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By William Rawles

THIS report is the first of a series planned by The Mineral Inquiry, organized by the American Institute of Mining and Metallurgical Engineers to make factual studies of the world's mineral resources in their political and international relations. The efforts of The Inquiry are directed toward filling certain notable gaps in available information, without duplication of many other investigations touching this field which are being conducted by other organizations, public and private. Much of its work is indirect-suggesting topics for study by other individuals and organizations and aiding in their planning and correlation. The present report is designed to show the nationality of the commercial control of mineral resources, in addition to the geographic distribution of production by nation-in other words, the overlapping of political and commercial control. Detailed accuracy cannot be claimed for the figures presented. For some companies division of ownership by nationality has been very difficult to ascertain, as many companies are reluctant to dis-close the extent of their holdings in other corporations, and the impossi-bility of tracing all stock ownership is obvious. Also there are frequent changes in the distribution of stock control. The percentages given rep resent only the participation that has been identified definitely, even though it is known in some cases with fair certainty that larger interests exist, as, for instance, American participation in foreign chromite companies. In bringing together these figures we have had the cordial co-operation of the United States Bureau of Mines, the United States Geologi-cal, Survey, the Mineral Division of the Bureau of Foreign and Domestic Commerce, the Brookings Institution, and of many specialists connected with the mineral industries covered. The report does not cover the entire list of minerals: Coal, although it is one of the most important minerals, was omitted because not more than one or two per cent of the world's production comes from mines that are owned by companies foreign to the countries where the coal is produced. Others, such as gold, are omitted because sufficient data have not yet been accumulated. It is hoped that some of these may be covered in subsequent reports. It is not our purpose here to discuss the significance of the figures sub-mitted, but only to point out the general nature of the problems on which they have a bearing.

Jan 1, 1933

By W. O. Philbrook, C. W. McCoy

The reduction of chromous oxide from lime silica alumina slags by carbon-saturated iron behaves as a first-order process having a rate of 0.001 grams Cr min 1 cm 2 (pct Cr ) , substantially independent of slag composition and temperature over an important range for iron smelting. The equilibrium ratio (pct Cr)/[pct Crl is below 0.04 for slags having lime-silica ratios above 0.6. MANY studies have been conducted on chromium in slag-metal systems under oxidized conditions. The Purpose of these investigations has been twofold; namely, (1) to determine those conditions which lead to greater chromium recovery in electric-furnace and open-hearth practice, and (2) to determine the nature of oxide inclusions and de-

Jan 1, 1959

By Arthur Phillips

The progress made in recent years in the art of dispersion-hardening has naturally led to an intensive study of alloy systems capable of yielding supersaturated solid solutions at ordinary temperatures. In general, the investigations have been confined to rather precise determinations of solubility limits and to experimental approaches designed to furnish more complete information regarding the rate and nature of precipitation under appropriate thermal conditions. Efforts are being made to focus more sharply on the atomic changes that are a direct consequence of the instability of the supersaturated solution. Here precision X-ray methods have come to be of considerable importance because lattice parameter measurements indicate very precisely the concentration of solute atoms in the solvent lattice. In spite of the general acceptance of parameter values as a criterion for the placing of solubility limits, it may be suggested that no thorough appraisal has been made of the several factors that conceivably may affect such measurements. More specifically, little attention has been devoted to the significance of surface energy conditions, specimen size and method of preparation, with particular regard to the genesis of the grains and the surface concentration changes as a consequence of heat treatment and etching. Stenzel and Weertsl recently published the results of a detailed study of precipitation reactions in aluminum-rich copper alloys. They found that, although copper lowers the lattice constant of aluminum, a 5 per cent copper alloy quenched from 150" and 225' C. had parameter values unquestionably higher than that of pure aluminum. Their results seem to substantiate, at least qualitatively, the earlier work of von Göler and Sachs,2 who indicated a parameter value, for the same alloy annealed for 24 hr. at 200° C., some 0.0008Å. larger than that of pure aluminum. Stenzel and Weerts attributed the abnormal lattice dimension to the effect of strain induced by the precipitation of CuA12. Weerts3 later

Jan 1, 1934

By W. O. Philbrook, H. E. Burner, F. S. Manning

The equation of continuity for the hydrogen reduction of hematite in a fixed bed of closely-sized particles is solved assuming a flat velocity profile, negligible temperature gradients, md negligible axial diffusion. A kinetic expression from the literature is used which assumes the reduction process is controlled at the oxide-metal interface. The integral fractional conversion is computed, and the importance of particle diameter, flow mte, temperature, bulk axial diffusion, and inter- and intra-particle mass trarnsfer is predicted. Comparison with experimental data suggests one or more additional undefined variable(s) is significant. Equipment modifications are suggested for fidture experimentcll work. WITH the increasing desire to "design" the ore feed of a blast furnace, it has become necessary to define more quantitatively the process variables and to evaluate the extent of their control upon the reduction process. The bulk of the work reported in the literature has centered about the reduction of single particles; however, the blast furnace process more closely resembles reduction of a fixed bed than that of single particles. To simplify this analysis, the isothermal reduction by hydrogen of a natural hematite in a fixed bed of closely-sized particles is examined. With appropriate modifications in the kinetic and flow rate expressions, the approach employed should be extensible to mixtures of carbon monoxide, hydrogen, and inert nitrogen, and to adi-abatic conditions, thus approaching the blast furnace process more closely. The fixed bed variables which are investigated in this study are particle diameter, flow rate, temperature, and bulk axial diffusion, as well as inter-and intra-particle mass transfer. Of particular interest is the effect of particle size upon fractional conversion for a bed operating under constant pressure drop. The constant pressure drop concept bears a close resemblance to the blast furnace process, where regions of larger particles may provide a greater permeability to divert most of the reducing gas flow from the regions of smaller ore particles. Under such conditions one would expect qualitatively that, for sufficiently small particle sizes where the flow rate is small and the total surface area is large, the reduction rate would be limited by the gas flow rate. Initially the gas entering the bed reacts very rapidly and the composition approaches the equilibrium conversion value a short distance from the reactor inlet. This concentration "wave-front" then moves up the bed as the flow of reducing gas is continued, leaving in its wake an ever increasing layer of reduced particles. Providing that the reducing gas leaves the bed at equilibrium concentrations, conversion is expected to increase with an increase in flow rate, and hence with an increase in particle diemater. Conversely, for sufficiently large particles the flow rate will be high but the surface area available for reaction will limit the reduction rate. Since the total surface area decreases with an increase in particle size, conversion, in this case, is expected to decrease as the particle diameter is increased. It is clear then that between these two extremes an optimum particle diameter must exist. THEORETICAL DEVELOPMENT Above the temperature where wiistite is stable (about 560°C) the reduction of hematite proceeds through the series Fe2O3/Fe3O4/FeO/Fe. On the basis of microstructural studies and earlier work, Edström1 has postulated a mechanism for the reduction of an ideal hematite lattice: 1) Iron phase formation at the boundary between wiistite, iron, and gas (for sufficiently porous iron). 2) Diffusion of iron across a wustite layer. 3) Phase boundary reaction of Fe3O4 to FeO. 4) Diffusion across a dense magnetite layer. 5) Phase-boundary reaction of Fe2O3 to Fe3O4. According to the mechanism postulated, gaseous reaction product has to be removed only at the boundaries between wüstite and iron or gas, the only possible exception being enveloped Fe3O4 specks. On this basis McKewan2,3 has proposed that one may consider the hematite reduction process as a simple two-phase system of oxide/metal. If, for FeO and Fe3O4 layers of negligible thickness, the hypothesis is made that the rate of formation of a

Jan 1, 1963

By Nicholas J. Grant, Klaus M. Zwilsky

EVER since the unusual high temperature creep resistance and structure stability of SAP (Sintered Aluminum Powder) and similar aluminum-alumina alloys were reported,'," there has been a need to determine whether other metal-metal oxide (or other hard stable particle) alloys, not so ideal as the Al-Al 2 O 3 system, would show similar high temperature strength and stability. Of the many possible methods of obtaining a metal-metal oxide alloy,a one that offers many practical and theoretical advantages is the simple mechanical blending of metal powders with hard stable particles, followed by pressing, sintering, and hot extruding. With this purpose in mind copper powder and silica and alumina were selected for experimentation because these materials are readily available, cheap, reliable, and lend themseives te the simplest processing and testing. Starting Materials—Two sizes of electrolytically deposited copper powders were used, a —200 mesh powder referred to as A powder in this investigation and a —325 mesh powder referred to as C powder. Silica was added in the form of pure Potter's flint from which a —10µ fraction had been separated. Alumina of the a variety was used in two size ranges. The first was a —10µ fraction separated from a coarser aggregate, the second a commercial product of 0.3µ average diam manufactured by Linde Air Products. Preparation of Powders—Five-hundred gram batches of A copper with 1, 3, and 10 volume pct of each of the three oxides mentioned above were prepared, as well as C copper containing 1, 3, and 10 volume pct of —lop silica. Powders were weighed out carefully and blended by ball milling in air for 24 hr. Since this treatment resulted in surface oxidation of the copper, the charge was hydrogen reduced at 260°C for 5 hr. The next step consisted of hydrostatically compacting the powder into a shape suitable for the required hot working. For this purpose a slug about 11/2 in. in diam and 31/2 in. in length was produced by placing the mixed powders into a rubber sleeve, holding in a perforated steel canister, and rubber stoppering at the ends; the assembly was then subjected to a hydrostatic pressure of 50,000 psi. The air was evacuated from the assembly prior to pressing in order to prevent

Jan 1, 1958

DESIRABLE as it is to summarize what has been set forth in preceding chapters, the task can only be approached with great hesitation. What follows represents the personal views of the author at the moment of writing, reserving the privilege to change them on more mature reflection or in the light of further evidence. With that reservation they may be stated somewhat as follows. Education for the mineral industries falls into two categories; general education and technical vocational, using the word vocational not in its usual sense but to signify preparation for specific activities, in which sense a law school is a vocational school. Even at the beginning, as indicated in the first chapter, mineral industry education was partly general and partly technical and that relationship still persists, because technical education requires a firm basis of general education. Our general American system is to provide free public general education through the twelfth grade, or completion of high-school work, though there are already many technical vocational high schools, and even in a community where nearly all the young people are preparing for entrance to college there will be some who wish to qualify for employment at the end of the high-school course, or even on completing junior high. Our educational system, therefore, has not only to provide education for those who intend to proceed beyond the twelfth grade but also for those who, for a variety of reasons, may wish or be forced to cease full-time education at any level between the first and twelfth grades. This study has been chiefly concerned with the problem of what kind and how much technical education to provide for those who have completed the twelfth grade and who wish to make their living in the mineral industries. The obvious fact that the mineral industries employ all sorts of trained persons,

Jan 1, 1941

By J. T. Eash, W. S. Crowell, E. M. Wise

The practice of dentistry, particularly the construction of artificial dentures and "bridges," involves a unique and difficult application of the precious-metal alloys. Appliances used in the mouth are continuously exposed to corrosive agencies which can hardly be described as mild, and must remain free from tarnish and be substantially immune to corrosion. Limitations with respect to space and weight demand high physical properties, while complexity of form requires ease of working. The high corrosion resistance required necessitates the use of alloys of high precious metal content. The usual expedient of resorting to mechanical working to produce the requisite strength and stiffness cannot be utilized because of the frequency of annealing and soldering operations. To meet these difficult conditions manufacturers of dental goods were early led, unknowingly perhaps, to the production of precipitation-hardening or temperable alloys. The excellent properties of iridium-platinum may have suggested the addition of platinum metals to the conventional gold-silver-copper alloys to produce greater strength and hardness. It was found that such quarternary alloys retained their high physical properties after passing through the usual soldering process; i. e., heating to 750° to 800" C. and cooling naturally in the air. Later it was discovered that they could be softened and rendered more ductile by heating to the same temperature and quenching in water. These early examples of precipitation hardening, for years the common knowledge of dental practitioners and laboratory technicians, escaped the attention of the scientific world and discovery of the transformation which was responsible for this hardening was disclosed by the Russian investigators of the system Au-Cu, Kurnakow, Schemtschushny and Zasedatelev~,(~)$ although the optimum conditions for securing good properties in aged alloys were not given attention.

Jan 1, 1932

By O. George Specht, Carl A. Zapffe

IN recent print, some remarkably contradictory statements have appeared regarding the importance to be attached to sponge iron,1-6 a metallurgical commodity whose history goes back at least to the time of Diodorus Siculus in the fourth century B.C. This disagreement, however, expresses the lack of a satisfactory method for producing sponge iron rather than defection in the commodity. The blast furnace is admitted to have certain inherent disadvantages, such as a general unsuitability for magnetite and the heating and blowing of vast quantities of undesirable nitrogen, so that a workable sponge-iron process remains attractive. In this respect, low-temperature gaseous reduction shows especial promise; but confusion persists regarding the factors involved. The present paper, therefore, has three principal divisions: (I) an exhaustive examination of all previous work on low-temperature gaseous reduction, (2) experimentation on the reduction of a magnetite with hydrogen, and (3) development of certain thermodynamic relationships in reduction, with a summarized depiction of the factors in the general process. PREVIOUS INVESTIGATIONS Gaseous media used in the reduction processes under discussion can be classified in three types: (I) H2, (2) CO, and (3) other gases. In the second, the CO is often admixed with H2. The third principally comprises hydrogeniferous gases, such as natural gas and producer gas, and in addition includes chlorine. Because hydrogen therefore features in all three, a study of hydrogen reduction based on investigations using pure hydrogen alone may be incomplete. The present paper reviews the three groups of investigations in the listed order, paying particular attention to hydrogen reduction. For the benefit of future workers, an exhaustive bibliography has been prepared and similarly classified. GROUP I: REDUCTION WITH HYDROGEN Equilibria Although the present problem is specifically one of kinetics, a first consideration is the equilibrium of the system, since the reactions to be studied comprise that equilibrium, and their direction and end points are defined by it. The historic development of these researches is interesting and informative.

Jan 1, 1946

By J. L. Byers

THE metals of the platinum group, ruthenium, rhodium, palladium, osmium, iridium and platinum, have certain characteristic effects on the structure and appearance of the cupellation bead. These effects are dependent not only on the particular member of the group present, but also on its concentration. The extent and quality of these effects, however, have not received investigation worthy of their importance. Bannister and Patching investigated the qualitative effects of some of these metals in 1913. This paper deals with a possible rapid qualitative and quantitative delineation of the effects exerted on the cupellation bead by the various metals in the platinum group. More particularly, the paper correlates quantitatively the presence of such metals with their characteristic structural and surface effects. Inasmuch as the various members of the group are more frequently associated with gold than with silver, the gold button will receive the greater consideration. The past two decades have seen a much greater interest manifested in this particular group of metals, because of the increased industrial demand for them. There has been a constantly growing need for assays that will not only express the silver and gold values but also indicate the presence of the other metals. If these indications could be used as quantitative criteria, their value would be greatly increased, because the methods of chemical analysis for the elements of the platinum group are lengthy, involved and unreliable except when the analysis is made by an expert and experienced rare-metal analyst. The materials for the X-ray diffraction examination of the different beads were prepared by filing and screening to -200 mesh, and were then rayed in a General Electric X-ray diffraction unit. The filed samples were treated magnetically in order to eliminate any possible steel particles. Sodium chloride and C.P. gold and silver were used as standard comparators.2 (See Table 1.)

Jan 1, 1932

By Walter Herd

FoR the past eight years No. 2 mine of the Cumberland Railway & Coal CO., Springhill, Nova Scotia—a subsidiary of the Dominion Coal Co., Ltd.—has had an unenviable reputation for bumps. As the workings extended in certain directions under a greater cover, these bumps increased in severity and it became apparent that some change in the system of extraction was necessary if the mine was to continue to operate. In September, 1924, following several fatalities resulting from bumps, the Mines Department of Nova Scotia requested from the U. S. Bureau of Mines the services of George S. Rice, Chief Mining Engineer of the Bureau, to report on the conditions then prevalent in No. 2 mine, Springhill. This request was promptly and courteously granted. Mr. Rice made a full investigation and a comprehensive and helpful report, which is embodied in the 1924 Annual Report of the Department of Public Works and Mines, Nova Scotia. Prior to 1925, the room and pillar method was employed and in January of that year (there being a cessation of work from March to August due to labor troubles) longwall retreating on the west side, on a limited scale, and in a small section on the east side of the mine was started. The major portion of the east side was not operated on this system till August, 1926, as there was developed a considerable area ready for pillar extraction between an arbitrary boundary and a point up to which bumps of any consequence had not been experienced. In the interval development work for longwall retreating below the 5900-ft. level was vigorously pushed. This longwall retreating system was suggested by Mr. Rice as a possible remedy and was heartily endorsed by the company officials. This paper describes the conditions and happenings subsequent to Mr. Rice's report and more especially the results with the longwall retreating system of mining under the peculiar circumstances pertaining to mining No. 2 Seam, Springhill, at depth, and records the conclusions which experience with several severe bumps under this mode of extraction would suggest. Except where necessary to make the paper intelligible as an entity any duplication of Mr. Rice's report will be avoided.

Jan 1, 1930

By W. A. Scheuch, J. Walter

Ordinarily secondary copper, unless electrolytically refined, is reclaimed directly as foundry ingots used in the manufacture of copper-rich alloy castings. This use does not require the elimination of the impurities to the degree required if the recovered'metal is to be used for electrical purposes where a high electrical conductivity is of prime importance. However, as a part of the general policy of reusing its own scrap and by-products wherever possible, the Western Electric Co. at its Hawthorne Works is recovering its secondary copper as wire bars which are delivered to its own rod and wire mill and there processed into wire of high electrical conductivity. This departure from the usual recovery scheme has been accomplished through the careful classification and sorting of the material entering the furnace charges and the careful control of the subsequent melting and refining in a reverberatory furnace. Tests conducted over a period of approximately four years have shown that the quality of wire bars produced from selected secondary copper is equal to that of wire bars produced by the electrolytic refineries. The interest which has been exhibited in the process by those who have seen it has prompted the following general description. It is the authors' opinion that the recovery of secondary copper will become more and more an important factor in the copper production industry. The description is largely of the refining furnace and its operation, but it must be remembered that careful classification and sorting of the scrap materials to eliminate impurities are just as important as the furnace operation toward obtaining a satisfactory final product. Classification and sorting do not lend themselves easily to description; they must, just be done. It should also be recognized at the outset that constant intelligent supervision is requisite to the success of the process because there are so many ways in which impurities can find their way into the final product. Secondary Copper Used for Wire Bars Only clean secondary copper of the grades known to the trade as Numbers 1 and 2 are melted for wire-bar manufacture. This material, supplemented by that obtained from various manufacturing processes

Jan 1, 1930

By Gustav S. Preller, A. M. Gaudin

For the past 20 years it has been generally accepted that the flotation process is made possible as a result of the action of certain chemical substances on the surface of the mineral particles. In fact, it has been suspected, but never demonstrated, that this action produces on the mineral particles a layer of chemosorbed ions that is of the order of magnitude of a monolayer; that is, of a layer one ion deep. It is the purpose of this paper to present certain initial results on the relationship of mineral surface area and collecting-agent requirements. Up to about eight years ago, all considerations involving the surface area of finely divided solids were limited by the fact that there was not in existence any general method for determining the extent of such surfaces, especially on mixed materials. However, the method invented by Brunauer, Emmett and Teller1 has changed the situation by providing a general procedure (BET method). This procedure has already been applied to mineral dressing problems2-4 and has now received confirmation as to accuracy by an entirely independent method.' This confirmatory or "absolute" method uses a very tedious calorimetric procedure and is not suitable for routine determinations; but still another method6 now is available to relate the results obtained by the BET method to those obtained calorimetrically. This Harkins-Jura method has the advantage that it does not require an assumption concerning the parking area per molecule of adsorbate (nitrogen). In the original work by Brunauer, Emmett and Teller the parking area per nitrogen molecule was calculated to be either 13.8?2 or 16.2?2. according as the nitrogen was assumed to be closely packed as in crystalline nitrogen or loosely packed as in liquid nitrogen. The initial experimental work from this laboratory2 supported the 13.8?2. figure; that work was done on glass spheres of measurable geometric area and it was based on the assumption that the glass spheres were truly smooth; any deviation from this assumption would, of course, have made the calculated parking area higher. Harkins and Jura's results suggest that the parking area is not the same for all substrata; furthermore, the average of the 87 measurements cited indicates a "preferred" parking area for the nitrogen molecule of about 15.2?2., with extreme values at 13.7 and 16.9?2. The average of 21 determinations made in connection with this study7 gave a parking area of 14.3 ± 0.27?². In view of this result and of the Harkins and Jura

Jan 1, 1947

By E. H. Rose

The present symposium on flotation machines provides a unique opportunity for group reappraisal of standard or habitual viewpoints. A symposium is by definition a trading post- for observations that might prove complementary when put together, thus leading to useful thoughts that might not have been evident from the original observations individually. The present paper, pertaining to power consumption in flotation, is deliberately an experiment of that kind. Data were solicited from the operating superintendents of several of the major flotation plants on this continent. The information received, covering a total of 14 separate operations in seven plants, has been collated in terms of power intensity; that is, the total power input per cubic foot of cell volume. This departs somewhat from the conventional expression of power per ton of ore treated, though the latter figure is also given for the plants concerned. Because of wartime restrictions, particularly in Canada, identifying names of plants and machines are withheld. Not as a firm conclusion, but as a tender for symposium discussion, the following points are made: 1. That flotation is a power operation in much the same sense as ball milling. 2. That contact time is the complement of power intensity and may be decreased as the latter is increased. 3. That a decrease in flotation power per ton of ore can result from an increase in power intensity. Analogy with Grinding In grinding, it has become axiomatic that the more the power put into a given operation, the greater the work performance. The analogous view is now proposed that the effectiveness of any flotation operation will be related to the mechanical energy usefully applied to that operation. Under this view, each increment of properly directed input energy should give either an increase in unit tonnage or an improvement in the metallurgical separation (concentrate grade or tailing grade), until either the theoretical limit imposed by mineral constitution or surface condition is reached, or until further increments of power become uneconomic under the law of diminishing returns. Thus, as in grinding, there are two forms of output that greater power input or improved utilization of power can produce. As for the law of diminishing returns, lower unit cost of power through improved generating efficiency in the past decade has pushed the limit back. Over and above this, however, there is strong indication in the operationg data herein presented that higher power intensity results in an actual economy of over-all power consumption. Like crushing and grinding, flotation accomplishes a rupture of the forces of molecular attraction, by taking particles from the common environment and placing them in the two separate environments of

Jan 1, 1947

By E. H. Rose

The present symposium on flotation machines provides a unique opportunity for group reappraisal of standard or habitual viewpoints. A symposium is by definition a trading post- for observations that might prove complementary when put together, thus leading to useful thoughts that might not have been evident from the original observations individually. The present paper, pertaining to power consumption in flotation, is deliberately an experiment of that kind. Data were solicited from the operating superintendents of several of the major flotation plants on this continent. The information received, covering a total of 14 separate operations in seven plants, has been collated in terms of power intensity; that is, the total power input per cubic foot of cell volume. This departs somewhat from the conventional expression of power per ton of ore treated, though the latter figure is also given for the plants concerned. Because of wartime restrictions, particularly in Canada, identifying names of plants and machines are withheld. Not as a firm conclusion, but as a tender for symposium discussion, the following points are made: 1. That flotation is a power operation in much the same sense as ball milling. 2. That contact time is the complement of power intensity and may be decreased as the latter is increased. 3. That a decrease in flotation power per ton of ore can result from an increase in power intensity. Analogy with Grinding In grinding, it has become axiomatic that the more the power put into a given operation, the greater the work performance. The analogous view is now proposed that the effectiveness of any flotation operation will be related to the mechanical energy usefully applied to that operation. Under this view, each increment of properly directed input energy should give either an increase in unit tonnage or an improvement in the metallurgical separation (concentrate grade or tailing grade), until either the theoretical limit imposed by mineral constitution or surface condition is reached, or until further increments of power become uneconomic under the law of diminishing returns. Thus, as in grinding, there are two forms of output that greater power input or improved utilization of power can produce. As for the law of diminishing returns, lower unit cost of power through improved generating efficiency in the past decade has pushed the limit back. Over and above this, however, there is strong indication in the operationg data herein presented that higher power intensity results in an actual economy of over-all power consumption. Like crushing and grinding, flotation accomplishes a rupture of the forces of molecular attraction, by taking particles from the common environment and placing them in the two separate environments of

Jan 1, 1947

By Gustav S. Preller, A. M. Gaudin

For the past 20 years it has been generally accepted that the flotation process is made possible as a result of the action of certain chemical substances on the surface of the mineral particles. In fact, it has been suspected, but never demonstrated, that this action produces on the mineral particles a layer of chemosorbed ions that is of the order of magnitude of a monolayer; that is, of a layer one ion deep. It is the purpose of this paper to present certain initial results on the relationship of mineral surface area and collecting-agent requirements. Up to about eight years ago, all considerations involving the surface area of finely divided solids were limited by the fact that there was not in existence any general method for determining the extent of such surfaces, especially on mixed materials. However, the method invented by Brunauer, Emmett and Teller1 has changed the situation by providing a general procedure (BET method). This procedure has already been applied to mineral dressing problems2-4 and has now received confirmation as to accuracy by an entirely independent method.' This confirmatory or "absolute" method uses a very tedious calorimetric procedure and is not suitable for routine determinations; but still another method6 now is available to relate the results obtained by the BET method to those obtained calorimetrically. This Harkins-Jura method has the advantage that it does not require an assumption concerning the parking area per molecule of adsorbate (nitrogen). In the original work by Brunauer, Emmett and Teller the parking area per nitrogen molecule was calculated to be either 13.8?2 or 16.2?2. according as the nitrogen was assumed to be closely packed as in crystalline nitrogen or loosely packed as in liquid nitrogen. The initial experimental work from this laboratory2 supported the 13.8?2. figure; that work was done on glass spheres of measurable geometric area and it was based on the assumption that the glass spheres were truly smooth; any deviation from this assumption would, of course, have made the calculated parking area higher. Harkins and Jura's results suggest that the parking area is not the same for all substrata; furthermore, the average of the 87 measurements cited indicates a "preferred" parking area for the nitrogen molecule of about 15.2?2., with extreme values at 13.7 and 16.9?2. The average of 21 determinations made in connection with this study7 gave a parking area of 14.3 ± 0.27?². In view of this result and of the Harkins and Jura

Jan 1, 1947

By E. T. Turkdogan, J. H. Swisher

The solubility of oxygen in zone-refined iron was determined in the temperature range.from 881" to 1350°C. The solubility in a iron at 881°C ms found to be about 2 to 3 ppm; in y iron, the solubility was found to increase from about 2 to 3 ppm at 950°C to about 25 ppm at 1350°C. The permeability of oxygen in an iron -0.1 pct Al alloy was determined in the y iron range, using an internal oxidation technique. By combining the permeability and solubility data, the diffzisivity of oxygen in y and a iron was calculated. The oxygen diffusivity in solid iron may be s~immarized as follows: 8820 For 6 iron and IN a recent paper, Hepworth, Smith, and Turkdogan1 reported on the solubility, permeability, and diffusivity of oxygen in 6 iron, together with permeability data for oxygen in a iron. In the present investigation, similar measurements were made in the ? phase region. In addition, a solubility measurement was performed in the a phase region to permit calculation of the diffusivity of oxygen in a, iron. References to early work on this subject are given in the previous publication.' EXPERIMENTAL Solubility Measurements. The oxygen solubility was determined by equilibrating cylindrical samples 0.3 in. diam by 14 in. long of zone-refined iron in water vapor-hydrogen gas mixtures. The zone-refined iron was prepared by B. F. Oliver of this laboratory, using an apparatus and technique described elsewhere.2'3 Six zone-melting passes were used to achieve a total impurity level of about 30 ppm. Of this 30 ppm, the combined nickel and cobalt content was about 20 ppm, oxygen was 4 ppm, and all oxidizable impurities less than 1 pprn each. A vertical resistance furnace wound with molybdenum wire was used for the experiments. The temperature was measured before and after each experiment with a Pt/Pt-10 pct Rh thermocouple. In the gas train, flow rates of hydrogen and argon were measured with capillary flow meters, and the resulting mixtures were passed through a column containing 90 pct oxalic acid dihydrate and 10 pct anhydrous oxalic acid to obtain predetermined ratios of H2O to H2. The vapor pressure of H2O above this mixture as a function of temperature is well-known.4 The exit gas was ana- lyzed periodically for H2O, and good agreement (+3 pct) with the calculated composition was obtained. The zone-refined iron specimens were held in the furnace for a sufficient length of time for equilibration, e.g., 18 hr at 1350°C and 1 week at 881°C, then quenched in a brine solution. After removing the surface oxide from the samples by machining, duplicate analyses were obtained by a combined vacuum fusion-infrared method; oxygen analysis was reproducible within 2 ppm. Permeability Measurements. The permeability of oxygen in alloys containing about 0.1 pct A1 was determined by internal oxidation and measurement of the subscale thickness as a function of time. The experimental alloys were prepared by adding aluminum to electrolytic iron (grade 104A plastiron) that had previously been vacuum-carbon deoxidized. The resulting ingots contained about 20 ppm O, 100 pprn C, 40 pprn Si, 50 ppm Mo, 20 ppm P, 20 ppm S, and 20 pprn Zr as the principal impurities. After hot rolling the ingots to 1-in.-thick slabs, specimens were machined from the stock in the form of rectangular plates, 4 by 5 by 2 in. The general procedure for the permeability experiments was the same as those for the solubility measurements. The specimens were cooled in a reducing atmosphere rather than quenched, however, in order to maintain a clean surface for measurement of the sub-scale thickness. This measurement was made on a polished cross section of each specimen, using a microscope with a micrometer stage. The inclusions formed at the lowest temperature 1033°C were too small to be seen with an optical microscope. An electron micrograph showing the size and shape of individual particles is shown in Fig. 1. The dark band in the picture is a boundary between two subgrains. The subscale thickness in these samples was measured with an optical microscope after heavily etching in 2 pct nital, which gave contrast between the subscale and the unoxidized zone.

Jan 1, 1968

By L. S. Birks

The bainite transformation in a 3.5 pct Ni-1.25 pct Cr steel was studied under various conditions of cooling and stress. Several characteristics may be specified: 1) transformation in the bainite region (925° to 575°F) is very little affected by the manner of cooling from the austenitizing temperature at 1600°F to 575°F)tothe upper limit of bainite transformation at 925°F; 2) starting time for the bainite transformation is the same order of magnitude for either isothermal transformation or continuous cooling, but the rate of transformation is somewhat greater for isothermal transformation; 3) tensile stress accelerates both isothermal and continuous cooling transformation, and 32,000 psi stress changes the form of the isothermal transformation diagram to correspond in appearance to the continuous cooling diagram; 4) transformation for nonlinear, continuous cooling may not be determined directly from the linear, continuous cooling transformation diagram, but may be predicted by assuming first that the fractional amount of austenite transformed in a given small temperature interval depends on the approximate linear cooling rate during that temperature interval and then by summing stepwise over the whole temperature range. IN a previous publication' an X-ray spectrometer was described with which the X-ray diffraction from a specimen could be observed continuously under controlled temperature and tensile stress. This instrument has now been applied to a study of the austenite-bainite transformation in a Ni-Cr steel for both isothermal and continuous cooling conditions, with and without stress. Certain characteristics of the transformation lead to a method of predicting the amount of transformation to be expected at a given temperature for any type of cooling curve. Material and Specimen Preparation The steel chosen for the investigation was a Ni-Cr steel having the composition in the following percentages: 0.30 C, 0.27 Mn, 0.019 P and S, 3.50 Ni, and 1.25 Cr. In order to fabricate specimens suitable for the X-ray spectrometer, a 1/4 in. plate was ground down to 0.060 in. and then cold rolled to about 0.035 in. Next it was heat treated by quenching in oil from 1650°F and tempering at 1200°F for 1 hr. Then it was etched in dilute nitric acid to reduce its thickness to 0.014 in. and cut into blanks in the shape of flat tensile specimens 3 1/4 Vi in. long, 7/16 in. wide, with a notch % in. long and 7/32 in. wide; see Fig. 1. X-Ray Technique Since the X-ray spectrometer has been described in detail elsewhere,' only a brief outline of the principles will be repeated here. A focusing, pow- der-diffraction arrangement' was used, as shown schematically in Fig. 1, and the specimen was mounted vertically in a vacuum furnace (not shown in the figure). The X-rays, moving in a horizontal plane, enter and leave the furnace through beryllium windows. As shown in the figure, X-rays diverging from the line source A are diffracted by the specimen B and converge at the detector slit C. The detector D and the slit C may be set at the proper angle in the horizontal plane to receive X-rays diffracted by either the face-centered phase (austenite) or the body-centered form (ferrite, bainite, martensite). The specimen is heated by electrical conduction between connectors E, and E,, and a Pt—Pt-10 pct Rh thermocouple spot-welded to the center of the notched region on the side away from the X-ray beam indicates the temperature continuously on a Brown recorder. Temperature control is exercised manually with a variable transformer on the input to E,-E,. Any desired time-temperature relationship is easily obtained by first drawing the desired curve on the temperature recorder chart and then adjusting the variable transformer during the run so that the thermocouple

Jan 1, 1957

By C. Laird, C. E. Feltner

IN previous workif2 we have shown that the steady state cyclic stress response of pure copper tested in the low cycle fatigue range was determined only by the plastic strain amplitude and the test temperature. hus, copper, at any given temperature, has a unique cyclic stress-strain curve independent of prior history. Cu-7.5 wt pct Al, however, showed a stress response for a given plastic strain amplitude and temperature which depended sensitively on prior history. From this work we predicted that all wavy slip mode materials, typified by copper, would have a unique cyclic stress-strain curve; whereas all planar slip mode materials, typified by Cu-7.5 pct Al, would not. This prediction has now been tested for a number of materials of widely varying crystal structure and slip character. Wavy slip mode materials studied include: Fe. Al, Cd, disordered FeCo-V, and Cu-3 pct Co (quenched and aged). Planar slip mode materials investigated include: Fe-3 pct Si, ordered FeCo-V, disordered Ni3Mn, ordered Ni3Mn, and Zn. The treatment and properties of these materials are listed in Table I. Cyclic stress-strain curves were determined by controlled plastic strain tests (see Ref. 1 for details) at room temperature for all materials in both the initially annealed and cold worked conditions. The results obtained for iron and Fe-3 pct Si are typical of wavy and planar slip mode materials, respectively. The cyclic stress-strain curves for these materials are shown in Fig. 1 and it can be seen that iron has a unique cyclic stress strain curve while Fe-3 pct Si does not. Aluminum, Cu-3 pct Co, and disordered FeCo-V showed a behavior like that for iron, while Ni3Mn in both the disordered and ordered condition behaved in the same manner as Fe-3 pct Si. These results therefore support the general conclusion drawn in Refs. 1 and 2 that. for wavy slip mode materials, a cyclic mechanical equation of slate it =t.(hcp, i. T) is approximated in which the satura-

Jan 1, 1970

By d&apos, D. L. Guernsey, J. C. Entremont, John Chipman

The reaction of aluminum with oxygen in liquid iron has been studied at 1740° and 1910°C. Interaction coefficients are very much smaller than those previously published. The equilibrium constant falls within the approximate range of earlier experiments and calculations. It is now well established that the "deoxidation constant" for aluminum in liquid steel at normal steelmaking temperatures is extremely srnall. Thus at 1600 the product [% Al] is of the order of 10- 14. At this temperature, therefore, great experimental difficulties are encountered in any attempt to obtain a direct measure of the constant. If the aluminum content of the metal is high enough to permit accurate analytical determination, that of the oxygen is too low. If the oxygen content is high, the aluminum is below the limits of detection. Our best values of the constant have come, therefore, from indirect calculations or by extrapolation downward from observations at higher temperatures.. For their studies in the range 1695° to 1866°C, Gokcen and chipman' restricted their aluminum concentrations to less than 0.06 pct. Oxygen analyses were made by the vacuum fusion method which appears to be dependable at these low aluminum concentrations. Experimental results, even at the highest temperature employed, are extremely sensitive to small errors in the analysis of either element. The slight change in the equilibrium constant with aluminum and oxygen concentration was utilized in the calculation of interaction coefficients expressing the effect of aluminum on the activity coefficient of oxygen and the reciprocal effect of oxygen on the activity coefficient of aluminum. The range of concentration, however, was so limited that only a rough value for the interaction coefficient could be obtained. This value was much more negative than that found for any other pair of reactants. In view of the very limited range of concentration employed, the reported values have always been regarded as very questionable. A redetermination was the object of the work reported here. EXPERIMENTAL METHOD At high aluminum concentrations, the vacuum fusion method is susceptible to grave error due to absorption of gas by aluminum distilled from the sample. Since it was desirable to extend the study to at least as much as 1 pct Al, another method for analysis was sought. In steels containing more than a few hundredths of a percent aluminum and no other deoxidizing element, it is safe to assume that

Jan 1, 1963

By C. W. Spencer, F. G. Hochgraf, R. F. Cheney

Columnar grained specimens of nickel, containing 0.25 pct Si and 0.22 pct Mn, have been exposed to liquid bismuth in the temperature range 670° to 1050°C. Under isothermal conditions the liquid penetration rate is constant. The activation energy for the process is 22,000 cal per g-atom. Small amounts of plastic deformation, introduced into specimens prior to exposure, increase the penetration rate. The slou. step in liquid film penetration is associated with a reaction which occurs at or near the leading edge of the film. Either transfer of nickel across the liquid-solid inteqace or diffusion in the grain boundary ahead of the liquid film is suggested. Aliquid metal, if brought into contact with the surface of an unstrained solid metal, will usually penetrate to some extent into the grain boundaries of the solid. Under isothermal conditions the extent of penetration after any particular time of exposure is related to the relative magnitudes of the interfacial tensions concerned.1,2 If the liquid-solid interfacial tension is less than one-half the grain boundary tension the liquid may penetrate at a relatively rapid rate for an indefinite distance into the grain boundary surfaces. If the liquid-solid interfacial tension is greater than one-half the grain boundary energy, liquid penetration occurs at a continually decreasing rate so that after the liquid has penetrated to a relatively short distance below the surface the process essentially ceases.3 Many observations of a qualitative nature concerning inter crystalline attack by liquid metals have been reported, for example, liquid bismuth upon copper,' liquid mercury upon brass,4 and liquid mercury upon nickel.' Scheil and Schessl determined the rate of penetration of liquid bismuth into the grain boundaries of hot rolled copper rod? At constant temperature, penetration rate was found to be independent of the depth penetrated, the rate in- creasing with increasing temperature corresponding to an activation energy of 20,000 cal per g-atom for the process. It was suggested that at lower temperatures the liquid travelled mainly along lines of three grain intersections while at temperatures greater than 1000°C essentially all grain boundary surfaces were covered. Recently, in a study of copper bicrystals having a common [loo] axis it was found that at 649°C bismuth penetrated 22, 25, and 63 deg boundaries while it did not penetrate 2, 12, 15, and 72 deg boundaries.' Elbaum reported that liquid gallium penetrates aluminum grain boundaries to a depth of 0.6 cm after 11 hr at 27°c.8 Assuming that the rate controlling step in the process was diffusion down the liquid film to the specimen surface, a diffusion coefficient of 10-5 cm2 per sec was calculated. This paper reports a study of the penetration of bismuth-nickel liquids into the grain boundaries of a nickel alloy, containing 0.25 pct Si and 0.22 pct Mn as principal alloying elements. The phase diagram

Jan 1, 1962