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By Thomas C. Baker

The Fresnillo unit of the Mexican Corporation, S. A., is situated at the old historic mining town of Fresnillo, Zacatecas, Mexico, 33 miles north of the city of Zacatecas and 750 miles south of El Paso, Tex. It is connected with the Mexican Central Railroad by a broad-gage spur 5.5 miles long, belonging to the company. Fresnillo is surrounded by a broad semi-arid valley on the Mexican plateau at an elevation of 7300 ft. The monotony of the valley is broken by a number of low hills. Near the town of Fresnillo is the " Cerro de Proano," an elliptic-shaped hill of gentle slope, rising out of the plain to a height of 325 ft.; the base has a major axis of 4500ft. and a minor axis of 3000 ft. In this hill is the silver-bearing mineralized zone, which comprises past and present mining operations. (In this paper money values are expressed throughout in American currency and the dry short ton of 2000 lb. is used.) The discovery of ore at Fresnillo is credited to the Spaniards, soon after the conquest of Mexico. There are, however, no authentic records to show the amount of work done by them. In 1832, the State of Zacatecas took possession of the property and operated it. Evidently the rich ore above the horizon of the plain had been fairly well exhausted, as an old record states that thirty shafts were used for unwatering, requiring 300 men and 1500 animals. The cost of pumping alone amounted to $150,000 a year. In spite of the fact that cheap convict labor was used, mining costs were reported as $20 and treatment charges as $20 per ton. In 1835, the state was obliged to seek foreign capital, and a company formed in London secured a controlling interest in the property. This new organization sank two shafts, one 11 by 19 ft. and the other 10 by 15 ft., to unwater the mines and extract ore. Large Cornish pumps were purchased in England and hauled overland from Vera Cruz; engines also were installed to operate the arrastres (grinding mills) in the patio process of ore treatment. Substantial buildings were erected and operations were conducted on a large scale, for that period. The patio, the largest in Mexico, was 1150 ft. square. The costs for 1850 were:

Jan 1, 1925

By L. C. Graton

THE Federal taxes on incomes and excess profits are of course heavy. In 1917, the value of the mineral production of the United States was a little in excess of $5,000,000,000. The total of Federal taxes for that year, for the mineral producing companies, as computed by themselves, amounts, according to tentative compilations, to about $207,000,000, and the total for the comprehensive group of mineral and metal indus-tries to about $766,000,000, which figures represent respectively 9.5 per cent. and 35.1 per cent. of the total tax paid by all corporations. Be-cause of greater complexities in applying the revenue laws to mineral properties than to most other industries, opportunity is afforded for wide differences of view. The taxes indicated above, therefore, are not final

Jan 11, 1919

By Larry Kaufman, Morris Cohen

THE solid phase equilibria' and the martensitic transformation in the iron-nickel system have been the subject of considerable study. In addition, there have been numerous investigations on the calorimetric and thermodynamic properties of iron-nickel alloys. The purpose of the present work is to extend the existing information concerning the martensitic reaction in the iron-nickel system, and to develop a general thermodynamic treatment which will encompass the equilibrium and non-equilibrium phase

Jan 1, 1957

By J. B. Scuffham, G. I. Warwick, J. B. Lott

The development of solvent extraction processes over recent years has led to their application on an increasing scale in metal extraction plants. The author's company has recently been awarded a contract for the design of the world's largest solvent extraction plant based on pump-mix mixer-settlers. The plant is designed to extract copper from a leach liquor and has an aqueous throughput of 12,000 imperial gpm. The design is based largely upon data obtained from the company's own research laboratories, where work has been undertaken on mixer impeller design, baffle design. settler area, organic entrainment recovery, etc. Investigations have been conducted into the effects of mixer impeller speed, recirculation rates, phase continuity, phase ratio, etc., on extraction efficiency, settler area, and organic entrainment losses. The implications of the results of this work on the design of a large plant using pump-mix mixer-settlers are discussed and the techniques used in overcoming certain scaling problem are outlined.

Jan 1, 1973

By Wm. B. Price

The work of Leon Guillet concerning the effect of nickel on the structural properties of brass is checked. The best value for the coefficient of equivalence t, that is, the amount of zinc replaced by 1 per cent. of nickel, is shown to be-1.1 per cent. The best hot- and cold-working nickel silvers, varying in nickel content between the limits of 4 and 18 per cent., are tabulated and plotted diagrammatically. Also, some data are given showing a comparison between the physical properties of a hot- and cold-working low copper-nickel silver, and a commercial cold-working nickel silver containing approximately 8 per cent. more copper. THIS investigation of low copper-nickel silvers was undertaken to check the work of Leon Guillet on special brasses and to determine, more accurately, the effect of the addition of nickel on the microstructure of the binary alloys of copper and zinc. It was hoped that the results could be successfully applied to the practical production of low copper-nickel silvers. To explain the results of his investigations on special brasses, Leon Guillet evolved his conception of "fictitious compositions." He states,1 in his general conclusions, that on the introduction of a small amount of a third metal to a copper-zinc alloy, it enters into solid solution with the normal constituents up to saturation, but by so doing it brings the ternary alloy into a state microscopically equivalent to a binary copper-zinc alloy of fictitious composition, and physically more nearly like the latter than the brass containing copper-zinc in the ratio actually present. The physical properties of the ternary alloy, when compared to the same properties of an actual brass of the fictitious composition, are modified by the natural properties of the third element. Beyond the point of saturation, a special constituent appears and the above generalization no longer holds.

Jan 2, 1924

By Leonard Waldo

The recent and rapid development of the physics of engineering materials at temperatures as low as that of liquid air and as high as that of the electric are, has drawn renewed attention to the absence of tables, properly printed and spaced, for the convenient and accurate translation of temperature from centigrade to Fahrenheit scales and vice versa. It is to be noted that the Fahrenheit scale is the almost universal usage in foundries and shops in the United States, though the laboratories of the same works employ the centigrade notation. The growing use of the electric furnace in Germany and France calls for much American citation all in centigrade high temperatures, and while the arithmetical calculation is simple, it becomes burdensome when often repeated. I have been surprised at the numerous reprints of Table I. from centigrade to Fahrenheit degrees, first privately printed for personal use, which have been made by works, blue-prints, text-books, and technical journals, and I hope that Table II., from Fahrenheit to centigrade degrees, will be equally useful. For mental calculation the easiest rule to convert centigrade into Fahrenheit is to add 32° to twice the centigrade reading less one-tenth of this product: Thus 1000' C. = 2000" — 200" + 32" = 1832" F., and to convert Fahrenheit to centigrade, subtract 32" from the Fahrenheit reading, multiply by 10 and divide by 2 and 9 successively : Thus 1000° F. = 1000° — 32° = 968° X 10 = 9680° - 2 = 4840° - 9 = 537.77° C. Another and often very convenient method is by 'use of a graphic construction as follows :

Jan 1, 1913

By D. A. Keyes

International Minerals & Chemical Corp. (Canada) Ltd. is presently exploiting by underground mining a potash-rich zone in the middle Devonian Prairie Evaporite formation near Esterhazy, Saskatchewan. Of the three main potash-bearing horizons denoted by Goudie as zones 1, 2 and 3 only the 1ower. two are present at Esterhazy and mining is confined to the lower or zone 1 horizon. The area in which the evaporites were deposited, although flanked on the west by a zone of geosynclinal deposition and tectonic activity, has been subjected to only very gentle epeirogenic activity. The sylvinite ore is coarsely crystalline and occurs in well-defined beds. The halite, sylvite and insoluble content of the ore bears a direct relationship to the lithological units, but the carnallite cuts across the beds. Local concentrations of salt produce blank spots in the ore horizon. Some of these appear to be salt-filled, post-ore channels and cracks while others have been formed by brines emanating upward from below the ore. INTRODUCTION International Minerals & Chemical Corporation (Canada) Ltd. is operating an underground potash mine near the town of Esterhazy in eastern Saskatchewan. The deposit was discovered by IMC in 1955. Subsequent drilling outlined extensive high-grade reserves, and in 1957 shaft sinking and plant construction began. Production from Yarbo No. 1 Shaft commenced in September, 1962 and quickly reached the initial capacity of one million tons of muriate product per year. Production is currently being expanded to 1.6 million tpy. The single mining level is 3140 ft below the surface at No. 1 Shaft. GENERAL GEOLOGY The Esterhazy district lies within the Interior Plains region of Canada and on the northeast rim of the Williston Basin (Fig. 1). Average dip of the rock formations in this area is about 40 ft per mile to the southwest. The potash ore occurs in the Prairie Evaporite formation of the Middle-Devonian Elk Point Group. The Prairie Evaporites are overlain by 3000 ft of Paleozoic shales and limestones and by Jurassic and Cretaceous sandstones and shales (Fig. 2).

Jan 1, 1967

AS If see it, then, the engineering advances of which yob have studied here at Golden, the continued growth of. industry that you see about you here in Colorado, and the country-wide progress that I have not time to discuss-these illuminating facts should clear away any doubts as to your future. You have little license to ask, "Where is the call for engineering or what the need? Yankee fashion I might ask you by way of reply, "Have all the mines been opened? Have all the power-houses and transmission lines been built? Have the last improvements in. mill and smelter been in-stalled?" We know that the general answer is No, and the rest of the answer, which tells where are those mines and power plants and what are the new methods and processes in mining and metallurgy, must be sup-plied by you engineers of the future. And anyone who has even casually observed what recent years have brought forth in our profes- sion cannot but envy you your job. Our reconnaissance excur-sion into your future should not be much longer extended, but before turning back there are four landmarks that I would like to point out-not lofty peaks but useful tie points that are worthy of your attention as you traverse the territory of your future work. Two of these are in fact low spots or depressed areas which call for engineering activity; these are commonly called "waste" and "average." The other two are of larger significance and are rather extensive regions in the domain you are to enter and occupy. These larger tracts bear the suggestive place names "fact-finding" and "human engineering" and perhaps will prove to be the heights from which the broadest outlook is to be had in this "pilgrim's progress:" In the first place, waste deserves your attention, al-though I realize that it is possibly the most unpopular word anyone hailing from Washington can publicly utter. Its unpopularity naturally follows from its overuse in the somewhat strong charges made against the industrial and business world some years ago, when the doctrine of conservation was first preached in the land. But waste is a word to be used in an engineering sense as well as for political effect. Properly used, waste is not a word to shy at-rather it is a challenge to the engineer. For example, at present, the loss of 1 kilowatt-hour to every 5 sold is a clarion call to the electrical engineer. Waste is your target to shoot at, the obstacle for you to surmount, the giant for you to slay.

Jan 7, 1928

By Chas Fettke

DURING the summer of 1916, while on a visit to the United States Agricultural Experiment Station at Mayaguez, Porto Rico, the writers were told by D. W. May, the director, that an occurrence of manganese ore had been reported from the mesa southeast of Mayaguez. A visit to the locality showed that the mesa is covered by a mantle of bright red soil resting upon serpentine. Here and there over its surface concretionary masses of limonite have been washed out of this soil. These were FIG. I.-MAYAGUEZ FROM NORTHWEST END OF MESA. apparently mistaken for manganese ore. On account of the similarity of this occurrence to the extensive iron deposits of northeastern Cuba, it was thought that a brief description based upon a two days' reconnaissance survey of the area would be of scientific interest. Mayaguez is on the west coast of Porto Rico, at Mayaguez Bay, which is the third in importance of the harbors of the island. The city itself is about ¾ mile inland on the low-lying plain at the mouth of the

Jan 3, 1918

By J. E. Strassner

Oilfield emulsions are stabilized primarily by film-forming asphaltenes and resins containing organic acids and bases. Adding inorganic acids and bases radically changes the physical properties of these films and their emulsion-stabilizing properties. Interfacial films show one of three different physical characteristics when retracted in pendent drop tests. These compressed films have rigid, soap-type or minimum film properties depending on the quantity of asphaltenes and resins in the crude oil and on the pH and composition of the brine. There exists for each crude oil-brine system an optimum pH range over which the adsorbed film exhibits minimum contracted filtn properties. In this range, intmfacial tension is high — frequently near its maximum value — indicating the absence of highly surface-active specier; crude oil-brine emulsions generally show minimum stability; and surfactant requirements for breaking these emulsions are significantly reduced — sometimes no surfactant is needed. About two-thirds of the world's crude oil is produced as emulsions that must be treated (demulsified) to be marketed.' Approximately three-fourths of all domestic crude oil produced must be treated. The percentage of crude requiring treatment increases as fields become older and more water is produced. Demulsification most frequently is attained through use of surfactants, heat and electric treaters. It is estimated that over 75 percent of all oilfield emulsions are broken by chemicals generally containing alkylene oxide condensates. Although acids and bases are known to affect emulsion stability:-' they rarely are used in the oil field except in batch treatment of the most severe emulsions. Nevertheless, pH adjustment by using acids or bases in demulsification has some advantages over other methods. Mainly, it is cheaper. Acids and bases frequently are cheaper to use than surfactants, or can appreciably reduce the amount of surfactant required for demulsification. Secondary advantages are that less oil is lost by emulsi-fication into the aqueous phase, and that less corrosion is encountered when the optimum pH is basic. Limitations to the use of pH include (1) use in brines containing high concentrations of reactive ions, (2) closer supervision for pH control than is required for surfactants and (3) need for corrosion protection when the optimum pH is sufficiently acidic. These factors indicate that the economics of pH con trol in demulsification will be maximized when relatively large treating facilities are needed, when relatively large surfactant concentrations are required to break an emulsion, when a relatively low concentration of the aqueous phase is emulsified in the oil and when the emulsified aqueous phase contains relatively low concentrations of reactive ions. Because there are no broad guide lines for using pH control in breaking oillield emulsions (and because the limited guides available are highly specific and frequently contradictory), this paper will attempt to clarify the principles involved in using acids and bases to break emulsions. These principles also should be useful in refinery separations and in other oilfield applications where stable or unstable petroleum emulsions are involved. Principles of Emulsion Stability Oilfield emulsions generally occur as water droplets dispersed in oil (w/o) and occasionally as oil droplets in water (o/w). These emulsion droplets are usually in the 0.1- to 10-micron range. However, more coarsely dispersed water droplets frequently are present in the emulsion. Pure hydrocarbons and water will not form stable emulsii except in extreme dilutions where the large distance brtween droplets inhibits coalescence. An emulsion breaks because interfacial tension acts to minimize the surface area of the dispersed drops by coalescence. However, emulsions can be stablized for long periods of time by the presence of a third phase that adsorbs at the oil-water interface and inhibits coalescence of the dispersed phase."' Emulsions generally are stabilized by (1) repulsive charges on the surfaces of the dispersed phase and (2) adsorbed films that, being preferentially wetted by the continuous phase, act as a physical barrier to inhibit contact between the dispersed droplets. Both these factors generally are important in stabilizing and in breaking o/w emulsions. However, repulsive charges are less effective in stabilizing w/o emulsions which generally are stabilized by adsorbed films.V or this reason the nature and importance of these films at oil-water interfaces were examined closely; as will be shown, pH changes were found to affect the films significantly, and this work led to laboratory tests of pH- adjustment in emulsion breaking. This paper will present evidence to show that emulsions are stabilized primarily by films that form around droplets

Jan 1, 1969

By R. F. Janke, J. F. Bossler

Introduction The commercial use of ion exchange resins to recover uranium evolved in the decade following 1950 when significant efforts were made to recover this vital element economically and efficiently from low grade ores. It was discovered that in both acid and alkaline systems, uranium exists as an anionic complex. This led to the application of anion exchange resins to concentrate and purify the uranium product. While this is the simplest statement of what an ion exchange resin does in the recovery of uranium, it should not be forgotten that the industry is continuing to evolve new methods in mining and processing which affect ion exchange operation. The inception of solution mining, the use of expanded bed ion exchange columns and the development of continuous ion exchange systems represent several examples of this continuing evolution in the industry. Throughout all of the changes in equipment designs and variations in solution compositions, the purpose of the ion exchange resin remains the same - to concentrate and purify uranium. Ion Exchange Resins When evaluating ion exchange resins for a uranium recovery project, the task that faces the chemist or process metallurgist is an assessment of the efficiency and, therefore, the economics of the various candidate resins for a given project. This assessment should include consideration of both physical factors such as particle size, density, hydraulic expansion and pressure drop as well as chemical factors such as the uranium loading and elution characteristics. For any given application, the differences in the physical and chemical behavior of ion exchange resins are a function of the conditions used to manufacture those resins. Therefore, an understanding of the way in which manufacturing variables affect resin behavior is important. Since most uranium recovery projects are concerned with recovery of the anionic complexes of uranium using anion exchange resins, this discussion will be restricted solely to the family of anion resins. The majority of the ion exchange resins used in commercial recovery operations look similar to the resins shown in Figure #1. [ ] Most of these materials are based on a styrene- divinylbenzene copolymer. The liquid monomers, styrene and divinylbenzene, are charged to a co-polymer reactor containing water. The water insoluble monomers are then mixed with the water to suspend oil-like droplets of the monomer mixture in. the water. The entire reaction mixture is then heated causing the monomers to polymerize into sol id thermoset plastic spheres. The spherical nature of the particle, the particle size distribution and the primary crosslinking level are fixed in this step in the production process. Figure 2 is a simplified illustration of this step of the process. [ ]

Jan 1, 1979

By V. Rajaram

The oil shales of the Green River Formation in the United States have been considered as a source of liquid hydrocarbons since 1908, with the first retort constructed in Colorado in 1917. However, it was not until 1944 that the mining characteristics of oil shale were investigated in a systematic manner. During the period 1944 through 1956, the Selective Mine and the Demonstration Mine (also referred to as the Anvil Points Mine) were operated by the U. S. Bureau of Mines (USBM) near Rifle, Colorado. Significant progress was made in developing a room and pillar mining method by which oil shale could be mined safely at a very low cost per ton. Mechanical properties of oil shale were determined, safe room spans and roof support techniques were established, and drilling and blasting methods for oil shale were developed. As a follow-on to this USBM effort, a consortium of six oil companies with Mobil Oil Company as project manager carried out a research program during the period 1964-68 at the Mobil mine, located in the vicinity of the Anvil Points mine. Rock mechanics investigations were conducted as a part of this research program, and consisted of laboratory studies, in-situ stress determinations, and roof and pillar instrumentation. This paper will discuss the findings at the Anvil Points mine and Mobil mine to illustrate the stability considerations in underground oil shale mining.

Jan 1, 1983

By R. A. Morgen

THE binary system lead-antimony has been the subject of compre-hensive investigations in these laboratories by Dean1 and his associates. The effect of a third constituent on this system, particularly on the lead-rich alloys in which dispersion hardening ,was found, has a commercial value as well as an academic interest. This paper covers the effect of the addition of copper, bismuth and tin, all of which are likely to be found in commercial lead-antimony alloys, and is divided into three parts, as follows: I. The System Lead-Antimony-Copper II. The System Lead-Antimony-Bismuth III. The Lead Corner of the System Lead-Antimony-Tin These three systems are of three different types, and hence may be considered as covering three general kinds of additions. Bismuth forms no compounds with either lead or antimony and forms solid solutions with both. Copper forms several compounds with antimony as well as solid solutions but with lead it forms a two liquid layer system and no appreciable solid solution. Tin is soluble in both lead and antimony in the solid state and also forms a compound with antimony. The effect of small amounts of bismuth on the lead-antimony alloys is small, having no appreciable effect on the solubility of antimony. The temperature of the solidus floor is lowered appreciably by the presence of bismuth, cutting down the range of heat treatment. Copper, on the other hand, due to compound formation, increases the apparent solubility of antimony. The excess antimony is tied up with the copper finally and so is not available for dispersion hardening. The net result of addition of small amounts of copper is to shift the dispersion hardening peak of the

Jan 1, 1927

By Robert M. Jimeson, James M. Grout

The competitive market potential for solvent-refined coal is estimated and the market advantages are enumerated. Markets are possible in combustion, railroad locomotion, and carbon electrodes. The combustion characteristics are consistent with expected air pollution restrictions on the emission of sulfur and particulate matter. A market potential of sufficient size exists to support the initiation of solvent refining in the United States. The market analysis should help fuel producers determine the advisability of their undertaking solvent refining of coal.

Jan 1, 1972

By R. J. Lutton

Empirical data from 91 rock excavations have been used to construct a family of slope curves on a chart relating excavation height and inclination. The highest and steepest slopes from each excavation are plotted and connected by a line. The 31 1ines appear to establish one or two geometrical slope fields through which the curves are projected. The curves apparently represent a lumped eflect of many factors too complex to be considered individually. Important factors such as geological structure or ground-water conditions can dominate the picture, but where these factors do not overshadow others, the slope chart should be useful for estimating or checking optimum inclination. The U.S. Army Corps of Engineers (USAE) has been engaged since 1962 with the U.S. Atomic Energy Commission in a joint research program to develop nuclear excavation technology. The Corps is responsible for collecting the requisite data on engineering and construction problems associated with nuclear excavation. The ultimate objective is to develop a capability to use nuclear explosives as a construction tool on public works projects such as harbors and canals. The present study on empirical inclination-height curves for conventionally excavated slopes is an outgrowth of an investigation' sponsored by the USAE Nuclear Cratering Group on applicability of data from existing excavations in establishing guides for engineering judgment in crater excavation. Data were generously contributed by over 50 mining companies among other organizations. Inasmuch as several companies preferred that their contribution be anonymous, all data are treated so here. Some Factors Affecting Stability Many factors affect or are suspected of affecting the stability of excavated slopes, e.g., adverse structural orientation, degree of structural ordering, ground water, climatic conditions, mechanics of excavation, and plan-profile configuration. Such factors are lumped together in developing a slope chart. Obviously geological structure and ground water can overshadow all other factors. Where such is the case, the simplification of slope charts may give an erroneous picture (not conservative enough). A further complication results from the fact that the concept of stability may vary according to the use of the excavations. For example, slope adjustments that would be regarded as failure in a powerhouse excavation, might be tolerable in a mining operation. Mine slopes are continually being modified by further excavation, and instability that would develop in a similar permanent excavation slope over a period of years might not have time to develop in a mine. Inclination vs. Height Charts Charts of inclination vs. height for particular formations or conditions have been used in the past as an aid for designing excavation slopes. Some of these have been based upon empirical analyses of collections of data and experience. MacDonald" and Lane have presented slope tables and charts for excavated and natural slopes in relatively weak sandstone and shale. Coates' has shown an inclination-height chart for slopes in incompetent rock. Most organizations have developed slope design criteria which relate bench widths, heights, and inclinations to use in various rocks. Slope data collected in present studies can be similarly used to develop inclination-height charts; however, a plot of all slopes on such a chart shows very little because of the wide spread of the data. Reasons for the dispersion of points are: (1) many slopes are not carried at optimum inclination, particularly in mines where maintaining roadways and following irregularities of ore bodies are more important than achieving steep inclinations; (2) many engineers and geologists with varied backgrounds and viewpoints have been involved in designing these slopes; and (3) each slope is characterized by a unique combination of factors affecting stability and in turn optimum inclination. Significant curves can sometimes be constructed where the points can be grouped into related clusters from the same excavation. The essence of this approach appears when only two slopes from each excavation are considered—the highest slope and the steepest slope, connected by a line segment (Fig. 1). This reduces considerably the usable data because in many cases only one of these two slopes is available. Nevertheless, the concession seems justified. Construction of Slope Curves Ninety-one pairs of points and connecting line segments were assembled in this study. The line segments were assumed to approximate a geometrical slope field (Fig. 2), and a family of curves has been visually projected through to represent the slope field. It should be

Jan 1, 1971

By E. H. Roberts, L. G. Swenson, F. C. Nix, R. A. Morgen

The binary system lead-antimony has been the subject of comprehensive investigations in these laboratories by Dean1 and his associates. The effect of a third constituent on this system, particularly on the lead-rich alloys in which dispersion hardening was found, has a commercial value as well as an academic interest. This paper covers the effect of the addition of copper, bismuth and tin, all of which are likely to be found in commercial lead-antimony alloys, and is divided into three parts, as follows: I. The System Lead-A~ili~r~ony-Copper II. The System Lead-Antimony-Bismuth III. The Lead Corner of the System Lead-Antimony-Ti11 These three systerrls are of three different types, and hence may be considered as covering three general kinds of additions. Bismuth forms no compounds with either lead or antimony and forms solid solutions with both. Copper forms several compounds with antimony as well as solid solutions but with lead it forms a two liquid layer system and no appreciable solid solution. Tin is soluble in both lead and antimony in the solid state and also forms a compound with antimony. The effect of small amounts of bismuth on the lead-antimony alloys is small, having no appreciable effect on the solubility of antimony. The temperature of the solidus floor is lowered appreciably by the presence of bismuth, cutting down the range of heat treatment. Copper, on the other hand, due to compound formation, increases the apparent solubility of antimony. The excess antimony is tied up with the copper finally and so is not available for dispersion hardening. The net result of addition of small amounts of copper is to shift the dispersion hardening peak of the

By L. F. Bryant, J. P. Hirth, R. Speiser

The surface, gain boundary, and twin boundary energies, as well as the surface diffusion coefficient, of cobalt were determined from tests at 1354°C in pure hydrogen. A value of 1970 ergs per sq cm was calculated for the surface energy, using the zero creep method. It was possible to measure the creep strains at room temperature because the phase transformation was accompanied by negligible irreversible strain and no kinking. Established techniques based on interference microscopy were used to obtain values for the other three properties. The gain boundary and twin boundary energies were 650 ad 12.7 ergs per sq cm, respectively, while a value of 2.75 x l0 sq cm per sec was determined for the surface dufusion coefficient. In the course of a general study of cobalt and cobalt-base alloys, information was required about the surface energy of cobalt. Hence, the present program was undertaken to measure the interfacial free energy, or, briefly, the surface energy, of the solid-vapor interface of cobalt. The microcreep method was selected for this measurement because other surface properties could also be determined from the accompanying thermal grooving at grain boundaries and twin boundaries. A brief summary of the methods for determining the various surface properties follows. At very high temperatures and under applied stresses too small to initiate slip, small-diameter wires will change in length by the process of diffu-sional creep described by Herring.1 The wires acquire the familiar bamboo structure and increase or decrease in length in direct proportion to the net force on the specimen. For a specimen experiencing a zero creep rate, the applied load, wo, necessary to offset the effects of the surface energy, y,, and grain boundary energy, y b, is given by the relation: where r is the wire radius and n is the number of grains per unit length of wire. The first results obtained from wire specimens were reported by Udin, Shaler, and Wulff.' udin3 later corrected these results for the effect of grain boundary energy. The grain boundary energy is determined from measurements of the dihedral angle 8 of the groove which develops by thermal etching at the grain boundary-free surface junction. For an equilibrium configuration: Measurements of the angle 8 can be made on the creep specimens4'5 or on sheet material, as was done in this investigation by a method employing interference microscopy.= If the vapor pressure is low, the rate at which grain boundary grooves widen is determined primarily by surface diffusion and, to a lesser extent, by bulk diffusion. The surface diffusion coefficient, D,, is obtained from interferometric measurements of the groove width as a function of the annealing time, t. As predicted by Mullins~ and verified by experiment, the distance, w,, between the maxima of the humps formed on either side of the grain boundary increases in proportion to if grooving proceeds by surface diffusion alone. For this case: where fl is the atomic volume and n is the number of atoms per square centimeter of surface. When volume diffusion also contributes to the widening, the surface diffusion contribution can be extracted from the data by the method described by Mullins and shewmon.8 Where a pair of twin boundaries intersects a free surface, a groove with an included angle of A + B (using the groove figure and notations of Robertson and shewmong) forms by thermal etching at one twin boundary-free surface junction. If the "torque terms", i.e., the terms in the Herring10 equations describing the orientation dependence of the surface energy, are sufficiently large, an "inverted groove" with an included angle of 360 deg-A'-B' develops at the other intersection. The angles A + B and A' + B' are measured interferometrically. When the angle, , between the twinning plane and the macroscopic surface plane is near 90 deg, the twin boundary energy is calculated from the relation: 1) EXPERIMENTAL TECHNIQUES Five-mil-diam wire containing 56 parts per million impurities was used for making ten creep specimens. These specimens had about 15 mm gage lengths with appended loops of wire and carried loads (the specimen weight below the midpoint of the gage length) ranging from 3.7 to 149.8 mg. The wires were hung inside a can made from 99.6 pct pure cobalt sheet. Beneath the wires were placed small specimens of 20-mil-thick, 99.9982 pct pure cobalt sheet from which the relative twin boundary and grain boundary energies and the surface diffusion coefficient were measured. All the specimens were annealed at a temperature of 1354" i 3°C which is 92 pct of the absolute melting point of cobalt. The furnace atmosphere was 99.9 pct pure hydrogen that was purified further by a Deoxo catalytic unit, magnesium perchlorate, and a liquid-nitrogen cold trap. As a precautionary measure the gas was then passed through titanium alloy turnings which were heated to 280" to 420°C and replaced after every test period. The hydrogen was maintained at a

Jan 1, 1969

By T. Egleston

DURING the year 1873, my attention was called to the frequent accidents, resulting from the breaking of rails, on the different railroads in this country, and I was requested to investigate the subject. The plan of investigation I proposed was to ascertain, in as many cases as possible, the exact history of broken rails, both in this country and in Europe; to collect information in Europe relating to the tests which rails used there were required to undergo, and to experiment upon the pieces of rails broken on the road, with a view to ascertain whether their fracture was due to their chemical constitution, bad manufacture, to a reduction in strength owing to temperature, or to physical changes in the constitution of the rail. The investigation was commenced by the collection of statistics, and for this purpose I spent several months in Europe, collecting information on the subject of broken rails, as well as the life of iron and steel rails generally, and inquiring into the systems of purchasing and of testing them employed by the railroads there, intending, on my return, to make a series of analyses of rails broken, both in this country and in Europe; to ascertain, if possible, how far great cold had an influence on the fracture ; to examine whether the rail broken, either on the road or afterwards, underwent, at or about the fracture, any physical change, and to make a series of experiments on the strength of rails manufactured in the United States or sold in the American market. Unfortunately, the panic of 1873 came on, just before my return from Europe, and prevented the carrying out of the larger part of the plan proposed ; as, however, I had collected in the meantime, a large number of statistics of different kinds from all parts of Europe, and had made a number of interesting experiments and investigations, I have thought it would be worth while to communicate some

Jan 1, 1875

By E. H. Bunce, H. M. Haslam

The "direct process" for the manufacture of pigment zinc oxide produces the oxide directly from ore. This is accomplished by reducing the zinc by means of carbonaceous fuels and immediately burning the evolved zinc vapor to zinc oxide. For many years this was done by smelting a loose charge of ore and fuel on perforated grates. Since this process was developed in America and was extensively used here, it has become known as the "American process." Alternative methods of producing pigment zinc oxide are the "indirect process " and the "wet process." In the indirect process the raw material is metallic zinc, which is volatilized and burned to the oxide. For a long time this has been done in externally fired horizontal refractory retorts. This process has become known as the "French process," from the country of its origin. The wet process precipitates the carbonate or hydrate from zinc-bearing liquors and then calcines the precipitate. This method has been but sparingly used for producing commercial quantities of zinc oxide. It appears to be advisable to restrict the use of the terms "American process" and "French process" to the methods of the earlier periods and to consider the terms "direct process" and "indirect process" as generic terms to designate, first, all methods of producing pigment zinc oxide directly from ores, and, second, to include all those methods of producing zinc oxide from metallic zinc and metallic zinc-bearing substances. American Process In 1796 John Atkinson was granted British Patent No. 2094/1796 entitled, "Manufacture of White Paint." This patent describes a method of producing zinc oxide in which roasted zinc blende or calcined calamine is mixed with charcoal, and the mixture heated in a muffle to liberate zinc vapor, which is then burned to obtain zinc oxide fume. About 1850 The New Jersey Zinc Co., at its plant in Newark, N. J., attempted to make zinc oxide by smelting, in a reverberatory furnace, a mixture of coal and ore from its Franklin mine. A considerable amount

Jan 1, 1937

By J. W. Clark, C. T. Sims

Wrought chromium-base alloys containing yttrium, cubic monocarbides of the Ti(Zr)C type, and similay alloys containing manganese and rhenium have been melted and fabricated. Strength has been studied by hot hardness and elevated-temperature tensile and rupture measurements, low-temperature ductility by tensile testing, and surface stability by oxidation testing. In additiod, studies have been conducted of the carbide stability, and of aging behavior. The carbide dispersion generates effective elevated-temperature strength, which is further enhanced hv strain-induced precipitation. The dispersion exhibits classical dissolution and aging response. The ductile-to-brittle transition temperature of these alloys is above room temperature. The alloys reported show fairly good oxidation resistance, but nitrogen contamination can cause fortnation of a hard Cr2N layer under the oxide scale. Manganese does not appear to be a promising alloying element in chromium. In the years 1945 to 1950, the metal chromium was considered as a possible base for alloy systems due to its considerably higher melting point than superalloys, its low density, its high thermal conductivity, and its apparent capacity for strengthening. However, this interest in chromium was short-lived. It was found difficult to melt and cast, to be exceptionally sensitive to the effect of minor imperfections, to have a lack of ductility at both room and elevated temperatures, and to be subject to a deleterious effect of alloying elements upon the ductile-to-brittle transition temperature.' Since then, chromium, as a practical alloy base, has remained virtually unstudied. Further, purposeful ignoring of chromium has been promoted by statements that its bcc structure would not allow it to be strengthened to useful values, when compared to the "austenitic" alloys.2 Recently, a new look has been taken at chromium-base alloy systems. Study of the literature will show that chromium, providing some of its disadvantages could be eliminated or minimized, actually has a rather attractive potential as an alloy-system base. Analysis of rather scattered data suggests that chromium is quite capable of being strengthened to high levels. Also, significant strengthening of its two sister elements in Group VI-A, molybdenum and tungsten, has been demonstrated in a number of commercial and exploratory alloys. Chromium should be similar. Since chromium does not readily form a volatile oxide like tungsten or molybdenum, it offers a much higher probability of giving birth to alloy systems with useful oxidation resistance. Concerns about possible high elemental vapor pressure have been mitigated by recent data.3 In addition, the physical properties exhibited by chromium are attractive for application as a high-temperature structural material. For instance, its thermal conductivity varies from 49 to 36 Btu-ft/hr-sq ft-°F over its range of usefulness (which is two to four times higher than most superalloys), its density is about 7.2 g per cc (20 pct less than most nickel-base alloys), its coefficient of thermal expansion varies from 4 to 8 x 10-6 per OF, and it has a relatively high modulus of elasticity, approximately 42 x 10' psi.4 Alloying studies on a chromium base in the past have usually encompassed rather sweeping solid-solution alloy additions for strengthening. This is not consistent with contemporary alloying practice in Group VI-A. For instance, molybdenum, also in Group VI-A, is primarily alloyed for strength improvement by use of heat-treatable carbide dispersions.5 Chromium and molybdenum are similar in their chemical activity and other properties. Thus, strengthening of chromium by carbide dispersions was studied. Chromium-base alloys are plagued with room-temperature brittleness, although high-purity unal-loyed chromium can be made ductile.4,8 Use of yttrium as a scavenger has done much to improve ductility and resistance to nitrogen embrittlement in chromium systems,7 so it was utilized in this program. It has also recently been found8 that small rhenium additions (1 to 5 pct) create improvement in the ductility of Type 218 tungsten wire. This is apparently related to the remarkable effect of rhenium additions near its terminal solid solubility in all Group VI-A metals.9'10 Investigation to establish if dilute concentrations of rhenium would also be effective in chromium appeared to be logical for this program. Since rhenium is too expensive to be practical in alloys for application as structural components, ductility improvements through solid-solution alloying were also sought by substitution of manganese for rhenium; manganese, like rhenium, exists in Group VII of the periodic system. The optimum amount of carbide dispersion for chromium-base alloys was obtained by analogy with molybdenum. Strengthening in molybdenum is achieved by use of Ti-Zr carbide dispersions. A

Jan 1, 1964