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By Games Slayter

NO reasonably well-informed person believes that the role of minerals, both metallic and nonmetallic, will be any less important in the future than it has been in the past. The contrary is true. Industrialization is based on mineral resources and man's ability to make use of them. A nation's standard of living, its political and military power, will continue to depend largely upon the extent to which it is industrialized-and minerals are the raw materials both of the machine and the power to run the machine. Minerals are also the raw materials of human health and stamina. The world's healthiest, most vigorous, and most long-lived peoples have always been those that have lived in regions of the globe where the earth is rich, and kept rich, in the phosphates and other minerals required for the production of the so-called growth foods. Only a small proportion of the land surface of the globe is suitable under any circumstances for large-scale production of these and other essential foods. As things stand, only a part of this land is capable of such production either because the soil minerals have been exhausted by cultivation, or because they never existed in the soil in sufficient quantities.

Jan 1, 1943

By S. Whinery

In these times of sharp rivalry, both as to price and quality, among the makers and venders of engineering explosives, it is often desirable to be able to determine the relative energy or value of the various explosives offered for sale, in order to purchase intelligently ; or, having contracted for a large amount of an explosive of a certain standard quality, to be able to ascertain if the manufacturer keeps his product up to the specified standard. The simple and inexpensive apparatus described below was devised by the writer while engaged on the improvement of the Tennessee River, at MuscleShoals, under the direction of' Major W. R. King, U. S. Engineers, in the summer of 1879. It answered the purpose so well that it is thought that a brief account of it may be of interest to other engineers. It consisted, essentially, of an old blacksmith's anvil and a common striking hammer, such as is used for driving rock-drills. The anvil was placed face downward on solid, level ground. In what was then the top of it, a vertical hole, one and one-fourth inch in diameter and about one arid three-fourths inch deep, was made with a ratchetdrill. The surface of the anvil immediately around the drill-hole was made as true and smooth as possible with a file. Next, a new striking-hammer, weighing nine pounds, with a turned and true face, was selected ; and a handle, eleven feet long and about one and a half inches in diameter, was fitted into it so that it

Jan 1, 1886

By J. Norman Bulkley

As electrical power is used to a greater extent on the Rand than in any other mining center, it is thought that a short description of the methods used and results obtained may be of interest. In comparing Rand practice with that on other fields, several general factors should be borne in mind: First, the mines are all working on large tonnages of low-grade ore (average. $6.50). The annual crushing rate is about 27,000,000 tons. Second, the mines are all grouped udder the financial and engineering control of mining houses, so that the results of a group, rather than an individual mine, are open for study, and practice follows more uniform lines. Third, coal of fair quality (about 12,000 B.t.u.) can be obtained for $2 to $3 per ton., Good supplies of condensing water are, however, scarce, and have to be carefully stored. Power Supply Power is supplied by the Victoria Falls & Transvaal Power Co., Ltd., and its subsidiary, the Rand Mines Power Supply Co. Both companies, which are practically one from an engineering point of view, operate the following stations, all feeding into the same system.

Jan 2, 1916

By A. W. Ashbrook

There are essentially three main classifications for extractants: acidic, basic, and neutral. The acidic and basic are also referred to as cationic and anionic, respectively. Some extractants are shown in Table 11-1. Acidic Extractants Acidic extractants which are of use, because of cost and/or insolubility in water, are alkylphosphoric, sulphonic, aliphatic monocarboxylic acids and naphthalene derivatives.

Jan 1, 1978

PITTSBURG MEETING The One Hundred and Ninth Meeting of the Institute, for the presentation and discussion of technical papers, will be held at Pittsburg, Pa., Oct. 8, 9 and 10, 1914. This meeting is to be under the auspices of the Iron and Steel Committee, the Committee on Petroleum and Gas, the Committee on Coal and Coke, and the Committee on Non-metallic Minerals. Thirty papers have been secured by these Committees and will be presented at the meeting. These papers will be published in the September and October Bulletins. The Local Committee of Arrangements for this meeting is as follows: SAMUEL A. TAYLOR, Chairman. FRANCIS C. PHILLIPS. GEORGE S. RICE. C. F. V. Rys. KENNETH SEAVER. JOHN S. UNGER.

Jan 9, 1914

By G. Carman Ridland

In conjunction with a geological investigation of the silver-bearing veins at Contact Lake, Northwest Territories, Canada, a survey was made with a Geiger-Miiller counter of the gamma-ray emissions from the rocks in the vicinity of the mine workings. Discontinuous pitchblende veins have been encountered occasionally in the silver-bearing fissures, and the geophysical survey was undertaken with the hope that abnormally high gamma-ray intensities, if detected, might lead to larger and more continuous pitchblende discoveries. Before the instrument was used at Contact Lake, preliminary tests were made, first with laboratory specimens at Princeton University, and later over known pitchblende deposits at the Eldorado property, LaBine Point, N.W.T. The Geiger-Müller counter, as adapted for field use, is described; the technique of transporting and operating the instrument is outlined; and the general precautions to be observed are discussed. The results obtained at Great Bear Lake show that the instrument is capable of detecting not only a pitchblende ore shoot in a shear zone, but also the mildly radioactive "host rock" at a considerable distance from the ore body. Hence, use of the Geiger-Müller counter is urged, not just for the detailed search for an ore body in a shear zone, but for the detection of possible radioactive "host rocks" in large-scale reconnaissance surveys of unexplored regions made by prospectors and members of federal geological survey parties. Location.—Along the rocky eastern shores of Great Bear Lake, in the Northwest Territories of Canada, lies one of the world's great radium-producing areas. The Eldorado mine, owned and operated by the Eldorado Gold Mines, Ltd., is at LaBine Point; while the Contact Lake mine, operated by Bear Exploration and Radium, Ltd. (B.E.A.R.), lies 9 miles to the southeast of LaBine Point and 2 miles south of Echo Bay, an indentation in the eastern shore line of Great Bear Lake. Geology.—The Eldorado company obtains its radium by the mining of the mineral pitchblende, which is found associated with a complex variety of metallic and nonmetallic minerals1 in quartz-carbonate veins occurring in metamorphosed pre-Cambrian sediment aries. Most of the pitchblende is intimately associated with a brown quartz and belongs to an early hydrothermal stage of mineralization during which safflorite-rammelsbergite and minor cobalt-nickel minerals were also deposited. Some pitchblende occurs with a group of minerals belonging to a later stage of mineralization in which the gangue is mainly dolomite and sometimes ferruginous rhodochrosite. Associated with this group are native silver and lead-zinc-copper sulphide minerals. The Contact Lake property owes its existence to the mining of rich, native silver ore shoots, which are

Jan 1, 1946

By G. Carman Ridland

In conjunction with a geological investigation of the silver-bearing veins at Contact Lake, Northwest Territories, Canada, a survey was made with a Geiger-Miiller counter of the gamma-ray emissions from the rocks in the vicinity of the mine workings. Discontinuous pitchblende veins have been encountered occasionally in the silver-bearing fissures, and the geophysical survey was undertaken with the hope that abnormally high gamma-ray intensities, if detected, might lead to larger and more continuous pitchblende discoveries. Before the instrument was used at Contact Lake, preliminary tests were made, first with laboratory specimens at Princeton University, and later over known pitchblende deposits at the Eldorado property, LaBine Point, N.W.T. The Geiger-Müller counter, as adapted for field use, is described; the technique of transporting and operating the instrument is outlined; and the general precautions to be observed are discussed. The results obtained at Great Bear Lake show that the instrument is capable of detecting not only a pitchblende ore shoot in a shear zone, but also the mildly radioactive "host rock" at a considerable distance from the ore body. Hence, use of the Geiger-Müller counter is urged, not just for the detailed search for an ore body in a shear zone, but for the detection of possible radioactive "host rocks" in large-scale reconnaissance surveys of unexplored regions made by prospectors and members of federal geological survey parties. Location.—Along the rocky eastern shores of Great Bear Lake, in the Northwest Territories of Canada, lies one of the world's great radium-producing areas. The Eldorado mine, owned and operated by the Eldorado Gold Mines, Ltd., is at LaBine Point; while the Contact Lake mine, operated by Bear Exploration and Radium, Ltd. (B.E.A.R.), lies 9 miles to the southeast of LaBine Point and 2 miles south of Echo Bay, an indentation in the eastern shore line of Great Bear Lake. Geology.—The Eldorado company obtains its radium by the mining of the mineral pitchblende, which is found associated with a complex variety of metallic and nonmetallic minerals1 in quartz-carbonate veins occurring in metamorphosed pre-Cambrian sediment aries. Most of the pitchblende is intimately associated with a brown quartz and belongs to an early hydrothermal stage of mineralization during which safflorite-rammelsbergite and minor cobalt-nickel minerals were also deposited. Some pitchblende occurs with a group of minerals belonging to a later stage of mineralization in which the gangue is mainly dolomite and sometimes ferruginous rhodochrosite. Associated with this group are native silver and lead-zinc-copper sulphide minerals. The Contact Lake property owes its existence to the mining of rich, native silver ore shoots, which are

Jan 1, 1946

By F. Selig, A. S. Odeh

A second-order approximation to the exact solution of the diffusivity equation corresponding to the pressure build-up of a well producing at a variable rate is derived. This approximation is applicable when the well's shut-in time is larger than the total time elapsed since the well was first produced. The resulting equations are compact in form and easy to use. Thus, the need for Horner's' theoretically precise but rather laborious solution to the above problem is eliminated. In addition, these equations apply where the use of Horner's widely known approximate method is questionable. From a practical point of view, the reported method is best suited for analysis of drill-stem tests and short production tests conducted on new wells. INTRODUCTION The utility of drill-stem and short production tests in reservoir studies has long been recognized by the reservoir engineer. If interpreted correctly they could lead to a wealth of information upon which may depend the success or failure of reservoirs' analyses. Initial reservoir pressure and the average flow capacity are two quantities that are normally sought from a drill-stem and/or a short production test analysis. Pressures are the most valuable and useful data in reservoir engineering. Directly or indirectly, they enter into all phases of reservoir engineering calculations. Therefore, their accurate determination is of utmost importance. The flow capacity kh of the reservoir is indicative of its commercial capability. In addition, it can indicate the presence of a darnaged zone around the wellbore and, thus, the necessity for remedial measures. Of the several methods used to analyze drill-stem and short production tests, Horner's' method is by and large the most common. It applies to an infinite reservoir and or a limited reservoir where the effect of production has not been felt by the boundary. Horner's method makes use of the so-called "point-source" solution of the diffusivity equation. The point-source solution is approximated by a logarithmic function and the superposition theorem is utilized to give the familiar pressure build-up equation where is the shut-in time, q is in reservoir barrels per day and the rest of the symbols conform with AIME nomenclature. Eq. 1 was derived for a well which produced at a constant rate q from time zero to time t and was then shut in. In actuality, such a constant rate of production does not normally obtain. Therefore, a correction must be applied to Eq. 1 to account for the varying rates of production. Horner suggested two methods. The first, which results in a theoretically accurate solution, is rather lengthy and laborious and, thus, it is not suited for routine analysis. The second which has been termed a "good working approximation" is the one used by the majority of the reservoir engineers. In the second method, Eq. 1 is modified by simply introducing a corrected time t, and writing where q is the last established production rate prior to shut-in, and t, is obtained by dividing the total cumulative production by the last established rate. Horner's original paper does not give any indication that this method of correction is based on any theoretical justification. In addition, there is a question as to what constitutes the last established rate. In case of a drill-stem test some engineers use the average rate obtained by dividing the total fluid produced by the total flow time, while others calculate the average rate by dividing the total fluid produced by the last flow-period time. Obviously, different results obtain for the different flow rates used. Because of this, a simple method to the varying-rate case was developed which is theoretically sound and which defines clearly the flow rate and its associated time to be used in the calculations. The final equation arrived at is where q* and t* are a modified rate and time, respectively, and can be easily calculated. In addition, it is shown theoretically that Horner's approximate method, if used for a variable-rate case, gives the correct pressure but would not be expected to give the correct flow capacity. MATHEMATICAL ANALYSIS The general equation governing the flow of slightly compressible fluid in porous media may be written as The elementary solution to Eq. 4, representing an instantaneous withdrawal of Q units volume of fluid at the origin at t = 0, is known as the instantaneous sink

J. E. Stead, Middlesborough, England (communication to the author): Prof. Howe's valuable paper on cast-iron brings forward most prominently the correct explanation of the part played by combined carbon in pearlite and cementite, in determining the strength and hardness of cast-iron. On a previous occasioil I have shown that castings made by melting a white Cleveland iron and glazed iron, one containing 1.5 and the other from 4 to 5 per cent. of silicon, and each about 3 per cent. of carbon, were stronger than those made of ordinary foundry-iron; the difference in the final castings being a differ-

Jan 1, 1902

By John V. Beall

HEAVY-DENSITY separation processes, a commercial application of the sink-float test used in mineralogical laboratories for the separation of mineral particles by their difference in specific gravity, are the biggest development in mineral dressing since flotation, which was at about the same stage of development thirty years ago. The scope of their application has broadened and, though still in the development stage, they are being accepted in a constantly increasing number of commercial installations. This progress in mineral beneficiation is especially satisfying when we realize that our high-grade ore deposits are fast disappearing and a big factor in determining whether a hole in the ground is being sat upon by a liar or an honest citizen is how economically the ore dressers can concentrate comparatively low-grade ores. As early as the middle of the nineteenth century attempts were made to use aqueous salt solutions in a heavy-liquid separation for cleaning coal. But the original and recovery costs of these liquids were high and further, the fact that they were corrosive, unstable, and toxic added to the difficulty in using them.

Jan 1, 1948

• The Venezuelan Trade Mission to the United States announced that Bethlehem Steel Corp. will begin exporting iron ore from its El Pao concession, south of the Orinoco River in Venezuela, in about three months. The ore will be transported by rail from the mines to barges on the Orinoco and transshipped to ore vessels at the coast for shipment to the Sparrows Point, Md., plant. The Latin American business men warned that projected increases in the United States tariff on petroleum imports from Venezuela would force that country into bilateral trade agreements with other countries and would mean drastic curtailment of Venezuelan imports from this country. •Bethlehem, South American Gold and Platinum Co., and U. S. Steel are investigating the possibilities of securing American foodstuff for their South American mining camp commissaries through the International Basic Economy Corp. IBEC buys in quantity to supply its subsidiary companies operating in Venezuela and Brazil. The mining companies will rid themselves of this burdensome task as well as realizing a saving from the bulk purchases of IBEC. •Oliver Iron Mining Co. has begun construction of a fine ore and taconite agglomeration plant at Virginia, Minn. It is expected to be ready in six months. The plant will be used to experiment with the making of clinker cakes and egg-sized lumps by sintering machines and nodulizing kilns respectively; about 1 million tons per year will be produced. • Roof pinning has been adopted at the iron mines of TCI, near Birmingham, to support overlying strata as mining progresses. Favorable results have been obtained in that dilution of the ore has been reduced by 50% which is attributable to this method of supporting the roof. •An American mining engineering team has gone to Turkey for a two-year assignment assisting Turkish government agencies in the $45 million ECA development, mechanization, and construction of cleaning plants for the Zonguldak coal field, 200 miles east of Istanbul on the Black Sea. The group consists of James Beeley, John E. Good, John S. Lambright, David Renshaw, and Charles R. Weir, all of the Paul Weir Co. •Arthur F. Taggart describes a new way of training engineers by emphasis on broad, basic engineering courses on page 460 of this issue. •Lawrence T. Tierney, chairman of the National Bituminous Coal Advisory Council, released a report stating that the increase in oil imports since the latter part of 194$ has caused significant damage to the U. S. fuel economy. It has reduced the strength of and employment opportunities in the coal, domestic petroleum, and transportation industries, as well as in related service and supplier fields. •Women, camels, and donkeys are the beasts of burden of the Sahara, according-to the UNESCO World Review. •Increased demand for magnesium sheet in airplane construction ana other phases of the national security program have led Alcoa to establish a sheet magnesium rolling division at its New Kensington, Pa., works which will begin operation shortly. Novel prospecting methods being used by the USGS in its search for uranium include: shock-mounted instruments in light trucks,. Geiger-counter probes lowered into augur holes, and experimental airborne prospecting.

Jan 4, 1950

By Robert Goodwin, Frank R. Milliken

IN September 1939, the Ohio Copper Co. inaugurated the treatment of its copper-bearing mill tailings at Lark, Utah. These tailings had been accumulated during the regular operation of the Ohio Copper mine and mill over the period 1907 to 1919. Gravity concentration had been employed except for a comparatively short period in 1919, when flotation was used. The ore milled during that period assayed about 1 per cent Cu. The chief copper mineral, chalcocite, was disseminated in a shattered quartzite, mainly along fracture or cleavage planes. The quartzite gangue was extremely hard and grinding to liberation resulted in excessive sliming of the "sooty" chalcocite, with consequent high tailings losses. Recovery on the seven million tons treated was probably less than 6o per cent of the total copper content. As early as 1918, attempts had been made to sample the dump. In 1928, a complete sampling program was undertaken. The sampling consisted of seventy-four 5-in. post auger holes drilled to the full depth of the dump at regular intervals of 250 ft. Each 10-ft. portion thereof comprised a sample for analysis. Each sample was screened, rolled, divided into three parts, dried and assayed. The reject was retained for testing purposes. From the depth of the auger holes a contour map of the dump was plotted, Fig.1, which gives percentages of tonnage and copper content. The tonnage within the limit of the drill holes was estimated at about five million tons with an average content of 0.42 per cent Cu, 31 per cent of which (0.13 per cent) was acid-soluble. A screen analysis of the composite dump sample is shown in Table I. Flotation tests by several companies and individuals were then made, the results of [ ] which ranged from 62 to 74 per cent recovery. On the basis of these, a Zoo-ton pilot plant employing straight flotation was built and operated for a few months. Operation of this plant was unsuccessful, as no provision had been made to handle the copper-bearing solutions resulting from the water-soluble copper, a point that was overlooked in the laboratory test work. Attempts to decant the copper-bearing solution for precipitation in the usual manner ahead of flotation were not satisfactory because of low water recovery (owing to poor settling characteristics of the pulp) and contamination of the copper precipitate with unsettled slime. Low copper prices in 1931 necessitated the termination of testing. With the stimulus of higher copper prices in 1937, a review was made of metallurgical

Jan 1, 1940

By J. J. Jakosky

The strategic importance of the metallic minerals in our industrial economy, and the declining rates of discovery have focused attention on means of exploration for new mineral deposits. A consideration of exploration techniques leads to an attempt to evaluate the effectiveness of geo- physics as a tool for mining exploration. One means of evaluation will be to compare the use of geophysics in petroleum exploration with its possible uses in mining.

Jan 1, 1949

By P. K. Currie, J. V. Walters

Solution mining of magnesium salts (Carnallite and Bischofite) is taking place near Veendam, in the northeast Netherlands. The magnesium salts are used for the production of magnesia sinter, used as a base material for the manufacture of refractory bricks for furnaces. This paper gives, first, an introduction to the operational procedure followed in Veendam, with the emphasis on some of the unique aspects, and then discusses rock-mechanical aspects of the cavity behaviour. The creep behaviour of magnesium salts is described, and Finite Element calculations on cavity stability and potential surface subsidence are discussed.

Jan 1, 1985

By C. Kremer Bain

DURING the past several years of diamond drilling in Washington County, Mo., the St. Joseph Lead Co. has discovered a concentration of commercial lead-zinc ore at four different points within an area of 36 square miles. The largest and to date the most promising group of these orebodies is located in the Indian Creek area. It was considered to be of sufficient value to warrant development. The Indian Creek area is in the center of the northern half of Washington County, 11 miles northwest of Potosi, Mo., the county seat. The location is readily accessible from Potosi by car or truck over the all-weather Missouri State Highway No. 114. The topography is one of rolling relief, varying from an elevation of 700 ft above sea level on Mineral Fork and Indian Creek to a maximum of 1176 ft at High Point Tower. It is divided in equal halves between the drainage to Mineral Fork and to Indian Creek. The shaft site at 1060 elevation is on the divide between the two drainage areas. The Indian Creek side is rough and heavily wooded, with only a few cultivated clearings. The slopes to Mineral Fork are more gentle and rounded, with much of the area cleared for farm land. Most of the surface is covered with Potosi and Eminence formations, which show little evidence of any structure. Ore structure was worked out by extensive diamond core drilling, with holes varying in depth from about 700 to 1300 ft. As of Oct. 1, 1950, 218 prospect holes had been drilled within the 36-square mile area. The ore is disseminated galena with considerable accompanying sphalerite in the Bonne Terre forma-tion in the shape of irregular blanket-type deposits. The main controlling structural feature of the outlined mineral zone is a buried pre-Cambrian rhy-olite-porphyry ridge extending partly through the Bonne Terre formation, which laps against the por phyry and also covers it. The mineralized zone parallels and forms an irregular halo around the porphyry ridge and is concentrated in the Bonne Terre formation where the La Motte sandstone is cut out by the porphyry ridge. This is a very common mineral occurrence in the southeastern Missouri lead belt district. The La Motte sandstone, which normally underlies the Bonne Terre formation, is thus cut out entirely. In this area the Bonne Terre is usually about 275 to 320 ft thick, the La Motte varying in thickness from zero up to 400 ft. Commercial concentrations of ore are indicated at several places, the most notable being at the shaft site where an orebody at least 4000 ft long with widths of 500 to 600 ft has been outlined. The total thickness of mineralized rock reaches 150 ft in some holes, although total ore thickness runs from 8 ft to about 60 ft, often in more than one layer. Preliminary Planning Ore reserves as outlined lend themselves to open-stope mining with trackless haulage and mobile loading machines and drilling equipment. This type of equipment has proved to be very efficient during recent years in the company's lead belt operations. After a study of bids for shaft sinking and an estimation of comparative costs, it was decided that the shaft would be sunk by St. Joseph Lead Co. personnel using company equipment. Since the plant site is about 26 miles from the company's nearest lead belt operations, it was necessary to plan a complete surface plant, including mill, shops, office, change room, and warehousing facilities. Immediately following the filing of an application for a certificate of necessity, a headframe was selected for which detailed drawings were already available. The order was placed for fabrication so that it could be delivered and erected in time to serve for sinking the shaft. This eliminated the expense of a temporary headframe. Drilling was started on two churn drill holes near shaft location, and two 1000-gpm deep well pumps

Jan 1, 1954

By David W. Brunton

(San Francisco Meeting, October, 1911.) MINE-DRAINAGE and the ever-increasing demand for water on the plains have within the past few years necessitated the driving of a great number of adits and tunnels, including many of considerable size and great length. In most instances, ex isting conditions have called for extreme rapidity of execution; and this necessity, coupled with the high altitudes at which most of the work has been carried on, excessive freight-rates, and difficulty -of access, has involved many complex and interesting problems. One of the most rapidly executed undertakings of this class is the Laramie tunnel, recently completed for the Laramie-Poudre Reservoirs & Irrigation Co. This tunnel is driven through Green ridge, a spur of the Continental Divide, which separates the Laramie river from the Cache-la-Poudre in Laramie county, Colo. Green ridge is extremely persistent, and further northward in Wyoming is known as Sherman hill, the highest point on the Union Pacific railway. At the point where the tunnel is driven, two opposing bends bring these streams within 2.5 miles of each other, with a difference in elevation of 500 ft. The rock exposed on the banks of the two rivers does not differ materially in hardness; and, without a geological study of the conditions involved, it would appear that the difference in the depth of erosion of the two streams is due principally to the greater volume of water at this point in the Cache-la-Poudre, which has a drainage-area above the tunnel-portal of 110 sq. miles, as against 30 sq. miles of natural drainage for the Laramie. To increase the water-supply at the tunnel, however, this latter amount has been augmented by two side collection-canals, which bring the available drainage-area up to 84 square miles. The nearest railroad shipping-point to the eastern portal is

Apr 1, 1912

By R. H. Coats

MINING occupies a position of less importance than manufacturing or agriculture in Canada, but its relative contribution has increased greatly during the post- war period. Mineral production was only 5.14 per cent of the net value I of production of all kinds of commodities in 1919, but by 1936 the pro- portion had risen steadily to 12.76 per cent. Mining felt the depression, hut unlike agriculture, which is still ' sorely stricken, it has passed from early convalescence to complete recovery. For each of the last two years new high records were established for the industry as a whole and for the quantity of most metals produced. Mining has had a notable effect on - the growth of the power industry in Canada. Water power has been developed in the same or adjacent areas wherever mining camps have been 1 established, with few exceptions. Consumption of electrical energy by the mining industry gained 72 per cent within a decade, rising from 1604 million kw.-hr. in 1926 to 2754 in 1935. In. 1935 alone the mining industry purchased electric power

Jan 1, 1937

By Robert A. Rapp, Jan E. Verfurth

From the measurement of internal-oxidation band widths in Ag-In and Cu-A1 alloys, products for the solubility No and the diffusivity Do of oxygen in silver and apparent NODo products in copper have been obtained over a range of temperature. The NODO products for silver are in agreement with the product of the individually determined No and Do values of Eichenauer and Müller. Although interstitial diffusion of oxygen in silver is expected, the temperature-independent factor Do of the diffusion coefficient does not agree well with the theory of Wert and Zener. For Cu-A1 alloys internal oxidation does not follow the expression derived for ideal kinetics, since the apparent NODo product calculated from internal-oxidation measurements is a function of the alloy content in the specimen. Thus, unequivocal values for No or DO or even the product NODO in copper are not available from the literature. RELIABLE values for the saturation solubility NO and diffusivity DO of oxygen in fcc metals are lacking and difficult to determine, partially because internal-friction measurements are not applicable. Permeability experiments and Sieverts7-type adsorption -desorption methods3 have met with difficulty; however, Eichenauer and Müller4 have recently reported on the solubility and diffusivity of oxygen in silver as determined by the latter technique . Rhines, Johnson, and Anderson,5 and independently Meijering and Druyvesteyn,' introduced the possibility of deriving values for the product NODO in a metal from measurements of the widths of internal-oxidation zones (subscales) formed during the internal oxidation of alloys. In addition to these authors, several other investigators7-9 have made such measurements in various silver and copper alloys at various temperatures, mostly using me- chanically polished specimen surfaces. The purpose of this investigation was to determine over a range of temperature the calculated products NODO in silver and copper from systematic measurements of the widths of internally oxidized zones in Ag-In and Cu-A1 alloys, using specimens with electro-etched surfaces. Consider the internal oxidation of a dilute solid-solution alloy in which the base metal is not oxidized. If diffusion of oxygen is the rate-controlling step, then the depth 5 of the internal-oxidation zone is given by where y is a dimensionless parameter and t the oxidation time. Based on the solution of the diffusion equation, wagnerl0 has shown that under certain conditions several mathematical simplifications may be used in the evaluation of y, so that Eq. [I] may be expressed for the case that y « 1, and y(Do/DB) 1, where N(so)the is the equilibrium solubility (mole fraction) of oxygen in the solvent metal for the given oxidizing atmosphere, is the mole fraction of the solute metal in the bulk alloy, 4 is the diffusivity of the solute in the base metal, and v is the ratio of oxygen atoms to solute atoms in the precipitated oxide BO,. Rearranging Eq. [2] Maak' has derived an expression analogous to Eq. [3] for the case that an external-oxide scale, in addition to an internal-oxidation zone, is formed. For this combined external and internal oxidation for the case that 5/2 where 5 is the distance of the internal-oxidation front from the original external s.urface, and X is the distance of the external oxide/metal interface from the original external interface. The function F is defined by the expression

Jan 1, 1964

By R. J. Fruehan

The oxygen activity and concentration were measured in Fe-Cr-0 melts in equilibrium with an oxide phase at 1600°C (2912°F). The activity was determined by ,use of the following solid oxide -electrolyte galvanic cell CY-Cr8,(s) I ZrOz(CaO) I Fe-CY-G(saturated)(l) The oxygen concentration decreases with increasing Cr concentration to about 270 ppm 0 at about 7pct CY and then increases gradually. The activity coefficient of oxygen (fo) decreases with increasing Cr. In melts containing up to about 20 pct Cr, log f is approximately a linear function of wt pct Cr with a slope (e q 2) of —0.037. The activity of chromium was calculated and found to exhibit a small negative deviation from Raoult's law. From the activity and solubility data for low chromium melts, the free energy of formation of chromite, FeCr204, was found to be -79.8kcal per mole where pure liquid chromium and oxygen at I wt pct in Fe are the standard states. ThE effect of chromium on the chemical behavior of dissolved oxygen in liquid iron is of great importance in controlling the deoxidation of steels containing a significant amount of chromium. Chen and chipman' equilibrated Fe-Cr melts in the presence and absence of slag with hydrogen-water vapor mixtures. They concluded that at 1595°C chromite was the oxide phase in equilibrium with Fe-Cr alloys containing less than 5.5 pct Cr while at higher chromium concentration Cr,O, was the stable phase. In the composition range 0 to 10 pct Cr they found that the interaction coefficient, was equal to -0.041. Turk-dogan,' Schenck and Steinmetz,, and pargeter4 measured egr) in a similar manner and found the value to be -0.064,-0.04, and -0.052, respectively. McLean and Be11 evaluated egr) from their data on the equilibrium of Fe-Cr-Al-0 alloys with H2/H20 mixtures and found it to be -0.058. However, McLean and Bell's value should only be considered an estimate because the effect of aluminum on the activity coefficient of oxygen is about a hundred times greater than that of chromium. Consequently, an error in the value of egl) used, which at the present time is not well-known, or an error in aluminum analysis, which is present in very small quantities, will result in a significant error in egr). Fischer et a1.6 determined the interaction coefficient (eEr) in Fe-Cr-0 melts not in equilibrium with an oxide phase and containing less than 18 wt pct Cr at 1600°C electrochemically. They determined a value of -0.031 for egr). Hilty et aL7 measured the oxygen content of Fe-Cr melts in equilibrium with an oxide phase containing up to 50 pct Cr. They found that the solubility of oxygen decreased as the chromium content increased to about 6 pct Cr and then increased gradually. They concluded that the equilibrium oxide phase was chromite below 3 pct Cr, distorted spinel from 3 to 9 pct Cr, and Cr,04 above 9 pct Cr. Adachi and lwamotoa also investigated this system, but did not find Cr30,. They X-rayed the equilibrium oxide phases and did not find the presence of Cr,O,. They also X-rayed the oxide phase extracted from a 65 pct Cr melt which was heat treated and did not find metallic chromium as would be expected if Cr3O4 were the equilibrium oxide phase as indicated by the reaction : 3Cr3O4 — 4Cr2O:, + Cr [lj It was the purpose of the present investigation to determine the effect of chromium on the activity coefficient of oxygen in Fe-Cr melts by measuring the activity and solubility of oxygen equilibrated with an oxide phase in the composition range 0.18 to 50.5 wt pct Cr at 1600°C (2912°F). The activity of oxygen in the melts was determined by use of the following galvanic cell: The relationship between the partial pressure of oxygen in equilibrium with the melt and the reversible electromotive force of the cell (E) is where 11 = 4, F is the Faraday constant, pb, is the oxygen pressure in equilibrium with the meit and is the oxygen pressure in equilibrium with Cr203 as determined from the free energy data compiled by Elliott et al? The oxide phase in equilibrium with pure chromium was assumed to be Cr If Cr30, were the equilibrium phase the activities derived would be approximately the same, since the best estimated free energy of formation of Cr,O,, if it does exist, is approximately % the free energy of formation of The activity of chromium in Fe-Cr alloys at 1600° C was also determined from the measured electromotive force. The activity of chromium (aCr) is related to the electromotive force as follows: , The oxide phase in equilibrium with pure chromium and Fe-Cr melts from 10 to 52 pct is assumed to be Cr203 so that n equals three. If future work proves the existence of Crs04 in equilibrium with Fe-Cr melts and pure chromium, the experimental results can be reevaluated using a value of $ for n in Eq. 141. A value of ^ for n will make the activities about 10 pct higher. In order for Eqs. 131 and [4J to be valid the electrolyte, ZrOa(CaO), must exhibit predominantly ionic conduction at the temperature and oxygen partial pressure of its use. Previous work1' has demonstrated that ZrOz(Ca0) is predonlinantly an ionic conductor

Jan 1, 1970

Executive.. CHARLES F. RAND, Chairman. JAMES F. KEMP, JOSEPH W. RICHARDS. ALBERT R. LEDOUX, BENJAMIN B. THAYER. Membership. BENJAMIN B. THAYER, Chairman. WALTER R. INGALLS, JOHN H. JANEWAY, Jr., JOHN D. IRVING, HERMAN A. PROSSER. Finance. EDWARD L, YOUNG, Chairman. KARL EILERS, JAMES GAYLEY. Library. JAMES F. KEMP, Chairman. JOHN HAYS HAMMOND,3 E. GYBBON SPILSBURY,2 ALES. C. HUMPHREYS 4 BRADLEY STOUGHTON.

Jan 7, 1913