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By Arthur Notman

THE mineral industries in this country have now had about a year of national planning. Al. though the period is short, the volume of activity and legislation designed to make that planning effective has been nothing short of enormous. Those who have been privileged to see and study a few of the codes to regulate our mineral industry, such as those for oil, coal, steel, and copper, are driven to the conclusion that nothing was really known about the proper way to conduct those industries in this country prior to June, 1933; or if anything was known, nobody in actual practice made use of that knowledge. And yet those industries, in days gone by, helped to make this country the most prosperous in the world, and to maintain a standard of living even today higher than that of any other country. Without wishing to assume any first-hand knowledge of the Russian standard of living, I must confess that the evidence seems to indicate that even with dictatorial authority, national planning encounters unexpected difficulties. Perhaps what really wants

Jan 1, 1935

By W. Bonfield

The microstrain characteristics of a polycrystal-line Cu 1.9 wt pet Be precipitation-hardening alloy have been determined for various conditions of aging. The friction stress remained constant for all the conditions investigated, whereas the microscopic yield stress (the stress to produce a plastic strain of 2 x 10-8 in. per in.) and the three-stage stress-strain curve in the microstrain region were sensitive to changes in dislocation and precipitate distribution. Correlations between the measurements of microplasticity and electron-nzicroscope observations of substructure are considered. ALTHOUGH the macroscopic mechanical properties of Cu 1.5 to 2.0 wt pet Be precipitation-harden ing alloys were established' in some detail, there has been no previous investigation of the nature of microyield-ing in these alloys. This paper describes a high-sensitivity extensometer determination of microplasticity in polycrystalline Cu 1.9 wt pet Be, in which the friction stress, the microscopic yield stress (the stress to produce a plastic strain of 2 x 10-6 in. per in.), and the rate of strain hardening in the micro-strain region were measured for various conditions of precipitation. The structural changes accompanying aging in this alloy were examined using transmission electron microscopy, a study which differed from previous investigations as, in order to minimize grain boundary precipitation effects,' the solution-treated alloy was cold-rolled to 40 pet reduction prior to aging. Hence the extent of recovery and recrystalliza-tion, as well as the variation of precipitate morphology and distribution, were assessed. From these results possible correlations between the microstrain characteristics and the observed precipitate and dislocation structure are considered. EXPERIMENTAL PROCEDURE The material investigated was a commercial copper beryllium alloy (Berylco 25), which had a com- position of 1.9 wt pet Be and 0.2 wt pet Co. The alloy was solution-treated at 800°C, quenched in water, and then cold-rolled to 40 pct reduction. Tensile specimens of gage length 1 in. and rectangular cross section of 0.18 by 0.06 in. were prepared from the solution-treated, cold-rolled material and aged for 15 min, 2, 24, and 100 hr at 315°C and 24 hr at 425°C to produce a range of precipitate structure. The hardness values associated with these conditions are listed in Table I. It can be seen that a maximum value is obtained after 2 hr at 315oC, which decreases with continued time at temperature to a minimum after 24 hr at 425°C. For comparison some as-solution-treated specimens were also aged for 2 hr at 315°C. The specimens heat-treated to a given condition were examined in two ways. First, the nature and distribution of the precipitate and dislocation structure was characterized using transmission electron microscopy. Thin foils were obtained from the specimens by electrolytic polishing in a 30 pet nitric acid-alcohol solution at -20oC, and were examined in an RCA EMU 3 electron microscope. Second, the mi-croplastic behavior of the specimens was measured with a Tuckerman strain gage, using the load-unload technique previously described2, 3 to determine the friction stress, the microscopic yield stress, and the variation of plastic microstrain with stress. RESULTS 1) Structural Changes During Aging. a) Annealing Processes. The solution-treated, cold-rolled Cu 1.9 wt pet Be had an irregular dislocation-cell structure,

Jan 1, 1968

By AIME AIME

THE MODEL LAW previously referred to', in these columns several times, prepared by Engineering Council, to be o ered in any state where legislation is introduced for licensing engineers, is given in abstract below. , Mining engineers throughout the country should watch legislation of this sort and see that the draft prepared by Engineering Council is in the hands of any state legislative committee which proposes to frame a licensing law. So far as this office is informed, the mining engineers are a unit against licensing, but if we must be licensed the most innocuous law that has been submitted is the draft prepared by Engineering Council. ABSTRACT OF MODEL LAW -FOR REGISTRATION OF PROFESSIONAL ENGINEERS, ARCHITECTS, AND LAND SURVEYORS

Jan 1, 1920

By F. L. Misaqi

The total amount of radon-222 released into the atmosphere by the US uranium mines and mills is only an infinitely small fraction of the total amount of radon released by the top layers of soil with a high concentration of uranium, such as is found in Grants, N. M. Even when compared to areas where mineable deposits of uranium are unknown, the amount of radon released by all US mining and milling operations is still relatively insignificant. Of course, higher local concentrations of airborne radioactivity may be observed around stockpiled ore and

Jan 8, 1976

By J. E. Warren

The mathematical problem considered by the author1 can be given another physical interpretation which is of some practical significance. The alternative physical problem involves the approximate behavior of a single well which is producing at a constant rate through an axially symmetric, horizontal fracture of infinite flow capacity which is located at the center, top or bottom of a uniformly thick, horizontal, homogeneous, anisotropic reservoir of infinite lateral extent which contains a single, slightly compressible fluid. Using Coats' asymptotic results, the wellbore pressure in the fractured system is given by the following equation.

By K. L. Young

The general energy equation, including change in kinetic energy, was solved by numerical integration and used to evaluate simplifying assumptions and application practices over a wide range of conditions. When extreme conditions were encountered, sizable errors were caused by large integration intervals, application of Simpson's rule and neglecting change in kinetic energy. A maximum error of only 1.31 percent was caused by assuming temperature and compressibility constants at their average value. It was discovered that a discontinuity can develop in the integral for the injection case. This discontinuity indicates a point of zero pressure change and is an inflection point in the pressure traverse. INTRODUCTION When a pressure in a gas well is to be calculated, one of the first decisions is to select a method of calculation. In many instances, this selection becomes a problem because the literature, at best, provides an evaluation of any method for only a limited range of conditions. Once a method has been selected, a question often arises as to the size of the calculation interval which should be used. The question regarding calculation interval arises because an analytic solution is not obtainable and approximate solutions must be used. This paper presents an evaluation of major assumptions and application practices of probably the two most widely used methods for calculating steady-state single-phase gas well pressures. The two methods are Cullender and Smith1-" (numerical integration), and average temperature and com-pressibility. The Cullender-Smith method assumes that change in kinetic energy is negligible and is normally applied in two steps with a Simpson's rule correcton. The average temperature and compressibility method, in addition to neglecting kinetic energy change, asumes that temperature and compressibility are constant at their average values. This method is normally applied for wellhead shut-in pressures of less than 2,000 psi, and in one step. Computer programs were written to compute bottom-hole pressure with and without the assumptions, using various approaches. Values of input parameters investigated are shown in Table 1. Flow rate was limited to a maximum of 5,000 and 10,000 Mcf/D for tubing sizes of 1.610 and 1.995 in. ID, respectively. Flow rate was also limited to 10,000 Mcf/D for a tubing size of 2.441 in. ID when wellhead flowing pressure was 100 psia. These limitations were imposed on flow rate so as not to exceed sonic velocity. The z factor routine available necessitated limiting bottom-hole temperature to 240F and wellhead pressure to 3,000 psia. Pressures were compared on the basis of percent deviation from the trapezoidal integration of Eq. l or 2 at 100-ft intervals. A preliminary investigation indicated that a 1,000-ft interval solution would differ from a 50-ft interval solution by less than 0.25 percent; therefore, the 100-ft interval was chosen for a base. For the purpose of comparison, deviations less than 1 percent were considered insignificant. where 111.1 qeC2/d p = kinetic energy term. Eqs. 1 and 2 can be evaluated numerically at specific depths using the trapezoidal rule as shown by Cullender and Smith. If change in kinetic energy is neglected and temperature and compressibility are assumed constant at their average values, Eq. 1 can be integrated to give the average temperature and compressibility equation,

By J. H. Henderson, H. J. Ledbetter, N. B. Gove, J. D. Griffith

INTRODUCTION The results of a series of laboratory flood tests using liquid Iso-butane to displace refined oils from test cores are pre- ented and interpreted on an empirical bask. The study Revealed the similarity of the miscible liquid displacement to that of the immiscible-fluid displacement mechanism. The efficiency of the iso-butane flood decreased markedly as the oil Viscosity increased. but the effect of injection rate on the effectiveness of the primary production stage was negligible over the range investigated. The presence of free-gas saturation prior. to iso-butane breakthrough increased the volume of iso- Butane required to recover a given percentage of the oil present. Injection of liquid i.e.-butane prior to water follicle sculpted in a marked improvement in oil recovery by the water flood. INTRODUCTION The production of petroleum is often enhanced by the injec-1i1)n of extraneous fluids into the reservoir. It has been suggeited that the injection or cycling of a wet gas or a liquefied petroleum gas would he instrumental in increasing the effic.ienr!; of oil recover! to a greater degree than the commonly injected fluids. dry pas and water. Although instances of injection of light liquid hydrocarbons are not unknown, a systrmatic recording of the result is unavailable and superfi- cially, the practice gives the impression of being economicaIIy unsound. For specific types of displacement, analytic: solutions have been advanced which aid in understanding the physical mechanisms involved. However, there is no generalized theoretical concept which permits adequate prediction of displacement efficiency from a knowledge of readily measured reservoir rock and fluid properties. The Buckley-Leverett approach to oil displacement by an immiscible phase is an admirable analysiy of that type of mechanism. Dykstra and Parsons have introduced a useful concept in their evaluation of the role of the mobility ratio and its merit in rationalizing displacement phenomena. Everett, Gooch and Calhoun3 in their report on the effect of viscosity ratio and miscibility have pointed out the lack of a comprehensive theoretical approach and the desirability of investigating the mechanism of miscible-miscible displacement. In lieu of a well-developed theory concerning miscible-111isci1)le displacement and in view of the scarcity of engineering information on actual LPG injection trials, the limited program of laboratory experimentation described below was undertaken. OBJECTIVES The original broad objectives of the program, to study the oil recovery process using LPG as the displacing phase, defined the direction and scope of the laboratory tests. The specific objective. of the experimentation were to evaluate

Jan 1, 1953

By E. R. Kaiser

COAL research during 1942 was directed in an important degree toward the solution of problems of wartime importance. A wider selection of coals for carbonization to meet the increased demand for coke, and the improved utilization of lower-grade coals for boiler fuel were made possible by fundamental studies on cod and ash behavior that had been started several years ago. The coal industry's interest in the work of the various laboratories brightened significantly as results were demonstrated on smokeless combustion in stoves, on stokers without coke trees, and on pulverized firing of forge furnaces. Despite the limitations of priorities and scarcity of materials, the mineral industries building of the West Virginia University was completed and equipped with facilities for research on coal min

Jan 1, 1943

By P. Marier, T. R. lngraham

The kinetics of the sulfation of MnO,, MnzO3, and Mn3O4 in SO,, SO3, and O, mixtures was examined and the descending order of sulfation rates at temperatures near 400°C was found to be Mn,O3 > MnO, > Mn3O4. The respective activation energies for the thermal decomposition of MnO, and Mn,O, are 39 and 47 kcal. At 900°C, the thernzal decomposition of MnSO, to MnzO3 is slower than that to Mn3O4. The respective activation energies are 62 and 51 kcal, respectitely. MANGANESE is used to improve the hot workability of steel in the proportions of approximately 13.5 Ib of ferromanganese per ton of steel produced. This requirement accounts for about 95 pct of its large industrial market in North America. The remaining 5 pct is used in the battery and chemical industries. In most North American ores, the percentage of manganese and the manganese-to-iron ratio are not suitable for the direct production of ferromanganese. Hence, most of the North American requirements for manganese are satisfied by importing ore. Typically, many of the studies done on native low-grade manganese resources have been directed toward the production of ore substittes" and the recovery of manganese from open-hearth slags.3 Of the wide variety of processes which have been proposed, the most popular involve compounds in the Mn-S-O system. The thermodynamic properties of manganese and its compounds were reviewed by ah' in 1960 and, more recently, lngrahams discussed the thermodynamics of some of the reactions involved in the Mn-S-O system at normal roasting temperatures. The conditions for producing manganese sulfide during the reduction roasting of manganese sulfate are discussed by Fuller and Edlund.9 A novel scheme was proposed recently by zimmerley7 for utilizing waste sulfur dioxide from stack gases to recover the manganese from ocean-mined manganese nodules. Very little of the work published on manganese compounds has been related to reaction rates. Singleton et 1.' studied the rates of reaction on the MnO-C and Mn7C3-3MnO systems and observed linear and parabolic kinetics respectively in the systems. Tatievskaya et a1.' studied the low-temperature reduction of Mn&, MnO,, and Mn& in HZ and CO, and reported activation energies in the range 1628 kcal. In this paper, the rates of some of the decomposition and formation reactions involving MnSO4, MnOz, MnzO3, and Mn3O4 will be examined after the conditions for the thermodynamic stability of the individual compounds have been designated. CONDITIONS FOR STABILITY OF MnSO4, MnOz, MnZO3, AND Mn3O4 The areas of stability for h'hSO4, MnOz, MnzO3, and h3O4 were established from the data of Mah4 and Ingrahams and are shown in the predominance area diagram,10 logpq- logpsq, in Fig. 1. The diagram is drawn for two temperatures, 700°K, solid lines, and 1100°K, dotted lines. The sketch for the lower temperature includes the conditions likely to prevail in the Zimmerley patent7 when manganese nodules react with sulfur dioxide and that for the higher temperature indicates the conditions for recovering MnzO3 or Mn3O4 from MnSO4 during a roasting reaction. From the fact that the boundary between the areas of stability of MnOz and hSO4 at 700°K is parallel to the abscissa, it is evident that MnOz and SO2 should react together to produce MnSO4, irrespective of the oxygen pressure in the system. If the source of sulfur for sulfation were from waste flue gases, it is likely that the oxygen content of the gas stream would be more than sufficient to oxidize any MnsO4 to MnzO3, 107 atm of O2 required, or even to convert any Mnz03 to MnOz, 0.02 atm OZ required, prior to sulfation. At 1100°K, the diagram indicates that MnSO4 may be converted directly to either MnzO3 of Mn3O4, depending upon the prevailing partial pressure of oxygen. When the gas stream contains more than 1 pct Oz, logpq = -2, only MnzO3 would be recovered from an experiment done under equilibrium conditions. At oxygen partial pressures of less than 1 pct, one would expect to bring about a reversible exchange between MnSO4 and Mn3O4 by appropriate adjustment of the partial pressure of SOZ. These various reactions will be described in the subsequent kinetic experiments.

Jan 1, 1969

By AIME AIME

THANKS to the excellent preliminary work of: the Division officers and the local committee the fall meeting of the Coal Division at Bluefields was a brilliant success. West Virginia was at its best with its beautiful mountains, good roads and foliage, just beginning to turn to autumn colors. The meeting began on time and was kept on time throughout. The papers were-well prepared and, being on subjects of live interest, provoked 'lively discussion. One factor in bringing this about was that they were not too numerous and that with one exception copies had been submitted in advance a sufficient time to permit of them having been studied. The Friday morning session was presided over by John .J. Lincoln of the Crozier Coal and Coke Co. and president of the Pocahontas Coal Operators Association. After brief announcements by Thomas H. Clagett, chairman of the local committee, regarding plans for the two day's involved, and by Howard N. Eavenson, chairman of the Division, the reading of papers was taken up.

Jan 1, 1931

By Francis J. Dennis

(San Francisco Meeting, October, 1911.) MANY factors govern the value of dredging-ground, and much capital can be wasted by the mistaken policy of contracting for the purchase of property and the installation of machinery before a thorough, examination has been made. To the uninitiated investor the presence of gold is generally the criterion,, and very superficial evidence is necessary to satisfy him as to this point. He considers the comprehensive report of a competent engineer as a wasteful extravagance and cannot understand why the engineer requires so much time and money to ascertain the information on which to base his conclusions, when the promoter can furnish him such pleasing and satisfactory data with but little expenditure of time and money. The uninitiated investor will often optimistically risk capital for purchase and equipment, and not until the venture comes to grief does he learn that the conditions are wholly unsuited for dredging. In many instances, a short preliminary examination by a competent engineer would have disclosed these facts. The mere presence of gold is by no means sufficient; some of the other factors necessary to be ascertained in determining the value of placer-ground for dredging-purposes are : (1) character and distribution of gold, and how much can economically be recovered; (2) character of bedding underlying the gravel, its contour, and whether its gold can be recovered by ordinary dredging-operations; (3) area and depths of gravel, surface contour, over-burden, water-level, proportion of fine material and boulders, and the presence of any material which might interfere with the dredging-operations and the recovery of the gold; (4) water-supply, power available, labor, transportation, and supplies, and cost of these ; (5) climatic condi-tions; (6) title to property, cost and royalties, and legal obstacles to carrying on dredging-operations. A brief reconnaissance may be sufficient to determine that some of the essential conditions for successful dredging are

Apr 1, 1912

By Eugene Guccione

It would be extremely difficult and unfair to compare the United States to Australia when wondering about which of the two countries offers the best opportunities for running a mining operation. However, if somebody would ask "Where is the best place to mine outside the US?"-I'd answer without reservations: Australia. Some of my Australian mining friends will disagree with me for my giving their country such a high rating. And they'll probably accuse me of being an optimist by telling me, as one of them did, that "the difference between an optimist and a pessimist is that the pessimist is better informed."

Jan 1, 1977

By Cyril S., Smith

THE phenomenon of air-hardening is well known in connection with special steels. It occurs when the rate of decomposition of austenite to marten- site is so retarded that it takes place on free cooling in air rather than on more rapid cooling in a quenching bath. If an air-hardening steel is quenched sufficiently rapidly it will remain in the soft austenitic state, while if it is cooled very slowly it will again become soft owing to growth of the carbide particles. It depends on a critical adjustment of the decomposition velocity and diffusion rate, and such alloys are rather rare, especially in the non-ferrous field. In carrying out some experiments on some copper- rich copper-cobalt alloys, the author found that these possess very marked air-hardening properties. The alloys are covered by a patent issued to M. G. Corson (1,723,022-1919), which states that an alloy containing between 2 and 5 per cent cobalt is hardened by simple quenching from above 850° C.

Jan 1, 1930

By Leo F. Reinartz

Part II of a four-part series on the history of steelmaking in the US, points out the inadequate safety and living conditions that existed in steel mills at the turn of the Century. Also defined are furnace and process developments. OPERATIONS in steel plants today are highly mechanized. Men work in light, clean, orderly melting shops, making it difficult for old timers to convince young men that primitive, hazardous conditions existed in steel plants at the turn of the century. Working conditions then were very poor as compared to present day standards. In small plants especially, sanitary, locker, and washroom facilities, first-aid practices and stations were un- known Accidents were frequent and severe. Workers had a fatalistic attitude toward getting hurt. He who had an accident was looked upon as a hero. A dirty bandanna often served as a bandage. Infections were frequent. Electric cranes were in their infancy and broke down often Cables had not as yet replaced chains. Pig iron and scrap iron were loaded by hand in the stockyard, and stockyard locomotives were un- known; mules served as the usual motive power. It was not unusual to see recorded a delay of ½ hr in charging a furnace because of a balky mule. Furnace operations A few plants had primitive charging machines, but most furnaces were charged by placing scrap or pig iron on the paddle of a long peel, which rested on a bar across the furnace door opening. Laborers at the handle end of the peel, using the bar as a fulcrum, would heave the material into the furnace by a down and sideward motion of the peel handle. In time they became expert in placing these materials in the furnace, but it was hard, hot work, and a long time was required for charging. Cold charges of 25 tons required more than 12 hr for melting and re- fining the steel. Ports, doors, and frames were not water cooled. The charging and working area in front of the furnace was covered with steel plates. They were hot and often warped by the intense heat of the un- insulated checker chambers directly below. In the summer, working conditions on the charging floor were almost unbearable. Silica refractories were of poor quality. Because of this, and the inadequate training of furnace men in fuel control and furnace operations, roofs, front and back walls, and ends burned out rapidly. Dolomite machines were unknown; consequently, furnace banks and hearths were fettled with dolomite by the use of hand shovels. The round system required six or more men. Each man took a shovelful of dolomite and, in his turn, deposited it on the back wall and bank by a dexterous forward swing and twist of the shovel. The upward swing of the shovel partially protected his face from the searing heat of the furnace coming out through the wide-open door. Considerable skill and stamina were required to do this job properly. Reverse valves, usually of the cast-iron butterfly type, were located below the charging floor. They were operated by long levers on the charging floor level men they became warped, because of heat and abuse, great strength and skill were required to reverse them. Furnace operations were difficult. The quality and quantity of producer gas coming from irregularly stoked, hand-operated gas producers was uncertain and unreliable. Furnace Linings and ports were quickly burned out. Poor bottom and side-wall refractories, indifferent and inexperienced crews, as well as irregular re-

Jan 1, 1961

THE progress in lead smelting practice in the United States during 1930 has been along previously defined lines. Since most of the material treated is high-grade concentrate relatively high in zinc, practically all the plants have been forced to adopt double sintering. This generally results in there being' no matte fall, and most of the copper in the charge is recovered in the furnace dross. The furnace dross is . smelted with. scrap iron and flux .in small reverberatories, giving a shipping matte or speiss high in copper and low in lead. Details of this reverberatory. furnace practice vary at the different plants. There is a decided tendency toward moreintensive filtration of blast- furnace and sinter fume. Bag capacity has been in- creased by using higher pressures and more frequent shaking.

Jan 1, 1931

By George S. Rice

GROUND movement from mining, whether it be for coal, metal, industrial minerals, or .oil, will always present many difficult problems. These are especially serious when valuable surface improvements may be badly damaged. The mine itself, if mining methods are not suitable to the formation, is subject to heavy falls of the main roof in the working places; and with certain structural conditions the movements may cause in coal mines disastrous bumps and outbursts of gas, and in deep metal mines rock bursts. In open-cut work rock and earth slides may result. Absolute prevention of ground movement from mining is impossible unless large pillars are left unmined,

Jan 1, 1937

By Robert K. Waits

The resistivity, temperature coefficient of resistance, stability at 200°C, and structure of annealed Si-Cr films have been studied as a function of film cowposition. Colorimetric analyses of the films indicated 20 to 60 wt pct Cr over the resistivity range of 1 to 10-4 ohm-cm. Resistors were delinealed by photolithographic etching, contacted with aluminum, and mounted in TO-5 packages. The average temperature coefjicient of resistance, a, between 50" and 150°C is related empirically to the film resistivity, p, by a (ppm per °C) = -2900 - 1140 log p (ohm-cm). Near a resistivity of 3.5 x 10-3 ohm-ctn (30 at. pct Cr) , the temperature coefficient changes from positive to negative. The temperature at which the resistance maximum occurs increases with decreasing resistivity. The conduction mechanism between —196" and +360 C appears to have two components—an activated conduction dominating a1 lord chromium content and higher temperatures and a linearly temperature-dependent conduction dominating at high chromium content and low temperatures. Electron diffraction patterns showed the films to consist of Cr3Si and amorphous silicon. Resistors thicker than 150A typically drifted less than 0.6 pct after 5000 hr stor-age at 200°C. Resistors as thin as approxinzately 80°A that had a silicon overlayer showed similar stability. Such films had sheet resistivities of 10 kilohm per square and temperature coefficients near —600 ppm per "c. THIN-FILM resistors having sheet resistivities greater than 1 kilohm per square are required in many integrated circuit applications. A process for producing such resistors should be compatible with present circuit fabrication and packaging, including exposure to maximum temperatures of 300° to 570°C during contact alloying, die-attach, and ceramic package sealing. In addition, the resistors should have a low temperature coefficient of resistance and change less than 1 pct during storage at temperatures up to 200°C for 1000 hr or longer. Reports of work beginning in 1949 at Battelle Memorial Institute indicated that, among other materials, the silicides of chromium, Cr-Co, molybdenum, tantalum, and tungsten were worthy of further study as high-stability resistive films. Later work on Si-Cr films vacuum-deposited by flash evaporation from a tungsten boat1 led to the conclusion that Si-Cr had "excellent properties for development into high- stability ... resistive elements". More recently, Si-Cr films have been vacuum-deposited from a tantalum boat,2 from a BeO-coated tantalum boat,3 by flash evaporation from an electron-beam-heated tungsten Source,4 and by triode sputtering.5 This paper describes a study of Si-Cr films vacuum-deposited by electron-beam heating of Si-Cr alloys. Resistivity, temperature coefficient of resistance, stability at 200°C, and structure were studied as a function of film composition. EXPERIMENTAL PROCEDURE Film Deposition. Si-Cr sources were prepared by vacuum-melting pressed pellets of mixtures of powdered chromium (99.9 pct, -100 mesh, Lunex Co., Pleasant Valley, Iowa) and silicon (99.99 pct, -325 mesh, United Mineral and Chemical Co., New York). A permanent-magnet focused electron-beam gun having a water-cooled copper crucible was used to heat the pellet until complete melting occurred. The mixture was then kept molten for an additional 5 min. The alloy thus formed was used as the source material for Si-Cr film depositions using the same electron-beam gun. Pieces of semiconductor-grade silicon ingots were used as sources for silicon depositions. The films were deposited within a standard vacuum evaporator having an 18-in.-diam Pyrex bell jar, a liquid-nitrogen-cooled trap, and a Consolidated Vacuum Corp. 6-in. diffusion pump containing Dow Corning DC-705 pump fluid. The substrates were thermally oxidized* silicon wafers 2 to 2.5 cm in diam. The

Jan 1, 1969

By Kehsin Kuo

DIE steel with 1.47 pct C, 0.42 pct Mn, and 8.22 pct W contains Fe,C and WC in the annealed state and WC embedded in a martensitic matrix in the hardened state (quenched from 800°C). The presence of a large amount of undissolved angular WC carbide particles makes this steel extremely wear-resistant. However, the WC carbide begins to dissolve in the austenite when the heating temperature is raised above 1000°C, but this solution process is still not complete at 1250°C although partial melting has already taken place at the austenite grain boundaries. At 1325 C, this steel contains austenite and liquid metal but no WC carbide, Fig. 1. On quenching into brine, the liquid metal solidifies into a constituent which etches differently from the austenite-martensite matrix. This constituent appears lighter than the matrix at the 1250°C stage when etched with 2 pct nital but darker in Fig. 1 when etched with Murakami's reagent. Such a constituent has also been found in burnt tungsten high speed steels. This constituent has been isolated from the matrix by anodic dissolution in a 5 pct HC1 electrolyte and was found by the X-ray powder method to be iso-morphous with &manganese, Table I. The agreement in line intensity between these two phases indicates that there is no ordering in this new phase. The calculated cube edge of this phase is 6.395A, somewhat larger than that of ß-manganese (6.30A). Besides this phase, the anodic residue also contains free carbon from the matrix and amorphous WO,, although the X-ray powder pattern of the residue shows the presence of only this phase. This makes it impossible to determine directly the composition of this phase from the residue. Attempts to prepare an alloy containing only this phase have hitherto been fruitless. The following experiments serve to show that this phase can only be obtained by drastic quenching from the liquid state and that its tungsten and carbon contents must be lower than those in the Fe,W,C carbide. On air cooling from 1325oC, the liquid metal solidifies into a eutectic consisting of austenite and the Fe3W3C carbide. The nature of this dark-etching Fe3W3C has also been ascertained by X-rays. This eutectic becomes coarser on furnace cooling. The solidification of a specimen cooled for 5 min from 1325" to 1200°C and water quenched is still not complete and the fine eutectic is formed during the quenching. Since this new phase can be replaced by a eutectic of austenite and the Fe,W,C carbide, its composition must lie somewhere between the latter two phases. The special features of this phase are: 1—it can only form directly from the liquid state by drastic quenching and 2—it is a ternary phase of iron, tungsten, and carbon. The ß-manganese structure of this phase is also interesting. In the Periodic Table, iron and tungsten lie on opposite sides of manganese; a certain combination of these two elements, in the presence of carbon, may have average properties similar to those of manganese. It has already been established that the x phase, a ternary one of iron, chromium, and molybdenum, has the a-manganese structure."' A similar phase has also been found in the ternary system Fe-Cr-W and in the following binary systems: Re-Cb, Re-Ta, Re-Mo, and Re-W.6 References 1 G. D. Preston: Philosovhical Magazine 11928) 5. 7th Series, p. 1207. - K. W. Andres: Nature (1949) 164, p. 1015. 35. G. McMullin, S. F. Reiter, and D. G. Eberling: Trans. ASM 11954) 46, p. 799. ' J. S. Kasuer: Acta Metallurgica (19541 2, p. 456. • H. J. Goldschmidt: Trans. ASM (19541 46, p. 807. P. Greenfield and P. A. Beck: Private communication.

Jan 1, 1957

By Klaus Schwerdtfeger

Activities of lead in Pt-Pb and Pd-Pb melts in the temperature range of 800° to 1200°C have been detev-mined from electromotive-. force measurements 202th the cells Both systems display strong negative deviations from Raoult's law. The data obtained with cell [1] were combined with available data on the activity of PbO in silica-satuvaterl PbO-SbO2 melts to calculate the standard free cnergy of formation 01- liquid PbO. FREE energies of formation of oxides and activities of components in metal and oxide melts can be determined with galvanic cells consisting of a metal phase, an electrolyte containing the oxide of one of the components of the metal phase, and an oxygen electrode. This technique has been used previously to measure the standard free energy of formation of solid sio2, 1 and activities in Fe-si, CO-si,2 Ni-Si,2 and CaO-P2O5 3 melts. The present paper reports activities in Pt-Pb and Pd-Pb melts as measured with the same experimental technique. EXPERIMENTAL METHOD General Considerations. The following cells were used: Pbl (PbO-SiO2)liquid, SiO2 Pt-Pb 1 (PbO-SiOz)liquid, SiO2solidO2 [2] Pd-Pb (PbO-SiOz)liquid, SiO2solid O2 [3] Liquid alloy and' oxide melt were contained together in a silica glass crucible of essentially the same design as described previously.1'2 The PbO-SiO2 melts are ionic conductors.' During the experiment, the silica glass crystalizes in a layer adjacent to the electrolyte. The electrolyte equilibrates with solid silica and hence attains the composition of the Si02-liquidus curve in the system PbO-SiO2 at any particular temperature. Molybdenum wires were used to establish contact with the liquid metal. The oxygen electrode, which reaches the surface of the PbO-SiO, electrolyte from above, consists of a platinum wire inserted into a ceramic tube and provided with a 2-mm-diam platinum bead at its end. Gas of known oxygen partial pressure (pure oxygen of 1 atm: air, or N2 with 1.04 pct 0,) is blown through the ceramic tube onto the surface of the electrolyte. The cell reaction is Pb (metal) + 1/2O2 (gas) = PbO (electrolyte) [4] No oxidation of platinum or palladium ("displacement reaction") occurs. This is to be expected from the noble character of platinum and palladium, but was also shown experimentally, as described in the next section. The galvanic electromotive force of the cell is given by where AG is the change in free energy for Reaction [4], E(=2) is the number of electrical equivalents necessary to form 1 mole of PbO, and F is the Faraday constant. Formula [5] is valid only if no junction potential exists within the electrolyte. Junction potentials occur only when the compositions of the electrolyte are markedly different at the electrodes. Such differences are negligible in the PbO-SiO, electrolyte, as shown in the next section. Since molybdenum contact leads are used, appropriate corrections were made on the measured electromotive forces to account for the thermoelectric effect of the Mo-Pt couple. The thermoelec-tromotive forces were measured separately with a Mo-Pt couple, and were found to vary linearly from 19 mv at 740°C to 40 mv at 1310°C with molybdenum being positive and platinum negative (cold junction at 25°C). Extrapolation of these values to higher temperatures yields values which are in satisfactory agreement with those obtained previously in the temperature range 1440° to 1630°c.1,2 The change in free energy for Reaction [4] is expressed as where chemical potentials of the species. The value of constant for a given temperature because the slag composition is fixed. Inserting [6] into [5] and using appropriate expressions for upb and uO2 the relation

Jan 1, 1967

By J. L. SCHUELER

THE writer has reread Mr. Ingalls' interesting article in the July, 1923, issue of MINING AND METAL- LURGY on "The Use of Spelter in Galvanizing." It seems that most writers, in commenting upon coatings of spelter on sheets and wire, dwell upon the thin coatings which these materials carry, and rightly so. However, they seem to forget that until very recently, in the case of wire, the manufacturer did not know how to apply a heavy coating of spelter to the wire, especially if the wire was to be woven into fence or fabricated in some other manner, because heavy coatings of spelter are exceedingly brittle. This is even true in the case of high-grade spelter, but to a lesser degree than with Prime Western. Because of this brittleness, it has been necessary for wire manufacturers to smooth the coating by passing the wire through tightly compressed wiping means of some kind, usually asbestos. This removes all of the excess spelter and allows only a thin coating to remain. The latter, as a rule, is malleable and the wire can be fabricated without material injury to the coating.

Jan 1, 1924