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By Kenneth S. Ritchie

THE discovery well of the world's -deepest oil producing structure, University 1-B of Group No. One Oil Corporation, in the Big Lake oil field, Reagan County, Texas, has had a remarkable record. The well is outstanding for the following reasons: (1) It is the world's pioneer well to produce. oil in commercial quantities from a structure 8500 ft. below the earth's . surface; (2) this well was the only. producer from the 8500-ft. pay for a period of 17 months and 24 days; (3) the flow of the discovery well has been free from-the customary changes at the casinghead, with the exception of putting on a back-pressure of 185 lb.; and, (4) the well's daily production of oil and gas increased rather steadily for 17 months and 18 days from an initial of 40 bbl. per day to a maximum of 2926 bbl. per day, and then six months later, after a period of decline and self-readjustment to subsurface changes caused by six more deep producers, the well set its real record for one day's production of oil at 2950 bbl

Jan 1, 1931

By L. E. Young

THE purpose of this paper is to start a discussion on: (1) methods of supporting the immediate roof, particularly of local areas of poor roof, during the mechanical loading of coal; (2) methods of increasing the rapidity of the movement of the mining faces so that, without the use of cribs, jacks, pack walls, and filling, there will be no danger to men, equipment,, and working places from the subsidence of the overlying strata. In the Pittsburgh district the application of mechanical loading devices in mines working in the Pittsburgh seam, has been retarded by the difficulties of holding and handling the draw slate. Normally the thickness of this slate averages about 8 in. but the hardness varies, and a cut of coal cannot always be loaded without placing posts or crossbars to support the slate. Locally, the slate may be thicker and special methods of support may be required. If crossbars are placed to hold the slate when the coal averages 5 ft. in thickness, the standard methods of transporting the coal cannot be followed, and the use of conveyors may be desirable. Very little information is available on the effect of increasing the rate of movement of advancing or retreating break lines or longwall faces. A few British publications have presented some data but all such data relate to longwall faces that have moved not more than 6 ft. a day. The most rapid rate of movement of longwall faces in Germany is 6 ft. per day. In the ordinary hand-loading mine in western Pennsylvania break lines on full retreat will move about 2 ft. per day. If loading machines are used under similar conditions the, rate of retreat may reach 4 ft. per day. In a mine where coal is loaded by hand on conveyors three shifts per day, the rate of retreat has ranged from 11 to 16 ft. per day, with an average of 13 ft. If mobile loading machines could be used to load on con-veyors on break lines, the rate of retreat should be increased substantially.

Jan 1, 1938

By P. B. Bucky

THE purpose of this paper is to present a scientific method for deter-mining the proper span and shape of roof for safe and economical mining; at present, these two vital factors wherever pillars are left to support the roof are determined by local practice or general experience. To develop the method described here, experimental laboratory work was done. The arch adopted was a segment of a circle, a flat roof being considered an arch with an infinite radius. Hitherto, arches have been used underground without the background of stress analysis that generally precedes arch construction on the surface. In many cases results have not been as expected, because of the lack of knowledge of the factors affecting its strength and behavior. A theoretical and experimental study of arches should furnish informa-tion that will make it possible to design safe and economical surface structures as well as underground openings. For example, on the subject of mine drifts and tunnels, the present idea is that arching their backs increases their strength; this paper will indicate that this is not always true, and if it can be shown that under certain conditions arching becomes unnecessary an economic saving will result. In room-and-pillar work a question may arise as to whether arching the roof and gobbing the excavated material will result in timber saving, and a decrease in the dan¬gers from falls of roof. It is to be distinctly understood that each mine must be treated as an individual problem, and that answers to these ques-tions and many others can now be found after experimental laboratory data have been obtained.

Jan 1, 1934

By G. S. Cole, G. F. Bolling

Fluid flow strongly influences ingl structure and the columnar -to-equaaxed transition. Artificial flow patterns siwzilar to the nuturul ones act to induce this transition, while dampening forces act to suppress this transition. It is shown here how simple mechanical forces can be applied to a systerrz in order to induce or slipPvess relative fluid flow and the change both the structure transition and the exact structures obtained. The example used is the effect of slow rotations and oscillations 012 a cooling- ingot (of laboratory scale). The details of rotution and oscillation for various cooling rates, lenlperal~ire gradients, and sizes of ingot are related to other solidzfication variables. THE grain structure of a casting can be changed by altering the fluid motion during solidification. Just how important these changes are depends directly upon the degree to which the fluid motion can be controlled. An early step in understanding the nature and influences of fluid motion was taken by studying natural thermal convection; when a static mechanical device was used to suppress natural flow the result was opposite to that obtained when an electromagnetic device was used to augnlent flow in a pattern similar to the natural one. ''2 Suppression allowed more columnar growth to occur, but "augmented natural convection" brought about an earlier columnar-to-equiaxed transition (CET). Since the solidification of a free ingot must have characteristics somewhere between those displayed during suppression and augmentation, we know that natural convection must influence the CET. Further, since heat transfer in the liquid is always some time-dependent combination of convection and conduction, it can easily be guessed that the temperature gradient in the liquid is the vital factor affecting the CET.1,2 It is obvious that the structure arising from the unadulterated solidification of an ingot, without external influence, is rarely if ever the best possible one. Although the pattern of the natural fluid flow may be considered efficient, the magnitude of the flow and the heat transfer decrease freely from the outset. For a

Jan 1, 1968

By O. W. Ellis

In view of the extensive use of the brasses and bronzes in engineering practice it is indeed surprising that so little scientific work has been done on the oxides in these alloys. Recognition of the ill effects of these compounds is universally accorded, both in foundry procedure and in such specifications as cover the melting of these useful mixtures. In the latter, limits, for example, are placed on the proportions of scrap metal In the charge, and clauses governing the use of fluxes are included, the addition of fluxes to the charge being made with the object of avoiding oxidation during the process of melting and of subducing and separating non-metal-lic matter from the melt.1 In the manufacture of brass it occasionally, though rarely, occurs that the virgin metals, copper and zinc, alone arc used. In the event of virgin metals being employed, that of the higher melting point is always melted first. If it is melted under suitable conditions, little or no oxidation will occur. Whether oxidation has occurred or not, however, can best be determined by microscopic examination of a sample taken from the melt. Avoidance of Oxidation in Furnace Practice When melting virgin copper in crucible practice, the avoidance of oxidation is not difficult, nor is it hard to forestall trouble in the electric furnace. In gas-fired furnaces of the barrel type, however, the avoidance of oxidation is almost impossible, no matter what the condition of the flame, the flux employed, or the amount of charcoal included in the charge. Copper melted in furnaces of this type is almost invariably so highly oxidized as to requirc very considerable additions of such deoxi-dizers as, for example, silicon copper to render it free from cuprous oxide. As a result,, the castings produced are decidedly inferior, on account of the. large amount of silica which is engendered in the metal as a result of the reaction, Cu2O + Si = SiO2 + 2Cu. The deoxidation of such oxidized copper could, of course, be effected by means of zinc with, however, even more disastrous results.

Jan 1, 1930

By T. A. Kauppila, V. Rajaram, R. L. Bolmer

With steadily increasing prices for imported oil, commercial production of oil from oil shale can become a reality in the near future. Presently we are importing about 43% of our oil needs and this reliance on foreign oil can be reduced by utilizing the vast resources of oil shale in the western US. The oil shale resources in Colorado, Utah, and Wyoming, averaging 0.06 m3/ton (15 gal per st) and occurring in beds at least 3 m (10 ft) thick, are estimated at 293 Gm3 (1842 billion bbl) of which only 97 Gdm3 (610 billion bbl) are recoverable with current technology. The full potential of this vast resource can be realized only if significant steps are taken toward improving mining and retorting technology and solving environmental problems. Oil shales with a grade of 0.08-0.10 m3/ton (20-25 gal per st) are amenable to mining and surface retorting; whereas lower-grade oil shales may be recovered by in situ retorting.

Jan 4, 1978

In a letter to Prof. L. P. Breckenridge, chairman, urging the continua-tion of the Fuel Conservation Committee of the Engineering Council, Edwin Ludlow calls attention to the millions of tons of culm in the an-thracite region that can be utilized in properly equipped plants and the electricity generated transmitted to. New York, Philadelphia, and other nearby cities. He says: "Experiments have shown the economic value of No. 4 Buckwheat, which passes through a 1/16-in. mesh and over a 1/32-in. mesh. Culm passing through a 1/32-in- mesh is pulverized until it passes through a 300 mesh and is then burned under boilers. Two plants of this kind are now in successful operation in the anthracite region. Another rather interesting experiment was using 30 per cent. of this pulverized coal with 70 per cent. of oil in the generation of steam in the place of pure oil. This utilization of the fine anthracite, which has always been a waste product and thrown away, is not only fuel conservation in its truest sense but in the case of a bituminous strike, when no strike is contemplated in the anthracite field, will furnish fuel to manufacturing plants that otherwise would be obliged to shut down."

Jan 12, 1919

E. B. WILSON, Scranton, Pa. (written 'discussion *).-Prof. Young's paper shows another application of electricity in solving problems in coal mining, and suggests that it may be possible to utilize the data he has collected in developing an electric firedamp detector. If electric lamps are to be adopted in gassy coal mines, the use of an electric firedamp detector becomes almost imperative, for safety lamps and electric lamps in the same mine are not always conducive to safety, and Liveings electric firedamp detector, is too cumbersome to meet with general approval. Three well understood facts are verified in a new way by Prof. Young's experiments: - 1. The temperature at which methane ignites. 2. The more inflammable gas present in an atmosphere, the hotter will be the flame, and the longer the cap in a safety lamp. 3. As the temperature at the source of ignition varies, the length of the gas-cap flame varies. Prof. H. B. Dixon collaborating with Mr. H. F. Coward, some years ago, made experiments on the ignition of various gases to find the tem-perature of their kindling points.1 From the results of their experiments, the writer has culled the ignition temperatures of some hydrocarbon gases, and has tabulated them with other data, in Table 1.

Jan 10, 1919

By A. C. Milner

In a gold standard world which possesses insufficient metal to meet the every-day needs of all, confidence becomes the vital factor, the very foundation upon which the machinery for the expansion of gold into currency, and credit, rests. The gold supply, affected by many influences, moves constantly from one point to another, but not always to that point where it is most needed. In the period 1928-1930, the combined gold holdings of the United States and France increased $1,370,936,-000, and this with new gold adding only $600,000,000 to the monetary gold stock.Theref ore, the gold stocks of other countries must have been depleted during the period by $770,936,000. This uncontrolled shifting throws the delicately adjusted instrumentalities of both credit and commerce out of equilibrium. If a given nation's gold stock shifts so as to bring it substantially below the legal reserve ratio set up against it for currency issues, the effect can easily extend to the currency issues and banking credit volume of one or more nations which may have based their gold exchange standards upon the gold stock of such nation. Thus the substitution of paper based on gold in place of the actual gold is an inflation of the currency, which carries through into an uncontrolled pyramiding upon the entire machinery of credit based on gold. In 1929 Europe, South America, Africa and Asia had overissued currency based on gold. America, Oceanica and Japan, which have not overissued their gold currencies, would in normal times require their entire present gold stocks and, as Continental Asia is largely upon a silver credit basis, from a domestic standpoint, it would appear that the gold problem is not so much one of maldistribution, as it is one of inadequate supply. It would appear that some method of increasing greatly the velocity of gold, within the safe reserve point, should be devised, or that silver, of which estimates indicate that 7,000,000,000 oz. are available for

Jan 1, 1931

By C. L. Berrien

MANY fires have occurred in the mines of Butte in recent years, and while all have been of a serious nature, simply because they were mine fires, six of them have been especially dangerous in respect to loss of life and property, and the expense of extinguishing or controlling them. It is not my intention to discuss the relative merits of methods used in fighting these different fires because the conditions under which they occurred varied in each case, and it was not always advisable to expend the large sum of money necessary to actually extinguish them if they could he bulk-headed off from the rest of the mine. It is needless to say that everything possible has been done to check all fires at the beginning, but without success in some cases; and it has then become necessary to bulkhead all connections to them, in which state several now exist. The mine fires of Butte, or fires in any mine, may be divided into two classes, namely: Those occurring in accessible workings, and those occurring in inaccessible workings; because these two conditions govern to the greatest extent the methods of fighting fires. Accessibility and in-accessibility in the case of mine fires concern not only new open workings and old closed workings, respectively, but also the condition of the ventilation in and about those places. When a fire is accessible at the start it should not be difficult to confine it to a small area and extinguish it in a relatively short time, but when it is impossible to actually reach a fire in old filled, abandoned workings, or there is no opening by which the gases may be conducted away from the fire zone, then the time consumed in changing those conditions permits the fire to increase to such an extent that it is a long, hard fight to overcome it.

Jan 6, 1915

By AIME AIME

BLANDFORD. C. BURGESS, the new Chairman of the Industrial Minerals Division, took the advice of Horace Greeley in reverse-he turned his hack on San Francisco and the Golden Gate, and after a few side excursions toward Alaska and Arizona, hit the trail eastward, not for the lonesome pine, but for Spruce Pine, N. C. Born Aug. 10, 1893, in San Francisco. Burgess found his first job, shortly after finishing high school at 19, as axeman for a surveying party of engineers working for the Southern Pacific Co. in Oregon. Later he moved on up with them into Alaska. He liked the engineering profession, and decided to equip himself further so he entered the University of California in the fall of 1913. and for the next two years devoted himself to acquiring an education in civil engineering.

Jan 1, 1945

By J. S. Harris

AS a result of the study of social problems to which so much thought has been given in this country and Europe in the last half century, many employers of labor have come to think that some provision should be made for their workingmen in case of injury. There has been a growing tendency so to administer the laws governing industrial pursuits in these countries as to add self-interest on the part of capitalists, to the plea urged by humanity, that every possible care should be taken to guard the workers from accident; but as no care can guarantee immunity, there is a necessity to supplement these precautions by some method of providing pecuniary aid that shall be available when disabling accidents do occur. It was once a favorite idea of theorists on political economy, that in the ideal state of society every man should take care of himself, and that the less care or control there was assumed by any man over others' private affairs, the better; but this gospel of selfishness has had its day, and it is now generally recognized that in the existing state of affairs the stronger and richer cannot escape the duty of being to some extent, the keepers of their less fortunate brethren ; and, on the other hand, that an assumption of care for them involving to some extent an exercise of authority, is not a thing to he necessarily and always resisted. Out of these convictions, many efforts for the amelioration of the condition of workingmen have grown—which or one result have produced various plans which combine the con-

Jan 1, 1884

By Albert J. Phillips

LEAD is an inexpensive metal produced and consumed in large quantities with certain chemical and physical properties that permit handling the molten metal in bulk. These properties are its low melting point, resistance to oxidation, and its negligible solvent action on iron and steel. Thus, lead is almost always melted in large iron or steel kettles, heated from beneath, and is seldom melted in either directly or indirectly fired furnaces or electric induction or arc furnaces. Even with a modest operation a kettle holding 2 or 3 tons is employed, and the size will range up to 215 tons in the large lead refineries. The methods of handling tin and its alloys are essentially the same as for lead because of the similarity in melting point and resistance to oxidation, although because of the cost of the metal the scale is more modest. In melting lead and its alloys preliminary to a casting operation it is seldom that the melting unit is completely drained of its contents. The usual procedure is to continuously charge solid metal and continuously remove small amounts of liquid metal, so that the kettle is maintained essentially full at all times. For type metals, linotype machines usually employ automatic means of adding the solid alloy to the melting pot in proportion to the removal of the liquid metal in casting slugs of type. In the casting of grids for storage batteries, frequently automatic means of charging solid metal in direct proportion to the consumption of liquid metal in the casting is used. In the manufacture of bearing alloys, new alloy is charged in direct proportion to the consumption of metal in the bearings being cast, so that at no time does the level of the metal in the melting pot lower to any great extent. Even in the manufacture of bulky commodities such as pipe, cable. sheathing, and slabs for rolled sheet, it is the practice to employ a melting kettle of several times the capacity of the casting being made. A substantial level of liquid metal in the melting kettle is thus maintained even after the casting is poured and the original metal level is quickly restored by promptly charging new metal, even though there is no immediate need to proceed with additional casting. This procedure is permissible because the amount of fuel consumed in keeping the lead molten and immediately available for use is negligibly small and the cost is more than offset by the convenience. However, this convenient procedure necessitates study and control of certain properties of lead and tin alloys that are not of serious consequence in most other alloys and for that reason are not well known. These properties are "drossing rates" and "melting segregation." DROSSING RATE Users of lead long ago observed that the rate of dross formation on the surface of the lead in their kettles or pots varied greatly from time to time. This was particularly common in places where both antimonial lead alloys and commercially pure lead were being handled.

Jan 1, 1946

By James E. Harding

The usual method of sampling mineral deposits is to drill holes and assay the sludge or core. Though the results thus obtained may not represent the true average value of the deposit, it is on these results that estimates of practically all large orebodies are made. In a large number of cases, the results of exploitation fall far short of the estimated value of the orebody. The standard method of making these estimates is to find the cubic contents of triangular prisms, in the apexes of which the drill holes are placed, by. multiplying the surface area by the average depth of the ore in the three drill holes and then multiplying the cubic contents by the specific gravity of the ore or rock to find the tonnage. The assay value is found by dividing the sum of the products of the depth of ore in each hole and the corresponding assay value by the sum of the depths of the ore in the three holes. As the latter part of this method is subject to many mathematical errors, it should not be depended on. Some engineers, therefore, use a discount factor, but as this factor is either arbitrarily selected or is obtained by obscure methods, the results are no better than guesswork. The standard method is correct when the drill holes are so laid out that the triangular prisms are equilateral in cross-section. But as ore deposits cannot always be drilled into at regular intervals and because of the human factor, if many holes are drilled, triangular prisms of all degrees of angularity are produced. In such cases it is necessary to assume that the influence of the different holes is not the same in all directions, which assumption of course is absurd. The area of the triangular prism is usually found by scaling; an ore-body of sufficient size to justify churn drilling is too large to be handled conveniently on maps having a scale larger than from 1000 to 1 to 1,500 to 1 and maps of such scales cannot be accurately measured. A variable is thus introduced in the first operation. In addition, the scaling is frequently done from blueprints, which sometimes shrink as much as 4 per cent. between printing, washing, and drying. The error due to scaling may be eliminated by surveying the location of each hole and

Jan 1, 1922

By H. L. Brunjes, G. B. Gould

The softening temperature of coal ash, as determined in the laboratory, has been used for years as an indication of the tendency of coal to form clinker and slag. It has not, however, provided an index of unfailing and complete reliability for forecasting the relative performance of different coals, even in the same plant and under the same conditions of operation. A large amount of investigation has been done in attempts to account for this, but practically all of this has been in the direction of studying the chemical constitution of coal ash. Much has been learned, but without much progress toward a better practical application of knowledge to the selection of coal. There has always seemed to be an important factor that eluded discovery. It has long been recognized that the ash-softening temperature as determined in the laboratory had one weakness, in that it represented the temperature at which a thorough mixture of the whole ash of the coal would melt, the mixing having taken place before the heal was applied. This does not, of course, simulate what takes place in practice. With certain exceptions, which will be noted later, almost all of the investigations that have been made, especially the chemical studies of coal ash, have likewise dealt with a mixture of the whole ash in the coal. The present investigation differs from these fundamentally in its approach to the problem. It started from the observation that some clinkering and slagging obviously takes place in a boiler furnace at temperatures below the laboratory-determined ash-softening temperature of the coal. Knowing that coal as it is shipped to market is a heterogeneous mixture of diverse mineral substances, each of which may act independently of the others in the initial stages of clinker and slag formation, it seemed logical to investigate separately the softening temperature of the ash in physically separable portions of the coal, and to determine the relative quantities of ash contributed by each portion. While the data are far from complete, covering as they do only a few coals, and while the conclusions to be reached from the data at this stage arc, in some measure, speculative, they are presented at this time because

Jan 1, 1940

By G. B. Gould, H. L. Brunjes

The softening temperature of coal ash, as determined in the laboratory, has been used for years as an indication of the tendency of coal to form clinker and slag. It has not, however, provided an index of unfailing and complete reliability for forecasting the relative performance of different coals, even in the same plant and under the same conditions of operation. A large amount of investigation has been done in attempts to account for this, but practically all of this has been in the direction of studying the chemical constitution of coal ash. Much has been learned, but without much progress toward a better practical application of knowledge to the selection of coal. There has always seemed to be an important factor that eluded discovery. It has long been recognized that the ash-softening temperature as determined in the laboratory had one weakness, in that it represented the temperature at which a thorough mixture of the whole ash of the coal would melt, the mixing having taken place before the heal was applied. This does not, of course, simulate what takes place in practice. With certain exceptions, which will be noted later, almost all of the investigations that have been made, especially the chemical studies of coal ash, have likewise dealt with a mixture of the whole ash in the coal. The present investigation differs from these fundamentally in its approach to the problem. It started from the observation that some clinkering and slagging obviously takes place in a boiler furnace at temperatures below the laboratory-determined ash-softening temperature of the coal. Knowing that coal as it is shipped to market is a heterogeneous mixture of diverse mineral substances, each of which may act independently of the others in the initial stages of clinker and slag formation, it seemed logical to investigate separately the softening temperature of the ash in physically separable portions of the coal, and to determine the relative quantities of ash contributed by each portion. While the data are far from complete, covering as they do only a few coals, and while the conclusions to be reached from the data at this stage arc, in some measure, speculative, they are presented at this time because

Jan 1, 1940

By M. P. Tixier

In several log interpretation methods, water saturation is evaluated by use of the ratio of the readings of a short spacing resistivity device and a long spacing resistivity device plus information on the mud filtrate and connate water resistivities, which is often derivable from the SP. These methods are valid over a certain range of conditions, usually specified by moderate invasion and R.. greater than R,. Since these methods involve no explicit evaluation of the formation factor, F, the saturafiion so found may be used in the standard Archie equation to derive a computed formation factor which, as a check, may be compared with the formation factor known from other independent measurements. Discrepancies in the two values of formation factor generally indicate that the ratio method is not within its range of applicability. If the computed F is too low, the corresponding S, is too low; if the computed F is too great, the corresponding S, is too great. By means of this "porosity balance" check, and some knowledge of the probable conditions of invasion, the interpretation can often be improved. The poqosity balance check is discussed for the cases of the Induction-Electrical Log Interpretation Method, the Rocky Mountain Method, and the R.,/R, Method. For the first method, a discussion is also given for the case of shaly sands. INTRODUCTION Al though many logging tools are available to obtain a practical value of porosity, the only logging method reflecting the water saturation is electrical logging. Water saturation is commonly computed from electrical log data by means of the basic Archie formula, Where F is the formation factor, R, the resistivity of the formation water, and R, the true resistivity of the formation. One difficulty in this procedure is a possible error in the evaluation of R, from the logs— for example, in the case of very deep invasion. There is no possibility, inherent in the procedure, which would provide a check of the accuracy of R, and, hence, of the computed saturation. Other approaches have been proposed which are based essentially on the ratio of the readings made with two dzerent devices: one device, with a short radius of investigation, provides a value close to the resistivity of the invaded zone; the second device, with a long radius of investigation, gives a value close to the true resistivity of the bed. By these methods, the determination of saturation is made independently of any direct knowledge of the formation factor. Therefore, if the formation factor (or porosity) is known from other sources (core analysis, neutron log, MicroLog . . .), it becomes possible to take advantage of this additional information in order to check the value of saturation derived from these latter methods. Inasmuch as this proposed check procedure relies on a knowledge of the value of formation factor or porosity, it has been deemed appropriate to call this verification a porosity balance. The purpose of this paper is to discuss the principle and the application of the porosity balance, depending on the method of interpretation being used. Basis of the Method There are in existence three interpretation methods by means of which the water saturation can bc found without a knowledge of the formation factor (or porosity). As just stated, they are based on the fact that the ratio of the two resistivities (one measuring the resistivity close to the hole, the other measuring the resistivity far from the hole) is independent of the formation factor since it affects the two resistivity measurements in the same way. Chronologically, the resistivity ratio methods are: (1) the Rocky Mountain Method, which has been used since 1943 and was explained in a paper in 1949;' (2) the R../R, Method or Shaly Sand Method, presented in 1954, which permits the calculation of the water saturation in both clean and shaly sands2; and (3) the Induction-Electrical Log Method, presented in 1957 for the interpretation of the induction-electrical log combination." Each method requires certain definite conditions in order for the interpretation to be reliable. The porosity balance method will let us know whether these conditions are fulfilled. In clean formations we know that the fundamental Archie relation (Eq. 1) must always be verified. This relation can be rewritten:

By F. H. Deily, Jean M. Quets, Milton E. Wadsworth, John R. 222-000-000-012 Lewis, D. S. Rowley, R. J. Howe

Samples of synthetic magnetite were reduced in hydrogen-water vapor atmospheres in the temperature range 450o to 900oC. The reaction was always surface controlled, indicating the final products of reaction are nonfirotective. Three separate cases have been identified from the kinetic results: Case I, reduction of magnetite to iron below 570°C; Case II, reduction of magnetite to iron above 570°C; and Case 111, reduction of magnetite to wustite above 570 oC. In Cases I and 111 the kinetics have been explained by the formation of oxygen anion vacancies in the magnetite surface followed by associated diffusional processes. In Case 11 the observed kinetics have been related to the concentration of iron cation vacancies in the wustite layer formed, followed by associated steady-state diffusional processes. The concentration of cation vacancies in the wustite is maintained constant by the magnetite-wustite equilibrium. THE reduction of the oxides of iron has been a subject of study and interest for many years. However, few attempts have been made to interpret the results in terms of the mechanism of reduction of an iron oxide by either hydrogen or carbon monoxide. Stalhane and Malmberg' using CO, H2, and CO-Hz mixtures, developed the rate expression: where m = mass of oxide reduced, t = time, k = a constant, s = surface area, P = partial pressure of of CO or H,, and P, = partial pressure of the reducing gas at equilibrium. The rate of reaction per unit area was proportional to the difference between the partial pressure of the reducing gas and its pressure at equilibrium. Hansen, Bitsianes, and Joseph2 studied the reduction of pellets of hematite to magnetite with mixtures of CO-CO,. They concluded that below 450°C the reaction proceeded according to a model in which CO reacts with the hematite surface producing an oxygen ion vacancy. The rate controlling step was then assumed to be oxygen ion diffusion through vacancies resulting in the formation of magnetite. They derived an expression giving the rate of reduction proportional to the cO/CO, ratio. Recently McKewan3 published results for the reduction of magnetite spheres in atmospheres below 570°C. He explained his results by an equation of the form where K, is the equilibrium constant for wustite-iron equilibrium attributed to the formation of wustite as an intermediate in the reduction of magnetite. According to McKewan, Kp is an equilibrium constant for H, -HO adsorption in which oxygen is deposited on the surface from the H,Oand subsequently acts as a poison for reduction by hydrogen. Sample Preparation and Experiments. In this work the authors used the same apparatus and experimental procedure employed in the hydrogen reduction of magnetite. Sintered disk samples weighing approximately 1.5 g and measuring 1.2 cm in diameter and 0.25 cm in thickness were prepared by a method described previously.4 Partial pressures of hydrogen and water vapor were controlled by bubbling hydrogen through a series of flasks containing distilled and deionized water maintained at constant temperature in an oil bath. The total flow rate of the reacting gases—hydrogen and water vapor—was approximately 0.5 liter per min. The entire external system was maintained at a temperature above the oil bath to prevent condensation of water vapor. This was accomplished by wrapping electrical resistance elements over all surfaces. The glass column containing the weighing system-a McBain balance suspended from a gold chain-was enclosed in an aluminum tube heated by nichrome resistance wire enclosed in an insulating material. The temperature of the glass column was held constant by means of a series of thermocouples connected in parallel to a Leeds and Northrup temperature controller. This was necessary since variations in temperature resulted in expansion and contraction of the glass column and could be readily observed with the cathetometer. The spring extensions were measured through a window with a gaertner cathe-

Jan 1, 1962

By F. C. Blake

The best method for the estimation of copper in ores and secondary products is that proposed by Dr. Steinbeck* for the award offered by the Mansfeld'schen Ober-Berg-und Hutten-Direction. It is based upon the decolorization of the blue ammonia solution of copper by potassic cyanide.7 It is necessary for the accurate estimation of copper in arsenides that the arsenic be separated from the copper before the ammonia solution is made. The presence of a notable amount of arsenic renders the titration by potassic cyanide inaccurate, the end reaction being obscured by the appearance of a yellowish-green tint towards the end of the titration. The change of the color of the ammonia solution from blue to the tint caused by the presence of arsenic cannot be used for an end reaction, for the intensity and quick appearance of the latter color depend upon the amount of arsenic present in the solution. In the analysis of speise, the method of separating the copper by an oxidizing and reducing treatment in the muffle, to volatilize the arsenic, gives poor results, and there may easily be some loss of the weighed sample. The separation of the precipitated sulphides of arsenic and copper by treating with sodic sulphide, gives good results, but the process is tedious. I have used the two following methods, which are simpler and more expeditious than those mentioned, with good results

Jan 1, 1881

By M. T. Simnad, G. Derge, Ling Yang

STUDY of diffusion in molten substances is important in at least two respects. Diffusion data, combined with thermodynamic and kinetic information, throw light on the structure of the liquid state. Moreover, a knowledge of diffusion coefficients and their temperature dependence is useful in ascertaining the controlling step in many metallurgical reactions. Although diffusion measurements have been made on a number of molten salts, slags, metals, and alloys,'-'" the results available are still limited and widely scattered, especially for the high temperature melts. It is the purpose of this investigation to establish reliable procedures for the measurement of self-diffusion coefficients in high temperature melts and to use these procedures to determine the self-diffusion coefficients of iron in molten Fe-C alloys of different carbon contents. Experimental Measurement of self-diffusion coefficients in high temperature melts is usually carried out by using one of two methods. In the first, diffusion takes place between two cylindrical samples of the same material, one of which is made radioactive. The diffusion coefficient is calculated from the radioactivity penetration curve in the solidified sample after the diffusion. In the second method, samples contained in capillaries of an inert substance are immersed in an infinite reservoir of the same material. Either the material in the capillary or that in the reservoir is made radioactive and the diffusion coefficient is calculated from the change of the radioactivity of the sample in the capillary after the diffusion. The second method is simpler because a radioactivity penetration curve is not needed for the calculation of the diffusion coefficient; however,.it is valid only when no convection has occurred in the capillary during the diffusion. A radioactivity penetration curve is therefore always useful in indicating that the required conditions for the diffusion are ful- filled. Towers and Chipman" recently studied the self-diffusion of calcium and silicon in CaO-Al,O,-SiO, melts by using the capillary method. Instead of measuring the change of the radioactivity of the sample in the capillary, they autoradiographed the sample after the diffusion and calculated the diffusion coefficient from the intensity distribution of the autoradiograph. Their method is useful when the radioactive isotopes are weak ß-emitters, but is very difficult, if not impossible, to apply to cases involving strong ß or y-emitters. For such cases, sectioning of the sample according to the method of Morgan and Kitchener' may be used for the construction of the radioactivity penetration curve. The self-diffusion of iron in molten Fe-C alloys has been studied in this manner and the experimental procedures are described as follows: The diffusion apparatus is shown schematically in Fig. 1. The bath consisted of about 200 g of an Fe-C

Jan 1, 1957