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By David White

The submission of carefully prepared estimates of the oil reserves of the United States calls for no apology or explanation. In this country, petroleum is a rapidly wasting asset and an occasional appraisal of the amount remaining in the ground is a simple business procedure to safeguard the general welfare and the prosperity of the republic. The rumored danger of failure, in the near future, of the foreign supply on which we depend in constantly increasing amounts makes the immcdiatc review of our available reserves the more imperative. The Director of the U. S. Geological Survey, in March, 1921, requested the American Association of Petroleum Geologists to cooperate in the preparation of new estimates of the oil remaining in the graund. With the members of this cooperative committee, state geologists, regional geologists, oonsulting specialists, and geologists and engineers attached to many companies worked both independently and through subcommittees. The reports for districts, counties, fields, etc., after review by local or state committees, were discussed by the joint cooperative committee in conferences that, in some instances, were attended by the original compilers of estimates for the states or smaller areas. Finally the data were reviewed and the figures revised by the joint cooperative committee, so that the totals given in Table 1 represent the opinion of the committee, which was composed of F. W. DeWolf, W. E. Wrather, Roswell H. Johnsont Wallace A. Pratt, Alexander W. McCoy, Carl H. Beal, C. T. Lupton, G. C. Matson, K. C. Heald, W. T. Thom, Jr., A. E. Fath, Kirtley F. Mather, R. C. Moore, and David White, chairman. Oil geologists and engineers understand well the speculative nature and the chances of error that must attend estimates of the petroleum in the ground when they cover not merely prospective territory, but possible territory. Neither the character nor the magnitude of the factors of uncertainty is to be disguised. Further, the inevitable differences of opinion between geologists of equal rank and experience must also bc

Jan 1, 1923

By David White

The submission of carefully prepared estimates of the oil reserves of the United States calls for no apology or explanation. In this country, petroleum is a rapidly wasting asset and an occasional appraisal of the amount remaining in the ground is a simple business procedure to safeguard the general welfare and the prosperity of the republic. The rumored danger of failure, in the near future, of the foreign supply on which we depend in constantly increasing amounts makes the immcdiatc review of our available reserves the more imperative. The Director of the U. S. Geological Survey, in March, 1921, requested the American Association of Petroleum Geologists to cooperate in the preparation of new estimates of the oil remaining in the graund. With the members of this cooperative committee, state geologists, regional geologists, oonsulting specialists, and geologists and engineers attached to many companies worked both independently and through subcommittees. The reports for districts, counties, fields, etc., after review by local or state committees, were discussed by the joint cooperative committee in conferences that, in some instances, were attended by the original compilers of estimates for the states or smaller areas. Finally the data were reviewed and the figures revised by the joint cooperative committee, so that the totals given in Table 1 represent the opinion of the committee, which was composed of F. W. DeWolf, W. E. Wrather, Roswell H. Johnsont Wallace A. Pratt, Alexander W. McCoy, Carl H. Beal, C. T. Lupton, G. C. Matson, K. C. Heald, W. T. Thom, Jr., A. E. Fath, Kirtley F. Mather, R. C. Moore, and David White, chairman. Oil geologists and engineers understand well the speculative nature and the chances of error that must attend estimates of the petroleum in the ground when they cover not merely prospective territory, but possible territory. Neither the character nor the magnitude of the factors of uncertainty is to be disguised. Further, the inevitable differences of opinion between geologists of equal rank and experience must also bc

Jan 1, 1923

COLUMBIA SECTION STANLY A. EASTON, Chairman, FREDERIC KEFFER, Vice-Chairman, L. K. ARMSTRONG, Secretary-Treasurer, P. 0. Drawer 2154, Spokane, Wash. D. C. LIVINGSTON FRANK A. Ross The first meeting of the Columbia Section was held on March 24, as a part of the 1916 Northwest Mining Convention which was held under the -auspices of the Spokane Mining Men's Club assisted by the Spokane Chamber of Commerce, the technical program being in charge of the Spokane Engineering and Technical Association assisted by the local sections of the A. I. E. E., A. S. C. E., and A. I. M. E. The program of the successive sessions was carefully arranged with view to its application to mining, and in addition to the technical program there were exhibits of ores, minerals, devices, etc., of interest to the delegates, who numbered over 500. A portion of the program was also arranged with special reference to the requirements of the prospector and miner. A reception, a banquet, a complimentary luncheon, a regular daily call' of the Stock Exchange, a visit to the High Schools and to one of the substations of the Washington Water Power Company and to the Union Iron Works kept the visitors entertained, the ladies being looked after by a special committee of ladies who held open house during the entire week. Several important resolutions were passed by the Convention and one by the Columbia Section, A. 1. M. E. With Stanly A. Easton, chairman, presiding, the Columbia Section, American Institute of Mining Engineers, occupied the time between 2.00 and 5.30 p.m., March 24th, the Moorish room of the Spokane hotel being filled with members and their guests. "The Apex Law and the Mineral Surveyor" was a paper presented by F. W. Callaway and generally dis-cussed because of its local application in the Coeur d'Alenes, the conclusions being reached after expensive litigation between two of the large mining operators in that district.

Jan 6, 1916

By M. F. Hawkes

Austenite grain size has long been recognized by metallurgists as an important property of steels because of its influence on toughness, hardenability, ma-chinability and creep strength. Much research has been carried out on wrought steels to develop methods for disclosing austenite grain size, and to, provide knowledge of the grain-size characteristics of steels produced and heat-treated in various ways. Much less work in these fields has been done on steel castings; partly because, owing to the variable and complex microstruc-tures of cast steels, it is frequently very difficult to obtain results that are not questionable. The object of this investigation, therefore, was to establish, for a wide variety of carbon and alloy cast steels, suitable methods for disclosing austenite grain size and some knowledge of the grain-size variations to be expected. The steel foundryman is interested in austenite grain size at two different stages in the manufacture of his products; one is just after the steel is cast, and the other is after any reheating operation carried out above the critical temperature range. In both, it must always be kept in mind that the grain size being sought is actually a previous austenite grain size, and that the austenite no longer exists once the steel has cooled to room temperature. The prob-lem of the investigator is always to use evidence obtained from the structure at room temperature to deduce this previous austenite grain size, which was established the last time the steel existed at a temperature above the critical range. Since most steel castings today are at least annealed or normalized, the measurement of austenite grain size established by heat-treatment will he considered first. More than 50 commercially produced cast steels rcpresenting a wide variety of compositions and melting practices were used in the study. For each steel, grain-size determinations were made after each of three widely varying heat-treating schedules namely, one hour at I550'F, one hour at I700°F, and six hours at 1700 F. The list of steels and results obtained on them will be found in the appendix. (See page 530.) A discussion of the knowledge gained on the applicability of various test methods and on grain-size characteristics of cast steels in general follows. MEASUREMENT OF AUSTENITE GRAIN SIZE ESTABLISHED BY HEAT TREATMENT Methods Suitable foR Determining Austenite Grain Size after Heat-treatment at Ordinary Temperatures and Times It was desired, as one of the results of this investigation, to be able to recommend to steel foundries a method, or methods, of disclosing grain size best suited to accurate

Jan 1, 1948

By M. F. Hawkes

Austenite grain size has long been recognized by metallurgists as an important property of steels because of its influence on toughness, hardenability, ma-chinability and creep strength. Much research has been carried out on wrought steels to develop methods for disclosing austenite grain size, and to, provide knowledge of the grain-size characteristics of steels produced and heat-treated in various ways. Much less work in these fields has been done on steel castings; partly because, owing to the variable and complex microstruc-tures of cast steels, it is frequently very difficult to obtain results that are not questionable. The object of this investigation, therefore, was to establish, for a wide variety of carbon and alloy cast steels, suitable methods for disclosing austenite grain size and some knowledge of the grain-size variations to be expected. The steel foundryman is interested in austenite grain size at two different stages in the manufacture of his products; one is just after the steel is cast, and the other is after any reheating operation carried out above the critical temperature range. In both, it must always be kept in mind that the grain size being sought is actually a previous austenite grain size, and that the austenite no longer exists once the steel has cooled to room temperature. The prob-lem of the investigator is always to use evidence obtained from the structure at room temperature to deduce this previous austenite grain size, which was established the last time the steel existed at a temperature above the critical range. Since most steel castings today are at least annealed or normalized, the measurement of austenite grain size established by heat-treatment will he considered first. More than 50 commercially produced cast steels rcpresenting a wide variety of compositions and melting practices were used in the study. For each steel, grain-size determinations were made after each of three widely varying heat-treating schedules namely, one hour at I550'F, one hour at I700°F, and six hours at 1700 F. The list of steels and results obtained on them will be found in the appendix. (See page 530.) A discussion of the knowledge gained on the applicability of various test methods and on grain-size characteristics of cast steels in general follows. MEASUREMENT OF AUSTENITE GRAIN SIZE ESTABLISHED BY HEAT TREATMENT Methods Suitable foR Determining Austenite Grain Size after Heat-treatment at Ordinary Temperatures and Times It was desired, as one of the results of this investigation, to be able to recommend to steel foundries a method, or methods, of disclosing grain size best suited to accurate

Jan 1, 1948

By Sir Albert E. Kitson

The manganese ore deposits of the Gold Coast, British West Africa, occur in very ancient rocks, of both sedimentary and metamorphic types. In certain respects they have a strong resemblance to those of India and Brazil, as contrasted with those of Tertiary age in Georgia, but in this paper no careful comparison with them can be made. Viewed from the present condition of the manganiferous rocks, the oldest deposits are in the sediments. Later than these are the progressively metamorphosed representatives of these sediments. Youngest are the products of decay and degradation with the concentration of manganese oxide in the rocks of both groups. The oldest occurrences are in argillaceous and siliceous phyllites and slates, which show only a moderate degree of metamorphism. They belong to a series which also includes mudstones, sandstones, grits, conglomerates and subordinate limestones, with tuffs and lava-flows, largely of basic types. This has been named the Birrim System. Its age is unknown, for no definite fossils have been discovered in it. Since these non-fossiliferous strata at many plaees are of a character which in many parts of the world are suitable for the preservation of fossils, and which contain them, it is assumed that the Gold Coast deposits are pre-Cambrian. These rocks of the Birrim System have normally a northeast-southwest strike, and are folded, but not to any very great degree except in certain belts. From the Eastern Province of the Gold Coast they may be traversed diagonally across their strike for upwards of 600 miles, to the extreme northwestern corner of the Northern Territories. Thence they probably extend much farther into French territory.

Jan 1, 1927

By E. A. Lawrence

The experiences of Canex Placer Ltd. in establishing vegetation on a lead-zinc tailing pond are presented, hoping others with similar challenges will be benefited. History The tailing ponds are the result of 23 years of mining and milling operations, which ceased in August 1970. Roughly 7.9 million tons of lead-zinc ore were removed in that time. The ponds are located between Salmo River and B.C. Highway 3, about 8 miles north of Nelway near the Canada-U.S. border.

Jan 1, 1975

By A. K. Mukherjee, J. E. Dorn, J. D. Mole

Investigations were carried out on the effect of polyslip on the strain hardening of aluminum single crystals. The orientations investigated were those lor which the tensile axis was in the [001], [111], [112], and [012] directions plus another for which the Schmid angles for {111}(110) slip were 1 deg. The experimental data were analyzed on a model based on the intersection of dislocations with particular emphasis on the effect of polyslip on the activation volume for inter-section. It is shown that the rate of strain hardening inreases for those orientations wherein attractive dislocation intersections occur and that those orientations which produce the greater number of such intersections exhibit the greater strain hardening. Good correlation of the data is obtained with the concept that attractive junctions, as proposed by Saada, Play an important role in accounting for the rate of strain hardening. EXISTING concepts on the nature and cause of strain hardening in fcc metals have been deduced principally from experiments on the deformation of single crystals under single slip. The effect of crystal orientation on the shapes of the stress-strain curves for single slip have been summarized by seegerl and more recently by Clarebrough and Hargreaves.2 Tensile specimens whose axes fall near the center of the [001]-[011] line of the standard triangle of the stereographic projection exhibit the longest range of easy glide (Stage I) and the lowest rates of linear hardening (Stage 11) whereas specimens whose axes lie near fie [001]-[111] line of the standard triangle have limited or no easy-glide range and exhibit somewhat higher linear strain-hardening rates. Specimens whose axes lie near the [001] or the [ill] poles do not exhibit easy glide and have the highest rates of linear hardening. Kocks3 has shown that the highest rates of linear hardening Occur under Polyslip when the tensile axis coincides with the [111] or the [ 001] pole. Since the rate of strain hardening is sensitive to specimen orientation and the incidence of polyslip, these relationships might help to discriminate between various dislocation models for strain hardening in fcc metals. Previous attempts to analyze the effect of orientation on strain hardening,1"3 however, did not provide a unique answer to this problem. Consequently the present investigation was undertaken wherein additional data, particularly that for the effect of polyslip on the activation volume for intersection, was also determined in order to provide more complete information on the details of strain hardening. Whereas analyses of these data reveal that several recommended models for strain hardening are at variance with the facts, good correlation of the data is obtained with the concept that attractive junctions4 play an important role in accounting for the rate of strain hardening. I) EXPERIMENTAL APPROACH seegerl demonstrated that slip in fcc crystals at low temperatures is dependent on thermally activated intersection of glide dislocations with forest dislocations. This has been confirmed by tests on single crystals of aluminum by Mitra, Osborne and Dorn5 and on polycrystalline aluminum by Mitra and Darn.' Thus in accord with Seeger's theory, the shear strain rate, ?, below a critical temperature, T, is where .V is the number of points of contact per unit volume between forest dislocations and glide dislocations, A is the area swept out per successful intersection, b is the Burgers vector, v is the frequency of vibration of the segment of the glide dislocation undertaking intersection, U is the activation energy for intersection, k is Boltzmann's constant, and T is the absolute temperature. For aluminum, which has an extremely high staeking-fault energy, the constriction energy is negligibly small and therefore the activation energy decreases practically linearly with the stress according to as will be recomfirmed later, where Uo is jog energy at the absolute zero, G and Go are the shear moduli at the test temperature T and O°K, respectively, L is the spacing of the forest dislocations, t is the applied shear stress for slip, and tGo is the stress field that must be surmounted athermally.

Jan 1, 1965

By O. D. Gonzalez

Existing measurements for the steady-state permeation of hydrogen in a iron above 100°C have been examined for contribution of determinate errors. The analysis leads to a recommended equation for the permeability of hydrogen in a iron: o= (2.9 ±0.5) x 10-3 exp - (8400 ± 400)/RT cu cm (ntp H2) cm-1 sec-1 atm-1/2 THE permeability of a iron to hydrogen has been the subject of numerous investigations over the past 40 years, and at present there are thirteen sets of published results for the rate of steady-state permeation of hydrogen in a iron above 100°C. The numerical values in each set of results are entirely self-consis-tent, but the spread among the sets is too large to be attributed solely to experimental error, i.e., to error other than in the specimen itself. Several reasons have been advanced to explain the disparities, but to date the relative importance of experimental inaccuracy to the spread remains uncertain. The purpose of this report is to examine in detail the sources of determinate errors inherent in the experiments and to assess as far as possible the contribution of the errors to the results. The ultimate goal is the selection of values for the permeability and heat of permeation most nearly representative of hydrogen in a iron. The analysis is limited to those experiments in which the permeation rate was observed at steady state—a condition in which traps for hydrogen within the metal are filled to a fixed level15 so that the trapping mechanism is not reflected in the rate of passage of the gas. Furthermore only data are examined in which surface processes are judged to have little or no influence on the flow. It is hoped with these restrictions to obtain values of the permeability and the heat of permeation which will be as closely related as possible to the mechanism of lattice diffusion. I) DEFINITION OF TERMS; UNITS In this report the data for permeation are given in terms of a coefficient oj permeability, ?, which is defined by the equation: jt=?A/?x{p1/2-po1/2) [1] where jt is the total flow of gas normal to the surface of a membrane of planar geometry, e.g., a disc, of area A and thickness ?x; pi and po are the pressures in the input and output sides, respectively. For flow radial to the walls of a membrane of cylindrical geometry, e.g., a tube, the corresponding equation is: where 1 is the length of the cylinder, and ri and ro are the inner and outer radii, respectively. The flux normal to the surface is given by Fick's law: j= -D(dc/dx) [3] At steady state the concentration gradient will be constant, and integration of Eq. [3] gives for the total flow through a disc of area A and thickness Ax: h =-DA(co - ci) [4] where c, and ci are the concentrations of solute at the output and input surfaces, respectively. When surface control is absent, co and ci are given by Sievert's law c = Kp1/2, and substitution therewith into Eq. [4] gives directly Eq. [I] where ? = DK. Integration of Fick's Eq. [3] in cylindrical coordinates will give Eq. [2] where again ? = DK and is thus shown to be independent of geometry (provided that surface control is negligible). The coefficient of permeability, or simply the permeability,* must be expressed in proper units. In *The term permeability will refer in this report always to the coefficient defined above; permeation will be used to specify the general phenomenon of gas passage through a membrane. this report ? will be expressed in the units of cu cm (ntp H2) cm-1 sec-1 atm-1/2. The variations of D and K with temperature are given by D = Do exp(-Ea/RT) and K = KO exp(-?Hs/RT) where E, is the activation energy for diffusion and AH, the heat of solution, each usually expressed in calories per mole of solute. The variation of permeability with temperature will thus be given (for conditions where surface control is negligible) by ? = ?o exp(-?Hp/RT) where ?0 = DoKo and ?Hp = Ea + ?Hs. The units of ?0 are the same as those of 6, and??Hp will be expressed in calories per mole H. 11) SUMMARY OF PERMEABILITY RESULTS Table I gives the values reported to date for the permeability of H2 in a iron in terms of ?o and ?Hp. Except where noted the parameters listed were taken directly from the numbers reported by the various investigators with only a change in units. The temperature limits within which the listed ?o and ?Hp hold are given in column 7; the limits marked in parentheses in this column indicate the entire temperature range covered in each investigation. The listed values of ?o and ?Hp are those giving a linear plot of ln? against T-1 at the higher temperatures in each set of measurements, and thus presumably represent the case for which surface control was negligible. Column 6 gives values of 9 at a representative tem-

Jan 1, 1970

By C. L. Mantell

When considered from the viewpoint of world annual output, tin is one of the rarest metals. Its annual production is exceeded by that of iron, copper, lead, zinc. aluminum, magnesium; probably by that of the ferroalloys of manganese, chromium, and silicon, and possibly by the world production of sodium; while it exceeds only the output of such common metals as nickel, antimony, mercury, tungsten, molybdenum, silver, gold and the precious metals. Cassiterite, or tinstone, until the second World War was the only mineral that was an important source of tin. This mineral is frequently called "tin ore." The use of the term should be restricted to the ore containing the mineral, and not, in addition, to the concentrates of the mineral obtained from the ore or from stanniferous alluvial deposits. There is a general misuse of the term "tin ore" in the Malay Peninsula and adjacent localities, particularly where most of the mineral is obtained from secondary stanniferous deposits. The term "cassit-erite" is exclusively used in mineralogical, geological, and other scientific writings; it is unfortunate that it is not mole frequently used when referring to the occurrence of the mineral on an economic scale. Ores "Tinstone" js a very convenient old English term deserving a more frequent use. Tinstone is a dioxide of tin, or stannic oxide. When chemically Pure, as in the very rare transparent variety, it has a metallic content of 78.6 per cent tin. Frequently, however, the crystals and grains contain appreciable amounts of impurities, chiefly iron and tantalum. The impurities here referred to are those actually in the mineral itself. Tinstone usually has a deep brown or black color with an adamantine luster. Several other colored varieties are known, among them red ruby tin, yellow rosin tin, and yellow wax tin. the names jn each case being descriptive of the mineral's appearance. Ainalite is a variety of cassiterite con-taining almost g per cent of tantalum pentoxide. Sparable tin, tooth tin, and needle tin, as a result of their acute dite-tragonal pyramidal crystalline form, re-ceive their names from their crystallo-graphic appearance. Wood tin is a compact variety of cassiterite composed of radiating fibers resembling dry wood. Toad's-eye tin is a similar variety on a smaller scale in which the fibers appear to resemble the eye of a toad. Stream tin is water-worn tin-stone. Float tin is sometimes employed to describe the cassiterite occurring in soil derived from the weathered surface of a mineralized area. Stannite is an ore of tin of lesser impor-tance than cassiterite. It is a sulphide of tin, copper, and iron, sometimes known as tin pyrites or bell-metal ore. Its chemical com-position is sometimes expressed by the for-mula Cu,S.FeS.SnSz with zinc usually present in varying quantities. The tin con-tent varies from 22 to 27 per cent and there is about 29 per cent of copper, 13 per cent of iron, and 30 Per cent of sulphur.

Jan 1, 1944

By Willard L. Hunter

Four solvent extraction systems were studied to determine their efficiency jor extraction and separation of tantalum and columbium. Aqueous feed solutions of varying HF-HCl concentrations and metal content were contacted with equal volumes of cyclohexanone, 3-methyl-2-butanone, and 2-pentanone and solutions of varying HF-H2S04 concentrations were contacted with equal volumes of 2-pentanone. One multistage continuous test was made in a polyethylene pulse column using cy clohexanone as the organic phase. In each system studied, columbium and tantalum purities in excess of 95 pct with respect to each other were obtained in single-stage tests at low acidities in the feed solution. Separation factors ranging from 1700 to 2400 were obtained when rising HF-HCl mixtures in the aqueous phase. Best results were obtained when a solution of HF-H2S04 was used as the aqueous phase and 2-pentanone as the organic phase. A separation factor in excess of 6000 was obtained in one stage with aqueous solution concentrations of 2 _N HF and 2N H2S0,. When acid concentrations were increaszd to 52 HF and 10 _N H2S0,, 99.9 pct of the tantalum and 98.2 pct of the columbium initially present in the feed solution were transferred to the organic phase. The separation of columnbium and tantalum obtainable by means of the solvent extraction systems presented in this paper was found to corn -pare favorably with other systems, including the HF-H2SO4-methyl isobutyl ketone system currently used by most producers for the extraction and separation of these metals. TANTALUM and columbium are always found together in minerals of commercial significance, although the proportion of the two metals in ores varies within broad limits. Columbium is estimated to be 13 times more abundant than tantalum. Five methods generally employed for the separat:ion of these metals are: 1) fractional crystallization (the Marignac process),2 2) solvent separation, 3) fractional distillation of their chlorides, 4) ion exchange, and 5) selective reduction. Of these methods, the one currently used by industry to the greatest extent is that of solvent separation. One of the early technical developments in solvent separation of tantalum from columbium was reported by the Bureau of Mines: the HF-HC1-methyl isobutyl ketone system; data were presented for both laboratory and pilot-plant experimentation.3 Of twenty-eight organic solvents tested for their ability to extract tantalum from an HF-HC1 solution of columbium and tantalum, 3-pentanone (diethyl ke-tone), cyclohexanone, 2-pentanone, and 3-methyl-2-butanone were chosen for further study. Data on the HF-HC1-diethyl ketone system has been published4 and data describing the use of cy clohexanone, 2-pentanone, and 3-methyl-2-butanone as the organic phase are included in this report. RAW MATERIAL The source of tantalum and columbium oxides for this study was ('Geomines" tin slag from the Manono Smelter, Cie Geomines, Gelges, S.A., Congo. In order to extract the valuable Ta-Cb content, the slags were carbided, chlorinated, and the sublimate from chlo-rination was hydrolized and washed free of chloride with water. The washed material was air-dried and stored in a stoppered container. Throughout the paper, "feed material" refers to this mixture of hydrated oxides which was employed because of its high solubility in aqueous solutions. Typical analysis of the hydrated oxides is shown in Table I. I) HF-HC1-CYCLOHEXANONE SYSTEM Batch Separation. Effect of Acid Concentration. To determine the effect of varying the acid concentration upon the transfer of tantalum and columbium, a series of tests was made in which approximately 2.5 g of feed material was added to 25 ml solutions of 2, 4, 6, 8, and 10 N HF and 0 through 5 N HC1. Tantalum pentoxide concentration of the solu%ons was approximately 21 g per liter and columbium pentoxide was 14 g per liter. These starting solutions were shaken with equal volumes of cyclohexanone in 100 ml polyethylene bottles for 30 min. The phases were carefully separated in 125 ml glass separatory funnels. The time of contact of the solutions with the separatory funnels was kept at a minimum to reduce silica contamination. The measured phases were separated into 400 ml polyethylene beakers and the metal contents of each were precipitated by addition of an excess of ammonium hydroxide. Precipitate from each phase was filtered on ashless filter paper, ignited at 800" to 1000°C for 45 min, weighed, and analyzed by X-ray fluorescence.5 Data tabulated in Table I1 and illustrated in Fig. 1, show that maximum separation of tantalum from columbium for each HF concentration was obtained with no HCl present. The purest tantalum product was obtained with some HCl present. The highest separation factor was obtained at 2 N HF and

Jan 1, 1970

By A. Ghosh, T. B. King

The kinetics of the discharge reaction: 20'- (in silicate melt) = O,(g) + 4e- at a platinum anode in lithium silicate melts have been studied al 1350°C by galvanostatic methods. Plots of the sleady-state overpotential, q, as a function of the logarithm of the current density, i, showed injlections and were linear only at high current densities. The value of the overpotential was influenced by bubbling gas through the electrolyte. The ocer potential was also studied as a function of time. The rise and decay of overpotential were very slow processes. At low current densities transport is the likely rate-controlling process but at high current densities passivation of the electrode, Presumably by an oxide film on the surface, seems to be a contributory functor. IT is well-established that molten silicates behave as electrolytes'5 and, except in a few cases,6 conduction is entirely ionic. Moreover, it is supposed that a possible, and perhaps predominant, mechanism for phase boundary reactions between metals and slags is similar to that in corrosion whereby anodic and cathodic processes occur at unrelated sites, the metal serving to conduct electrons.1'8 Thus electrochemical studies of some slag-metal reactions would seem to be a useful way to diagnose the rate-controlling steps in the overall reaction. The electrochemical method is, in principle, a better diagnostic tool than the direct chemical method for the following reasons: 1) The partial electrochemical reactions, which are simpler than the overall reaction, may be studied individually. 2) The rate of reaction can be controlled at will and independently of the concentrations of reactants. 3) Fast reactions can be studied by relaxation methods.' Esin and his coworkers5'10"12 have pioneered such studies in silicates and have deviloped some ingenious techniques. Not all of their findings, however. can be accepted without a good deal of further work. In this investigation, the kinetics of the oxygen discharge reaction: 202- (in silicate melt) = Oz(g) + 4e- [I] at a platinum electrode were studied by both steady-state and transient galvanostatic techniques. Interest in this reaction was first developed as a result of the findings of Fulton and chipman13 that the reduction of silica, in a silicate slag, by carbon, dissolved in liquid iron, is a very slow reaction. Subsequent work, for example, by Rawling and ~lliott,'~ has demonstrated that the reaction under these conditions must be slow, because the rate is limited by diffusion of oxygen in the iron to the metal-crucible phase boundary at which a CO bubble may be nucleated. Further work by Tarassof,'~ in which the reduction of silica by aluminum dissolved in copper was studied, has shown that under these conditions, where carbon monoxide evolution is not involved, control of the reaction rate resides in diffusion of silica in the slag phase. However, there is no practical way of inducing sufficient convection in the system to make it clear that the phase boundary reaction is indeed fast. The overall reaction of silica reduction involves the discharge of silicon ions at cathodic sites and oxygen ions at anodic sites. In the examples cited, the discharged ions are dissolved in a liquid metal. In the present study of oxygen ion discharge, gaseous oxygen may be evolved at high current densities or oxygen may simply dissolve, possibly as oxygen molecules, in the silicate at very low current densities. The discharge of an oxygen ion at an anode must, in silicates less basic than the orthosilicate composition, be preceded by a reaction in the vicinity of the electrode, such as: which makes oxygen ions available. Platinum was chosen as the working electrode since it is comparatively inert to oxygen and is, therefore, expected to come rapidly into equilibrium with the electrolyte and with gaseous oxygen. Minenko, Petrov, and Ivanova16 have measured the electromotive force at a platinum electrode in molten silicates as a function of the partial pressure of oxygen in the atmosphere, the concentration of oxide ions in the melt, and the temperature. They found platinum to behave as a reversible oxygen electrode. At two different oxygen pressures, Po2 (I) and Pq (11). the electromotive force is given by: where F is the Faraday constant, equal to 23,060 cal per v equivalent, indicating that the electrode reaction is as written in Eq. [I.]. Platinum has been similarly used in molten silicates by other inve~ti~ators. "'~~ In this investigation platinum was used only as an anode, since a current deposits other elements on its surface and changes its characteristics.

Jan 1, 1970

By D. J. McAdam, G. W. Geil, D. H. Woodard, W. D. Jenkins

.In a series of papers, the authors and their associates have shown that the resistance of a metal to fracture is a function of all three principal stresses. Consequently since a technical cohesion limit is defined as the technically deter-minable resistance to fracture under a specific stress system, the technical cohesive strength comprises an infinite number of technical cohesion limits corresponding to the infinite number of possible combinations of the principal stresses. As shown in the previous papers, the technical cohesive strength increases with plastic deformation, with decrease in temperature, and with increase in the strain rate. The technical cohesion limit, therefore, is affected by the same factors that affect the flow stress,$ namely, the stress system, plastic deformation, temperature, and the strain rate. The effect of each of these factors on the fracture stress is qualitatively the same as its effect on the flow stress. The effect of any of the factors may be represented by a curve of cohesion limits, although only one point on the curve may represent actual fracture. Since the term "fracture stress" has come into general use with the same significance as technical cohesion limit, the authors are here using the shorter term with the understanding that it does not always refer to actual fracture. In the general investigation described in the previously-mentioned papers, 10-18,20,21,23 the influence of the stress system on the fracture stress was studied by means of tension tests of notched specimens. When a circumferentially notched cylindrical specimen is subjected to longitudinal tension, the minimum cross section is under transverse radial tension. The mean radial stress increases with the depth and sharpness of the notch, but is always less than the longitudinal stress. The greatest principal stress (S1), therefore, is longitudinal, and since the radial stress is effectively equal to the circumferential stress, the transverse principal stresses are equiaxial in that plane (Sz = S3). By the use of notched specimens in tension tests it was shown that the fracture stress increases with increase in the radial stress ratio (s3/s1) The evidence is based not only on the results of tests to fracture at various constant temperatures, but also On results of two-stage tests, in which each specimen was plastically deformed a predetermined

Jan 1, 1949

By Thomas Watson

Introduction THE occurrence of zircon in pegmatites of acidic composition is recorded by many observers both in this country and abroad, and they form one of the most important geologic modes of occurrence of the mineral.' As is well known, commercially the most important American locality for zircon is near Zirconia in Henderson County, North Carolina, where many tons of the mineral have been obtained from a kaolinized pegmatite dike 100 ft. wide and traced for 1 ½ miles along the direction of strike N. 50° E. Zircon may be developed in pegmatites as inclusions in the principal rock-forming minerals, chiefly quartz and feldspar, and as a separate megascopic constituent in the form of grains and crystals not exceeding, as a rule, 2 in. in size, and usually smaller. In the Henderson County, North Carolina, pegmatite, zircon occurs in prismatic crystals with pyramidal terminations measuring up to 30 mm. in diameter, associated chiefly with the feldspar. In some of the apatite veins of Canada, which are closely allied to pegmatite dikes, zircon is reported in crystals upward of 6 in. in length and 2 in. 'and more in thickness. Zircon in large masses occurs in Virginia in the well-known pegmatites near Amelia in Amelia County, and near Gouldin in Hanover County. Both localities are in the middle eastern portion of the Piedmont Plateau province, and are separated by a distance of about 40 miles in a northeast-southwest direction. The rocks of both areas, including the pegmatite bodies, are in an advanced stage of decay, and, the hard and moderately fresh rocks are concealed beneath a cover of variable thickness of rock decay derived by the normal processes of weathering. Exposures, there-

Jan 7, 1916

By J. W. Schroeder

SEAMLESS pipe, the product produced from piercing a solid round billet of steel by the Mannesmann process, was first produced in the latter half of the 19th century, the Mannesmann machine having been patented in 1885. The products of other processes also have been termed seamless pipe; for example, the cylindrical section produced by "cupping," which consists of forming a cup from a flat plate or disk and further elongating the cup into a tube by passing it through a set of reducing dies. The purpose of this paper is to discuss some of the more important metallurgical factors and their relationship to the economical production of seamless pipe produced by the Mannesmann piercing process. The first seamless tube plant in America was established at Shelby, Ohio, in 1891, and was employed in the manufacture of bicycle tubing. For a number of years the bicycle industry was the only user of seamless tubing, and this tubing was produced by hot-rolling pierced billets imported from Europe and finishing on the cold drawbench. At the turn of the century, the automotive industry was responsible for an increase in the demand for seamless tubing. The growth of this industry was the dominant factor leading to the phenomenal growth of the petroleum industry, which in turn created a tremendous demand for seamless pipe. In addition; the old lapweld iron boiler tubes for stationary and locomotive boilers were replaced gradually by seamless tubes. Since 1929, the production of seamless steel pipe and tubes has increased over loo pct. In 1929, 1,459,9031 net tons of seamless pipe was produced, including both hot-finished and cold-drawn material, as compared with 3,087,3122 net [ ] tons in 1948. Table I gives the distribution of seamless pipe by classes for 1948. METALLURGICAL PROBLEMS From a metallurgical standpoint, the production of seamless pipe has presented many problems. Practically every type of steel, carbon and alloy, with the exception of the superalloys developed during World War II, has been pierced and rolled successfully into tubing. This includes bessemer, open hearth, by the stationary and duplex processes, and electric steels. The range of sizes produced is no less staggering to the imagination, when it is considered that the hypodermic needle, which is 0.016 in. diam with a wall thickness of 0.004 in., and pipe for gas or oil transmission lines, with a 26 in. OD, are both seamless tubes. Between these extremes, the range of diameters and wall thicknesses meets most present-day demands for seam-

Jan 1, 1951

By D. J. McAdam, G. W. Geil, D. H. Woodard, W. D. Jenkins

INTRODUCTION IN a series of papers, the authors and their associates have shown that the resistance of a metal to fracture is a function of all three principal stresses. 10-18,20,21,23,[1] Consequently since a technical cohesion limit is defined as the technically determinable resistance to fracture, under a specific stress system, the technical cohesive strength comprises an infinite number of technical cohesion limits corresponding to the infinite number of possible combinations of the principal stresses. As shown in the previous papers, the technical cohesive strength increases with plastic deformation, with decrease in temperature, and with increase in the strain rate. The technical cohesion limit, therefore, is affected by the same factors that affect the flow stress,§ namely, the stress system, plastic deformation, temperature, and the strain rate. The effect of each of these factors on the fracture stress is qualitatively the same as its effect on the flow stress. The effect of any of the factors may be represented by a curve of cohesion limits, although only one point on the curve may represent actual fracture. Since the term "fracture stress" has come into general use with the same significance as technical cohesion limit; the authors are here using the' shorter term with the understanding that it, does not always refer to actual fracture. In the general investigation described. in the previously-mentioned papers,10-18,20,21,23 the influence of the stress 'system on the fracture stress was studied by means, of tension tests of notched specimens. When a circumferentially notched cylindrical' specimen is subjected to longitudinal ten-, sion, the minimum cross section is under " transverse radial tension. The mean radial stress increases with the depth and sharpness of the notch, but is always less than the longitudinal stress. The greatest principal stress (S,), therefore, is longitudinal, and since the radial stress is effectively equal to the circumferential stress, the transverse principal stresses are equiaxial in that plane (S2 = S3). By the use of notched specimens in tension tests it was shown that the fracture stress increases with increase in the radial stress ratio (S3/SI). The evidence is based not only on the results of tests to fracture at various constant temperatures, but also on. results of two-stage tests, in which each specimen was plastically deformed a predetermined

Jan 1, 1948

By John R. Anderson, Michael B. Bever

CARBON may affect the alloys of copper in several ways. Provided an alloying element does not oxidize preferentially, even minute quantities of carbon dissolved in liquid alloys of high copper content will form insoluble carbon oxide gases under oxidizing conditions. Gas porosity in castings of high-copper alloys can originate in this way. In certain alloys of low copper content carbon may have considerable solubility and may be an effective deoxidizer. In these alloys carbon will tend to suppress porosity. Carbon that is dissolved in the molten alloy is likely to be retained in the solidified metal. The effects of carbon on the physical properties of the metal are determined by the form in which it is present. Depending on the alloying elements and also on the cooling rate, carbon may precipitate as graphite, may form a carbide or may remain in solid solution on cooling. As solid copper does not dissolve a measurable amount of carbon, a carbon-bearing solid solution can occur only if the copper is alloyed with a large excess of an element that forms such a solution. The effect of graphite or of carbides on the properties of an alloy will depend on the size and distribution of the precipitated particles. As Hensel pointed out in discussion,1 the formation of an alloy carbide may interfere with the age-hardening properties of a copper alloy. One would also expect that the presence of carbides or of graphite will under certain conditions promote corrosion or high-temperature failure in nonferrous alloys. Since carbon has an effect on the soundness of castings and affects the structure and behavior of solid copper alloys, its solubility in the liquid alloys is of practical importance. The isothermal change of carbon solubility with alloy composition is of interest from a theoretical standpoint. The binary alloys of copper with manganese and with nickel are used industrially and serve as a base for more complex alloys. The solubility of carbon in each of these metals is known, but its solubility in their alloys has not been determined. EARLIER DATA The solubility of carbon in molten pure copper is about 0.0001 pct at 1100 °C and 0.0004 pct at 1475°C.1 Various authors2-6 have published data on the solubility of carbon in molten manganese. There is agreement on a value of about 6.7 pct in the temperature range 1217° to 1245°C. This solubility value corresponds to the formula Mn3C. It increases very little with increasing temperature. Corson7 states that carbon is soluble in copper-manganese alloys and that the

Jan 1, 1947

By Michael B. Bever, John R. Anderson

Carbon may affect the alloys of copper in several ways. Provided an alloying element does not oxidize preferentially, even minute quantities of carbon dissolved in liquid alloys of high copper content will form insoluble carbon oxide gases under oxidizing conditions. Gas porosity in castings of high-copper alloys can originate in this way. In certain alloys of low copper content carbon may have considerable solubility and may be an effective deoxidizer. In these alloys carbon will tend to suppress porosity. Carbon that is dissolved in the molten alloy is likely to be retained in the solidified metal. The effects of carbon on the physical properties of the metal are determined by the form in which it is present. Depending on the alloying elements and also on the cooling rate, carbon may precipitate as graphite, may form a carbide or may remain in solid solution on cooling. As solid copper does not dissolve a measurable amount of carbon, a carbon-bearing solid solution can occur only if the copper is alloyed with a large excess of an element that forms such a solution. The effect of graphite or of carbides on the properties of an alloy will depend on the size and distribution of the precipitated particles. As Hensel pointed out in discussion,' the formation of an alloy carbide may interfere with the age-hardening properties of a copper alloy. One would also expect that the presence of carbides or of graphite will under certain conditions promote corrosion or high-temperature failure in nonferrous alloys. Since carbon has an effect on the soundness of castings and affects the structure and behavior of solid copper alloys, its solubility in the liquid alloys is of practical importance. The isothermal change of carbon solubility with alloy composition is of interest from a theoretical standpoint. The binary alloys of copper with manganese and with nickel are used industrially and serve as a base for more complex alloys. The solubility of carbon in each of these metals is known, but its solubility in their alloys has not been determined. Earlier Data The solubility of carbon in molten pure copper is about o.oooi pct at II00°C and 0.0004 pct at 1475°C.l Various authors2""6 have published data on the solubility of carbon in molten manganese. There is agreement on a value of about 6.7 pct in the temperature range r2170 to 1245°c This solubility value corresponds to the formula Mn3C. It increases very little with increasing temperature. Corson7 states that carbon is soluble in copper-manganese alloys and that the

Jan 1, 1947

By John R. Anderson, Michael B. Bever

Carbon may affect the alloys of copper in several ways. Provided an alloying element does not oxidize preferentially, even minute quantities of carbon dissolved in liquid alloys of high copper content will form insoluble carbon oxide gases under oxidizing conditions. Gas porosity in castings of high-copper alloys can originate in this way. In certain alloys of low copper content carbon may have considerable solubility and may be an effective deoxidizer. In these alloys carbon will tend to suppress porosity. Carbon that is dissolved in the molten alloy is likely to be retained in the solidified metal. The effects of carbon on the physical properties of the metal are determined by the form in which it is present. Depending on the alloying elements and also on the cooling rate, carbon may precipitate as graphite, may form a carbide or may remain in solid solution on cooling. As solid copper does not dissolve a measurable amount of carbon, a carbon-bearing solid solution can occur only if the copper is alloyed with a large excess of an element that forms such a solution. The effect of graphite or of carbides on the properties of an alloy will depend on the size and distribution of the precipitated particles. As Hensel pointed out in discussion,' the formation of an alloy carbide may interfere with the age-hardening properties of a copper alloy. One would also expect that the presence of carbides or of graphite will under certain conditions promote corrosion or high-temperature failure in nonferrous alloys. Since carbon has an effect on the soundness of castings and affects the structure and behavior of solid copper alloys, its solubility in the liquid alloys is of practical importance. The isothermal change of carbon solubility with alloy composition is of interest from a theoretical standpoint. The binary alloys of copper with manganese and with nickel are used industrially and serve as a base for more complex alloys. The solubility of carbon in each of these metals is known, but its solubility in their alloys has not been determined. Earlier Data The solubility of carbon in molten pure copper is about o.oooi pct at II00°C and 0.0004 pct at 1475°C.l Various authors2""6 have published data on the solubility of carbon in molten manganese. There is agreement on a value of about 6.7 pct in the temperature range r2170 to 1245°c This solubility value corresponds to the formula Mn3C. It increases very little with increasing temperature. Corson7 states that carbon is soluble in copper-manganese alloys and that the

Jan 1, 1947

By Lucius W. Mayer

The iron-mines of the Ilsede Hütte Co. are at a town called Peine, about 20 miles east of the city of Hanover, on the railroad to Brunswick (Braunschweig). Hanover, the capital of the province, is a military city, of approximately 250,000 inhabitants, and Brunswick, 33 miles to the westward, has half this number. The mines here described are located in a hamlet called Bülten. The Ilsede Hütte Co. operates two mines, 1.5 miles apart, in this district, Gruber Bülten Adenstadt and Gruber Lengede Bodenstadt. It also operates an iron-mine north of Hanover, known as Eiserhaven, and one in the Harz mountains, the Georg Friedrich, at Grauhof. At Bülten a coarse conglomerate, a, Figs. 1 and 2, contains nodules of limonite, cemented together by calcium phosphate. The ore contains Fe, 25 to 45; Mn, 3 to 4; P, 0.6 to 1.4; S, 0.02 to 0.09; and CaCO3, 40 per cent. Directly above the conglomerate is limestone, b, followed by a mixture of clay and sand, c. Below the conglomerate is a hard clay floor, d. The ore-body, from 10 to, 12 km. long, and from 3 to 4 km. wide, has a maximum thickness of 20 m. It clips approximately 10° S.E., and strikes N. 45° E. Diamond-drill prospecting shows that the thickness diminishes to 1 m. as the end of the deposit is approached to the northward. At this point the deposit is 250 m. below the surface. In Fig. 2, the arrow, A, indicates the general direction of the work along the face, a, which is carried forward in a straight line for its entire length. At B, a train is approaching, which has come from the bench-track, shown at G, by a circuitous route, and is dumping the overburden behind the face, in the space left by the excavated rock. Formerly the work at this mine was essentially open-cut, the deposit having a very strong outcrop. Figs. 1 and 2 show also

Sep 1, 1908