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THE research and policy committee of the Committee for Economic Development, a non-profit research organization composed of leaders in industry and the professions, including such prominent figures as Dwight D. Eisenhower, Paul G. Hoffman, and Charles E. Wilson, recently published a report entitled "How to Raise Real Wages." Since its founding in 1942 the CED has initiated many objective studies on matters of national economic policy, and has gained a fair measure of prestige from its activities. The CED's latest report cites the more than three- fold rise in real wages in the United States in the past 50 years and attributes the accompanying improvement in the standard of living to the great in- crease in production per man hour. The report states that in order for production to continue rising in the future with the attendant increase in real wages four basic conditions must be manifest: (1) better methods, (2) more capital, (3) better training of workers, and (4) better management. The report cautions that although prospects for increases in output per man hour are good "it is desirable that steps be taken to encourage such a rise."

Jan 8, 1950

By Louis D. Huntoon

SHORTLY after publication of the article in the July, 1924, issue Of MINING AND METALLURGY, entitled "Canada as a Gold Producer," requests were received to determine the ownership of production. Advices have also been received that considerable discussion has taken place on the same questions both in Canada and Great Britain. The author is indebted to R. H. Coates, Dominion Statistician, and George C. Bateman, Secretary, Ontario Mining Association, for the following figures and takes this opportunity of expressing his appreciation. There have been no statistics compiled as to ownership of production. Statistics were compiled as of Dec. 31, 1921 relative to the distribution of stocks, bonds and "other securi¬ties" in industrials, agriculture excepted, throughout the Dominion, and "distribution of ownership of securities issued by mining companies incorporated and operating in Ontario" for the same year. Stock registration does not necessarily represent actual ownership' as large blocks may be endorsed and not transferred; neither does registration actually represent production. When the charts are studied individually and collectively one cannot help but be impressed with the fact .that in the mineral industry of Ontario and the Dominion at large, Canadian registration predominates, the United States registration is about half that of Canada, and Great Britain is about half that of the United States. When the nickel-copper industry is excepted the British registration falls to a very low percentage. Since Dec. 31, 1921, British capital has commenced to flow into mining enterprises in Ontario and it has been already rewarded by the discovery of valuable ore deposits.

Jan 1, 1925

By Ogden Tweto

The classes of ore deposits in the mountain province of Colorado that have been the most productive in the past and that offer the greatest promise for the future are: (1) disseminated or stockwork molybdenum deposits associated with Tertiary stocks; (2) combination precious- and base-metal veins in Tertiary volcanic rocks; and (3) base-metal replacement deposits and veins in Paleozoic sedimentary rocks. Veins in Precambrian rocks, including precious metal-bearing sulfide veins, gold-silver telluride veins, and tungsten veins, have been mined extensively in the past, but their aggregate output has been far subordinate to that of the groups named above, and the outlook for major output from them in the future is poor. Principal ore deposits of south-central Wyoming are sedimentary iron ores of Precambrian age and uranium deposits in Tertiary sedimentary rocks. Precambrian deposits of several kinds are scattered through the mountains of both states. The most promising of these, based on present indications, are vanadiferous titaniferous magnetite in southern Wyoming and southwestern Colorado and thorium-niobium rare-earth deposits associated with alkalic intrusive complexes in Colorado. Most of the mining districts of Colorado are in the Colorado mineral belt, a generally narrow but somewhat irregular belt that extends northeastward across the north-trending mountain ranges and the north-northwest trending geologic grain of the state. The belt is characterized by intrusive rocks of Laramide and younger age and by ore deposits, and it occupies environments ranging from Precambrian crystalline rocks through Paleozoic and Mesozoic sedimentary rocks to Tertiary volcanic rocks. Two ages of intrusion and ore deposition recently have been recognized in the mineral belt. One is Laramide (late Cretaceous and early Tertiary), and the other is Oligocene. As interpreted herein, the major replacement deposits and most of the sulfide vein deposits in Precambrian and sedimentary rocks are Laramide in age, and the molybdenum deposits, the tungsten and the gold telluride veins in Precambrian rocks, and the precious- and base-metal veins in volcanic rocks are Oligocene in age. In general, the Laramide deposits are mesothermal in aspect, and the Oligocene deposits are principally epithermal. The existence of two mineralization stages, in considerable part characterized by different suites of metals, has many applications in exploration.

Jan 1, 1968

By Lyon F. Terry

IN contemplating the prospects of natural gas being transported from the fields where it is produced to such distant points as Philadelphia, New Jersey, New York City, and New England, let us review the advance that natural gas has made and the projects currently scheduled for construction. This may give us a perspective of the point in the long-range development of the natural gas business in which we now find ourselves, and some basis for judging the further expansion of the industry. Authentic statistics of the total marketed production of natural gas in the United States have been compiled by the Bureau of Mines since the year 1906. The growth of the business is indicated by the following data on marketed production for each ten-year interval since 1906:

Jan 1, 1947

By AIME AIME

I am happy to welcome you to the twenty-third conference of the National Open-Hearth Committee, and our joint conference with the Blast Furnace Committee, of the American Institute of Mining and Metallurgical Engineers. It is appropriate that, for our fifteenth year anniversary, we should meet in the hotel and the city where this Open-Hearth Committee was inaugurated in 1925. At that first meeting, only a handful of men from a number of steel companies met to discuss ways and means to start a movement to improve the practical and metallurgical technique of open-hearth operations among independent manufacturers, as the United States Steel Corporation had carried on for many years.

Jan 1, 1940

By Richard H. Mote, W. C. Schroeder

The endlessly changing pattern of mineral supply and demand offers opportunity to the alert and can bring disaster to the unwary. The discovery of ore bodies, the invention of extractive processes, the provision of new transport facilities, the political stabilization of underdeveloped areas, and many other changes can increase supply dramatically. Such new outpourings of mineral wealth from ore bodies bring fortunes to their developers, and consumers frequently find their competitive positions decidedly improved by new and cheap sources of supply. On the other hand, operators of marginal properties can find competition from newly opened high-grade mines intolerable. Consumers that have depended on the products of nearby, high-cost mines may find new, remote, low-cost supplies advantageous only to their competitors. The invention of new prospecting methods can have spectacular effects. Shortly after World War I the discovery rate of petroleum pools began to decline. The leading prospecting technique of that day, the projection downward of surface reflections of geologic structure, was proving less rewarding. Prophets foretold an oil shortage in the near future. But at that very moment scientists were perfecting the application of seismic waves to reveal underground oil-bearing geologic structures. As these geophysical methods were put into commercial use the whole outlook changed-the problem of the 1930's became how to cope with the surplus from discovery, not how to meet the ever rising demand. Many lead mines were being abandoned as unprofitable about this same time because the penalties charged by smelters for the zinc in the ores and concentrates more than counterbalanced the payments for lead and silver. Then selective flotation (at the time called differential flotation) appeared,

Jan 1, 1959

By A. M. Beebee

IN the present century the coal and manufactured gas industries have been eclipsed in public interest by oil, natural gas, and hydro- electric energy, which have had the benefit of rapid development and novelty. I sometimes wish that our social- order were such that hydro power had been developed first, that the use of gas from coal had never been seriously considered, and that our domestic energy requirements were supplied by other fuels. Sup- pose the manufacture of gas from coal should then come on the scene at the present time with the current plight of the railroads, coal regions, and labor generally, presenting the fact that it could increase the amount of coal mined and shipped by the railroads by some 16,000,000 tons, and increase the coal used at existing u plants five times. Imagine the great public interest that would be manifested; it would supply the cooking and water-heating requirements of a community with a superior character of service at a cost to the customer approximately half that which had obtained previously. Would not such a situation be heralded as the salvation of our country and all help be given it?

Jan 1, 1940

By GUY C. RIDDELL

THE recent purchase by an American investment trust of a substantial block of shares in a British owned Venezuelan copper operation directs attention to mining activities that have been quietly gaining momentum in that country for a number of years. We hear so much of oil work in Venezuela that attention to its metal-mining activities is in most quarters casual. In gold and copper the country has made some interesting mining records, and two of the old districts are ,digging in for a come-back. Copper Copper production centers in the state of Yaracuy. The Aroa-Cumaragua mining region has had a long and eventful history. The Aroa mine itself, 50 miles from the coast in West-Central Venezuela, was discovered in 1605. First mined in 1632, owned at one time by Simon Bolivar, it has been reopened many times and is now , the basis of substantial operations by the South American Copper Syndicate, Ltd. of London. The latter has operated the property profitably, off and on, for a number of years, paying heavy dividends on a small investment-at times over 300 per cent annually.

Jan 1, 1929

By AIME AIME

FEATURES of the second fall meeting of the Petroleum Division for 1941, held at the Ambassador Hotel, Los Angeles, Oct. 29-30, were the forum on the Paloma Plan on Thursday after- noon, the large attendance from east of the Rockies, and the dinner on Wednesday evening sponsored by the Southern California Section and at which President Suman spoke on the strategic minerals and metals situation. The attendance was large and the technical fare uniformly good ; the presiding officers had the proceedings well in hand at all times and kept things humming. Some- times it was necessary to taper off the discussion because of pressure on time. All this was due to careful groundwork before the respective sessions. These presiding officers deserve citation: L. W. Huebel, Howard Pyle, E. K. Parks, Carlton Beal, E. G. Trostel. R. W. French, Jr., John Dodge, and H. N. Marsh. The Los Angeles local commit- tees and the Southern California Section deserve much credit for the arrangements, which were recognized by suitable resolutions at the end of the meeting.

Jan 1, 1941

Jan 1, 1884

By Arthur R. Still, Paul Gilmour

The ore deposit of the Iron King mine occurs in a group of steeply-dipping metamorphosed eugeosynclinal volcanic and sedimentary rocks of Precambrian age. Within this sequence, the ore deposit lies at the contact of a unit made up of rhyolitic tuff and interbedded andesite and a structurally underlying series consisting of andesitic tuffs, minor rhyolitic tuffs, and argillaceous sediments. Field evidence suggests that these rocks have been overturned. The ore deposit is made up of a series of overlapping, conformable or bodies consisting of massive pyrite and associated lenses of massive quartz. These contain recoverable amounts of gold, silver, lead, zinc, and copper. A parallel zone of copper mineralization occurs within the hanging-wall rocks. The deposit is considered to belong to a large and important group characterized by mineralogical composition and the lithology and structural type of the host rocks. Evidence regarding the origin of the deposit is reviewed, and it is concluded that the ore bodies were formed through the agency of volcanic hot springs on, or near, a submarine surface of deposition

Jan 1, 1968

By A. M. Gsudin, F. W. Bloecher, C. S. Chan-s, P. L. De Bruyn

M ANY elements can now be obtained in radioactive form. The radioisotopes have the same chemical properties as the corresponding inactive forms, differing from them only by their nuclear instability. This combination of properties permits radioelements to act as atomic tracers, the tracer atoms revealing themselves at the time of their decay with emission of electrons and positrons (beta radiation), helium nuclei (alpha radiation), or electromagnetic radiation (gamma radiation). The tracer technique is particularly attractive for the study of surface chemistry problems in general and flotation problems in particular because of its extreme sensitivity. A large proportion of the ionizing events, initiated by the characteristic decay emissions in a radioactive sample, can be recorded by radiation probes of suitable design and geometry. An idea of this sensitivity can be gathered from the following example: assume that 0.001 mg of pure RaD (radiolead), a beta-ray emitter, is used in a flota¬tion tracer experiment. This is 1210 X 10-1 mole; since the fraction trans¬formed per second (the so-called decay constant), is 9.92 X 10-10, the number of ionizing events per second would be (6.023 X 1023 X y,,, X 10-1) X 9.92 X 10-10 = 2.845 X 106. (The decay constant is expressed in sec-'. Its product with the half life, expressed in seconds, is the pure number, natural logarithm of 2 = 0.693. The half life is the length of time required for decay of one half of the total number of radioactive atoms of one particular type.) (See reference (1) at the end of this article.)

Jan 1, 1948

By Otto H. Henry, Edward L. Badwick

Up to the present time, according to Hansenl and Haughton,² the constitution of the bismuth-indium system has not yet been published. The generally accepted value for the melting point of indium, as listed in most scientific journals and textbooks, is 155°C. Recently, however, H. M. Davis3 has determined a new melting point for indium of 157.3²C O.l°C. Since bismuth has been used in preponderance as an alloying element in the majority of low-melting alloys, and indium has been used with considerable success in lowering the melting points of low-melting alloys, 4,6 an interest has been developed in the application of these two metals, making a complete knowledge of the constitution of its alloys desirable. In this investigation, the melting point of indium reported by H. M. Davis has been found to be substantially correct. A value of 157. ²°C ± O.5°C was determined. The two eutectic compositions have been placed at 34 and 50 pct bismuth with their respective eutectic temperatures as 72.4°C ± 0.5°C and 90°C ± 0.5°C. The bismuth-indium phase diagram has been determined by thermal and microscopic analysis and is shown in Fig I. Thermal Analysis Granulated bismuth and indium shot, having a guaranteed purity of 99.99 and 99.95 pct, respectively, were melted in a carbon crucible by means of a laboratory heater. To minimize oxidation of the alloys, a heavy mineral oil (Nujol) having a high- flash point was used. A platinum-platinum rhodium thermocouple of fine wire encased in a thin-walled Pyrex glass tube, about 1/8 in. in diameter, was connected to a type K potentiometer for temperature measurements. The thermocouple was calibrated against the melting points of tin, bismuth, and the silver-copper eutectic and the boiling point of water. Since the temperature readings could be reproduced to 0.²°Cl and the accuracy of the temperature standards in this range is slightly better than 0.5°C, it scems reasonable to assume that the temperature readings are reliable to approximately 0.5°C. The cooling rate could be controlled by varying the amount of insulation surrounding the crucible. Three or four layers of asbestos paper, 1/16 in. thick, sufficed to give a cooling rate of from I° to ²°C per minute. Undercooling was slightly noticeable. This condition was minimized by vigorous stirring, since the advantage of using slower rates was too small to justify the greater expenditure

Jan 1, 1947

By Otto H. Henry, Edward L. Badwick

Up to the present time, according to Hansenl and Haughton,² the constitution of the bismuth-indium system has not yet been published. The generally accepted value for the melting point of indium, as listed in most scientific journals and textbooks, is 155°C. Recently, however, H. M. Davis3 has determined a new melting point for indium of 157.3²C O.l°C. Since bismuth has been used in preponderance as an alloying element in the majority of low-melting alloys, and indium has been used with considerable success in lowering the melting points of low-melting alloys, 4,6 an interest has been developed in the application of these two metals, making a complete knowledge of the constitution of its alloys desirable. In this investigation, the melting point of indium reported by H. M. Davis has been found to be substantially correct. A value of 157. ²°C ± O.5°C was determined. The two eutectic compositions have been placed at 34 and 50 pct bismuth with their respective eutectic temperatures as 72.4°C ± 0.5°C and 90°C ± 0.5°C. The bismuth-indium phase diagram has been determined by thermal and microscopic analysis and is shown in Fig I. Thermal Analysis Granulated bismuth and indium shot, having a guaranteed purity of 99.99 and 99.95 pct, respectively, were melted in a carbon crucible by means of a laboratory heater. To minimize oxidation of the alloys, a heavy mineral oil (Nujol) having a high- flash point was used. A platinum-platinum rhodium thermocouple of fine wire encased in a thin-walled Pyrex glass tube, about 1/8 in. in diameter, was connected to a type K potentiometer for temperature measurements. The thermocouple was calibrated against the melting points of tin, bismuth, and the silver-copper eutectic and the boiling point of water. Since the temperature readings could be reproduced to 0.²°Cl and the accuracy of the temperature standards in this range is slightly better than 0.5°C, it scems reasonable to assume that the temperature readings are reliable to approximately 0.5°C. The cooling rate could be controlled by varying the amount of insulation surrounding the crucible. Three or four layers of asbestos paper, 1/16 in. thick, sufficed to give a cooling rate of from I° to ²°C per minute. Undercooling was slightly noticeable. This condition was minimized by vigorous stirring, since the advantage of using slower rates was too small to justify the greater expenditure

Jan 1, 1947

By Walter J. Mead

By American tradition, if not by rational decision, publicly owned natural resources have been transferred to private industry for processing. The process of transfer requires specific determination of the price which the patentee, buyer, or lessee must pay to the government in exchange for the right to develop a resource, and selection of the patentee, buyer, or lessee from among several possible contestants. Pricing of natural resources owned by the government presents a set of problems quite different from ordinary commodity pricing. Natural resources in situ are not homogeneous commodities. Within any class of natural resources, specific leasable parcels will differ in value by reason of location and accessibility, as well as quality and quantity. Thus, there is no "going price;" every lease within a specific resource class will have a different value. To complicate further the pricing and buyer selection problems, competition may not be reliable. Natural-resource markets are characterized by oligopsony conditions. In a significant number of cases, as will be shown later, there has been only one bidder for a given lease, and in most lease sales the number of bidders is equal to or less than three. As a further complication, there is great uncertainty regarding the value of specific resources, even among the best-informed buyers, as well as within the leasing agency. In some instances, particularly with regard to oil and gas resources, there may be uncertainty about the presence of resources, as well as the quantity and quality of any resources contained in the tract offered for lease. In other cases, such as oil shale and some deep ocean minerals where new technologies are involved, the presence of the resource is clearly established. There may be a relatively high degree of knowledge about the quantity and quality of the resource, but there is great uncertainty concerning the cost of production. These problems in total make it difficult for the leasing agency to appraise accurately the resource to be leased, as well as for the potential bidder to calculate a bid price that will yield him a normal profit. The pricing goal of the federal government as the seller or lessee may be to capture the economic rent; that is, the price of a resource might equal its discounted present value. A required price substantially above this amount would either generate no bids, or, in the long run, would bankrupt the buyer. A price below this amount is a disguised subsidy to the lessee. A subsidy to mineral lessees, as to any other economic interest group, as a minimum should be justified by a clear showing of net external benefits from the economic activity. In the case of timber sales by the U.S. Forest Service, the Forest Service Handbook asserts that "the aim in national forest stumpage appraisal is to determine market value,"8 and "market value" is equated to "fair market value." Regarding minerals, there is no reference in legislation or regula-

Jan 1, 1976

By Gary E. Parish

TABLE OF CONTENTS Contents I. Introduction II. Purpose of the Paper III. Historical Perspective A. Existing Sources B. New Sources (NSPS) C. Hazardous Pollutants (NESHAPS) D. Enforcement/Judicial Review 1. Title I Enforcement 2. Title III Enforcement 3. Information Gathering E. Summary IV. The Clean Air Act Amendments of 1977 (1977 Act) A. SIP-Related Provisions 1. Section 107(d) - Geographic Boundaries 2. Section 108 - Air Quality Criteria 3. Section 109 – NAAQS 4. Section 110 – SIPs 5. Section 122 and Sections 402 and 403 of P.L 95-95 – Unregulated Pollutants 6. Emission Offsets – Interpretive Ruling (I.R.) B. PSD Provisions - Part C. 1. Regulations Under the 1970 Act 2. The 1977 Act 3. Regulations Under the 1977 Act C. Visibility Protection - Part C, Subpart 2 D. Non-Attainment Provisions - Part D E. Monitoring and Modeling F. NSPS G. NESHAPS H. Enforcement/Judicial Review 1. Title I 2. Economic Enforcement 3. Title III Enforcement/Judicial Review (a) Section 304 (b) Section 307 4. Summary V. Special Problems and Opportunities for the Uranium Industry A. End Use B. Transportation C. Milling/Processing D. Extraction E. Exploration/Discovery F. General VI. Conclusions Appendix A Footnotes

Jan 1, 1979

By A. W. Fahrenwald

FLOTATION practice in Idaho is now about 13 years old. The advance has been steady during these 13 years. The operators have been alert to take advantage of the newest developments and they have themselves made a constant effort to improve their work. The metallurgical improvements are due to the development of (1) better equipment, (2) better reagents, and (3) better understanding and control of the process. During the eight years the writer has been in this district, there has been continuous experimentation by several companies to improve the ore dressing by flotation methods. Gravity concentration has fought hard to hold its place, and although it is true that gravity processes have been improved during this period, nevertheless, in several of the important mills of the district the few tables that managed to hang on have finally given way. On the straight-lead ores, tables and jigs are still used; and, due to better classification, their hold on this job has been strengthened. ORES OF THE DISTRICT The ores of the district are of two general classes: (1) clean lead ores, such as those from the Bunker Hill and Hecla mines, and (2) complex lead-zinc ores. The general impression prevails that the clean lead ores, class 1, are simple and that it is easy to obtain high recoveries and good grade products. This, in a way, is a false impression; there is quite a high percentage of locked middling in these ores at 100 and 150-mesh sizes. Improved classification preparatory to table treatment of this type of ore has made it possible to segregate effectively a high-grade middling which is further comminuted and floated. The complex lead-zinc ores of the district, of which the ore from the Morning mine of the Federal Mining & Smelting Co. is a typical example, always have presented a difficult problem. It always has been comparatively easy to make a clean lead concentrate, but it never has been possible to concentrate sphalerite with a-specific gravity of 4.10 from siderite of gravity 3.88. Also, a large percentage of the galena and sphalerite of this class of ore refuses to separate out until the crushing has been carried

Jan 1, 1928

By Herty, C. H.

One of the numerous requirements of many grades of present- day steel is that the steel shall be free from non-metallic inclusions. These inclusions may be composed of oxides, sulphides, complex oxy- sulphides, and nitrides, which enter the steel with the furnace charge, result from sulphur absorption from the furnace gases, or are formed in the steel during the deoxidation process. Although few' data are available which indicate in any quantitative manner the specific effects of inclusions in steel, there is a large mass of circumstantial evidence which points to the advisability of producing steel free from these impurities for many purposes. At the present time there is a growing feeling among metallurgists that non-metallic inclusions should be divided into two distinct types: (I) those readily visible under the microscope at ordinary magnifications; and (2) those in colloidal suspension or in solid solution. Both types are profoundly influenced by the character of the charge, the manipulation of the furnace slag, and the method of deoxidation. The work described in this bulletin deals primarily with inclusions visible under the microscope at ordinary magnifications, but the steels made by the various methods of deoxidation are being used LO study certain effects which may be ascribed to the second classification, named above. This latter work will be the subject of further bulletins on the effect of deoxidation practice on the physical properties of the steels involved.

Jan 1, 1957

By B. C. Allen, W. D. Kingery

Surface tension and its temperature dependence have been determined for pure liquid Fe, Cu, Co, Ni, and Sn and for Fe-C, Co-C, and Ni-C alloys. The temperature coefficient of surface tension is negative for all these liquids. The surface tension and wetting behavior of tin and tin-titanium alloys on A120,, Si,N,, MoSi,, and Sic, as well as the behavior of titanium-containing nickel alloys on A1 20, have been determined over a wide temperature range. For all the solids investigated titanium additims markedly lower the contact angle. Some limits for the solid-surface energies have been calculated from liquid surface tension and wetting behavior. SURFACE tension and interface energy are important variables in a number of metallurgical and ceramic phenomena, and have been discussed at some length in connection with determining micro-structure of polyphase systems,' solid-state sintering,' thermal etching of grain boundaries, heats of solution and fine powders,'1 grain-growth phenomena,' the mechanical behavior of fine foils and fibers, nucleation, soldering and brazing,' and other phenomenz of academic or practical interest However, until recently few quantitative data have been available for high-temperature systems. Among available data are some indicating positive temperature coefficients for the surface tension of liquid copper,*,11,'2 cast iron,l3 and iron-carbon14 alloys. Although carbon was found to be not surface active in iron at 1570" some preliminary studies had indicated the possibility of a positive temperature coefficient for the eutectic composition at lower temperatures.16 One part of the present study has been largely concerned with determining the temperature coefficient of surface tension for several metals at elevated temperatures, In addition to surface-tension studies, the wetting behavior of alloys containing titanium has been investigated over a wide temperature range. Previous measurements indicated that titanium was selectively adsorbed from nickel at a liquid nickel-solid alumina interface,17 and the use of titanium hydride or titanium-alloy techniques for metal-ceramic soldering is well known. In the present study, previous data have been extended to new alloy systems, and measurements have been carried out with other oxidation-resistant ceramics. EXPERIMENTAL The sessile-drop method was employed to measure liquid surface tension and contact angle between liquid and solid, utilizing apparatus and techniques which have been described previously.'g The shape of a sessile drop depends on equilibrium between forces of surface tension tending to form a spherical surface of minimum area and forces of gravity tending to flatten the drop. Typical sessile drops are shown in Fig. 1. From precise measurements of maximum drop diameter and drop height the surface tension and drop volume were calculated. Four solid materials were employed as supporting plaques for the liquid-metal drops. Aluminum oxide (99.9 pct, J, T. Baker, reagent grade) was pressed and sintered at 1800°C. Molybdenum-disilicide powder (99.0 pct, Electro Metallurgical Co.) was pressed and sintered at 1650°C. Plaques were cut from silicon carbide (99.4 pct, hot-pressed at Alfred University) and silicon nitride (95.1 pct, with Al, Fe, 0 as major impurities, Norton Co.) rods. All plaques were polished, cleaned, and dried prior to use. A number of metals and alloys were employed. Chemical analyses of vacuum-melted ingots of iron, nickel, cobalt (National Research Corp.), commercial nickel-base alloys, electrolytic copper (International Smelting and Refining Co.), and tin (Mal-linckrodt Chemical Works) are given in Table I. Alloys were prepared in the laboratory by vacuum melting the base metal with either titanium hydride (Metal Hydrides, Xnc.) or spectroscopic-grade carbon (National Carbon Corp.). Nickel-titanium alloys contained between 0.001 and 0.005 pct oxygen and the ferromagnetic metal-carbon alloys contained 0.001 pct. Cylindrical metal specimens (1 to 2.5 g) were machined and bevelled at the bottom to insure a uniform advancing contact angle on melting. Before use the samples were acid-etched, cleaned with acetone, and rinsed in petrol ether.

Jan 1, 1960

By Robert A. Rapp, Ronald L. Pastorek

Solid-state electrochemical measurements by three alternative experimental procedures were made with the cell FeO, Fe3O4 |Zro.85Cao.15O1.85 |Cu| Zr0.85CaO.15O1.85 | FeO, Fe304 to establish the solubility and diffusivity of oxygen in solid copper in the temperature range 800" to 1030°C. The solubility of oxygen in solid copper and the diflusivity of oxygen in solid copper Dgu = 1.7 X 10-2 exp(-16,000/RT) Cm2/sec were determined and confirmed in alternative experiments. The enthalpy of solution of oxygen in solid copper equals —10,000 cal per mole; the partial excess entropy of the oxygen atoms in the Cu-O dilute solution is approximately the same as that found for interstitial atoms in other metals. The diffusivity of oxygen in solid copper is consistent with that expected for an interstitial atom. RELIABLE values for the saturation solubility N(s) and diffusivity DO of oxygen in solid copper have not been unambiguously established in the literature. Following three early determinations by others,1"3 Rhines and Mathewson4 reported that the solubility of oxygen in solid copper increased from 0.007 at. pct 0 at 600°C to about 0.015 pct at 1050°C. Phillips and skinner,, using essentiially the same analytical procedure, reported that the solid solubility increases from 0.0018 at. pct 0 at 550°C to about 0.0075 pct at 1050OC. The only previous value for the diffusivity of oxygen in solid copper was reported by Ransley.6 Ransley deoxidized Cu-Cu2O alloys in an atmosphere of carbon monoxide gas to yield a solubility-diffusivity product. He used the solubility data of Rhines and Mathewson to calculate the diffusivity values. Another method for obtaining the solubility-diffusivity product (N(s) DO) is by measuring the widths of internal-oxidation zones in copper alloys as reported by Verfurth and Rapp.7 However, the calculated N(S)Do products depend upon the alloy content of the specimen, so that the internal oxidation of copper alloys does not follow ideal internal oxidation kinetics. As a result, unequivocal values for the N(s) DO product were not obtained by this procedure. A solid-state coulometric titration technique similar to that employed in this work was introduced by C. Wagner8 to study the dependence on silver activity of the Ag/S ratio in silver sulfide in the temperature range of 160" to 300°C. Similar experiments have been carried out by C. Wagner and co-workers9-11 to study the stoichiometry range of silver and copper tellurides, cuprous sulfide, and cuprous selenide. Numerous authors have carried out electrochemical measurements with a solid oxygen-ion-conducting electrolyte to determine the solubility and/or diffusivity of dissolved oxygen in several liquid metals.12-l6 Rickert and Steiner17,18 have used solid-state electrochemical measurements to determine the diffusivity of oxygen in solid silver from 760" to 900°C. Two different cell geometries were used. In the cell of linear geometry Fe, FeO | ZrO2 + (CaO) | Ag + [0 (dissolved)] [1] oxygen diffused from the interior of the silver electrode to the silver/electrolyte interface where the oxygen activity had been lowered from a fixed initial value to practically zero by the application of voltage to the cell. The diffusivity of oxygen in solid silver was determined from the solution of the diffusion equation and the time dependence of the cell current. However, this determination of the diffusion coefficient depended upon a knowledge of the solubility of oxygen in solid silver. A cylindrical geometry was used for the cell Pt, O2(Po2 = 0.21 atm) | ZrO2 + (CaO) | Ag + [0 (dissolved)] [II] which also allowed the diffusivity of oxygen in solid silver to be determined. These values were in agreement with other available data.l9 Recently, Raleigh20,21 used a method involving the measurement of diffusion-limited currents in a cell involving the AgBr solid electrolyte to determine the diffusion coefficient of silver in Ag-Au alloys at 400°C. Diffusivity values on the order of l0-14 sq cm per sec were measured in the alloy composition range 10 to 60 at. pct Ag in a single experiment. From numerous electrical conductivity and galvanic cell measurements,9'22"26 the solid solution Zr0.85 Ca0.15 O1.85 has been established as an electrolyte with predominant oxygen ion conduction over a wide range of intermediate and high oxygen activities. For interrelating the thermodynamics and the kinetics of the dissolution of oxygen in solid copper in this investigation, a galvanic cell was constructed with FeO-Fe3O4 as the reversible reference electrode, the Zr0.85Ca0.15 O1.85 electrolyte, and a pure copper specimen under-saturated in oxygen as the other electrode. THEORETICAL ANALYSIS Three variations of a high-temperature electrochemical technique were used in this study to provide two determinations each of the solubility and diffusivity

Jan 1, 1970