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By C. J. Rosa, W. C. Hagel

An attempt is made to determine the diffusion coefficients of oxygen ions in hypostoichiometric zirconium oxide. A phenomenological theory is developed for three-phase, unidirectional volume diffusion of a gaseous species from a planar source. Knowledge about oxygen diffusion in a and ß zirconium and experimentally measured rates of movements of interfaces permit the evaluation of oxygen ion diffusivi-ties in ZrO2-x. The results conform to the relationship: sq cm per sec, for the temperature range of 875" to 1050° C. DIFFUSION coefficients of oxygen ions in stoichio-metric oxides have been studied by many investigators. The obtained results not only supplement the knowledge about the lattice-defect structures of oxides and conduction mechanisms but also provide information of technological importance. Rate processes such as oxide sintering, high-temperature creep deformation, and oxidation of metals and their alloys are directly dependent on diffusion phenomena. Unfortunately, diffusion coefficients obtained from studies on stoichio-metric oxides cannot be treated without restraints when applied to oxidation kinetics, if precise evaluations of oxidation rates are desired. Oxides formed on metals are usually nonstoichiometric and exhibit nonuniform distribution of either cation or anion vacancies across their thicknesses. Debuigne and Lehr1 extended Danckwerts'2 mathematical analyses and furnished a semitheoretical treatment for evaluating oxygen diffusion coefficients in zirconium oxide in terms of weight gain measurements during oxidation of zirconium in the temperature range 400° to 850°C. Their calculations are based on theoretical partitioning3 of the total amount of oxygen between a zirconium and its oxide phase. An inherent discrepancy appears to continue throughout their calculations. The amount of oxygen confined to the oxide phase should be corrected by multiplying the calculated oxide thickness by the inverse of Pilling-Bedworth ratio, if expansion of zirconium dioxide is taken into account. The purpose of the present investigation is to provide a new semitheoretical treatment for evaluating diffusion coefficients of moving species in hypostoichiometric oxide. The analyses are relevant to unidirectional volume diffusion. Although the presented method is quite general, its applicability will be discussed in terms of kinetic measurements from oxidation of zirconium at temperatures above the a/ß transition, for reasons stated in the later part of this paper. EXPERIMENTAL Pure, 99.93 wt pct, zirconium samples of approximately 2 by 1 by 0.35 cm were exposed to oxygen for various times at four temperature levels: 875°, 950°, 1000°, and 1050°C. High-purity, better than 99.9 vol pct oxygen was passed through a cold trap and columns containing anhydrous CaSO4 to remove residual water vapor. Before exposing to oxygen at a pressure of 500 Torr, specimens were subjected to wet abrasion on 200- through 600-grit Sic papers and polished with 1—p diamond dust. Prior to oxidizing, all zirconium samples were vacuum-annealed at 10-6 mm Hg for about 15 min at the test temperature. The temperature variation across the uniform heat zone was ±2°C from the preset value. Final polishing, for phase thicknesses measurements, was performed by using 8- and 1-p diamond dust and followed by vibrator polishing with 0.05-µ ? Al2O3 solution. Measurements of phase thicknesses were made by projection on a metallographic viewing screen. Conventional powder X-ray analyses for the oxide were employed. RESULTS Fig. 1 is an example of the cross section of oxidized zirconium. Designations of phases given below this figure are the same as those used in the three-phase diffusion system represented by Fig. 5 in the following section. Zirconium oxidized for longer exposure times showed two types of oxides: white oxide at the surface and an underlaying layer of gray oxide. X-ray powder patterns of these oxides at room tern-

Jan 1, 1969

By G. W. P. Rengstorff, R. B. Fischer

A study was made of the effect of impurities on the bend ductility of cast molybdenum. High purity molybdenum was repared by re-melting under high vacuum. The ductility of "transverse-grain" specimens indicated that intergranular brittleness decreased with an increase in purity of the metal. THE production of as-cast molybdenum with high ductility at room temperature would make working of the metal easier and increase the usefulness of the as-cast metal. Furthermore, a .knowledge of the factors that influence the ductility of as-cast molybdenum might be applied to the problem of making fusion weldments having satisfactory room-temperature ductility. Individual grains of commercial as-cast molybdenum are slightly ductile at room temperature. However, the presence of carbides at the grain boundaries may cause the metal to fracture in a brittle manner. This behavior has been discussed.' The amount and distribution of the impurities in as-cast molybdenum would be expected, from previous research on the metal, to have considerable influence on its ductility. Some effects of oxygen and carbon on the mechanical behavior of the metal were discussed by Parke and Ham,2 Woodside,3 and Zappfe. Landgraf, and Worden.4 Parke and Ham2 found that, if a sufficient number of molybdenum oxide particles were present at the grain boundaries, the intergranular cohesion was reduced to the extent that arc-melted molybdenum would rupture intergranularly during hot forging. They also found that if the oxygen content was less than 0.003 pct, the cast molybdenum was hot forgeable. It is suspected, however, that forgeable molybdenum may contain a small amount of oxide that could reduce the ductility of the as-cast metal at room temperature. Also, there is the possibility of the unfavorable distribution of other impurities having a detrimental effect on the ductility of cast molybdenum. The results of a study of the influence of purity on the room-temperature ductility of cast molybdenum are presented here. Vacuum Arc-Melting to Produce High Purity Mo One way of determining the effect of impurities on the ductility of molybdenum is to prepare and test metal as free of all impurities as possible. Accordingly, the present investigation was undertaken with this in view. Arc melting in high vacuum (less than 0.1 micron of mercury) was chosen as the method for reducing the impurities below the concentrations occurring in commercial molybdenum. Commercial arc melting of molybdenum is carried out at about 50 microns pressure. During the arc melting, carbon and oxygen in the metal react to form carbon monoxide. By virtue of the vacuum process, the partial pressure of carbon monoxide is maintained at such a low value that the reaction greatly lowers oxygen and carbon contents. An excess of at least 0.03 pct C is used in commercial arc melting to insure that the oxygen content will be below 0.003 pct. The excess carbon remaining after the deoxidation step forms carbides on freezing. Some of the carbides precipitate at the grain boundaries and, as will be shown, have an unfavorable effect on the room-temperature ductility. In the present work, only the small amount of carbon (0.003 pct) contained in the commercial powder-metallurgy molybdenum used for melting stock was present. Partial removal of oxygen from the melt probably occurred as the result of the volatilization of molybdenum oxides, or by distillation of oxygen at the high melting tem-

Jan 1, 1953

By G. W. Healy, W. Craft, D. C. Hilty

By means of a theoretical extension of the Cr-C temperature relation in molten chromium steels to low chromium contents and by a correlation of the ratios of chromium to iron in the slag and metal, a method has been developed for estimating the amount of metallic oxidation during the oxidizing period of a chromium steel heat. Application of this method has indicated that due to temperature limitations metallic oxidation may be excessive for very low carbon steels charged with more than a small amount of chromium. IN the melting and refining of chromium steels the oxidation of carbon to a low level is accompanied by the oxidation of chromium and iron in considerable amounts. For the subsequent recovery of chromium and associated iron from the slag, the amounts of metal oxidized must be known for efficient reduction and control of composition. Further, in order to arrive at an accurate understanding of the process, so that chromium-bearing scrap can be used effectively, information is required on the relation between composition of the charge and weight of metal oxidized to reach the desired carbon content. Crafts and Rassbach1 recently developed an empirical relation between chromium, iron, and manganese oxidized per ton of steel charged, and final carbon content and temperature. This relation did not show any dependence on amount of chromium charged. However, it was felt that such a dependence might be present, so a further analysis of the data was undertaken. Cr-C Relation at Low Chromium Levels Crafts and Rassbach's results were based on temperatures estimated from the Cr-C relation previously established experimentally by Hilty,2 and on a single temperature observation (immersion thermocouple) on a heat made at low temperature from a charge of carbon steel scrap containing only a small amount of residual chromium. The temperatures estimated from the Cr-C relation were for heats charged with chromium-bearing scrap and which contained substantial amounts of chromium (2 to 10 pct) at the end of the oxidizing period. No data, other than that from the low temperature heat just mentioned, were available for the low and intermediate chromium ranges. In order to extend the range in which temperature may be estimated, the Cr-C relation requires further consideration. The Cr-C relation, expressed as suggests that carbon is zero at zero chromium in the bath. This is obviously absurd, because as chromium approaches zero the carbon content must approach the limit established by the Fe-C-O equilibrium. It is evident, therefore, that the Cr-C relation as defined by Eq. 1 is not valid below some minimum chromium content that may vary with temperature. On the other hand, it is probable that any such limiting chromium content is less than 4 pct at 3200°F, since the experimental data from which the Cr-C relation was derived included several observations at that level with no deviation. In any event, it is apparent that further evaluation of the results presented by Crafts and Rassbach is dependent upon a means for estimating the Cr-C temperature relation in the low chromium region. From the observations of Chen and Chipman9 and thermodynamic data given in Basic Open Hearth Steelmaking,4 the following relation can be calculated for melts containing small amounts of chromium and carbon assuming a carbon monoxide pressure of 1 atm: % Cr -21,250 K' = (%C)2; logK1 == —t— +13.88 [2] Moreover, by plotting Eq. 2 for any given temperature on cartesian coordinates, it can be extrapolated graphically to the limiting carbon content at zero chromium for the specified temperature without serious complications. By means of Eq. 2 and its extrapolation, the Cr-C temperature relations originally established experi-

Jan 1, 1954

By J. D. Rice, P. L. Wearden, W. L. Hensou

Solutions to the unsteady-state partial water-drive reservoir performance problem can be obtained through the use of analogue computers or high-speed electronic digital computers. The solutions that have previously been resolved for use on digital computers, however, demand a knowledge of the aquifer parameters. Generally, the analogue computers now in use do not require this knowledge. A solution is presented herein where the aquifer performance, expressed in terms of difference equations, is related to the reservoir performance as expressed by the modified Scbiltbuis material-balance equation. A numerical procedure for a medium-sized digital computer also is presented in which a solution to the set of equations defining the aquifer and reservoir performance is obtained and the aquifer parameters (permeability and sand thickness) are automatically optimized while simultaneously matching the known pressure behavior. Predicted pressure behavior can be calculated using rates from any assumed future production practice. The procedure provides an output format which presents the cumulative, incremental and average rate of natural water influx, the per cent gas-cap expansion, the calculated reservoir pressure, the measured reservoir pressure, and the difference between the measured and calculated pressures. Results of a test problem are presented in comparison with results obtained by the Bruce Analyzer, Ohio Oil Co. 's Pace General Purpose Analogue Computer, and Sun Oil Co.'s Single-Pool Electronic Reservoir Analyzer. These results indicate that unsteady-state reservoir perlormance for a single-pool system can be adequately simulated by a numerical method employing a digital computer and that the special-purpose analogue computer can be supplanted by this method. INTRODUCTION The numerical approach to the unsteady-state partial water-drive reservoir performance problem heretofore has been limited in that solutions have been resolved only for certain fixed parameters. Also, prior to the advent of high-speed electronic digital computers in the last few years, calculations were so tedious and time-consuming that they ordinarily were neglected, or some other means of obtaining the solutions were used. The analogue approach had been used for obtaining solutions to the transmission-of-heat problem and, consequently, means were developed for applying the electrical analogue to the unsteady-state reservoir performance problem. Bruce submitted a paper for AIME publication in Sept. 1942, in which he described an electronic device (now called the Bruce Analyzer) for analyzing the water-drive performance of any reservoir, based on either steady or unsteady-state flow characteristics. 1 Sun Oil Co. adopted the analogue approach in 1949 and now has two special-purpose high-speed electronic reservoir analyzers in use.2,3 Two main features of Sun's analyzers are (1) the high repetitive rate of reproducing the entire history of reservoir performance cyclically a number of times per second, and (2) the elimination of the necessity of knowing the properties of the associated aquifer. Since the advent of larger and faster digital computers, the possibility of incorporating this second feature into a numerical approach appeared feasible. Previous work has been done and material published covering the application of numerical methods to the behavior of the pressure with respect to time at any point in an associated aquifer? However, the aquifer parameters must be known from some source. The material presented in Ref. 4 has been used to a great degree in developing the numerical method described herein. DIFFERENTIAL EQUATION AND BOUNDARY CONDITIONS The problem of simulating the performance of a reservoir and the associated aquifer is to determine the characteristics of the aquifer such that the

By J. B. Clemmer, P. E. Churchward, C. Rampacek

A cyclic method for processing manganese ores using sodium sulphate as the basic reagent is described. Sodium sulphate is electrolyzed in a diaphragm cell to give an anolyte-containing agentisdescribed.Sodiumsulphuric acid and a catholyte-containing iselectrolyzedincaustic soda, a part of which is carbonated in a cyclic manner to form soda ash. The reduced ore is leached with the anolyte to dissolve the manganese and the impurities are precipitated by addition of catholyte. Manganese in the pregnant todissolvethemanganeseandtheimpuritiessolution is precipitated as synthetic rhodochrosite with a carbonated catholyte, and sodium sulphate is regenerated. Calcining the manganese carbonate gives a high grade product and the carbon dioxide is returned to the carbonation step. The results of laboratory tests using cells equipped with synthetic-fiber diaphragms and permselective membranes, which permit transfer of anions or cations during electrolysis, are described. A METHOD which has been considered for pro-cessing manganese ores under emergency conditions to recover a product suitable for smelting to ferromanganese involves reductive roasting of the ore for leaching with dilute sulphuric acid followed by precipitation of the manganese from the purified pregnant solution with sodium carbonate. Although the process is operable and involves no novel or untried steps, it is noncyclic in regard to reagents. Research seemed warranted to determine if a cyclic process could be developed by electrolyzing the sodium sulphate formed during precipitation of the manganese with soda ash to regenerate sulphuric acid and sodium hydroxide. Reduced ore would be leached with acid anolyte to dissolve the manganese. The iron, alumina, and other dissolved impurities would be precipitated with the caustic catholyte, and the manganese in the purified pregnant solution would be precipitated as artificial rhodochrosite with carbonated catholyte to regenerate simultaneously sodium sulphate for electrolysis. Waste boiler gas and CO, from calcining the manganese precipitate would be recycled for carbonation of the caustic catholyte. There is a surprising lack of data in the technical literature on diaphragm electrolysis of sodium sulphate. One of the more comprehensive papers, by Atwell and Fuwa, describes the problem involved in electrolyzing byproduct sodium sulphate from the viscose process with particular regard to the design and operation of asbestos diaphragm cells. Frisk' also investigated electrolysis of sodium sulphate from viscose-spinning baths to recover caustic soda and sulphuric acid. The objective in these investigations was to produce, by electrolysis and evaporation, a concentrated caustic-soda solution and a sulphuric-acid solution low in sodium sulphate. Because of these requirements, the process was not too attractive despite a favorable yield of caustic and acid with a reasonable power consumption. Because strong acid and base are not required for processing manganese ores and nonelectrolyzed sodium sulphate is not objectionable in either reagent, the present problem was somewhat simpler than that of these investigators. The purpose of this report is to summarize briefly the results of laboratory electrolysis of commercial sodium sulphate in diaphragm cells of different types and the application of the acid and caustic for processing manganese ores in a cyclic manner. Electrolysis in Permeable Diaphragm Cells The principal problem in electrolyzing sodium sulphate in a permeable diaphragm cell is to prevent mixing of the acid and base formed in the anode and cathode compartments. It is not enough to separate the anolyte and catholyte by a single diaphragm. A three-compartment cell in which the sodium-sulphate solution is fed to the center compartment and flows through the permeable diaphragms to the anode and cathode compartments is more efficient electrically. Diaphragms should be porous enough to allow flow of solution to outer compartments but tight enough to prevent gross mixing of the anolyte and catholyte. In addition to being resistant to acid and alkali, the diaphragms should offer minimum resistance to the flow of current. It is also important that the electrolyte contain a high concentration of sodium sulphate to furnish an abundance of sodium and sulphate ions and thereby decrease the current carried by hydrogen and hydroxyl ions. A practical limitation of sodium-sulphate concentration is imposed by the decreased solubility of sodium sulphate with decreasing temperature. At 20°C, a concentration of 200 g per liter sodium sulphate can be maintained. Little is gained in conductivity by using a concentration greater than 200 g per liter. The small-scale continuous electrolysis tests were made in a 12x12 in. open-top bakelite cell equipped

Jan 1, 1956

The President was authorized to appoint. a liaison committee to cooperate with the American Mining Congress in respect to the establishment of a Secretary of Mines and Mining in the President's Cabinet. He appointed Edwin Ludlow, Chairman; Mark L. Requa, and J. E. Johnson, Jr. It was resolved to accept the invitation from the Chicago Section to hold the. 120th meeting of the Institute in Chicago during the week of Sept. 15, 1919. The action of the Executive Committee in appointing Past President E. Gybbon Spilsbury as representative of this Institute to visit France upon the invitation of the Société des Ingénieurs Civils de France was approved. The final budget for 1918 was approved. Tile President was authorized to appoint a committee, of three members, on the Development of Activities of the Institute. The committee was requested to report at the February meeting of the Institute, and the Secretary was requested to invite each local section to have a member present to discuss the subject. The President appointed J. W. Richards, Chairman; P. N. Moore, and Allen H. Rogers. Thirty-six members, ten associates, and five junior associates were elected; one change of status from associate to member was granted; two members were reinstated; and eight resignations were accepted. An extension of time was granted to nine members. The dues of eight members were suspended on account of their being in active service.

Jan 2, 1919

The following is an incomplete list of members and guests who. called at Institute headquarters during the period Dec. 10, 1917 to Jan. 10, , 1918: A. A. Arluck, Camp Merritt, N. J. W. Spencer Hutchinson, Boston, Mass. C. L. Bruns, Santiago de Cuba. William F. Jahn, New York, N. Y. Henry C. Carr, New York, N. Y. C. H. James, Tucson, Ariz. L. J. Charles, Santa Fe, N. M. Charles Janin, San Francisco, Cal. W. A. Deane, Waxhaw, N. C. Joseph T. Kupferstein, Shreveport, Pa. P. St. John Dixon, Rio de Janeiro, Brazil. Richard Lamb, New York, N. Y. M. C. Drake, Marquette, Mich. Walter R. Malm, San Francisco, Cal. F. W. Draper, Petrograd, Russia. W. H. Nash, Buffalo, N. Y. Paul W. Gaebelein, Boise, Idaho. Edmund Newton, Minneapolis, Minn. H. F. E. Gamm, Rutherford, N. J. Guy C. Riddell, Port Pirie, South Australia. C. A. Grabill, El Paso, Tex. Williams A. Simkins, San Francisco, Cal. William H. Hampton, New York, N. Y. Henry B. Smith, Northampton, Mass. R. M. Henderson, Brackenridge, Colo. H. E. Smith, Chicago, Ill. Geo. B. Holderer, Northpines, Ont., H: C. Spaulding, Washington, D. C. Canada. Y. Wakabayashi, Tokyo, Japan. H. H. Howry, Camp Upton. N. Y. A. P. Watt, Mine La Motte, Mo. L. Douglas Anderson", superintendent of the Midvale, Utah, smeltery of the United States Smelting Co., has been appointed manager of smelteries for the company at Salt Lake City, Utah.

Jan 2, 1918

By T. H. Aldrich

(San Francisco Meeting, October, 1911.) THERE are two conditions generally prevailing upon the earth-those within atmospheric influence, tending towards oxidation, and those away from atmospheric influence, tending towards reduction. Practically all mineral substances from mines of any depth are in a reducing condition. Since the cyanide process, in order to dissolve silver or gold, requires that the prevailing conditions under which it operates shall be oxidizing, and the materials usually acted upon being of a reducing character, it becomes necessary to supply oxygen to the solution carrying the cyanide. This oxygen is usually supplied through the medium of dissolved air in the solution, or through the medium of various chemical compounds, which upon combining with the solution or the ore give off a part of their oxygen. Strange as it may seem, practically all mineral substances are partly soluble in water, especially water carrying alkali or cyanide. The greater the surface exposed and the finer the material is ground, the greater will be the rate of dissolving of the reducing agents from the ore into the cyanide solution. In most cases, if the solution carrying the ore particles is agitated with air, the air will dissolve into the solution faster than will the reducing-agents; but in some cases the reducing-agents will dissolve more rapidly on account of easy solubility or greater surface exposed. It is a dissolving race between the oxygen from the air and the reducing-agents from the ore, and if the reducing-agents predominate, cyanide will not dissolve the gold from the ore. In many cases it will dissolve some of the gold, because in a mass of irregular shape some of the gold particles might be exposed upon the outside surface of a particle of rock;' but if the solution had to penetrate through cracks, the side-walls of which were lined with reducing-agent-

Feb 1, 1912

By E. K. Landis

IK connection with the interesting paper of Mr. Glenn on "Sampling Ores Without Use of Machinery " (page 156 of the present volume), I venture to offer the results of ten years' experience in the sampling of iron-ore by a method adopted when I first became

Jan 1, 1892

By J. J. Brown

Wilkes-Barre Meeting, Julie, runs., THE ore-hearth was the earliest type of furnace used in smelting Mississippi Valley lead-ores, which are very pure, and low in silver-content. The first smelters made no attempts to recover lead from the smoke; and since about 15 per cent. of the lead -in the charge escaped in this manner, early practice with the hearth was decidedly wasteful. At most of the large smelting-plants blast-furnaces with auxiliary roasters were substituted for the hearths long ago. But, upon the introduction of the Lewis and Bartlett bag-process for collecting fume, the ore-hearth was used by companies engaged in the manufacture -of pigments, simply on account of the large percentage of fume made by it. In fact, the extraction of lead was kept down by the use of hot blast and other devices. During recent years, however, several smelting companies have realized that the preliminary roasting of galena for the blast-furnace is not economical, and have, therefore, replaced the roasting-furnace with a modification. of the old Scotch hearth, in which a large percentage of the lead in a charge is recovered directly as pig-lead, while the remainder passes partly into fume and partly into slag low enough in sulphur to be charged into the blast-furnace without further treatment. The results obtained have proved so satisfactory, both As to recovery and operating-expense, that one eminent metallurgist has predicted the universal use of the ore-hearth on non-argentiferous ores. The-ore-hearth, thus employed as an adjunct to a blast-furnace plant, is rather a desulphurizer than a smelting-furnace proper,-the chief object being to make a blue slag suitable for the cupola-furnace. Hence, no special care is taken to obtain from it a large lead-extraction. * Head of Department of Ore Dressing and Metallurgy, Oklahoma School of Mines and Metallurgy, Wilburton, Okla.

May 1, 1911

The following discussion occurred on the afternoon of Sept,. 22, 1930, as part of the fall meeting of the Iron and Steel Division at Chicago. About seventy-five men attended this session. C. B. Murray opened the meeting, as follows: C. B. Murray, Cleveland, Ohio.—It is very encouraging to see so many here this afternoon to discuss this important matter of beneficiation. The producers of ore, I am sure, are anxious to furnish the grade of ore that the consumer wants. The consumer sometimes wants that which cannot be economically produced and often the producer cannot understand why the consumer wants certain things. It was to bring together these two interested parties that this meeting was proposed. I was appointed the chairman of the meeting, chiefly because I happened to be the chairman of the Iron Ore Committee of the Institute. I know a little about iron ore but have not perhaps kept up with the times in blast-furnace practice. I am asking Mr. Sweetser, who is well informed from both sides, to take over the meeting and carry on the discussion. R. H. Sweetser, Columbus, Ohio.—We want to have a free discussion between the iron-ore men and the blast-furnace men as to just what we are trying to reach in the beneficiation of iron ores. Many of those present have had a great deal of experience. There are men here from the ranges who have been passing through the experimental stage of beneficiation of iron ores, and there are some who have already gone on to commercial production. We have reached the point where the beneficiation of iron ore is important to the whole iron and steel industry. The connection between iron-ore beneficiation and the cleaning of coal is so close that I think we can profit by working very close to the coal people. Some Aspects of the Iron-ore Situation W. G. Swart, Babbitt, Minn.—I was very much interested in Mr. Richards'* paper on tonnages and the 20-year life. There is one interesting thing about the ore reserves; that is, the irregular distribution of that tonnage. On the Mesabi Range, for example, the United States Steel Corpn. owns between 70 and 75 per cent. of the reserve tonnage. They ship bctween 40 and 50 per cent. of the annual Lake Superior

Jan 1, 1930

By Arthur F. Taggart

Some years ago, A. M. Gaudin and one of the authors published a paper showing removal of tar acids from solution by sulfides preferentially as compared to gangues (specifically by galena as compared to quartz).' The underlying phenomenon was classed as adsorption, and the paper went on to develop the general thesis that so far as water-soluble frothing and collecting agents in flotation are concerned, the phenomenon of adsorption is one of controlling importance. Adsorption was defined in that paper as "a process of rearrangement of a system, which results in establishing a difference in concentration, as between the interfacial layers and the bulk of the phases, of a substance or substances initially uniformly dispersed in one or several of the phases." The paper went on to develop the relation between adsorption and surface cnergy according to Gibbs' equation (which may be thrown into the form U/c = KdT/dc, where U = excess concentration in surface layer, c = concentration, T = surface tension, and K is a constant), and pointed out that, according to this equation, degree of adsorption and change in surface tension vary directly. The present paper offers a somewhat different definition for the term adsorption; and sets up, in sweeping terms, the generalization that simple chemical reaction underlies the functioning of the flotation reagents which control mineral collection, when these reagents are soluble in and act from solution in the water of the pulp. Adsorption According to the modified definition, adsorption means concentration at an interface between different phases in a heterogeneous system (thus far the definition runs as before), by the action of some mechanism, of which nothing is properly implied in the word, and concerning which the user of the word is probably in entire ignorance. Thus defined,

Jan 1, 1930

By David R. Mitchell, R. M. Fleming

MANY trends were evident in the coal industry during 1951. Some were favorable for the industry; others were not. Probably those having the most far-reaching consequences are those affecting coal's markets. The rapid dieselization of many railroads and the continued trend toward oil and natural gas for home heating has caused serious dislocations in various mining districts. Mines have been forced to close down or to work on a reduced time basis. Conversely the increased activity in the metallurgical industries has increased the demand for coking and special purpose coals, and the growing production of electric energy has increased the demand in certain areas for steam coals. The increased demand for metallurgical coal and for steam raising by the large utilities is more than equal tonnage-wise to the loss of coal to railroad dieselization and conversions to oil and gas in the domestic market. Since much of the expansion is at captive mines of large corporations, many commercial operators supplying railroad and domestic users have had their markets curtailed without any compensating demand from other sources. Feverish activity was in evidence in many areas by commercial operators attempting to find new markets. The Norfolk and Western Railway is the, only major American railroad committed to the burning of coal. It has an exceptionally good cost record. During 1951, fifteen additional modern coal-burning steam switching locomotives were authorized for construction in the company's Roanoke shops at a cost of about $1,450,000. When the new order is completed the road will own a total of sixty locomotives of the modern-switcher type, including thirty acquired by purchase last year. The Norfolk and Western today is the only American railroad building its own motive power. All of these locomotives burn coal. Production Coal production in the year 1951 will approximate 570 million tons of anthracite, bituminous coal, and lignite. Of this, approximately 7 pet is anthracite. Total production is approximately 30 million tons more than in 1950 and reflects the increase in general industrial activity. Exports are expected to be close to 50 million tons. The industrial stockpile is close to 75 million tons, the highest it has been since 1943. With the exception of the usual local stoppages the year 1951 was unmarked by labor disputes. It was a year of good labor-management relations with a negotiated wage increase unmarred by a work stoppage. This may be the beginning. of an era of sensible negotiations to find agreeable settlements of disputes without the usual protracted bickering and industry-wide strike. The United Mine Workers of America has condemned wildcat strikes, stating that in nearly every, instance proper grievance procedures have not been instituted. Government defense organizations, perhaps profiting by their experiences during World War II, are pursuing a more enlightened program with regard to the fuel requirements of the nation. Many prominent officials have stated that wherever possible coal should be considered the primary source of fuel in all defense expansion. With the increased consumption of steel by defense projects, approval of transportation facilities for liquid and gaseous fuels have been refused where these fuels would enter a coal producing area. Liquid and gaseous fuel producers also have failed to provide satisfactory evidence that they have sufficient reserves and are capable of supplying their product in adequate amounts for the periods of time required. Realization has at last become prevalent that the hydro-electric power installations in several areas are insufficient to handle increased demands.' Steam generating plants are being constructed in these areas and equipped to burn coal. Most notable of these, is the TWA area whose supplemental steam power plants are expected to consume 10 million tons of coal per year when completed. The Pacific Northwest is another area which is expected to follow the same pattern. Nearly all new steam-power generating plants are being equipped to burn coal either as a primary fuel or as an emergency measure. Metallurgical Coal The steel and other metallurgical industries are expanding rapidly to meet increased industrial demands and defense orders. Since these industries are dependent on coke, coke has had a year of high production and can be expected to break all existing records when steel-plant expansions are completed. Most notable of the expansion projects is that of the Delaware River area where the iron ore will be received by ship from Canada and South America. U. S. Steel is only one of several steel corporations that are planning on putting integrated steel producing units in this area. The Defense Solids Fuels Administration announced in December that through. November 30, 1951. 29 projects in eight states, with a total cost of

Jan 1, 1952

By John D. Roach

DURING an investigation of the yttrium-hydrogen system aimed at producing solid yttrium hydride specimens containing various amounts of hydrogen, it was observed that yttrium containing approximately 2 wt pct H exhibited a tendency to crack and crumble to a powder on standing in air at room temperature. It was also observed that longer hydriding times, at a given temperature, increased this susceptibility to powdering without an increase in hydrogen content, also that moisture in the air is necessary for the observed effects to occur. Even if cracking did not occur, there was a continual formation of a light gray powder on the as-treated surface of the hydrided yttrium and this reaction continues until the entire hydrided piece has been reduced to a powder. Storing the hydrided specimens in the absence of air or removing the surface either by machining or grinding were effective means of preventing this disintegration of hydrided yttrium. In an attempt to determine the reason for this powdering phenomenon, the surfaces of a number of as-hydrided yttrium specimens were examined by X-ray techniques. In all cases the X-ray pattern obtained showed the major phase to be yttrium hydride (YH2) as would be expected since the specimens contained 2 to 2.2 wt pct H. In some cases a trace of yttrium oxide was observed. There was also a third phase present on the surface of these hydrided specimens which could not immediately be identified. This unknown phase was a face-centered cubic material, NaC1-type structure, with a lattice parameter of 4.855 and a calculated density of 5.914 g per cc. Very slight hand polishing of the surface of the hydrided yttrium specimens completely removed both the unknown phase and the traces of oxide so that only the yttrium hydride pattern remained. Based on the X-ray patterns the quantity of the unknown phase on the surface of the hydrided yttrium appeared to be directly related to the susceptibility of the material to powdering. Work at the Denver Research Institute on the yttrium-nitrogen binary system showed that yttrium nitride (YN) is a face-centered cubic material with a lattice parameter of 4.878A and a density of 5.890 g per cc. They also noted that this compound rapidly disintegrated to a powder on standing in air. The unknown pattern observed in the above specimens corresponds very closely to that of the nitride—fcc structure, 4.885 parameter, and density of 5.914 g per cc. The presence of this thin film of nitride on the surface of the hydrided specimens probably accounts for the observed powder formation and crumbling. The nitride reacts with the water vapor in the air (verified by private communication from Dr. C. Huffine, General Electric Co.) to yield yttrium oxide and ammonia. Ammonia is readily detected when hydrided yttrium specimens were allowed to stand in bottled moist air. The powder formed on the surface of the hydrided specimens was shown by X-ray analysis to be yttrium oxide. This reaction appears to occur primarily at the grain boundaries since discrete particles of yttrium hydride separate from the specimens during this powdering process. The reaction of yttrium nitride with water vapor is believed to be as follows: 2YN + 3H2O - Y203 + 2NH3. Despite the fact that this nitride is present only as an extremely thin surface film, if the above reaction is not prevented by removing this film from the surface either by machining or grinding, the reaction continues until the entire hydrided piece has been reduced to a powder. To account for this continuation of the reaction, it is believed that the following reactionalsooccurs: 2YH2 + 2NH3 -2YN + 5H2. The nitride produced by the latter reaction reacts in turn with water vapor. The reaction therefore becomes autocatalytic and continues until the hydride has been consumed and the entire piece reduced to oxide powder. The amount of nitride required to initiate this reaction is quite small and this nitrogen contamination can occur from a number of sources—hydrogen gas employed, minute leak in the hydriding apparatus or even from degassing of the reaction vessel itself. Longer hydriding times increase the possibility of nitrogen contamination and this is especially true when a dynamic gas system is employed in the hydriding process. The production of stable, solid hydrided yttrium is dependent on the complete absence of nitrogen contamination during processing. If such contamination does occur, powdering of the hydrided product can be prevented by removing the nitride from the surface e.g. grinding or by preventing access of air to the pieces e.g. sealing in wax or plastic. The author wishes to express his appreciation to General Electric Co. for sponsoring this research and for permission to publish the results of work under Subcontract AT-93.

Jan 1, 1962

By H. J. Ramey

Conventional calculation of total system isothermal compressibility for a system containing a free gas phase involves, among other things, evaluation of the change of oil and gas formation volume factors and the gas in solution with pressure. Preferably, this information should be obtained from laboratory measurements made with particular oils and gases. Often, experimental measurements are not available. In this case, it is necessary to obtain pressure-volume-temperature relationships from general correlations such as those of Standing' for California oils. In order to speed estimates of compressibility, generalized plots have been prepared of the change of both oil formation volume factors and gas in solution, with pressure from Standing's correlations. A generalized plot for estimating the change in the two-phase (oil and gas) formation volume factor with pressure is also presented. Usually, the effect of gas dissolved in reservoir water upon the total system compressibility is neglected for gas saturated systems, due to the low solubility of gas in water. Results of this study indicate that the increase in total system compressibility caused by solution of gas in water is often as large as the compressibility of wafer, and can be magnitudes larger for low pressure systems. Generalized results for estimating the change of gas in solution in water with pressure are presented in tabular and graphical form. INTRODUCTION During the past decade, pressure build-up and drawdown techniques have gained an important place in reservoir engineering. Build-up and drawdown analyses are only two special applications of the broad field of transient fluid-flow theory. All solutions of transient fluid-flow problems contain a parameter called the total system isothermal compressibility. This property of fluids and porous rock is a measure of the change in volume of the fluid content of porous rock with a change in pressure, and it may vary considerably with pressure. Evaluation of total system isothermal compressibility is not difficult, but it is tedious and time-consuming. Often compressibilities are estimated roughly, or transient flow methods are neglected completely. The benefits of using accurate system compressibility in properly-executed build-up or drawdown analyses are: 1. Better planning of pressure build-ups may be achieved to avoid unnecessary loss of revenue due to excessively long shut-in periods, or to shut-in periods too short to yield useable data. 2. Better and more reliable estimates of static formation pressures for reserves estimates and rate performance estimates. 3. Reliable information for evaluation of well completion effectiveness, and planning and interpretation of well stimulation efforts. The purpose of this paper is to clarify the nature of the total system isothermal compressibility, and to present useful methods for estimation of compressibility, particularly for systems containing a gas phase. DEVELOPMENT Numerous publications have presented solutions to transient single-phase flow of slightly compressible fluids, stressing pressure build-up applications. In transient flow, a compressibility* term arises to permit volume content of fluids in porous rock to change as pressure changes. The basic nature of the compressibility term is usually taken for granted. Problems arise in practical applications of transient fluid theory because most published works consider only one flowing fluid—in an ideal porous system containing only one fluid. In 1956, Perrine2 presented an intuitive extension of single-phase flow pressure build-up methods to multiphase flow conditions. Later, Martin- established conditions under which Perrine's multiphase build-up method had a theoretical foundation. Perrine has shown that improper use of single-phase build-up analysis in certain multiphase flow situations can lead to gross errors in estimated static formation pressure, permeability and well condition. It is likely that, much pressure build-up data for oil wells should be analyzed on the basis of multiphase flow. For both single-phase and multiphase build-up analysis, the isothermal compressibility term in dimensionless time groups often should be interpreted as the total system compressibility. All real reservoirs contain one or more compressible fluid phases. In addition, rock compressibility can contribute in an important way to the total system compressibility. The proper total system compressibility expression may contain terms for compressibility of oil, gas, water, reservoir rock and terms for the change of solubility of gas in liquid phases.

Jan 1, 1965

By HOMER L. WILLIAMS

WHILE some of the mining companies have been pumping a small amount of water for some time, it is only in recent years that large quantities of water have been encountered in the Tonopah district. The water appears to be in different zones or belts so that the draining of one property does not necessarily affect the one adjoining. Consequently, each company has its own pumping plant and its own conditions. The companies panes handling the largest amount of water are the Tonopah Extension Mining Co., Halifax Tonopah Mining Co., West Tonopah Consolidated Mining Co., and Great Western Consolidated Mining Co. The Halifax shaft is on the eastern end of the district and the other three properties on the western. The ore-bearing formation occurs at greater depth on -the eastern and western ends, hence the water problem in these properties.

Jan 1, 1921

By S. A. Braley

DRAINAGE water from coal mines is probably the most serious water pollution problem today, varying in importance according to location of the mines and geological structure. Drainage may be either acid or alkaline in character. Acid discharge, the most severely detrimental to a stream, is caused by natural oxidation of the sulfuritic material (FeS2) in the strata associated with the coal seam. Since the acid is the result of a natural reaction the acid water differs because it does not cease with abandonment of the mining operations. There is no known economical method of neutralizing acid mine water or any practical method to prevent oxidation of exposed pyrite. Since production of acid from a mine does not stop when mining stops, the total quantity produced depends entirely upon the excavated areas. The increasing volume of acid water in manv mines has greatly increased operating costs. Pumping is expensive and acid mine waters are destructive of all equipment, especially metals in pumps and piping, and necessitate the use of corrosion-resistant materials. Discharge of the acid mine drainage into streams neutralizes their normal alkalinity, causes them to become acid, and produces an environment unfavorable for aquatic life and unsuited for industrial or domestic use without costly treatment. Mine drainages vary in percentage composition over wide limits, although the usual dissolved substances are ferrous and ferric iron, aluminum, calcium and magnesium sulfates, and lesser amounts of sodium, potassium and manganese sulfates and chlorides. Some alkaline discharges may contain heavy concentrations of iron as iron bicarbonate. These waters may produce iron hydroxide deposits in the receiving stream but do not cause it to become acid. In the extensive literature on acid mine water there appears to be a great deal of confusion about the importance of various components and the methods for their determination. In many instances faulty conclusions have been drawn from use of unsuitable methods of analysis. It is desirable that the factors and terms used in evaluation of analyses of mine waters should be so clearly defined that any interested person could properly appraise any analytical report. Some analysts report complete chemical analyses of mine waters and neglect to record drainage volumes. Others report only a minimum of analytical data after taking no precautions to preserve the original composition of the water during the time elapsing between collection and analysis. Some use methods of analysis intended for so-called pure waters of the potable and boiler water classes. These methods are not applicable to highly buffered waters such as mine water. Probably the most common criteria for evaluation are pH, free acidity, or acidity or alkalinity to methyl orange or methyl red, total acidity or acidity to hot phenol-phthalein, and the sulfate content. If these determinations are made on carelessly collected samples after a few days to weeks standing in warm rooms, they do not in any way represent the character of the water flowing from the mines. It is hoped that a brief discussion of the fundamental value of some of these factors may lead to a bettqr understanding of the need for more careful evaluation of mine water discharges. The term pH is one used by chemists to express relative acidity or alkalinity in terms of concentration of effective hydrogen ion in a solution. It is defined as the negative logarithm of the hydrogen ion concentration or activity in equivalents per liter. pH = logarithm A neutral solution, which is one containing the same number of hydrogen and hydroxyl ions, has a pH of 7. As the hydrogen ions increase and the solution becomes more acid, the pH decreases toward zero; and as the hydroxyl ions increase and the solution becomes more alkaline, the pH approaches 14. When dissolved in water to a dilute solution acids like sulfuric and hydrochloric, commonly known as strong acids, ionize completely, and the pH or hydrogen ion concentration varies with molar concentration of the dissolved acid. However, in high concentrations of such acids, the pH or hydrogen ion concentration is less than the acid concentration because the acid does not completely ionize. In only very dilute solutions does the pH represent the total amount of acid that can be neutralized by an alkali. All ionization reactions are equilibrium reactions. If other chemicals are added to the solution of an acid and the added chemical produces an ion that is the same as one of the ions of the acid, the degree of ionization of the acid is altered and the pH changes to some value that represents the active hydrogen ion of the new solution. Thus if iron sulfate is added to a solution of sulfuric acid the pH increases, since the common sulfate ion suppresses the degree of ionization of the sulfuric acid and decreases the effective hydrogen ion. However, the total acidity of the solution is increased. There are two salts composed of iron and sulfate— ferrous and ferric sulfate. In these salts there is no hydrogen ion that can ionize to give an acid solution, but when they are dissolved in water, the pH is less than 7 and the solution becomes acid. This is caused by a reaction known as hydrolysis and is represented by the equations FeSO4 + 2H2O ? Fe(OH)2 + 2H + SO,: or Fe,(SO,)3 + 6H2O ? 2Fe(OH)3 + 6H+ + 3504 A solution with a total acidity of 5000 ppm according to the first equation will have a pH of 4.40 but one with an acidity of 75 ppm, according to the sec-

Jan 1, 1958

By A. E. Gorum, J. Washburn, E. R. Parker

Experimental evidence was obtained in support of the idea that cleavage fracture can be initiated by dislocation pile-up. The high ductility of MgO crystals when tested in bending comPared to their relative brittleness in tension was explained on the basis that large pile-ups are more likely in a tension specimen. CLEAVAGE fractures have been a problem of major concern for many years. A number of large steel structures have failed in a brittle manner, usually suddenly and without warning; often the failures occurred for no obvious reason and at nominal stress levels well within the generally accepted range. A great deal of data have been collected about factors that contribute to failures,1 but the physics of the fracture process has never been revealed. cottrel12 has recently developed a theory of brittle fracture in ductile materials which was based upon the concept that dislocations moving on two intersecting planes can unite to form a crack nucleus. This theory accounts for the known effect of grain size and for the effect of testing temperature. There has, as yet, been no experimental evidence published that would substantiate this or the earlier theories based on stress concentrations due to piled-up dislocations. The study reported herein was conducted to obtain information that would either substantiate or disprove the

Jan 1, 1960

By Fred Bond

WHEN some materials are ground dry in a ball mill, a stage of comminution is reached at which the finely divided particles begin to adhere to the balls and to the mill lining. As grinding progresses, a coating accumulates upon the grinding media, which tends to cushion the impacts and thus retard reduction of the material, and finally becomes so thick that all grinding ceases. At this stage, the characteristic noise produced by the grinding media dur-ing normal mill operation changes to a dull, muffled sound. In most instances, the formation of the coating marks the practical limit of size reduction. Industrial requirements for fine grinding frequently meet with this obstacle, and the tendency in many com-mercial operations to grind materials to a higher degree of fineness than formerly makes the solution of this problem an im-portant one. The phenomenon is of far greater importance, therefore, than the limited amount of research and technical discussion devoted to it implies. In order to learn more about the coating of different materials when ground dry to a high degree of fineness, certain labora-tory tests were made from which it was found that different materials form coat-ings at widely different size distributions. It is probable that most materials will coat if they are ground fine enough; the exceptions have inherent lubricating qual-ities, like coal and graphite.

Jan 1, 1940

By J. G. EVANS

It is with a certain amount of trepidation that a man considers gathering his family of six, traveling across a continent, two oceans and a sea, and going to live in a foreign land. But "pioneering" is still possible, and a nation is "foreign" only until one has lived in it. We've had eight years of pleasant experiences in South Africa on which to base that contention. It was in January 1938 that my brother first extolled the virtues of South Africa to us, and just three months and a thousand small problems later my wife, two daughters, three sons and I were boarding a ship in New York, bound for Cape- town. We arrived in May, and within a week had found a furnished home with beautiful lawns, tennis, court, a garden, and everything needed for family comfort. The children were soon located in school, and I settled down to the task of entering the importing business, as had been my original intention. The importing business started out slowly but was coming along nicely when on Sept. 3, 1939 the war started in Europe and a declaration of war by the Union of South Africa was made on the following day. With the declaration came import and export controls. In fact we were controlled completely out of business in one stroke. Liquidating the business, I went to Johannesburg intending to find work in one of the mines. Government health and safety regulations require that all underground mine employees have a red ticket from the Miners Phthisis Bureau certifying that they are not susceptible to silicosis, the scourge of the Witwatersrand gold mining industry. I made application to the Bureau, completed a form covering my whole past life, and was given a complete physical examination. The following day I was startled to find that I had not only been refused a red ticket but had been classified with a green ticket which for- ever bars one from working underground in any scheduled mine in the country, and all this in spite

Jan 1, 1949