being accomplished by block movements or * Investigator, Rolling Mill Section, Research Division, New Jersey Zinc Co. f Investigator, X-ray Laboratory, Research Division, New .Jersey Zinc Co. 1 Variations of structure throughout the cross-section of wire have been reported in the literature. 2 This alloy contained, in addition to zinc, 1.0 per cent copper and 0.01 per cent magnesium. Its crystal form is hexagonal close packed, the sarne as that of pure zinc. 3 H. Mark, M. Polanyi and E. Schmid: Vorgange bei der Dehrlung von Zink-kristallen. Zlsch. f. Phys. (1922) 12, 58. 4 C, H. Mathewson and A. J. Phillips: Plastic Deformation of Coarse-grained Zinc. Proc. Inst. Met. Div., A. I. M. E. (1927) 143. C. H. Mathewson: Twinning in Metals. Proc. Inst. Met. Div., A. I. M. E. (1928) 7. The results of a further study of plastic deformation of zinc as related to twin-

Jan 1, 1932

By D. Moskowitz

IN the course of a general investigation of boride systems, sponsored by the Office of Naval Research, various vanadium boride powders of relatively good purity were prepared which could be used for a determination of the phases present. The X-ray pattern of one of these lots showed, in addition to the known VB1 and VB22 phases, an additional phase, almost certainly of composition V3B4, isomorphous with Cr3B4, Cb3B4, Ta3B4, and Mn3B,. Its pattern fitted in well with the indices worked out by Kiessling for Mr3B4.3 The unit cell for this new compound is orthorhombic, with the dimensions a = 3.030A, b = 13.18A, c = 2.986A7 V=119.2A.' Table I lists the X-ray diffraction data for V.3,.

Jan 1, 1957

Jan 1, 1961

By Donald A. Brobst

The minerals barite (BaSO4-barium sulfate) and witherite (BaCO3-barium carbonate) are the chief commercial sources of the element barium and its compounds whose many uses are nearly hidden among the technical complexities of modern industrial processes and products. Barite, the major ore mineral, is extremely vital to the petroleum industry which in 1980 consumed at least 90% of the world's production of 8.8 million tons as a major ingredient of the heavy fluid, called mud, that is circulated in rotary drilling of oil and gas wells. The remaining 10% of the barite production was consumed chiefly in the manufacture of barium chemicals and glass and as a pigment, filler, and extender. Barite occurs throughout much of the world and is available from three major geologic types of deposits-vein and cavity filling, residual, and bedded-in sufficient quantity at competitive prices to meet current demands. The world's demand for barite is expected to increase, and geologic circumstances are favorable for the discovery of new deposits of commercial value. Witherite is much less common and abundant than barite, although it is more desirable in many ways as a raw material for the production of barium chemicals. The United States has not produced witherite since about 1950; England is currently the chief producer of witherite. End Uses Most of the world's barite production since 1926 has been used as a weighting agent for the muds circulated in rotary drilling of oil and gas wells. The muds fundamentally are mixtures of water, clay, and barite in different proportions that vary according to local reservoir conditions. Muds with a specific gravity as great as 2.5 are used. The mud is pumped down the hollow drill stem, passes through the bit at the bottom of the hole, and rises to the surface in the space between the drill stem and the wall of the hole. In the course of this circulation the drill bit is cooled, cuttings are removed, the drill stem is lubricated, the walls of the hole are sealed, and the hydrostatic head of the column of weighted fluid helps to confine high oil and gas pressures. The latter feature aids in prevention of gushers, thus reducing both environmental pollution and waste of oil and gas resources as well as conserving the natural reservoir pressure for greater production and rate of recovery of the products contained in the rocks. Barite is particularly well suited for drilling mud because it is clean, easy to handle, soft (nonabrasive), heavy, virtually inert chemically, and relatively inexpensive compared to many other available heavy materials. Barite is used in the manufacture of glass in continuous tanks. The addition of barite homogenizes the melt and gives greater brilliance and clarity to the finished glass. Ground barite, both unbleached and bleached by sulfuric acid, is a common industrial filler, extender, and weighting agent. The rubber industry is a major consumer of barite as a filler. Barite also is added to bristolboard, heavy printing paper, playing cards, rope finishes, brake linings, clutch facings, plastics, and linoleum, to name but a few uses. Bleached barite has long been an extender in white lead paint because of its weight. The low index of refraction of barite, however, makes its ability to cover marks poorer than some other substances, but its low capacity for absorption of oil is a good feature. Off-color or unbleached barite can be used as a filler in colored paints. In the construction industry, some lump barite is used in concrete aggregate to weigh down pipelines buried in marshy areas and to shield nuclear reactors. Because barite absorbs gamma radiation well, its use reduces the amount of expensive lead shielding otherwise

Jan 1, 1983

By R. E. Heithecker

Almost every oil well drilled into limestone formations in Kansas is treated with hydrochloric (muriatic) acid upon completion: to increase potential capacity of well and thereby increase its "daily allowable" production; to shorten time required to produce recoverable oil; and to increase quantity of oil recovered ultimately from reservoir. Acid treating marked a forward step in the producing fields of Kansas; in fact, many old limestone fields that almost had reached their economic producing limit were "rejuvenated" with acid and their capacities to produce increased several times. It also caused a marked increase in the ultimate oil recovery of some old and nearly depleted fields of Kansas. The effect of the acid was due to the cleaning-out action by the acid at the face of the limestone, the enlargement of the small drainage channels, and the apparent penetration of the acid to previously undrained porous and saturated strata. Studies of the effects of acid were made in the Fairport field, three groups of wells in the El Dorado field and the Shutts field. Estimation of increased recoveries resulting from acid in these fields and groups of wells ranged from 1000 to 2400 bbI. per acre. Limestone structures that had been tested by drilling and found noncommercial were later completed as commerical oil-producing formations through the use of acid. The Kansas City formation, Valley Center field of Kansas, is an example. Increased oil production and revenue from the old fields justified the reconditioning of equipment, which in most cases had become in poor mechanical condition. The first treatment with hydrochloric acid of an oil well in Kansas was in October 1932, and by the end of 1937 almost 6000 wells had been treated. Many wells were treated more than once and the total number of treatments exceeded 8000 by the end of 1937. Approximately 12 3/4 million gallons of acid was required for these treatments. The report includes 15 illustrations and 16 tables.

Jan 1, 1939

By R. E. Heithecker

Almost every oil well drilled into limestone formations in Kansas is treated with hydrochloric (muriatic) acid upon completion: to increase potential capacity of well and thereby increase its "daily allowable" production; to shorten time required to produce recoverable oil; and to increase quantity of oil recovered ultimately from reservoir. Acid treating marked a forward step in the producing fields of Kansas; in fact, many old limestone fields that almost had reached their economic producing limit were "rejuvenated" with acid and their capacities to produce increased several times. It also caused a marked increase in the ultimate oil recovery of some old and nearly depleted fields of Kansas. The effect of the acid was due to the cleaning-out action by the acid at the face of the limestone, the enlargement of the small drainage channels, and the apparent penetration of the acid to previously undrained porous and saturated strata. Studies of the effects of acid were made in the Fairport field, three groups of wells in the El Dorado field and the Shutts field. Estimation of increased recoveries resulting from acid in these fields and groups of wells ranged from 1000 to 2400 bbI. per acre. Limestone structures that had been tested by drilling and found noncommercial were later completed as commerical oil-producing formations through the use of acid. The Kansas City formation, Valley Center field of Kansas, is an example. Increased oil production and revenue from the old fields justified the reconditioning of equipment, which in most cases had become in poor mechanical condition. The first treatment with hydrochloric acid of an oil well in Kansas was in October 1932, and by the end of 1937 almost 6000 wells had been treated. Many wells were treated more than once and the total number of treatments exceeded 8000 by the end of 1937. Approximately 12 3/4 million gallons of acid was required for these treatments. The report includes 15 illustrations and 16 tables.

Jan 1, 1939

By C. A. Siebert, D. J. Girardi

PRACTICALLY every metallurgical process in-volves, at some stage or another, the contact of a metal with a gas. Because of this, gas-metal re-actions are of great practical importance and have been subjected to numerous investigations. It has long been recognized that the presence of cuprous oxide in liquid copper has an important effect on its casting characteristics and .physical properties. This has led to the desirability of determining the quantitative relationships between cuprous oxide in the liquid copper and the usual gases present during processing. Such data are not only of practical importance but also of a theoretical interest in that they provide a means of applying the principles of physical chemistry to problems in applied metallurgy. The object of this investigation was to determine the quantitative relationship at equilibrium between the gases carbon monoxide and carbon dioxide and the cuprous oxide content of liquid copper. The reaction and its equilibrium constant may be expressed as follows: 2 Cu (liq) + CO2 (g) = Cu2O + CO (g) acu2o X aco/a2 cu X aco2 Here the underlined symbol Cu2O designates cuprous oxide dissolved in liquid copper and (a), the activity of the various constituents. The activities of carbon monoxide and carbon dioxide are assumed to be directly proportional to their re- spective partial pressures and the activities of cuprous oxide and copper are taken to be proportional to their respective mol fractions. The equilibrium constant may then be expressed as follows: K2 = Ncu2o X Pco [Ncu]2 X Pco2 where N = mol fraction The solubility of carbon monoxide and carbon dioxide in liquid copper is a rather controversial subject.'-' A review of the literature is given by 0. W. Ellis.' It appears that carbon monoxide and carbon dioxide are both only very slightly, if at all, soluble in liquid copper. Volskii and Slobodskoi5 determined the equilibrium between carbon monoxide, carbon dioxide, and liquid copper at 1100°C. Their results show a higher cuprous oxide content for a given CO/CO2 ratio than found in the present work. The system hydrogen, water vapor, and liquid copper was investigated by Allen and Hewitt8 over the temperature range of 1090" to 1350°C. Equilibrium values for the system carbon monoxide, carbon dioxide, and liquid copper calculated from these data agree reasonably well with the present work. Materials and Procedure The copper used was oxygen free, designated as OF and analyzed as 99.98 pct copper with no appreciable amount of any one impurity based upon spectrographic determinations. The carbon dioxide was cylinder gas averaging about 99.95 pct CO2 with air as the major impurity. The carbon monoxide was produced by passing carbon dioxide over heated charcoal. Alundum combustion boats were used as containers for the liquid copper. No appreciable reaction took place between the copper and the alumina. This was evident from the fact that the copper sample after a run did not ordinarily adhere to the bottom of the boat and that the

Jan 1, 1951

By T. B. Counselman

"C" VERYONE who has to calculate cyanide circuits, -¦-' using either thickeners, filters or both, realizes the headaches involved in solving a set of simultaneous equations. When you calculate a large number of these, based on experimental data, trying to arrive at the best flowsheet, you can spend days at the task. T. B. COUNSELMAN, Member AIME, is Manager, FluoSolids Division, The Dorr CO., Stamford, Conn. AIME New York Meeting, Feb. 1950. TP 2783 B. Discussion (2 copies) may be sent to Transactions AIME before March 31, 1950. Manuscript received Aug. 23, 1949. Herewith is presented a short method, equally accurate with the standard simultaneous equation method, and much quicker. Here for instance is the standard simultaneous equation method, for 100 tons per day of $10 ore, with the conditions assumed as below (fig. 1). Conditions Assumed a. 100 tons of ore per day crushed in cyanide solution. b. Discharge from all thickeners with 50 pct moisture. c. $10 value dissolved per ton of ore. d. 50 pct in mill and 50 pct in agitators. e. 400 tons of solution from thickener V precipitated to $0.02. f. Agitation with a dilution of 2 of solution to 1 of solids. g. Let V, W, X, Y and Z represent value in dollars per ton of solution discharged from the resvective thickeners. Equating Out of and Into Each Thickener 1. lOOVplus 400V = 500W plus (0.50 X $10 X 100) 2. 1OOWplus 600W= 500X plus lOOW plus (0.50 X $10 X 100) plus lOOV 3. lOOXplus 500X = 1OOWplus 500Y 4. 1OOY plus 500Y = 1002 plus 1OOX plus (400 X 0.02) 5. 100 Zplus l00Z = l00Y plus 100 tons of water (value $0.00) Simplifying: 1. v = W plus 1.00 2. W = X plus 1.20 3. X = Y plus 0.24 4. Y = 0.2Zvlus 0.064 5. 2Z= Y

Jan 1, 1951

By T. B. Counselman

"C" VERYONE who has to calculate cyanide circuits, -¦-' using either thickeners, filters or both, realizes the headaches involved in solving a set of simultaneous equations. When you calculate a large number of these, based on experimental data, trying to arrive at the best flowsheet, you can spend days at the task. T. B. COUNSELMAN, Member AIME, is Manager, FluoSolids Division, The Dorr CO., Stamford, Conn. AIME New York Meeting, Feb. 1950. TP 2783 B. Discussion (2 copies) may be sent to Transactions AIME before March 31, 1950. Manuscript received Aug. 23, 1949. Herewith is presented a short method, equally accurate with the standard simultaneous equation method, and much quicker. Here for instance is the standard simultaneous equation method, for 100 tons per day of $10 ore, with the conditions assumed as below (fig. 1). Conditions Assumed a. 100 tons of ore per day crushed in cyanide solution. b. Discharge from all thickeners with 50 pct moisture. c. $10 value dissolved per ton of ore. d. 50 pct in mill and 50 pct in agitators. e. 400 tons of solution from thickener V precipitated to $0.02. f. Agitation with a dilution of 2 of solution to 1 of solids. g. Let V, W, X, Y and Z represent value in dollars per ton of solution discharged from the resvective thickeners. Equating Out of and Into Each Thickener 1. lOOVplus 400V = 500W plus (0.50 X $10 X 100) 2. 1OOWplus 600W= 500X plus lOOW plus (0.50 X $10 X 100) plus lOOV 3. lOOXplus 500X = 1OOWplus 500Y 4. 1OOY plus 500Y = 1002 plus 1OOX plus (400 X 0.02) 5. 100 Zplus l00Z = l00Y plus 100 tons of water (value $0.00) Simplifying: 1. v = W plus 1.00 2. W = X plus 1.20 3. X = Y plus 0.24 4. Y = 0.2Zvlus 0.064 5. 2Z= Y

Jan 1, 1951

By Maurice Magee

The Ducktown ore deposits have been known, explored, and mined for 120 years. Eight massive sulfide ore bodies occur in highly folded and metamorphosed graywacke, graywacke conglomerate, mica schist, chloritegarnet schist, and staurolite schist of Precambrian age. The ore deposits are tabular bodies that have been extensively folded, generally conform to the enclosing rocks, but show local complex differences. The ore deposits, ranging in size from 250,000 tons to over 20 million tons, are composed principally of the minerals pyrrhotite, pyrite, chalcopyrite, sphalerite, and magnetite. Gangue minerals are quartz, calcite, actinolite, tremolite, hornblende, garnet, and masses of schistose wall- rock. Three fault systems are present that have influenced ore control and ore body configuration. Hydrothermal effects are evident in wall-rock alteration. Evidence of retrograde metamorphism is extensive in the wall and ore associated rock. Preliminary isotopic age dates have indicated four possible metamorphic events during the Paleozoic Era. Ore genesis is considered to be hydrothermal replacement of receptive beds, predominantly highly calcareous zones, quartzitic zones, and brecciated shear zones. Ore deposition is thought to have occurred during the Devonian Period, with later mobilization and recrystallization of the ore and gangue during Middle and Late Paleozoic times.

Jan 1, 1968

By Clarence W. Balke

SMALL buttons of fused tantalum have been produced by arc fusion in a vacuum, by drawing an arc between sticks of pressed tantalum and a tantalum-faced water-cooled copper block. However, ingots of appreciable size can be produced only by the heat-treatment of bars pressed from powder. The following outline covering the production of finished bars of tantalum by the methods of powder metallurgy is also used for the production of columbium, taking into account the difference in the melting points of these two metals. PRESSING THE POWDER With possibly a few exceptions, a pressing operation is one of the essential steps in the practice of powder metallurgy. In fact, the author's experience with a number of high-melting-point metals and with numerous types of hard carbide compositions has led him to believe that this operation is often one of the most important in the entire process, and frequently one of the most difficult to carry out in a satisfactory manner. Defects due to improper pressing can readily lead to a defective finished product. It is the author's opinion that rarely is a bar or other article pressed from metal powder in such a way that all parts of the piece are uniformly pressed. The nearest approach to uniformity of pressing is possibly attained when the powder is contained in a flexible receptacle, such as rubber, and is pressed under a liquid by hydrostatic pressure. However, this method is not generally applicable. Hydraulic pressing in steel dies where one or two punches are forced into the die must usually be resorted to. As the pressure in such a die is built up, the powder begins to cling to the walls of the die with a tenacity dependent upon the nature of the powder, and this results in a bridging action, so that the layers of powder adjacent to the moving punch are pressed more heavily than those further removed in the mass. Frequently, as the pressure is carried higher, there may be a mass slippage of the powder upon itself, with the result that slip cracks are formed within the pressed

Jan 1, 1938

By S. Warren Hobbs

The section of the Northwestern United States that includes the northern Rocky Mountains and adjacent areas to the west and east is one of large mineral production and important mineral potential. The metallic ore deposits vary widely in age and type and their geologic settings are similarly diverse. A brief resume of the region's physiographic characteristics and geology sets the framework for the selected ore districts that are described in following papers and makes it possible to place these ore deposits in their proper reference to space and time.

Jan 1, 1968

By Robert B Sosman

The relative temperature distribution within a coke oven and among the ovens in a battery can be obtained automatically for the operator's guidance by sighting a total-radiation pyrometer on the face of the coke as it is pushed out, and recording the surface temperature. Keeping the instrument clean and keeping its view of the coke unobstructed by smoke and dust are the principal problems. Typical records from three plants are presented in this paper, showing that the temperature patterns are reproducible. Development OF Method The method of coke pyrometry described in this paper was introduced in 1936 by E. A. Lee, then Assistant Superintendent, now Superintendent, of the Coke Plant at Lorain Works, National Tube Co., Lorain, Ohio. At the request of the Coke Committee of the United States Steel Corporation, the Research Laboratory of the Corporation undertook to adapt the method to the somewhat different conditions met with at the Gary Works of the Carnegie-Illinois Steel Corporation, Gary, Ind., and at the Clairton Works of the same Corporation at Clairton, Pa. This work was done in cooperation with the Leeds and Northrup Co. of Philadelphia and later with the Brown Instrument Co. Division of Minneapolis-Honeywell Regulator Co., Philadelphia. We of the Research Laboratory wish to express our appreci- ation of the courtesies extended by Mr. Lee, by A. N. Cole, Superintendent of the Gary coke plant, and by D. P. Finney, Assistant General Superintendent in charge of coke-plant operations at Clairton. We are also indebted to the instrument companies for the loan of a part of the equipment. At Gary and Clairton the instruments were installed and various experiments were made by J. W. Bain, of the Research Laboratory of the United States Steel Corporation. Pyrometry of Coke The coke inside a by-product oven is almost completely inaccessible to pyro-metric instruments. The temperature in the walls can conceivably be measured with thermocouples, but the atmosphere is usually strongly reducing, a condition well known to be destructive to the accuracy of the customary high-temperature couples. In some plants, periodic readings are taken with an optical pyrometer sighted into the top of the combustion flues. This is a useful measure for safety and general control, as it tends to prevent the damage that would result from overheating of the ovens. It does not, however, tell much about the temperature of the coke itself, because of the continually changing gradient in the wall between the coke and the combustion chamber. The best indication of the temperature of the coke itself must therefore be obtained by observation of the product as it is pushed out of the oven. The human eye is very sensitive to variations in brightness of a surface, and particularly to differences in brightness over a continuous hot surface.

Jan 1, 1943

By Robert B. Sosman

The relative temperature distribution within a coke oven and among the ovens in a battery can be obtained automatically for the operator's guidance by sighting a total-radiation pyrometer on the face of the coke as it is pushed out, and recording the surface temperature. Keeping the instrument clean and keeping its view of the coke unobstructed by smoke and dust are the principal problems. Typical records from three plants are presented in this paper, showing that the temperature patterns are reproducible. Development OF Method The method of coke pyrometry described in this paper was introduced in 1936 by E. A. Lee, then Assistant Superintendent, now Superintendent, of the Coke Plant at Lorain Works, National Tube Co., Lorain, Ohio. At the request of the Coke Committee of the United States Steel Corporation, the Research Laboratory of the Corporation undertook to adapt the method to the somewhat different conditions met with at the Gary Works of the Carnegie-Illinois Steel Corporation, Gary, Ind., and at the Clairton Works of the same Corporation at Clairton, Pa. This work was done in cooperation with the Leeds and Northrup Co. of Philadelphia and later with the Brown Instrument Co. Division of Minneapolis-Honeywell Regulator Co., Philadelphia. We of the Research Laboratory wish to express our appreci- ation of the courtesies extended by Mr. Lee, by A. N. Cole, Superintendent of the Gary coke plant, and by D. P. Finney, Assistant General Superintendent in charge of coke-plant operations at Clairton. We are also indebted to the instrument companies for the loan of a part of the equipment. At Gary and Clairton the instruments were installed and various experiments were made by J. W. Bain, of the Research Laboratory of the United States Steel Corporation. Pyrometry of Coke The coke inside a by-product oven is almost completely inaccessible to pyro-metric instruments. The temperature in the walls can conceivably be measured with thermocouples, but the atmosphere is usually strongly reducing, a condition well known to be destructive to the accuracy of the customary high-temperature couples. In some plants, periodic readings are taken with an optical pyrometer sighted into the top of the combustion flues. This is a useful measure for safety and general control, as it tends to prevent the damage that would result from overheating of the ovens. It does not, however, tell much about the temperature of the coke itself, because of the continually changing gradient in the wall between the coke and the combustion chamber. The best indication of the temperature of the coke itself must therefore be obtained by observation of the product as it is pushed out of the oven. The human eye is very sensitive to variations in brightness of a surface, and particularly to differences in brightness over a continuous hot surface.

Jan 1, 1943

By Wallace E. Pratt

TO SERVE their primary function of balancing supply with demand. crude-oil prices must not only return full cost plus a reasonable earning to the efficient producer but they must also offer an additional reward to stimulate exploration sufficiently to maintain adequate reserves. High prices increase the volume and efficiency of exploration; low prig e- -Idle exploration. Over the last decade average prices for crude oil have been much lower than for the proceeding ten years, and lower even than the average over the life of industry. Under these circumstances no one should be surprised to learn that over this same recent period of discovery of new oil fields has also lagged and fallen below its average level for the previous decade. Crude oil prices have been too ion to support the required activity in wildcatting.

Jan 1, 1941

By E. A. Gulbransen, J. W. Hickman

ONE of the important factors that determine the resistance of a metal or alloy to further chemical reaction is the structure of the superficial oxide film A thorough understanding of the physical and chemical structure as well as the stability of the oxide film formed on the surface as a function of time and temperature of the chemical reaction might furnish clues as to the nature of the reaction process and the protective nature of the film A comprehensive program has been undertaken to study these phenomena This paper summarizes the structure of the oxide films formed on the metals iron, cobalt, nickel, chromium and copper at temperatures up to 700°C Before the introduction of the electron diffraction technique, it «as necessary to use either direct chemical analyses or X-ray diffraction analyses to determine the nature of the oxide film formed on the metal or alloy Chemical analyses yields information on the percentages of the several atomic species present in the film while X-ray diffraction analyses yield information on the atomic geometry In special cases the information obtained may be identical, but in general both view-points are necessary Much of, the early work was carried out on the oxidation of bulk samples where thick films were obtained The products were identified after cooling to room temperature by X-ray diffraction and chemical analyses Although much useful information has been obtained in this manner, little could be learned about the character of the protective oxides during the period when the films were actually protective Evidence concerning the chemical structure of thin oxide films has been made possible by the development of the electron diffraction reflection technique In this method the most fruitful investigations have been made by carrying out the reaction in situ at the temperature at which the film is actually protective LITERATURE The oxidation of iron has been extensively investigated by X-ray and electron diffraction Jackson and Quarrell1 found that oxide films formed and examined at the same temperature differed considerably from those allowed to cool to room temperature The results showed that below 400°C the oxide that was stable in intimate contact with iron was Fe304, between 515° and 900°C the stable film was FeO Above the upper change point of iron the oxide was found to be Fe304 prom 400° to 515°C , FeO, Fe304 or a mixture of the two oxides was found Recrystallization of the air-formed film below 400° and above 900°C led to the formation of Fe304 In the range where thicker films consisted of FeO, the air-formed film was converted to a new hexagonal oxide not previously described

Jan 1, 1946

By J. V. N. Dorr

DEADWOOD and the Black Hills were familiar names to me from childhood, for. I had an uncle who was among the earliest eastern investors there and I used to hear of the Uncle Sam mine and its rich ore back in the eighties. The spring of my junior year at college, in 1893, brought me an offer of summer work at the Deadwood & Delaware smelter, in Deadwood, and full of the thrill of the long journey from New Jersey, I went out as chemist and stayed four months. Within a week or two of my arrival, I went through the tragic experience of seeing an associate drink cyanide by mistake and die within a few moments. I shall never forget the horror of feeling that my lack of knowledge of an antidote might be responsible for his death, but I found later that the solution he drank was so strong that nothing could have been done. A year after graduation, when I had settled down to chemical research work in New York, an offer came to go back to the smelter in Deadwood, and within a few days I was again tramping down "the Gulch" with my lunch bucket and putting in the standard assay office shift of that day, from 7 a.m. to 6 p.m., with a half-day off on Sundays. During my absence East, the D. & D. smelter had been changed from a pyritic smelter, using native pyrite, and Homestake concentrate to matte the siliceous gold ores, into a copper-matting smelter using copper ores brought from Butte, over the newly-completed Burlington rail-road. The work was interesting, and the laboratory offered many opportunities for making improvements. I remember also undertaking experiments at home on a new method of gold precipitation for the chlorination process and leasing a mine in Strawberry Gulch that promised great things, but soon petered out.

Jan 8, 1927

By R. R. Boucher, O. J. C. Runnalls

A pronounced thermal effect has been observed on heating or cooling a1wninum-rich Al-U and Al-Pu alloys. From microscopic and X-ray diffractionstudies, the effectl has been attributed to trnsfor)nations in the inlemetallic phases UAl, and PuAl , involuing rearrangement or cluslering of vacancies The transformation obsrved in Al-20 wi oct U alloys occurred near the a Al-UAl4 eutectic tem-perature of 646°C making it difjicult to detect from heating curves. When cooling, howeoer, thermal mad X-ray analyses indicnted that the high-temperati~re phase labeled p UAL, precipitated initially during euitectic solidification. As solidification continued and after an induction period o-f 5 lo 20 tnin the nu-cleatiorz and growth of the low- twmperature phase, a UAl4 produced an euolution of energy which raised the observed alloy temperature by 1° to 2°C. in Al-Pu alloys the transformation occurred at 645°C, 5 deg below the eutectic solidification temperccture. The eslimated latent heat of transformation was 25 +5 cnl per g PuAl,. The high-tetnpevcl-ture forms of UAl, and PuAl, were easily 9-etccined by chill casting Al-U and Al-Pu alloys and on reheating the alloys the trcltzsforrnation to the a phase was sluggish even above 600°C. Separated single cryslals o-f UAl4, joy example, showed no evidence Of transformalion after heating for 16 hr at 620°C. The transformation rates increased yapidly enough with increasing temperature, however, that a a spontaneous liberation of energy lens observed on occasion when bealing cast Al-20 wt pet U to neal- the RECENT phase studies on A1-Pu alloys have indicated that earlier reported equilibrium diagrams should be modified to take account of several poly- morphic transformations in the intermetallic compound PuAl,.' During the course of the latter work an unexpected heat evolution was observed while cooling a solid alloy consisting of a mixture of a aluminum and PuA1,. The evolution occurred at 645°C, y below the a A1-Pu A1, eutectic solidification temperature. Subsequent thermal-analysis experiments with A1-U alloys showed that heat was evolved there also at a temperature nearly coincident with the a A1-UA1, eutectic solidification temperature of 646°. A search of the literature revealed that similar thermal effects had been observed before for both A1-U and A1-Pu but had never been fully explained.2,3 The purpose of the present paper is to describe thermal-analysis and X-ray diffraction experiments which have led to the conclusion that the thermal effects are due to transformations which involve the rearrangement of vacancies in the intermetallic compounds UA1, and PuA1,. EXPERIMENTAL PROCEDURE The A1-U alloys were prepared by heating super-pure aluminum (99.99 pct +) obtained from the Aluminum Co. of Canada in a graphite crucible surrounded by an induction coil. At 1000°C high-purity uranium metal produced by the Eldorado Mining and Refining Co., Ltd. was dropped into the liquid aluminum and was dissolved completely within 15 min. The impurities in the uranium were A1—4 ppm, Ca-4, C-70, Cr-3, Cu-6, Fe-30, Mg-2, Mn-10, Ni-25, Si-25, and Zn-2. The A1-Pu alloys were prepared by reacting plutonium dioxide with liquid aluminum under cryolite (3 NaF . AlF,) for 10 min at 1100°C in graphite crucibles exposed to the air. The plutonium was 99.8 pct pure, containing trace impurities of Ca, Cu, Fe, Pb, Si, and Zn. The liquid alloys were usually poured into water-cooled molds to provide castings of uniform composition from which samples could be cut for heat treatment and thermal-analysis experiments.

Jan 1, 1965

By N. Jaffee, J. E. Dorn

An activation energy of 27,400 5 1000 cal per mole was obtained for the creep of poly crystaLline aluminum over the temperature range of 273° to 350°K, at strains varying from 0.003 to 0.230. Stresses varied fronz 2250 to 6000 psi, strain rates from 0.1145 x 10-5 to 29.5 x 10~s min.-1. A strain temperature-compensated time correlatzon was oblained indicating that the structure was depedent solely upon the strain at a given stress; X-ray diffraction analyses and tensile tests on precrept specimens verified this. PREVIOUS investigations1 have revealed that the apparent activation energies for creep of high-purity polycrystalline aluminum are insensitive to the applied stress, strain, and strain rate. On the other hand, the apparent activation energy is dependent on the temperature1,2 as shown by the data reproduced in Fig. 1. Each plateau of this curve is associated with a unique rate-controlling dislocation mechanism for thermally activated creep. It is now very well-established that over the high-temperature range, where the activation energy is about 35,500 cal per mole, the creep rate is controlled by the dislocation climb mechanism. 3 Over the intermediate range of temperatures, from about 260° to 370°K, another unique activation energy, namely 28,000 cal per mole, is obtained. Current evidence strongly supports the contention that cross slip is the rate controlling mechanism for creep in this case: 1) Crystal recovery can occur by a number of mechanisms prominent among which are climb and cross slip. Astrom,4 using the Borelius micro-calorimeter, reported rapid crystal recovery of cold-worked polycrystalline A1 at 340° to 370°K giving an activation energy of 28,000 cal per mole and additional recovery at 455° to 478°K giving an activation energy of 3 6,000 cal per mole. Whereas the latter recovery process was clearly associated with the dislocation climb mechanism, the former, 28,000 cal per mole process could have arisen as a result of the cross-slip mechanism. 2) Single crystals of high-purity A1 favorably oriented for octahedral glide exhibit an activation energy for creep of about 3400 cal per mole over the range from 0° to 400°K and that of about 28,O:O cal per mole over the range from 600° to 775°K . Whereas the lower activation energy process is accompanied by the development of sharp slip-band traces, the 28,000 cal per mole process was uniquely characterized by extensive cross slip. 3) Theoretical calculations by Seeger and schoeck6 suggest an apparent activation energy for cross slip in A1 of about 24,000 cal per mole and another theoretical estimate by Friedel 7 gives the observed 28,000 cal per mole as the theoretical activation energy. It is therefore consistent with this evidence to, at least tentatively, ascribe the 28,000 cal per mole creep process in A1 to the operation of cross slip as the rate controlling mechanism. Although creep has been rather well-explored in the dislocation climb range, very little, excepting perhaps the activation energy, is known about creep in the cross slip range. This investigation was undertaken, therefore, to reconfirm the activation energy for creep in polycrystalline A1 in the intermediate temperature range and to study the strain-time relationship for creep at a constant stress in the cross slip region. EXPERIMENTAL PROCEDURE AND TECHNIQUE The three types of high-purity A1 alloy specimens described in Table I were used in this investigation. Specimens were milled from 0.100 in. thick cold-rolled sheets with their tensile axes in the rolling direction following which they were given a recrys-tallization and grain growth heat treatment at temperatures well above those which were subsequently employed in the creep tests.

Jan 1, 1962