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By Lester C. Uren

Tars paper reviews the industrial trends and changes in educational concepts that have led to the development of the modern petroleum engineering curriculum. A trend toward emphasis on engineering fundamentals is noted. While most universities are committed to the traditional four-year engineering program, it is agreed that more than four years is necessary for academic preparation of the petroleum engineer in all phases of his profession. The author proposes a coordinated program of undergraduate and graduate training that will permit of adherence to the general pattern of the present four-year engineering course, with provision for extension of the program into specialized graduate courses of professional character. In the latter, emphasis may vary with the interests and objectives of the individual student. A specific undergraduate curriculum is proposed in which upward of 80 per cent of the available time is devoted to engineering fundamentals. A broad survey of the professional field is afforded in courses grouped in the third and fourth undergraduate years, but detailed treatment of the professional aspects of petroleum engineering is reserved for the graduate program. INTRODUCTION Of necessity, engineering curricula must ever be changing to reflect the new techniques, the changing concepts that are presented as the engineering industries develop and unfold. Particularly is this true of the younger engineering curricula representing comparatively new and rapidly changing industries such as the petroleum industry. Institutions that planned their petroleum engineering curricula a decade or two ago now find that the petroleum industry has become vastly more technical in its requirements. En¬tirely new methods and techniques have come into vogue and must be given place in the curriculum, and some of these are of a character that demands changing emphasis in the fundamental preparatory subjects. College and university faculties cannot complacently assume that curricula in this field that were considered appropriate 10 or 20 years ago still reflect the needs of the industry that they are designed to serve. If they do, their graduates will be poorly equipped to meet the requirements imposed upon them by a rapidly changing industry. Perhaps it is not too much to expect academic authorities to anticipate the trends of industry and equip their graduates with what they will need to attain leadership 10 or 20 years after graduation. Whether or not this desirable objective is possible, there is no excuse for allowing curricula to fall behind the current needs of industry. DURATION OF CURRICULUM The majority of our engineering schools and colleges still adhere to the four-year curricula and there appears to be a definite sentiment among many engineers engaged in industry that work should be so planned that the engineering student may secure the essential academic preparation for his profession in a terminal four-year program. Yet, in recent years, it has become increasingly apparent that four years of

Jan 1, 1941

By M. S. Abrahams

Germanium has been rolled in the temperature range of 700o to 800°C. The thickness has been decreased by as much as a factor of four, from a thickness of 0.032 in. to a thickness of 0.008 in. For deformations below 60 pet, the true strain per pass is found to be a constant; from the temperature dependence of this slope, an activation energy of about 2.5 ev is obtained. This energy agrees with that for dislocation climb in germanium . For reductions greater than 60 pet, complete rings are seen in the Lave photographs, new grains are observed in the microstructure, considerable softening occurs, and the hole mobility is very low. This evidence indicates that the recrystallization of gertnanium has occurred. GERMANIUM has been deformed in many ways1 including tension, compression, torsion, and bending since Gallagher2 first described its plastic nature at elevated temperatures. All of these studies indicate that the glide plane in germanium is (111) and that the glide direction is (110). Rolled germanium specimens were used by Kolm, Warekois, and Kulin3 in their X-ray study of deformed semiconductors, but no information is given on the rolling itself. The present experiments deal with the rolling of germanium at various temperatures and for different orientations. In all previous deformation studies, the phenomenon of recrystallization (i.e., the transformation of a single crystal into a polycrystal) in germanium has not been observed4 despite relatively large deformations at elevated temperatures. The proposed reason4 for this was that sufficient energy could not be stored in the deformed germanium lattice. In contrast to the earlier studies this work will present evidence indicating that recrystallization occurs in germanium during rolling at an elevated temperature. I) EXPERIMENTAL PROCEDURE A) Test Specimens. The samples used for rolling were in the form of rectangular parallelepipeds measuring 0.3 in. long, 0.06 in. wide, and 0.035 in. high. They were cut from an undoped single-crystal ingot of p-type germanium with a resistivity of 24.4 ohm-cm, a Hall mobility of 2300 sq cm v-' sec-l, and a hole concentration of 1.1 x 1014 cm"3 at room temperature. The surfaces of the specimens were metallographically polished prior to rolling. The initial dislocation density of the samples was about 10' cm-' as determined by etching in CP4. Two different specimen orientations were used. In the first case, the direction of rolling was parallel to (251), the surfaces in contact with the rolls were of the form (1021, and the normal to the third face was parallel to (211). The corresponding di-

Jan 1, 1964

By Don B. Carson, Donald L. Katz

NATURAL gases under pressure form crystal-line hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methane-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbonrich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. INTRODUCTION Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villard1 and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies.2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Deaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on temperatures and pressures of hydrate formation for pure methane, ethane, propane, n-butane, methane-ethane mixtures, methane-propane mixtures, methane-butane mixtures, and some 15 natural gases, all in the presence of excess water. However, up to the present time no method has been available for predicting the temperature at given pressures or the pressure at given temperatures at which natural gases will form hydrates if saturated with water. This paper pre¬sents data on the methane-propane-water, methane-pentane-water and methane-hexane water systems in four phases, one of which is the hydrate. The application of the phase rule to the methane-propane-water data proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1941

Engineers who are in charge of industrial operations, and their number is legion, sense as much as anyone the present feeling of unrest in the' country and more than anyone else realize the present inefficiency of labor. Undoubtedly the two phenomena are closely correlated and no doubt are due to a multitude of causes which it will be impossible to enumerate. From my experience in mining I estimate that the present efficiency of labor is only about two-thirds of what it was under pre-war conditions. In the mining industry, at least, we have not a large surplus of men looking for work and usually under these conditions men are rather more independent and will not work as efficiently and faithfully as if they felt there were plenty of men ready to take their places. Wages in metal mining have advanced more than the increased cost of normal and sane living. The result is that the men often work fewer days in a month and do not seem to have very much interest in their work while actually engaged in it. Then again, they have been listening to the more or less vague propaganda of the I. W. W. and the radical wing of the socialists, who are harping on the fact that the distribution of newly created wealth is unfair and that the laborer really is not working for himself or his fellow laborers but is carrying on his exertions for the benefit of a small and lim-ited class of exploiters. A continued harping on this view is bound to influence the judgment of even a conservative workman who is not a student of economics and who hears little or nothing upon the other side. I am a great believer in the common sense of the American people and in the long run I do not think that they will be carried away by unsafe doctrines. The trouble with so many of these propagandists of industrial in-equality is that they do not differentiate between production and dis-tribution. Even if we admit that distribution is unfair, unless goods are produced there will be nothing to distribute. A great many unthinking people seem to feel that wages are paid out of a pot which is inexhaustible and do not realize that eventually what comes out of the pot can never exceed what is put into it. The workman is not paid in money but is paid in goods, money as we all know being used simply as a measure of value and a medium of exchange, and that all that can be used to pay the laborer is what he produces.

Jan 11, 1919

By R. A. Pallanch

Probably one of the most perplexing problems with which a mill operator contends is the proper evaluation of his mill results. True, he accurately determines his recoveries of metals and grades of products monthly, weekly, and often daily. These figures do not of themselves directly translate to mill economics. When one figure is unusually good there may be an offsetting circumstance. The advantage of high lead or zinc concentrate grade may be offset by poorer recovery; high lead recovery may be offset by poorer zinc recovery, or vice versa; and so on. Besides, grades or recoveries may not of themselves mean more than a reflection of the grade and character of the ore during the period under study. What the operator sorely needs is some one measuring stick that tells him when he has achieved his greatest return, regardless of grades or recoveries—for if he knows his methods and practices are yielding the optimum return he need no longer concern himself with the assays of products and tailings, or the corresponding distribution of metal values. At first blush it would appear that the obvious answer to this is the actual money return to the mill. Paradoxical as it may seem, however, money return does not make a dependable yardstick any more than do grades and recoveries, as ore condi- tions would vary enough to bring about greater money return during periods when the actual metallurgical work is not as good. The mill operator, of course, should always aim for the greatest return on the ore, once it is in the mill bins, with proper attention always to mill treatment cost. The need of a proper yardstick becomes more imperative with the increasing complexity of the problem. In the case of a simple, single-product operation on a fairly uniform ore, in which only one metal is of significant importance, the need is not great, as grade and recovery pretty well tell their own story. At the other extreme is the operation that makes three or four separate marketable products from a complex mixture of heterogeneous ores that vary tremendously in individual metal contents and ratios, degree of oxidation, and other characteristics, and in which gold, silver, copper, lead and zinc are all significant values. Economic Recovery The first attempt at obtaining a proper single yardstick for a fairly complex ore with which I am familiar is the use of the ''Economic Recovery" term at the lead-zinc flotation mill of the Sunnyside Mining and Milling Co., Eureka, Colorado. This method had been applied there early in Sunnyside flotation-mill history (not later than 1920) and credit for the innovation I believe belongs to Messrs. Kuryla and Marquand. The term "Economic Re-

Jan 1, 1949

By E. F. Johnson, F. H. Brinkman, H. J. Welge, A. L. Hicks

A method is presented for predicting the character of gas or water displacement in a radial system, which can be either horizontal or inclined. The latter case would comprise cone-shaped or dome-shaped symmetry. The method conriders the one dimension of radial distance, taken parallel to the bedding planes. Approximate allowance can be made for segregation of the two fluids perpendicular to the bedding planes. A complete saturation history can be obtained in about a day's time with the use of a desk calculator. Results of an example calculation agree well with the performance of simulated gas drive in a large model representing a section of a cone. This pie-shaped, sand-packed model was 8-ft long and 4-in. thick. The method of solution is useful in handling other partial differential equations of first order and first degree. INTRODUCTION A new analytical method has been developed for predicting the performance of gas or water drive in a reservoir having radial or cone-shaped symmetry (see Fig. 1). In addition, this new development offers a general method of handling partial differential equations of first order and first degree. This work extends those methods developed previously'- "or predicting the displacement of oil by gas or water in linear systems. The method of calculating oil recovery in a radial system involves two major parts. The first part is a calculation of the distribution of saturations at various times of depletion. The second part is the calculation of oil recovery and producing gas-oil or water-oil ratios through volumetric balance on the saturation distributions obtained in the first part. This second part differs only slightly in principle from similar calculations made with linear systems, for instance. The basic assumptions used in the calculations are as follows. 1. One-dimensional radial flow. An approach is explained later for approximating a second vertical dimension. (With- drawals of oil, and of the driving fluid after breakthrough, are assumed uniform around the periphery of the dome.) 2. Constant-volume fluid flow. Thus, in a gas drive there is no change in gas solubility, or in oil or gas volume due to viscous and gravity pressure drops. 3. Capillary forces are negligible. 4. Constant rate of injection. A program has been written for carrying out the calculations needed on a digital computer. However, a prediction can also be arrived at using a desk calculator; this latter method of work requires about a day's time for each prediction made. CALCULATION OF SATURATION DISTRIBUTION For definiteness, we describe the development of our method for the case of gas drive from the crest of the structure. The reader will note, however, that the method is just as applicable to an advancing radial water drive. The equation describing gas flow over an infinitesimal

By Benjamin N. Webber

THE peninsula of Nicoya contains virtually all of the known manganese deposits of Costa Rica. These are south and west of the Tempisque River, which flows across the peninsula near its juncture with the mainland. This peninsula forms the westernmost part of the province of Guanacaste, which is the northern of the two Pacific Coast provinces of Costa Rica. The larger villages are connected by ox-cart roads and trails. The area may be covered on horseback without difficulty except during the rainy season, when rivers are in flood and difficult to ford. This is particularly true of the Rio Seco-Guayjiniquil area, where there are no inhabitants and few open trails through the tropical jungle. Santa Cruz and Sardinal are served by the Taca Airlines, two planes a week from San Jose and Puntarenas. The port of Puntarenas has excellent loading facilities but none are available nearer the manganese districts; there ore must be lightered to vessels standing offshore. PHYSIOGRAPHY In Costa Rica there are three physiographic divisions: (I) the central plateau (Mesa Central), a somewhat dissected lava platform upon which are superimposed volcanic peaks, some of which are still active: (2) the Atlantic low-lands and (3) the Pacific lowlands. The peninsula of Nicoya and the larger part of the province of Guanacaste lie within the Pacific low lands. The term "lowland" indicates relation to the central plateau, as the peninsula of Nicoya is largely mountainous. The mountains of Nicoya form the southern extremity of a range of low hills, which are almost continuous along the Costa Rican coast to the Nicaraguan border. The coast line shows evidence of subsidence. The Gulf of Nicoya obviously is the drowned valley of the Tempisque River. The west coast of Nicoya shows many rocks, shoals, bays, inlets and small islands as evidence of a sea encroachment. The altitude of the manganese deposits ranges from o to 800 ft. Topography is of the mature type of wide valleys and low hills, often with abrupt slopes. The climate is tropical and humid; rainfall of 125 in. falls largely between Sept. I and Jan. I. Vegetation often is very dense, the Rio Seco-Guayjiniquil area being truly tropical jungle, containing many hardwoods. HISTORY AND PRODUCTION The production of manganese ore in Costa Rica apparently dates from the first World War. It reached a peak of about 10,000 tons in the year 1919, then declined rapidly. Evidence of this period of prospecting has rotted away or been swallowed by the jungle. The war now in progress apparently revived the interest in Costa Rican manganese and has encouraged further prospecting. Deposits long known have been redenounced and trails have been cut through the jungle to them. Many new deposits have been discovered in the last

Jan 1, 1942

By V. S. Tuman

In the first part of this paper, an estimate is made of the magnitude and extent of the thermal stresses which result from mud circulation. Our study is made for the period of relaxation, i.e., when the drilling operations are terminated and mud circulation is discontinued. In the second part, we have shown how the thermal stress can affect the wave propagation. An example is worked out for a Carbondale sandstone (Illinois basin). It is concluded that, in extreme cases when differential temperature is about 100°F, the travel time will be affected by about 2 microsec/ft. For more refined permeability studies, such corrections would be desirable. MAGNITUDE AND EXTENT OF THERMAL STRESSES RESULTING FROM MUD CIRCULATION When geological beds are penetrated by boreholes, it is observed that the formation temperatures increase with depth; however, the temperature profile varies considerably from place to place. During drilling operations, mud pumped from a pit at atmospheric temperature absorbs heat from the lower beds. As a result, the drilling fluid returning to the surface is at a higher temperature than the surrounding beds. The temperature gradient in a well depends on the rate of mud circulation and other factors; normally, this temperature gradient is smaller than the natural gradient in the formations. (See Fig. 1.) The temperature difference between the mud column and the surrounding beds gives rise to therma1 stresses (which are also important in the phenomenon of fracturing), and it is expected that they will affect the transit time of the sonic front in velocity logging.1 It is evident chat beds near the surface will undergo various cycles and will have a complicated dynamical and thermal-stress history. A limestone bed which is just penetrated will act as a source of heat, warming up the cold mud pumped down a few minutes earlier from the surface pit. The same limestone bed a week later will act as a sink, absorbing heat from the drilling mud which has already warmed up sufficiently to be at a higher temperature than the bed in question. No doubt a large section of the hole will undergo a heat treatment, which will make the calculation of the exact magnitude of the thermal stresses very difficult. In the solution of wellbore thermal equation, it is assumed that the rock around the wellbore is elastic and isotropic, and that the system is radially symmetrical. A complete dynamical solution of the thermal stresses set up at different horizons during the drilling operations would require a comprehensive history of the mud circulation, the surface temperature of the pit and the number of hours in which mud was not circulated. CONDUCTION OF HEAT AND THERMAL EQUATION OF STATE

By Robert U. King

The Climax Molybdenum Company's mine is situated on the Continental Divide at Fremont Pass in Lake County, Colorado. Elevations at the mine range from 11,000 it. to over 12,000 ft. The ore body is on the south flank of Bartlett Mountain, a prominent peak in the Ten Mile Range. A horizontal section of the mine, such as the Phillipson level (Fig. I), shows the outer ore zone as an annular ring varying in width from 300 to 800 ft., surrounding barren silicified rock. In vertical section the outer ore zone is dome shaped (Figs. 2 and 3), the apex of which is truncated at the surface by glaciation, exposing part of the ore body. The outer ore zone overlies the barren core and is itself overlain on the flanks of the dome with unmineralized rock. An ore zone of similar shape underlies the barren core of silicified rock, known as the Central Ore Zone (Figs. 2 and 3). Molybdenite is distributed uniformly through a zone of moderately silicified granite, schist and quartz monzonite (early) porphyry, around a highly silicified core. The molybdenite occurs in veinlets associated with fine granular quartz and pyrite, replacing altered and fractured granite, schist, and porphyry, and as coatings on numerous fractures cutting these rocks. Intense fracturing of all rocks is a characteristic feature of the Climax ore body. Most fractures are mineralized and no longer represent planes of weakness. Much fracturing is postmineral, however, and these fractures are generally filled with sericite or gouge, or remain as unmineralized joints separating otherwise massive rock into blocks of various size. Study and Mapping of Caving Characteristics Important differences in the behavior of caving of various blocks of ore at Climax have been recognized, involving arching of the rock over caved stopes, tendency of caved rocks to funnel, and size of caved rocks. Also, new problems have arisen associated with future mining on the Phillipson level, and may occur with proposed development of lower levels, such as excessive stress on mine pillars caused by large masses of overlying stable rock, and higher costs in maintenance of mine workings in soft, weak rock. To explain the differences and to provide solution for these problems, a study of geologic structure was undertaken early in 1944, to determine whether it would be possible to map cavability of rock from physical features exposed in mine workings and in diamond-drill cores. A comparison of known caved areas was made and rocks were classified structurally according to strength or degree of cavabil-ity. As nothing of this nature had been done before at Climax, the approach to the problem was rather indefinite. Several trials were made with negative results, but collectively indicated a suitable method. This was to examine all mine workings and diamond-drill cores, record-

Jan 1, 1946

By L. G. Graper, E. L. Ramsey

The present program of increased production of armament and lend-lease material for mechanized war has created a problem for the shops that must do the machining. They have naturally turned to the steel producers to provide them with a steel that can be accurately machined with the greatest possible speed. The adding of sulphur to steel as an aid to machinability has long been practiced; however, it may cause red shortness in rolling and may result in billets with seams and cracks, which must be removed before rolling can be continued. This conditioning of billets slows down production and adds to the cost of making steel. Experience with various grades of sulphur steel made to different specifications has shown that Bessemer sulphur steels roll better than similar grades made in the open hearth, and also that low-carbon steels that are open or semikilled as tapped roll better than completely deoxidized or killed steels. This has led to the belief that oxygen plays an important part in the rolling qualities of sulphur-bearing steels. It is generally held that the red shortness of sulphur steels is due to the low melting point of the sulphide compounds that separate out at the grain boundaries when the steel solidifies. At the rolling temperature of steel these sulphide compounds melt and cause cracking. Adding Sulphur as a Sulphite These difficulties can be avoided if sulphur is introduced into the stecl by means of an anhydrous sulphite, such as sodium sulphite or sodium bisulphite, which—upon decomposition—forms sulphur dioxide. It is assumed that, in this case, the oxygen of the sulphur dioxide forms part of the sulphide inclusions in the steel, and raises their solidification temperature enough so that the formation in the steel of a low-melting eutectic is prevented. The result is the prevention of hot shortness and a more uniform distribution of inclusions. Fig. I shows photomicrographs of steels made with sulphur, while Fig. 2 illustrates the structure of steels made with sodium bisulphite. These samples were cut from the steels as cast—that is, before rolling— and were polished and lightly etched to bring out the grain boundaries. Fig. I shows that sulphide inclusions segregate more or less at the grain boundaries, and it can be seen how the continuity of these low-melting inclusions would cause red shortness. Fig. 2 shows that the sulphide inclusions arc more or less uniformly distributed throughout the matrix. This arrangement of inclusions has no apparent effect on the rolling qualities of a steel. This statement has been substantiated by the observation of the rolling of over 6000 tons of steel made with a sulphite addition. Results As stated before, the sulphur dioxide is added to steel by means of the decomposi- 27

Jan 1, 1942

By Albert C. Harding

For several years barite (BaSO4) production has topped such better known minerals as feldspar and fluorspar in annual tonnage and is now well established among our foremost nonmetallic industries. Description Of widespread occurrence in the United States, barite is relatively soft (hardness, 2.5 to 3.5), inert, heavy (specific gravity, 4.5), and is also called "barytes" (sometimes pronounced "bear-i-tease"), "heavy spar" and "tiff." It occurs with granular and earthy structure but usually has coarse, orthorhombic crystallization. It is commonly white, and although occurring in various shades of red, yellow, and gray, barite always gives a white streak and can be scratched by the ordinary prospecting pick. Its softness and weight are usually sufficient to establish field identification. Another aid is the "rotten egg" odor of H2S which sometimes emanates from freshly fractured surfaces. Barite can be readily distinguished from two other minerals which have somewhat similar occurrences and characteristics. The relatively rare celestite, strontium sulphate, has a specific gravity slightly less than 4.00 and gives a distinctively crimson color in a flame test. The very rare wither-ite, barium carbonate, has a specific gravity of 4.3 but readily effervesces with dilute hydrochloric acid. Occurrence All known commercially important barite deposits in the United States occur as re- placements or cavity fillings in schists, shales, limestones, dolomites, and quart-zites, or as residual deposits from such formations. In Georgia, Tennessee, North Carolina, and Missouri, high-grade barite is recovered as fragments from residual clays covering quartzites and dolomites. In Arkansas, Nevada, and California, barite, usually of lower grade, is mined from replacement deposits. These seven states contributed the entire production reported by the U. S. Bureau of Mines for 1945 as given in Table I. Table i—Crude Berile Sold or used by Producers in 1945 State Short Tons Arkansas................... 260.660 Missouri.................... 225.467 Georgia..................... 110,393 Tennessee................... 32,812 Nevada..................... 28,919 Other States............... 37,811 Total..................... 696,062 ('other states,, included only california and North Carolina. Such a large part of this undistributed production came from California that that state probably outranked both Nevada and Tennessee. For the second consecutive year Arkansas was the leading producing state, particularly worthy of note because there was no commercial production of barite there prior to 1941 and because the entire production of Arkansas has come from one large deposit which is being operated by two companies. Consumption The 1945 consumption as reported by the Bureau of Mines was: 482,442 tons as ground barite 139,288 tons in making lithopone 99,173 tons in producing barium ------- chemicals Total 720,903 tons

Jan 1, 1949

By E. A. Gulbransen, W. S. Wysong

THE behavior of molybdenum and its surface oxides in oxidizing and reducing gas atmospheres and in high vacua at elevated temperatures is a question of scientific and technical importance The use of molybdenum as a metal or as an important component in alloys in oxidizing atmospheres at elevated temperatures has been limited because of the unprotective nature of its oxide film and the volatility of this oxide at moderate temperatures. This communication will present results of a vacuum microbalance study 1,2 of the following problems. (11) the oxidation kinetics in the temperature range of 250° to 450°C; (2) the reduction with pure hydrogen of thin oxide films formed on molybdenum; (3) the volatility of the thin oxide films, and (4) the vacuum oxidation of molybdenum at high temperatures. Molybdenum is an interesting metal to study for the following reasons: (I) although the oxide-to-metal-volume ratio is greater than one, the metal is not considered protective; (2) the metal oxidizes readily at temperatures of 250°C and higher; (3) the oxides of the metal are reduced at temperatures as low as 500°C by pure hydrogen; (4) the oxide MoO3 melts at 795°C; and (5) the oxides of molybdenum are volatile at moderate temperatures. The following variables are studied in the oxidation kinetics. time, temperature, pressure, surface preparation, surface area, concentration of inert gas in the lattice, cycling procedures in temperature, vacuum effect and high temperature vacuum oxidation The general interpretation of many of these factors has been previously discussed. LITERATURE The oxidation of molybdenum has not been studied critically. Although" many studies have probably been made on the kinetics of the oxidation process, none has been reported in the literature available to us. The crystal structures found in the oxidation of molybdenum have been studied by Hickman and Culbransen 4 Their results showed that MoO2 is the oxide which is stable in contact with the metallic subgtrate throughout the temperature range 300 to 700°C. As the film thickens in the low temperature range, MoO3 becomes predominant on the surface. Above 400°C, Mo03 is no longer observed, Mo02 being the only oxide found. Hagg and Magneli5 have shown from an X ray study that the a-phase, orthorhombic MoO3 is stable up to 1050°C. Two other phases, ß and ß', with compositions close to Mo02 90 are also obtained The formula for the ß phase is not given but that of the ß' phase is defined as Mo9026. The ß' phase is found to be built upon a monoclinic unit cell. A -?-phase is isolated from a preparation M00275 heated for 17 hrs at 670°C. This phase is

Jan 1, 1947

By A. G. Guy

IN the course of a research on steady-state diffusion it became necessary to make diffusion calculations for a finite solid. This problem was found to be sufficiently different from the corresponding problem for the semi-infinite solid for an entirely new approach to be necessary in obtaining a useful solution. The assumption of an exponential variation of the diffusion coefficient with concentration' was no longer a practical necessity, so that the new solution offered the possibility of handling diffusion in semi-infinite solids for arbitrary variations of the diffusion coefficient with concentration. In discussing the principle on which this method of calculation is based, it is convenient to consider the relatively simple problem of one dimensional diffusion into a matrix that initially contains none of the diffusing substance. The solution of the set- ond Fick Law,?C/?t=D0?2C/?x2, for diffusion into a semi-infinite solid is3 C/C=1-F(x/2vD0t [1] where C is the concentration of the diffusing substance at a depth x cm below the surface after dif- A. G. GUY, Member AIME, and M. GOLOMB are Professor of Metollurgicol Engineering and Professor of Mathematics, respectively, Purdue University, Lafayette, Ind., A. S. YUE, formerly with Purdue University, is now with the Research Laboratory, Dow Chemical Co., Midland, Mich. TP 4505E. Manuscript, July 18,1956. fusion has occurred for t seconds; C, is the concentration of the diffusing substance at the surface of the matrix; Do is the diffusion constant, expressed in sq cm per sec; and + represents the Gauss error function. The corresponding solution for diffusion into a finite solid of thickness, 1, is conveniently written for the change in concentration, C+, at a point midway through the matrix and for times, t, great enough for the following equation to be used4 c1/2/C1=(1/2-2/?e-?2D0t/l2) [2] In Eqs. 1 and 2 the diffusion coefficient is represented by the symbol Do (rather than by D) to emphasize that these equations are valid only for constant values of D. To understand how these equations can be modified to take account of actual variations of D, such as that shown in Fig. 1, first consider the fact that for a given time of diffusion theconcentration at a given point is determined, not by the D value alone, but by the ratio x/vD0 in Eq. 1 and by a similar ratio, l2/D0 in Eq. 2. Even though in fact D varies, it is possible to keep this ratio constant by using a special coordinate system, x,, that varies with D in the appropriate manner. The necessary character of this special coordinate system can be easily visualized by imagining that

Jan 1, 1958

By Sylvan Z. Beer

The factors that determine the yield and crystal size in the two-temperature synthesis of A lp were examined. Low yields and small crystals were associated with low temperatures and pressure. Attempts to grow large crystals in the critical and supercritical region of phosphorus were unsuccessful. Crystal size increases markedly at elevated temperatures. Crystals grown at temperatures as high as 1450° C fluo-resced, under uv excitation, at energies close to the estimated band gap of about 2.4 ev, while crystals grown at lower temperatures tended to fluoresce in the red region of the spectrum. Those grown in the supercritical region showed no ALP fluorescence. Heating the high-temperature-grown ALP under vacuum greatly increased its fluorescence efficiency and moved the emission peak to higher energies. I HE III-V compounds, with few exceptions, have been prepared by the two-temperature method. In its classic form this technique is applicable to closed systems where at least one of the components, in this case the column V element, is a liquid or a solid with a high vapor pressure. One advantage of this method over flow systems is in its simplicity. In addition, because it is a closed system, it can, under the circumstances to be described later, be run at higher pressures of the volatile species than in flow systems. In instances where the III-V compound is soluble in the parent III metal to about 1 mol pct or higher, solution growth can be made to take place by slow cooling. This, for instance, is one way in which single-crystal GaP1 and Inp2 have been grown. Initial attempts to synthesize and grow A1P by this technique were not too successful; the yield was low and the crystals obtained were exceedingly small. The conditions required for improving the yield and growth by this technique were, therefore, sought. Two obvious conditions which could be controlling were examined. These were the temperature of the aluminum and the pressure of the phosphorus. The range of temperatures studied extended from about the melting point of aluminum, 660° to about 1450°C. The latter is dictated by the vapor pressure of aluminum which reaches about 1 Torr at that temperature and the limitations of the materials of construction as described in the next section. The pressure range of interest covers from below 1 atm to above the critical pressure of phosphorus, 82.2 atm. EXPERIMENTAL The Temperature of Aluminum as a Variable. A series of experiments were run in the conventional two-temperature manner. All refractories and quartz were dried by heating at 800° to 900° for a minimum of 24 hr, and usually much longer, before use. The aluminum

Jan 1, 1969

By P. D. Hunt, I. Johnson, M. G. Chasanov, H. M. Feder

The solubilities of the transition metals from scundium to nickel, inclusive, in liquid cadmium were determined by sampling saturated solutions. At 400°C these solubilities (ppm) are:Sc, Co, 22; Ni, 12000. Relative partial molal enthalpies and excess partial molal entropies at infinite dilution for the solutes Cr, Mn, Fe, and Co are compared zoitlz similar data for the post-transition metals. Three new intermetallic phases, ScCd,, TiCd, and Ti,Cd, encozaztered in the course of this work, are reported. Measurements of the solubility of the 3-d transition metals in liquid cadmium have been reported' only for iron. The present measurements for the entire series were made as an aid to the study of the systematics of alloy formation. EXPERIMENTAL The apparatus and sampling techniques used for the solubility determinations were similar to those described by Martin etal.' Temperatures were measured with a Pt/Pt-10 pct Rh thermocouple sheathed in recrystallized alumina and immersed in the solution. The thermocouple was recalibrated periodically during the course of the investigation. Thermocouple voltages were measured to the neares 0.01 mv with a Rubicon model 2732 potentiometer. A scaled-down version of the apparratus, in which the total metal charge was about 90 g, was employed to measure the solubility of scandium. Two-mm ID Vycor filter pipets were used to sample the scandium-cadmiurn solutions; the samples weighed about 2g- Cadmium with a minimum purity of 99.95 pct was used; the only impurities detected spectrochem-ically were C'u and Mg, both less than 10 ppm. The purities of the other metals were: scandium, 99.9 pct; titanium. 99.92 pct; vanadium, 99.9 pct; chromium, 99).99 pct; manganese, 99.9+ pct; iron, 99.90 pct; cobalt, 99.95 pct; and nickel, 99.96 pct. Solidified melts were routinely analyzed spectro-graphically. No significant contamination by the crucible, sampling pipets, or other materials of construction was observed. The entire specimen obtained by sampling was dissolved to preclude analytical errors due to segregation on cooling. Colorimetric methods3 were used for the analyses of cobalt (2-nitroso-l-naphthol), manganese (permanganate), nickel (dimethylglyoxime), titanium (peroxide), and vanadium (thiocyanate).4 Chromium, iron, and scandium were neutron-irradiated to produce The dissolved samples were gamma-counted to determine solute concentration.For the separation of intermediate phases from cadmium-rich alloys selective leaching by saturated ammonium nitrate solutions was employed. The concentration of cadmium in the successive leaches was followed polarographically and the process was terminated when the rate of cadmium dissolution decreased markedly. For the further investigation of intermediate phases 1/4- in. diam powder compacts were pressed at 80,000 psi and annealed in argon at 315" to 330°C for 10 days. Larger quantities of alloys were prepared in sealed tantalum capsules heated in a rocking furnace.

Jan 1, 1962

By Edwin T. Myskowski, Alfred H. Hesse

The development by the U. S. Bureau of Mines of a process for purifying manganese by electrolysis has stimulated interest in manganese alloys. While recent publications have shown some alloys of manganese and copper to possess rather unusual properties, none have included information on tensile properties, which have an important bearing on the usefulness of the alloys. Manganese-copper alloys can be heat-treated, since the single phases that exist at high temperatures may be retained by quenching. According to Persson,1 when quenched alloys containing from about 30 to nearly IOO per cent manganese are reheated, alpha manganese is precipitated (Fig. I). Calculations based on Persson's X-ray data indicate that this decomposi-tion is accompanied by a change in volume of as much as ; per cent. The reason that this large volume change has not been noted probably is the slow rate at which equilibrium is reached by these alloys. In an investigation on hardening by cold-work and heat-treatment, Dean and Anderson3 found that quenched alloys increase in hardness with manganese content and that high-manganese alloys harden very slowly with cold-work, while high-copper alloys harden much more rapidly. Heat-treatment has little effect on manganese-copper alloys containing less than 40 per cent Mn, and affects those alloys containing more than 40 per cent in accordance with their manganese content and heat-treating temperature. Dean and Anderson4 also found that cold-work increased electrical resistance of alloys containing from 50 to 80 per cent Mn, and that heat-treatment of alloys containing from 40 to 96 per cent Mn altered the electrical resistance considerably. Dean, Anderson and Potter6 have shown that the high vibration damping capacity that characterizes manganese-copper alloys containing 40 to go per cent Mn is affected by cold-work and heat-treatments. Highest vibration damping capacity at low stresses was obtained by heating for 2 hr. at 450°C. (842°F.) after quenching from solution temperatures. Preparalion of Alloys.—The alloys for these tests were melted in a 17-lb. basic-lined high-frequency induction furnace using electrolytic manganese, grade A ingot copper and a 70-30 CU-Mn master alloy (69.80 per cent Cu, 0.12 Fe, 0.04 Si, 0.006 S, 0.07 C, balance Mn). The manganese was heated slowly to expel excess dissolved gases and melted before the addition of copper. No fluxes or covers were used. The melts were cast in tapered iron molds and the ingots were reduced go per cent when forged to 1/2-in. rounds. These rods were given 2-hr. solution treatments at temperatures that depended upon the composition (Table I). Tensile Tests.—The tensile specimens, 0.313-in. diameter (1.25-in. gauge length),

Jan 1, 1942

by their overdogmatic picture of geology and their resulting drastic oversimplification and idealization of geologic features. I am in hearty disagreement with the recommendation that geophysics should be done by cooperative work between a geologist and a geophysi-cist. That arrangement would be comparable to doing petrography by having a physicist at the microscope and a geologist sitting by his side. The interpretation of the geological significance of geophysical data can be done efficiently only by a physicist who has become also a good geologist or by a geologist who is also a good geophysicist. Less Well-trained Men The rank and file, composing perhaps two-thirds of the personnel of exploratory geophysics, is not, and should not be, composed of highly trained men. The routine, stereotyped character of the work and the impossibility of promotion of more than a few from these lower ranks even under the best circumstances justify companies in filling the bulk of these rank and file positions with men having only a bachelor's degree at the most. There can be a wide range of training for such positions, although certain lines of study are preferred for certain kinds of work, and different employers have different preferences. For work in gravitational and magnetic prospecting, first preference will be for men having geological training and second for men with civil engineering training. In seismic work, men with geological training are preferred by some employers for computers; physicists, electrical engineers and all whose technical education has covered radio circuits are preferred for the other technical positions. Collegiate training in geophysical prospecting brings no preference and by many employers is given a slightly inferior rating. One large company seldom hires men who have just graduated with a major in geophysical prospecting. This prejudice is based on the reasoning that much of what is learned in college is obsolete or obsolescent, that most of the techniques learned in college will have to be unlearned, because different from those used by the employing company, and that in the long run additional courses in basic physics, mathematics and geology are of more value to a man than the courses on geophysical prospecting. DISCUSSION [This discussion refers to the five papers beginning on page 23 and ending on page 74.1 L. W. Blau,* Houston, Texas.—I have had some rather sad experiences with forecasting. For example, I could not foresee 10 years ago my present occupation, and I do not profess to be able to look ahead 10 years and tell anyone what he will be doing then. Referring to the point raised in the discussion, I do not know, for example, what the price of oil will be 10 years from now. If an appreciable number of

Jan 1, 1940

By J. E. Chappelear

We are concerned with the problem of calculating the forces produced by passing waves on a submerged object (in particular a drilling barge) located on the ocean floor. We employ the linearized theory of waves (the Airy1 theory), since solutions are generally more easily obtained in such a theory. It will be indicated how an approximate solution to the problem can be obtained for waves of finite height by use of a linear combination of Airy waves. We shall assume the submerged object has an infinite length, thus neglecting diffraction and making the problem two-dimensional. We find that there is not a considerable difference between our solution and the usual engineering solution. The force, as a function of time, is plotted in Figs. 4 and 5, together with the usual solution for easy comparison. So far, no experiments have been found to compare with the results. As will be shown, the calculations can be extended to waves of finite height (Stokes2-Struik3 waves) in an approximate fashion. This can be done by calculating the force produced by each Fourier component of the wave, separately, and omitting the coupling between the various harmonics produced by Bernoulli's theorem. The problem and its boundary conditions will be briefly stated. We seek a function, +, the velocity potential, which is harmonic, ?2?=0...........(1) and which satisfies the boundary conditions ??/?n =0 .......(2) (the normal derivative of + is zero) on the ocean floor and the sides of the barge, and s??/?y = ?..........(3) on the ocean surface, where s = g/w2........(4) The physical reasons for these choices and an interpretation of ? are given by Lamb.' As previously stated, we assume also that the problem is two-dimensional. We set up our coordinates such that x = 0 is the center of the barge and y = 0 is the ocean floor. The coordinates are shown in Fig. 1, together with the location of the barge on the bottom. Our solution may be decomposed into a function which is symmetric about x = 0,?e, and one which is antisymmetric, +,, ? = ? + ?o...........(5) Thus directly above the barge we have as boundary conditions that for x = 0, ?o = 0, ...........(6) and ??e/?x = 0........(7) Now, far from the barge, we have that (for x positive and assuming the waves are incident from the left) ?e ? Ae cosh ky cos k (x + a) , . . . (8) and ?e ? Ao cosh ky cos k (x + ß) . . . . (9) where + means ". .. approaches ... for x large." Let us put Ae, Ao, and k equal to one, and remember that, in accordance with the derivation of Eq. 3, a sinusoidal time factor is to be supplied. Then we may rewrite Eq. 8 for ?e, and we find that

Jan 1, 1958

By J. Moore Samuel

THE CHAIRMAN (WALTER DOUGLAS, NEW YORK, N. Y.).-Perhaps there is no problem that causes the modern metallurgist more worry than the question of unaccounted for loss. He has not the advantage of the metallurgist of the early days here, who could sleep peaceably with the settled conviction that there were certain copper mineral constituents of the ore which were volatile, and there was therefore nothing to worry about. The slag contents and volatilization accounted for the balance of the copper that went in the top of the furnace after the weighing of the bullion. There have been great strides in recent years toward reducing this loss. Perhaps the Anaconda company is the one we have to thank for the original pioneer work along the lines which we are all today following. We would be glad to hear from some gentlemen present with reference to their experience with this question of dust losses. E. P. MATHEWSON, Anaconda, Mont.-You mentioned the Anaconda company, Mr. Chairman. I would like to say something about what we have been doing there, and the troubles we have been having. We have a tremendous volume of .gas to handle. We adopted the system of large chambers, lessening the velocity of gases, and incidentally cooling the gases. Unfortunately in one sense and fortunately in another, we were compelled to increase the amount of gas handled in the flue system, and the results were then not so good. Still, we get a very good recovery. Our system of taking a sample is similar to the one described by the writer of the paper. We have tried all kinds of apparatus for getting a fair sample. We divided the area of the flue into imaginary squares, and have taken samples for a certain period of time from each square; and have used the asbestos bags. At present, there is a large unit of the Cottrell apparatus almost ready to connect up on the roaster flue to catch the dust from flotation concentrates. The worst things smelters have to handle at the present clay, they are coming in the Southwest as well as the Northwest, are of material much of which is as small as 500 mesh, and the ordinary methods of catching dust will not apply to flotation concentrates. The Cottrell process is going to be tried out at our plant for this material. We have devised special forms, with a view to preventing the formation of dust from this material, and we are pleased with the results so far obtained. There is another point in connection with this subject that I want to put before the members here, so they will be thinking about it. You know there has been a great deal of litigation between the farmers

Jan 12, 1916

By E. H. Kelton, R. D. Grissinger

In designing structural members of steel and some other materials the design engineer has available recognized values of elastic modulus and safe working stress that may be substituted in well-known engineering formulas to give him desired cross-sectional areas and deflections for a particular part. Zinc, on the other hand, has no generally recognized modulus. It flows under continuously applied loads. Therefore, the designer of structural members must use a range of working stresses depending on the continuous load and the amount of permissible distortion. The only method of obtaining these values is by creep testing. Creep testing of zinc has been carried on for some 20 years by this laboratory, covering a wide range of zinc and zinc alloys. Types of test included tension, compression, and simple and cantilever beams at temperatures ranging from o to I50°C. Specimen conditions ranged from as-cast or as-rolled to accelerated aged in steam or dry air. Effects of plating were investigated also. It is not the intention of this paper to expound all these factors but rather to present the final data on well-known zinc die-casting alloys and to suggest means of applying these data to engineering design. Early Work In the early work on creep testing of zinc, the direct-loading tension method was used. However, direct loading of die castings was unsatisfactory because of the high loads required. For instance, a standard die-cast tension bar having a cross-sectional area of about 0.049 sq. in. would require a direct load of about 1000 lb. for a unit stress of 20,000 lb. per sq. in. Also, tests were made at nominal room temperature, but normal variations caused fluctuations greater than those due to experimental error or other causes, so that control of this variable within ±1/2°C. seemed essential. These two factors led to the development of an apparatus described by J. Ruzicka,' in which the specimens were loaded by means of a lever and were held at constant temperature by means of an oil bath. While Ruzicka's apparatus yielded excellent check results, it seemed desirable to have some setup by which literally hundreds of die-cast specimens could be tested at the same time. This would permit the conducting of a number of low-load tests designed to run 10 years or longer and still leave capacity for current high-load work. Beam testing in a constant-temperature room was the answer. Test Method Preliminary work indicated that die-cast beams of various lengths and cross scctions yielded the same result within reasonable limits regardless of whether they were tested as simple beams, uniformly loaded beams, or cantilevers. Accordingly, the simplest type was adopted. This was a,

Jan 1, 1945