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By Arthur C. Simmons

In common with all other producing areas of the United States, Pennsylvania enjoyed increased activity and prosperity during 1937 (Table I). Prices of crude oil were better than for any year since 1930, and the Bradford average was $2.599, compared with an average price of $2.60 in 1930. Production and drilling activities were increased over 1936, although drilling for oil represented almost entirely a program of secondary development in both the water-flood areas and the air-gas repressuring areas. Bradford Oil Field The Bradford oil field continued to produce the major portion of Pennsylvania oil; however, no changes occurred in oil-production methods during 1937. Practically all of the production in the Bradford field is by water-flooding and the total number of oil and water wells completed within the area increased from 3205 in 1936 to 4112 in 1937; an increase of approximately one-third over 1936 completions. The percentage of water wells is approximately one-half of the total completions, although any specific five-spot development will have a proportion of 55 to 60 per cent water wells and 40 to 45 per cent oil wells. Offsetti~ig and boundary oil wells probably will result in a division or percentage of 50 per cent oil and 50 per cent water wells. The quoted figures for well completions include the entire Bradford field, approximately 12 per cent of which is in Cattaraugus County, New York. It is possible to make a segregation of production, but it is not possible to segregate well completions. Production in the Pennsylvania end of the Bradford field in 1937 totaled 15,076,000 bbl., or a daily average of 41,300 bbl. compared with a daily average of 37,000 hbl. in 1936.

Jan 1, 1938

By P. F. Gnirk, J. B. Cheatham

Single bit-tooth penetration experiments under static load were conducted on six rocks at confining pressures of O to 5,000 psi using sharp wedge-shaped teeth with included angles ranging from 30 to 120° In general, the force-displacement curves for all rocks exhibit an increasingly nonlinear and discontinuous behavior with decreasing confining pressure. The confining pressure at which a rock exhibits a macroscopic transition from predominantly ductile to predominantly brittle behavior during penetration vmies from about 500 to 1,000 psi for the limestones to greater than 5,000 psi for dolomite. The correlation between calculated values of force per unit penetration based on plasticity theory and experimental values is quite encouraging, even at confining pressures as low as 1,000 psi A qualitative correlation between volume of fragmented rock per unit energy input for a single bit-tooth and drilling rate for microbits appears to exist over a confining pressure range of 0 to 5,000 psi. INTRODUCTION Laboratory experiments utilizing a small-scale drilling apparatus have demonstrated that penetration rates are reduced considerably as a result of increasing the confining pressure from atmospheric to a few thousand psi?-3 This undesirable situation can, in general, be attributed to a combination of decreased efficiency of chip removal at the bottom of the borehole, increased rock-failure strength, and a possible change in the mechanism of chip generation and rock fragmentation with increasing confining pressure. To more fully understand the principles underlying the last circumstance, it is the purpose of this investigation to experimentally study the mechanism of single bit-tooth penetration into dry rock at low confining pressures and, in particular, to establish the confining pressure at which the penetration mechanism may undergo a brittle to ductile transition for various rock types commonly encountered in drilling. Confining pressure as used here refers to the differential pressure between the borehole fluid pressure and the formation-pore fluid pressure. EXPERIMENTAL PROCEDURE Using an experimental apparatus previously described: a single, sharp wedge-shaped tool was forced under a "statically" applied load into an effectively semi-in finite dry rock sample subjected to a prescribed confining pressure. To prevent the invasion of the con fining-pressure fluid into the pores of the rock sample during penetration, the exposed surface of the rock was jacketed with a layer of silicon putty.* Electrical instrumentation incorporated into the apparatus yielded a graphical plot of force on the tool as a function of penetration or displacement of the tool into the rock during an experiment. During the course of the experimentation the following conditions were maintained constant: (1) pore pressure — atmospheric (i.e., the rock was dry); (2) temperature — 75F; (3) rate of loading — essentially static (approximately 0.002 in./sec); (4) bit tooth — a sharp wedge-shaped tool loaded normal to the rock surface; (5) rock surface — smooth and flat; (6) drilling fluid — hydraulic oil; and (7) maximum depth of penetration — approximateiy 0.1 in. In addition, each experiment was performed on a different rock sample so the rock surface is free of a layer of cuttings and of any previous indentation craters. The influence of the corners of a borehole was neglected, since each rock sample was cemented inta a section of aLuminum tubing to simulate a semi-infinite body. Indentation experiments were made on a sandstone, two limestones, a marble, a dolomite and a schist with a 60' bit-tooth over a range of confining pressures from atmospheric to 5,000 psi and at a constant confining pressure of 1,000 psi for a variety of bit-teeth with angles ranging from 30 to

Jan 1, 1966

By John C. Branner

No precise geographic limits can be given for the zinc- and lead-region of North Arkansas. In general terms it lies N. of the Boston mountains and W. of the St. Louis, Iron Mountain and Southern railway; but the prospecting and the development of the ore-deposits have not gone far enough to outline more than vaguely the areas over which workable deposits are to be expected. The tardiness of the development of the region is due in part to its topography, as a hilly and partly mountainous country, through which there have been no railways until recently. There is no longer any doubt, however, about the existence in that region of large bodies of zinc-ores. I. General Geology. The general geology of the region is, in the main, quite simple, but that of the ore-deposits is less so. The zinc-regions of North Arkansas lie about the southern flanks of the Ozark dome. The rocks are approximately horizontal, but have a gentle southward dip away from the axis of this dome. Figs. 1, 2 and 3 show the broad features of the to-. pography and geologic structure. South of the zinc-region, the sandstones and shales of the lower Coal-Measures form the north-facing escarpment of the Boston mountains. Beneath the Coal-Measure rocks are the limestones and cherts of the Lower Carboniferous; and these rest upon Silurian and Ordovician beds. The uppermost beds (Coal-Measures) have been cut into by erosion along the mountain-slopes so that their edges or outcrops have a meandering or dendritic form. The same thing happens with the Lower Carboniferous beds; but these, haying been more or less protected by the overlying Coal-Measured, have broader bases, and cover a much larger area. In places,

Jan 1, 1902

By B. B. Cox

Iraq, formerly called Mesopotamia in Asiatic Turkey, became a kingdom under British Mandate after the world war and is expected to gain its independence in 1932 when it enters the League of Nations. The kingdom is shown on Fig. 1 in its relations to neighboring countries, to the Mediterranean Sea and to the Persian Gulf. It is slightly smaller than the State of Texas with its capitol, Baghdad, inland about as far from the Persian Gulf as Breckinridge, Tex., is from the Houston Shipping Channel. The oil fields lie 180 to 225 miles north of Baghdad, or about as far as from Breckinridge to Oklahoma City, and about as far from the Mediterranean as Fort Worth is from Hobbs, N. M. A narrow-gage railway runs from Basra, the Persian Gulf port, to Baghdad. From there another narrow-gage runs into the Kurdish hills east of the Tigris to Kirkuk. A standard-gage, part of the old Berlin-Baghdad system, follows the west bank of the Tigris northward from Baghdad to Baiji, a village about 100 miles south of Mosul. No railway exists between Iraq and the Mediterranean, though the Anatolian Railways in southern Turkey come to within 50 miles of the Iraq frontier and 120 miles of Mosul. Surveys have been completed for a railway through British Mandates from Haifa to Baghdad as well as for a railway through French Mandated Syria from Tripoli to Abu Kemal near the Iraq border. Wagon roads, excepting those constructed by the oil companies, are few and indifferent in Iraq and no road exists across the desert to the Mediterranean, but contrary to prevalent beliefs the surface is firm and free from sand dunes so that motor cars can go almost anywhere in dry weather, with ease. Frequent motor car and airplane service exists between Baghdad and the Mediterranean ports and motor car service may be had between Kirkuk and Nisibin, Turkey, where on two days each week through Wagons Lits service is available to Paris. Baghdad is about 21 days distant from New York City with present transport facilities. The climate is semiarid, similar to Imperial Valley, California, the average rainfall outside the mountainous parts amounting generally to

Jan 1, 1932

By F. M. Walters

In order to isolate the effect of an element on some property of an alloy, the effect of the other alloying elements must be elimi-nated, either by reducing their quantity to the extent that they may be neglected or by determining the specitic effect of each. The success of Grossmannl in calculating hardenability from chemical composition by means of factors suggested such a

Jan 1, 1943

By A. E. Wells

In this paper are described various comparative tests made on cracked and straight run gasolines. The results of these tests may be briefly summarized as follows: Samples of 54 to 55° Bé. gravity cracked gasolines, with end point of about 442° F., and with a somewhat larger proportion of the less volatile fractions than conformable to government specifications, were used in a single cylinder variable compression engine under the same conditions as were samples of straight run gasoline of 58 to 59° Bé. gravity, and of which one had a greater proportion of the more volatile fractions than called for in government specifications. The cracked gasolines showed decidedly less tendency to knock, hence could be used at higher compression ratios and thereby developed from 10 to 20 per cent. more power than did the straight run gasolines. These figures may be taken as one measure of the superiority of the cracked gasolines under test with the straight run gasolines. It is not claimed that all cracked gasolines are superior to all straight run gasolines to the extent indicated by the above tests; cracked gasolines vary as do the straight run products. Cross's work and that of others have indicated that certain cracked products may have a much greater superiority over straight run than that determined above. From various sources and by different methods of testing data are being obtained to show the definite and generally quite considerable superiority, as an anti-Cetonating fuel of cracked gasolines over straight run gasolines. It is now becoming generally recognized that by increasing the production of cracked gasoline motor fuel from those heavier petroleum fractions, which otherwise would be used for burning purposes, the petroleum industry is not only working in the interest of the conservation of the world's supply of petroleum, but is at the same time making available to the gasoline-consuming public a product distinctly superior to the straight run gasolines.

Jan 1, 1927

By Gordon E. Frantti

Under the auspices of the Geophysical Committee of Michigan College of Mining and Technology, an investigation was made in Michigan's Upper Peninsula to obtain geophysical data related to the regional subsurface geology in the area covered by Paleozoic sediments. The area surveyed includes that portion of the Upper Peninsula which lies between R18W to R26W and T41N and T49N, covering approximately 1300 square miles. On the index map, Fig. 1, it is represented by the cross-hatched zone west of Munising. Four of the five sites of detailed investigation are indicated by the letters A, B, C, and D. A detailed gravity and magnetic survey had previously been conducted by J. G. Wilson near Perkins, 8 miles north of Rapid River, on a local anomalous area. Results of his work, which showed a large positive magnetic anomaly associated with a gravity anomaly, aroused interest in the possible economic significance of the formations underlying the Paleozoic sediments in this part of the Upper Peninsula.

Jan 1, 1956

By C. Hirayama

THIS investigation was undertaken to determine some of the factors contributing to the embrittle-ment of glass-coated silver wire on heat treatment. The materials used in this investigation were 22 and 23 AWG silver wires obtained from Handy and Harman as "fine quality, soft temper." A wet analysis of one sample showed 99.8 pct Ag. The 23-gage wire was covered with a double layer (2.5 mils thick) of electrical grade fiber glass (aluminum borosilicate glass containing a relatively high concentration of calcium, and a very small amount of

Jan 1, 1960

By S. W. Churchill

A digital computer was used to obtain an exact numerical solution for the transient behavior of the insulation and earth adjacent to an isothermal, submerged flat surface for a single set of parametric values. Comparison of the computed results with analytical solutions for limiting conditions revealed that a complete and general solution for all parametric values could be constructed from these limiting solutions. Complete and general solutions for insulated spheres and cylinders can also be constructed from limiting solutions. The procedure is illustrated in part for an insulated spherical tank. The heat flow was found to fall rapidly to a pseudo-steady state; after some time, it then decreased slowly to zero for a flat plate and cylinder, and to a low steady-state rate for a sphere. The accumulative heat flow during the initial falling-rate period may be a significant fraction of the heat flow during the entire first year. INTRODUCTION Underground storage of liquefied natural gas and liquefied petroleum gas has received considerable recent attention. The rate of heat flow from the earth to the storage cavity and the resulting temperature field in the earth are important factors in the technical and economic evaluation of such storage facilities. The objective of this paper is to indicate how complete solutions can be developed for the transient flux and temperature field for various geometrical configurations. The representative properties and dimensions, and the resulting parameters utilized in the illustrative results, are indicated in Table 1. The results presented herein are for dry earth. The effect of the latent heat of solidification of water in the soiI will be described in a subsequent paper. The temperature field in the insulation and earth is determined by energy balances, boundary conditions and initial conditions. The physical problem can be described mathematically with virtually no idealizations insofar as physical properties are known. It appears possible to solve the equations by numerical integration on a high-speed digital computer for any geometrical configuration and conditions. For complex situations, however, the computations are expensive and the results are highly specific. Analytical solutions have been developed for a few simple but important geometrical configurations and conditions, including one-dimensional heat transfer from (or to) earth at an initially uniform temperature to (or from) flat plates, spheres and circular cylinders. The solution for an insulated flat plate has also been derived but is in the form of a slowly converging series involving taklated functions. It was planned to use a computing machine to evaluate this series for a number of representative conditions. However, upon examination of the results of preliminary computations it was discovered that a complete, general and accurate solution could be developed by interpolation between several much simpler solutions for limiting conditions. This technique then was used to develop a a complete solution for an insulated sphere. The equations presented herein are derived in Carslaw and Jaegerl and other books on applied mathematics, or they are simple extensions of these previous results. Hence, all derivations are omitted. Emphasis is instead placed on the results and their

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Jan 1, 1938

By Norman C. Britz, Mortimer P. Buck

THIS PAPER DEALS WITH the practices used at the Huntington, Nest Virginia works of The International Nickel Company, Inc., in hot and cold rolling nickel and high-nickel alloys. The practical metallurgical aspects are discussed and a brief description of equipment given. The alloys covered may he divided into three main groups. based on their major constituents: 1. Nickel alloys, 2. Nickel-copper alloys. 3. Nickel-chromium alloys. The nominal compositions of the various alloys which are produced in most common mill forms are given in Table 1. Nickel, a commercially pure grade of nickel containing about 0.05 pct carbon as' the chief alloying element, is produced in all common Mill forms. "L" Nickel is commercially pure nickel in which the carbon content is held as low as possible, usually less than 0.01 pct. This grade of nickel is used chiefly for spinning and for special high temperature applications where its low carbon content enhances its corrosion resistance. "D" Nickel contains 4.5 pct manganese to provide improved resistance to sulphur embrittlement at elevated temperatures. "Z" Nickel is an age hardening grade of nickel containing carbon, aluminum, and silicon as the age hardening elements. This alloy combines the cor-

Jan 1, 1948

By M. D. Cooper

LUCIEN EATON, Ishpeming, Mich.-It is not the custom in the Lake Superior region, as far as I know, to employ shot-firers. Each man, or pair of men (most of the contracts are given to two men) do their own firing; each contractor keeps his powder separately. The general custom is to distribute powder (dynamite only is used) to the mines 2 days a week. The boxes, marked with the contract number and the level, are taken underground and the men take them to their working places. They are kept in boxes, which must not be nearer together than 50 ft. and are usually away from the timber roads or traveling roads. When holes have been drilled, one man usually takes down the machine, and the other man makes up the charge. He cuts the fuse, puts in the caps, etc., at a distance from the powder box. He then carries the powder charges to the working place where both men charge the hole. They do their own firing and warn others coming from any direction that the holes are being fired.

Jan 4, 1917

ENGINEERS AVAILABLE (Under this heading mill be published notes sent to the Secretary of the Institute by members or other persons introduced by members.) Member, technical graduate, aged 35, with experience as surveyor, sampler, assayer, and cyanide superintendent, desires position as engineer or cyanide operator.. No. 157. Member, technical graduate, aged 34, with 12 years' experience, including engineering, construction, and management of gold, silver, copper, and quicksilver mines, desires position of 'superintendent of gold or silver property. No. 158. Technical graduate, aged 24, with experience as mine surveyor and instructor in chemistry, desires position as instructor in mining. No. 159. Member, aged 29, technical graduate, with experience in exploration, prospecting, mining, concentration, smelting, and as assayer and chemist, engineer, and draftsman (smelter) in United States, Canada, Africa, South America., and Australia, desires to become connected with a firm of consulting engineers. Speaks Spanish. No. 1130.

Jan 11, 1914

By N. S. Stoloff, M. Gensamer

Pyramidal (1122) slip was observed in cadmium single crystals deformed in compression and bending at room temperature and —196°C. Crystals tested in tension twinned with no evidence of pyramidal slip. A critical resolved shear stress law for the propagation of twin nuclei appears probable. Twinning and low-stress kinking are believed to inhibit the appearance of pyramidal slip under ordinary experimental conditions. SEVERAL reports of nonbasal slip in cadmium have appeared in the literature recently, two of the reports having appeared after work on this project was in progress. Brown1 reported cross slip on electron micrographs, but did not identify the cross-slip plane. Wernick and Thomas2 observed nonbasal slip traces parallel to [1123] on a crystal bent with a pair of tweezers, but this too was an isolated observation, with no confirmation of the glide plane. The critical stress for pyramidal glide, and the temperature and strain rate dependence of glide on this system were not discussed. price3 has reported some observations of nonbasal slip in thin films of cadmium with the aid of transmission electron microscopy, but a full publication of these observations was not available at this writing. Pyramidal (1122) <1123> slip also has been observed on zinc single crystals4, 5 and (1122) <1010> slip on magnesium single crystals,6 all oriented with the basal plane nearly parallel to the specimen axis. Since the choice of slip system in the hexa- gonal metals is generally believed to depend on the axial ratio, with basal slip predominating for high-axial ratios, the occurrence of pyramidal slip in zinc and cadmium is unexpected. The objectives of the present investigation were to confirm the existence of nonbasal slip in cadmium, to identify the slip system, and to obtain an estimate of the critical resolved shear stress, assuming that the resolved shear stress law is applicable. EXPERIMENTAL PROCEDURE Two purities of cadmium, 99.95 pet and 99.99+ pet, were employed. As received bars were cold swaged to 3/16 in. rounds. Bicrystals and tricrystals were prepared by passing the polycrystalline rods through a gradient without seeds. It was desired to obtain a large yield of single crystals oriented xo* < 5 deg, in order to be able to suppress basal slip during deformation by keeping the resolved shear stress on the basal plane to a minimum. Cylindrical single crystals of cadmium were prepared by a seeding technique developed by Weiner,7 to obtain a predetermined orientation. The single-crystal rods were sectioned to specimen size by an acid-cutting technique originally developed for zinc crystals.&apos; An aqueous solution of nitric acid was the cutting agent. The acid was picked up by a plexiglass disc spinning at an optimum cutting speed through the acid, which was contained in a sump-like arrangement. The section to be cut, the acid bath, and the spinning disc were enclosed in a plexiglass case. The rod to be sectioned was coated with a thick layer of collodion. At the points at which sectioning was to be effected, the collodion was removed over a length of about 1/8 in. by dissolving it in acetone. To prepare a surface suitable for microscopic exam-

Jan 1, 1962

By W. H. Meyer

Although an aerial photograph is not a map, most of the information that is necessary for compiling a map is recorded in the photograph provided some form of radial-line method is used to determine the true position of images. The slotted- templet method, which is based on the well-established radial-line principle, has made it possible to construct accurate mosaic maps at a cost comparable with that formerly charged for the average mosaic. It makes possible the securing of these results with far less ground control, which is always expensive. It has expanded widely the possible use of aerial photographs for mapping. ALTHOUGH a vertical or oblique aerial photograph is not a map, most of the information that is necessary for compiling a map is recorded in the photograph. Some ground controls or data are needed, the number and accuracy to be governed by the mapping method to be used and the scale and final accuracy desired in the finished map. RADIAL-LINE CONTROL It is essential that the principle of radial-line control in the use of vertical aerial photographs be understood and accepted before any confidence in the slotted-templet method can be gained. A simple sketch and some enlargements showing the Empire State Building will serve to illustrate the cause of displacement of an image that is above the datum plane as recorded in the photograph. The top of the tower of the Empire State Building is directly above the base, and when the image of the top is shown almost two blocks away from the center of the base, it is evident that the image of the top of the tower is not the true location, and in this particular case we know where the true location is; namely, over the center of the base of the tower. If the top of the tower were the top of a hill 1250 ft. high, we would have no way of knowing by inspection the true position of the top of the hill, so it is very important to have a method whereby the true location of any such point can be determined, and thereby make it possible to convert the detail of an aerial photograph into accurate information for mapmaking.

Jan 1, 1939

By J. S. Levine, M. Prats

Several methods are available for calculating the performance of solution-gas-drive reservoirs from the PVT properties of the oil and from the relative permeability and other properties of the formation. These methods require a number of simplifying assumptions. The present method of computation has made use of a high-speed computer to solve simultaneously the nonlinear partial differential equations that describe two-phase flow by solution-gas drive in order to calculate the performance of a reservoir. Some of the results obtained by the nonlinear partial differential equation solution are compared with those obtained with an approximate method, which has been called the semisteady-state solution. The pressure and saturation profiles from the wellbore to outer boundary calculated by the two methods are compared for one constant-terminal-rate case and two constant-teminal-pressure cases. The agreement in these profiles, as well as in the values of average reservoir pressure and cumulative recovery, leads to the conclusion that, for most engineering calculations, the semisteady-state method will give a reasonable approximation to the numerical solution of the differential equations describing solution-gas drive. An unfavorable (as regards ultimate oil production) set of relative permeability curves was used in the calculations in the belief that the effect of the parameters which were studied would be emphasized to a greater degree. Furthermore, the reservoir was assumed to be completely homogeneous, and these results should not be considered applicable to any other type of reservoir. Gravity effects are not considered. The absolute permeability was varied from 25 to 0.5 md. At an economic limit of 2 B/D, the recovery for a 25-md reservoir is about 1.8 times as great as that for a 0.5-md reservoir. The effect of permeability on the producing gas-oil ratio is minor. Once PVT properties of the oil and the relative penneability properties of the reservoir are fixed, the pro- during gas-oil ratio is found to be a function of the fraction of oil recovered. Well spacings of 10, 40 and 80 acres were considered. For the assumed homogeneous-reservoir properties, the effect of spacing on recovery at an economic limit of 2 B/D was very slight. Certain dimensionless groups can be used to extend the results to other fields having different penneabilities, spacings, reservoir thicknesses, well radii and porosities, so long as the PVT and relative permeability properties are similar to those used in this paper. INTRODUCTION An important aspect of reservoir engineering is the prediction of the performance of the reservoir based on the limited information normally available early in the life of a field. Usually, soon after a field has been discovered, it is necessary to decide upon the spacing to be employed and the production program to be used for most efficient utilization of reservoir energy. Where these decisions have not been dictated by legal or political considerations, they have frequently been based on experience factors which indicate that two fields with similar characteristics will probably have similar performances. To the extent that the industry has been successful in economically exploiting oil reservoirs, this rule-of-thumb method has been found to have merit. A large amount of theory has been developed with which it is possible to predict the performance of a reservoir by using certain known properties of the oil and the formation. Because of the difficulties of the mathematics involved for a drainage area having square or rectangular boundaries, the problem usually has been simplified and idealized by assuming each drainage area to have radial symmetry and the field to be represented by a number of these drainage areas. Muskatl was one of the first to formulate the theory for two-phase flow and to solve the equations for a few cases by numerical integration, using the relatively slow means of computing available at that time. His equations describing

By Eugene A. Stephenson

In November, 1932, Dr. Lacey, of the California Institute of Technology, presented before the American Petroleum Institute some of the results of his research under Project 371. The investigations described dealt particularly with changes in the physical properties of petroleum that result from the solution of natural gas therein. The solubility of Santa Fe Springs dry gas, containing 87 per cent methane, 8 per cent ethane and 5 per cent propane, had been determined in various crudes at 100&apos; F., and 2000 lb. pressure per square inch as shown in Table 1 and Fig. 1 herewith. Originally the computations were made in terms of cubic feet per barrel, but&apos; for a more uniform basis of comparison the results are also shown as cubic feet of gas2 per cubic foot of oil.

Jan 1, 1935

By Hans Lundberg

IN ORDER to comprehend the help and information that may be expected from electrical prospecting, it is necessary to have at least a general knowledge of the methods and principles involved in preparing and interpreting results obtained in the field. Electrical prospecting is rather complicated, both in theory and practice, and in order to make a brief description clear to the practical mining man it has been necessary to idealize and generalize the problems, at the risk of having such simplification criticized by the theoretical man. This simplification must not be misinterpreted as showing a lack of theoretical knowledge. FIG. 1.-FLOW OF CURRENT IN AND AROUND A CONDUCTING BODY. For its operation, electrical prospecting mainly depends on-the fact that most metallic ores conduct an electric current much more readily than barren rocks. If an electric current flows through a block of ground within which a body of chalcopyrite is enclosed in country rock of schist, the current will find less resistance to its passage through the chalcopyrite than through the schist, even though the passage through the latter be much shorter. This is because the longer path through the chalcopyrite offers less resistance, owing to the superior electrical conductivity of the chalcopyrite (Fig. 1).

Jan 1, 1928

By E. T. Turkdogan, P. Grieveson, J. F. Beisler

Experimental results are given for the rate of reduction of silica from silicate melts by paphite-saturated iron in the presence of carbon monoxide. It is shown that, when gas bubbles are present at the slag-metal interface, the interfacial chemical reaction is the rate-controlling process in the transfer of silicon from slag to metal. From the silicon-concentration profiles in the metal sample, the diffusivity of silicon in paphite-saturated iron is found to be (5.4 * 0.4) x 10 sq cm per sec at 1600°C. Some consideration is given to the transport of oxygen from the slug-metal interface to the walls of the gvaphite metal container as becoming the rate-controlling process in the absence of gas bubbles at the slag-metal interface. ATTEMPTS were made by Fulton and chipman1 to investigate the kinetics of reduction of silica from calcium alumino-silicate melts by graphite-saturated iron in an atmosphere of carbon monoxide. In these experiments with 400 to 500 g of metal and slag, both phases were stirred in such a manner that the interface was essentially undisturbed. Initially, the graphite-saturated iron contained about 15 pct Si and, after about 8 or 10 hr of reaction time at 1600°C, the silicon content of the metal in- creased by about 0.2 pct. In a written discussion on this paper of Fulton and Chipman, schuhmann2 pointed out the possibility that this observed slowness of the reduction of silica could be due to the transport of oxygen across the liquid metal boundary layer at the slag-metal interface. Although this explanation of Schuhmann is quite feasible for the experimental data of Fulton and Chipman on silica reduction, such a reasoning should not be extended to other rate data on slag-metal reactions unless sufficient evidence is available satisfying the boundary conditions for such a transport process. The hydrodynamics of stirred liquids are very complex and even for a simple method of stirring there is no exact mathematical solution which will predict the mass transfer coefficient accurately. The best available solution of this problem is that given by Lewis&apos; and later modified by mayers~ for a two-liquid system where liquids are stirred by counter-rotating stirrer blades without disturbing the interface. In such a system the mass transfer coefficient is estimated from an empirical relationship using the data on viscosity and density of the two liquids, rate of revolution, the length of stirrer blades, and the diffusivity of the element which is transferred from one phase to the other. It was found in these investigations&apos; that the estimated and observed mass transfer coefficients, in systems containing two immiscible aqueous solutions, agreed within *40 pct. Although this is not considered to be an unreasonable error for the study of industrial processes, uncertainties of this magnitude cannot be tolerated in any theoretical study of reaction kinetics. In view of the complexity of the

Jan 1, 1963

By M. Cohen, D. J. Blickwede

Quantitative observations concerning the carbide phases in high speed steel are of importance for two general reasons: (1) the carbides, being inevitable constituents of the final structure, exert a direct influence on the properties of the steel; and (2) a substantial proportion of the total alloy content is tied-up in the carbides, and hence the extent of their solution on austenitizing governs the composition of the steel matrix. The latter relationship has a vital bearing on the response of the steel to tempering as well as on its performance in subsequent service. Accordingly, in the course of a long-term study of the behavior of high speed steels, the authors were confronted with the problem of securing quantitative data on the carbide phases. The obvious method for acquiring such information is to isolate the car-bides from the steel and subject them to chemical, X ray diffraction and other measurements. There are well-known extraction techniques which involve the chemical or electrolytic solution of the less noble matrix (ferrite, marten-site or austenite), thus leaving a residue of the carbide phases. However, the results obtained must be scrutinized carefully1,2 since the carbides may be affected by the chemical or electrolytic action. It is the purpose of the present paper to describe the experiments leading to an electrolytic-extraction technique for quantitatively isolating the carbides from both I and hardened high speed steel. Particular attention is paid to the amount, as well as the composition, of the carbides so that the matrix analysis becomes ascertainable by subtraction from the overall steel composition. Illustrative results are given for the M-2 grade of tungsten-molybdenum steel. Review of the Literature The chemical method of dissolving the matrix selectively with respect to the carbides makes use of dilute non- oxidizing reagents such as hydrochloric or sulphuric acid. Although this simple procedure has led to the determination of the cementite composition,3,4 it achieved only limited success because of the interaction between the acid and the carbide residue. Some of the carbides may not only be destroyed in this way, but the hydrogen released is likely to remove part of their carbon as hydrocarbon gases. The electrolytic technique of isolating carbides has the advantage of rapidly dissolving the specimen (anode) in the presence of less reactive solutions than are practicable with the chemical method. This reduces the possibility of chemical attack on the carbides, and furthermore, the hydrogen evolved during the electrolysis is released at the cathode which is not in close proximity to the carbides. The common electrolytes adopted for this purpose are hydrochloric and sulphuric acids.5-l1 Aqueous solutions of ferrous salts have also been used.12,13 A considerable advance in experimental technique was introduced by Treje and Benedicks14 who developed a double-compartment cell for electrolytic extraction, the anode and cathode chambers being separated by a porous diaphragm. A solution of 15 pct sodium citrate, 2 pct potassium bromide and 1 pct potassium iodide was selected for the anolyte, while the catholyte consisted of a 10 pct solution of copper sulphate, with copper serving as the cathode. This type of cell has a number of desirable characteristics: 1. The anolyte has a pH value close to 7, at least at the beginning of the run. 2. The iron that dissolves from the anode-specimen forms a water-soluble complex ion with the citrate, thereby preventing the precipitation of iron hydroxide (which would contaminate the carbide residue) despite the neutrality of the solution. 3. Copper deposition instead of hydrogen evolution occurs at the cathode, and this avoids an increasing concentration of hy-droxyl ions which (in an otherwise neutral solution) might cause the precipitation of insoluble hydroxides. 4. Contamination of the anode chamber by copper sulphate is inhibited by the porous diaphragm. Houdremont and coworkers15 applied the above method (with the further refinement of excluding oxygen during the electrolysis, washing and drying) to the extraction of carbides from a series of plain carbon steels after various heat treatments. They had quantitative success only with specimens in the annealed condition, and concluded that the size and shape of the carbide particles play an important role in the isolation process, with large spheroids exhibiting the least tendency to decompose during the electrolysis. Up to the present time, the citrate double-cell has not been used to any extent for isolating the carbides of high alloy steels, apparently on the grounds that the complex carbides are more resistant than cementite to attack in the simpler acid electrolytes. In particular, Bain and Grossmann7 and Gulyaev10.10a have employed the hydrochloric acid cell for their investigations of the carbides in high speed steel.* It will be demonstrated here that this type of cell is capable of yielding quantitative results in the case of high speed steel, and actually has certain advantages over the more complicated double cell. However, in order to provide a rigorous test of the quanti-tativeness of electrolytic procedures for the problem at hand, both methods were studied in considerable detail.

Jan 1, 1950