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By HAROLD A. KNIGHT

The Miami Copper Co., Arizona, is asking Congress to reimpose the import duty of two cents per pound on copper which, by law, has been suspended until June 30, 1950. C. Donald Dallas, chairman of Revere Copper and Brass, champion of a duty-free regime as regards the red metal, has been answering E. H. Westlake, Miami president, now that Mr. Westlake's statement to stock- holders has been salted away for posterity on wire recorders. Even prior to this action and at the instigation of two prominent consumers of pig lead, the House of Representatives has, in the confines of committee, not yet reported out, as of June 16, a bill to suspend the duty on lead for another year from expiration of the present law June 30, 1949. But apparently the bill was started too late. Thus the tariff issue becomes a Rip Van Winkle again after having slept for several years in the mountains of metals scarcity. During the wartime scarcity and the boom days that followed, most metal producers welcomed a considerable influx of foreign metal since it gave them a little surcease from constant teleibhone calls asking why that delivery of 300 tons of lead, 250 tons of zinc, and 1000 tons of copper had been delayed. These were the days when it was such an undisputed sellers' market that the sellers had even thrown away their certificates of ownership. Another development that brings home the tariff situation, small in it- self but perhaps indicating a trend, has been the announced closing of

Jan 1, 1949

By E. I. Alessandrini, A. U. Seybolt

Selective oxidation (preferential oxidation of a single alloy component) can be an important oxidation mode in the case of alloys such as Si-Fe, Al-Fe, and so on, when heat-treating in atmospheres of low oxygen potential. It was the purpose of this work to identify the oxide films formed on iron containing 31/4 pct Si at low oxygen potentials, and to make some observations on the H2O/H2 ratios required to form them. EXPERIMENTAL METHOD HYDROGEN of varying water content offers a very convenient method of establishing a wide range of oxidizing power, or oxygen potential. The method chosen to provide a desired H2O/H2 ratio was to nearly saturate hydrogen at room temperature by bubbling the gas through water at room temperature, and then to wring out the excess water by passing the wet gas through a long glass spiral immersed in a refrigerated liquid at a desired dew point. After oxidation, the samples were examined by electron diffraction in order to identify any film which might be present. PREPARATION AND TREATMENT OF SAMPLES The samples were prepared from a Si-Fe alloy made in the laboratory using electrolytic iron and 96 pct ferro-silico11, vacuum-induction melted, hot-rolled then cold-rolled to 0.015-in. thickness. After the cold-rolling the samples were annealed at 1000°C. Transmission Laue X-ray patterns showed very little evidence of preferred orientation, but it is likely that a weak texture could have escaped notice. The chemical analysis was as follows: 3.34 Si, 0.01 Al, 0.001 0, 0.006 C, 0.002 N. Before each sample was oxidized, it was polished through 4/0 emery paper, cleaned and dried using benzene, carbon tetrachloride, acetone, absolute alcohol, and ether. The method of oxidizing the samples was as follows: Samples about 1/2 by 1 by 0.015 in. were held in the upper, cool part of a vertical vacuum furnace until the desired temperature was established in the furnace, Fig. 1. The sample was then lowered into the uniform hot zone where it was heated quickly to the desired temperature, and subjected to hydrogen of controlled moisture content (dew point) as mentioned previously. Temperatures from 400" to 1000°C were used, and dew points from room temperature to —78°C were explored. In general, the runs lasted about 6 hr, but a few runs were of different duration, as will be indicated later. After the predetermined period of time had elapsed, the specimens were withdrawn by the hollow stainless steel-quartz holder to a cool zone at the top of the furnace. EXPERIMENTAL RESULTS The results are summarized in Table I. Most of the electron-diffraction patterns were obtained by glancing-angle reflection, but in a few cases it was possible to strip the oxide films from the surface by a total immersion in a 3 pct bromine-methanol solution. Some of the thinner stripped films yielded quite satisfactory transmission patterns. However, both diffraction techniques yielded the same results; the patterns while most frequently showing a (low) tridymite, also showed a (low) cristobalite in some cases. A few patterns showed evidence of both phases. Because of the known nonequilibrium behavior of silica, it is not surprising that both forms of silica could coexist on one sample. It was noted that at fairly low dew points such as —40°C, there was a tendency for diffuse diffraction rings, suggesting a very small crystallite size. Also some subsequent experiments to be reported later show that thin silica films can be amorphous.

Jan 1, 1959

By E. J. ENGEL

The New York talc deposits of commercial importance are in St. Lawrence and Lewis counties, in the northwest Adirondack Mountains (Fig 1). All of the deposits are of pre-Cambrian age and occur within highly deformed and recrystallized marble of the Grenville series. The deposits in St. Lawrence County, near Gouverneur, are the largest and most productive of their type known in the Western Hemisphere. In 1948 the seven mines which are in operation will produce about 130,000 tons of ground talc. All talc production in Lewis County is from one mine. There the annual production ranges from 15,000 to 30,000 tons. These so called talcs of New York State include earth materials of differ- ent chemical and mineral compositions. In general the mineral talc is sub- ordinate in amount to other minerals in both the Gouverneur and Natural Bridge deposits.

Jan 1, 1949

By John G. Hall

The unstable metal market during 1949, with resulting lower metal prices, has focused every mine operator's attention on the problem of reducing operating costs. Improvement in mining, methods, use of modern mechanical mining equipment, and increasing the efficiency of the labor force are the tools with which we will have to work. Careful planning is necessary to coordinate all phases so that no one phase is overdone. A mine may become over-mechanized if, for instance, capital charges against new equipment exceed the savings in labor costs, or where a large enough tonnage is not produced. The cooperation, of labor is essential to any mechanization program. There have been too many instances where mechanization and improvements have done nothing more than make up for a decrease in labor efficiency, thus bringing the production of labor back to its old standard. The operator has gained little and labor has gained only a "softer job." In any mechanization program there are gains to be had by both the operator and labor. By the efficient application of modern equipment and improved mining methods the operator should gain by decreased costs, and labor may profit by receiving a share of these decreased costs.

Jan 1, 1950

By F. M. Waring

produced when zinc is substituted for a certain amount of tin are decidedly unsatisfactory. The substitution of aluminum for tin is entirely impractical, and such castings are worthless. This does not, however, exhaust all the possibilities of substituting other metals for tin in the copper-tin-lead alloys, but it is my opinion that the substitution of any other metals, in those alloys, can be made only by sacrificing the quality of the alloy. The possibility of substituting alloys of an entirely different type presents an attractive field for research. The copper-tin-lead alloy has attained its position as the most desirable bronze bearing alloy, but this does not mean that some other alloy may not be found which may give equally good or better results. In the search for such a substitute alloy it should be borne in mind that a bearing metal should possess the following properties: (1) It should be sufficiently rigid to support the load or resist the impact, but yet not so brittle that it will easily crack. (2) It should have as great a yielding or plastic nature as is consistent with its ability to support the load or resist the impact without deformation of the bearing as a whole. (3) The ideal structure combines a hard matrix to support the load and a softer metal or alloy contained within such matrix, to permit the bearing surface to adjust itself to irregularities of service. (4) It should be easy to handle in the foundry and machine shop. (5) It should be capable of being remelted without deterioration. (6) For use in babbitt-lined bearings, it should be capable of being tinned, so that the babbitt can be applied thereto. (7) It should have good heat conductivity in order to dissipate the heat generated by friction. Pennsylvania Railroad Anti-friction and Bell Metals F. M. Waring," Altoona, Pa.—Thc necessity for conserving tin has recently been very forcibly brought to the attention of all consumers, and efforts are now being made to reduce the tin content in certain alloys or to substitute other alloys not containing tin. The approximate composition of the non-ferrous alloys in general use on the Pennsylvania Railroad are given in the accompanying table. Phosphor bronze is used principally for rod bushings, main-rod brasses, and crosshead shoes. Ex. B bronze is used to a small extent for backs of car and coach bearings, but the majority of these are now made of the car-journal bronze, which contains, on the average, about 5 per cent. tin.

Jan 1, 1919

By Daniel T. O’Brian

Mineral exploration activities are benefiting from new interpretive techniques which have become economically practical with computers. Government agencies, educational institutions, and industry have each contributed research and development efforts for improving the mathematical analysis and graphical display of exploration data, resulting in operational aids not foreseeable a decade ago. Progress has been worldwide and is expanding rapidly. Books 1-10 are supplementing the periodic literature, at least one abstracting service is now active, 11 and an association has recently been formed to encourage and publicize advances in this field. 12 With the diversity of applications, only partial coverage of the subject can be made at any single symposium. Four of the six papers in this section report on the current state-of-the-art in selected areas of interest: graphics, time-sharing, mathematics, and economic analysis. The remaining two papers are descriptions of advanced statistical techniques for gaining additional information during exploration, and illustrate methods which will become more commonly applied in the future. "Computer Graphics: A New Tool for Exploration and Mining" describes the use of a computer and accessory equipment as an information retrieval device, graphically merging and displaying pertinent information for visual inspection and interpretation. This is a rapid means of studying information which has been pre-stored in a form accessible to the computer. Time-sharing is a means of achieving a comparable rapid response when calculations are being performed. The paper, "Some Applications of Time-Sharing in Mining Geophysics," describes the experience of one company using a time-sharing facility for geophysical computations. Another paper on this subject, stressing mining applications, has recently been published. 13

Jan 1, 1969

By Martin Epner, Eric Gregory

DURING the past decade, considerable work has been carried out on various cermet systems in an effort to produce materials suitable for high-temperature applications in gas turbines. Most of the materials have not, as yet, met the requirements of the engine manufacturers, primarily because of their lack of room-temperature ductility and thermal shock resistance. In the field of tool materials, however, although ductility is still of prime importance, much has been accomplished by improving design parameters and the quality of carbide materials with a view to using cermet compositions successfully. The systems described in this paper were designed primarily for application in this field, although their development was a natural outcome of work on similar compositions designed for high-temperature service. In steel-bonded titanium carbide, the steel binder imparts heat treatability to the system while the carbide provides abrasion and wear resistance. Combining the carbide and the steel matrix in carefully controlled proportions results in a composite material which, when the steel is hardened, has man of the properties of cemented tungsten carbide. In the annealed condition, this material can be readily machined by the conventional chip-removal techniques. Titanium carbide has certain distinct advantages over many of the other carbides when combined with a steel matrix. It is among the hardest of the carbides and is one of the most stable. Liquid iron wets titanium carbide, and this wetting assists in the formation of a dense cermet. Once the composite structure has been formed, the titanium carbide acts as a relatively inert phase during the heat treatment of the matrix. PREPARATION OF ALLOYS The steel-bonded titanium-carbide materials described in this paper were prepared by the liquid-phase sintering technique. The titanium carbide used had an average particle size of 6 to 7 p, a total carbon content of 19.4 pct and 0.35 pct free carbon. This was blended with the elemental metal powders by ball milling them together in a hexane medium. After drying, paraffin wax was added to the blend to provide green strength in the pressed briquettes, and compacting was performed at 15 tsi. Liquid-phase sintering was carried out in vacuum at temperatures which depended on the chemical composition of the system involved, but which were usually around 2640° F. The resultant materials had a density approaching 100 pct of theoretical. The

Jan 1, 1961

By John C. Kleiber, George M. Meisel

From time to time since the initial installation of an experimental flotation section in 1940, Permanente Cement Co. has made efforts to beneficiate the low-grade limestone fraction which occurs in its deposits at Permanente, Calif. The encouraging results outlined in this article are the result of Permanente's latest effort. THE PERMANENTE LIMESTONE AND THE REASON FOR ITS BENEFICIATION The Permanente deposit is a sheet of Calera limestone over 700 ft thick lying within the Franciscan sediments of the San Francisco peninsula. Limestone suitable for cement manufacture underlies, overlies, and is interbedded with low-grade limestone and chert. Andesite intrusions are found as a secondary gangue. The limestone is identified as follows:

Jan 3, 1964

By R. A. Meussner, C. T. Fujii

Chromium solution in wustite depresses the oxygen activity in a nonideal manner and expands the lattice slightly. Gravimetric measurements of the equilibrium compositions of wustite containing 0.00 to 1.38 wt pct Cr define the oxygen potential (CO2-CO atm) and the limits of the phase field at 1000°C. These data extrapolate to a maximum solubility of 2 wt pct Cr. The lattice parameter data, room-temperature measurements of quenched samples, differ significantly from those in the literature. Both pure and chromium wus-tites contract at uniform and equal rates as the oxygen content (metal deficit) increases. The a. US metal deficit relationships are straight lines showing none of the curvature previously reported. At constant metal deficit, the a. expands by 0.002? on alloying with 0.4 to 0.5 wt pct Cr but is insensitive to further chromium additions: a small expansion rather than a marked contraction. These results require a modification of the accepted alloying mechanism. IN the high-temperature oxidation of Fe-Cr alloys in Ha-H,and CO2-CO atmospheres the vapor transfer of oxygen from the continuous wustite outer scale to the porous inner scale/alloy interface sustains the high oxidation rates.1"3 The driving force for this transport is the difference in the oxygen activity of the outer wustite and that at the inner scale/alloy interface. In pure CO2, as well as in CO2-CO atmospheres, carburization of the alloy accompanies this oxidation. Current efforts to evaluate the parameters controlling this carburization have shown that the process is not simple; i.e., the carbon concentration in the alloy initially increases rapidly, reaches a maximum, and then decreases slowly as the oxidation time is extended. This is the same pattern reported by McCoy for the more complex oxidation-carburization of stainless steels and an Fe-Cr alloy in CO2 at lower temperatures.4 These changes in the carburization process occur while the overall oxidation rate and the lattice parameters of the scale layers remain constant. If this invariance of the lattice parameter is assumed to indicate a constant scale composition and thus a constant oxygen potential, the carburization results are not easily explained. Electron microprobe traces across the thickness of these outer scales, however, have revealed distinct chromium gradients penetrating 10 to 50 µ from the inner surface where the chromium concentrations were estimated at a few tenths percent. The variation of the chromium cmcentration on the inner surface of the scale, and the resulting change of the oxygen activity, during the oxidation process is considered to be important in defining the carburization process. Thus, to gain an understanding of the complex oxidation-carburization proc- ess, it was necessary to measure the properties of wustite containing known amounts of chromium (chromium wustite). Although the general features of the Fe-Cr-0 equilibrium diagram between 900° and 1300°C have been fairly well established by Richards and white: Wood-house and White,6 Seybolt,7 and Katsura and Muan,8 there have been no detailed studies of the limits of the chromium wustite phase field or the properties of these alloyed wustites. The recent results of a limited study of chromium wustite by Levin and wagner9 indicate that more than 0.67 wt pct Cr is soluble in wustite above 850°C and that this alloying is accompanied by a substantial lattice contraction. This change in the lattice parameter was not evident in the X-ray diffraction patterns of wustite layers from the oxidation experiments;1,3 the lines were sharp even though a chromium gradient existed in the scale. The present paper describes gravimetric equilibrium experiments which delineate the boundaries of the chromium wustite single-phase field at 1000°C and define the changes in the oxygen activity and the lattice parameter of wustite as functions of chromium and oxygen contents. The lattice parameter data of chromium wustite obtained from these equilibrium and special quenching experiments differ considerably from those reported.9 Those for pure wustite show significant differences from the widely accepted data of Jette and Foote.10 Since the causes of these differences are not easily assignable, and since the literature contains many sets of data on wustite which if not in conflict are at best not in harmony, the experimental procedures are discussed in the present paper. EXPERIMENTAL Oxide Preparation. The specimens used in these studies were porous pellets compacted from high-purity (Fe,Cr)2O3 or Fe2O3 powders. These powders were prepared from electrolytic chromium (99.8 pct purity) and electrolytic iron purified by consumable-electrode, vacuum arc-melting processing (299.9 pct purity).11 The oxides were produced by standard analytical procedures: solution of the metals in acids (HC1, then HNO3 added), coprecipitation of the hydroxides (NHaOH), and filtering and washing these precipitates. Initial dehydration of the coprecipitated hydroxides was done in a porcelain evaporating dish heated by a Meker-type burner, final dehydration by firing in a recrystallized alumina crucible at 1000" to 1050°C for 20 hr in an electrically heated furnace. Spectrographic analysis detected the following impurities: silicon, 0.01 pct or less; aluminum, 0.001 pct to trace; manganese and copper, 0.0001 pct to none. Each of these levels is at least one order of magnitude lower than in commercially available CP grade ferric and chromic oxides. Fluorescence analy-

Jan 1, 1969

By Henry Fernald

THE accounting system or bookkeeping methods of any company are principally the concern of that company and of those who are in control of its affairs. Its published financial report is, however, primarily intended for those who are not already fully informed regarding its operations and finances. Whatever may be the advantages of standardization of accounting and bookkeeping methods, it must be admitted that a company has a certain right to handle its accounts and keep its books and records in whatever manner may seem to it best adapted to its affairs, even though such methods may differ materially from those generally adopted by others. In its financial reports it should not, however, either ask or expect that the statements it makes or the terms which it uses will be given in its case a meaning and interpretation different from that which they are ordinarily considered to have in similar reports and statements of other companies. The particular form and arrangement of such reports is a matter concerning which there may be much difference of opinion. It is of little importance whether current assets come first or last in the Balance Sheet, but it is important that there should not be included under this designation any items which are not properly current assets within the generally accepted meaning of that term. The extent to which stockholders or others interested are to be made acquainted with the full details of a company's business is a question which the proper authorities must in each case decide. It should, however, be recognized that there are certain facts regarding a mining com-pany which must be set forth in a financial statement if it is fully to cover the conditions and affairs of the company. For example, a financial, statement which does not include or is not accompanied by a statement, of the ore reserves of the company does not fully set forth its financial condition. This is true whether the absence of such a statement of ore reserves is because it is not desired to make public the figures or whether it is because the ore reserves themselves are not definitely known, or accurately measured.

Jan 1, 1928

E. A. H. Tays, San Blas, Sinaloa, Mex. (communication to the Secretary*):—The results obtained by Messrs. Hofman and Hayward in their experiments, proving that a low percentage of copper sulphate with a variable percentage of salt, depending on the ore, gives the best results, confirm practical mill-work which I did in 1895. I have none of my notes, taken at the time, to refer to, so have to rely solely on memory, which precludes the conciseness that is alway desirable. In 1894 I took charge of the plant of the San Rafael Company, near Chinipas, Chihuahua, Mex., which at that time was treating a very refractory ore carrying about $15 in gold and from 20 to 25 oz. of silver per ton, the bullion being about 300 fine in gold. The silver in the ore was in the form of a sulphide. Although carrying an average of 0.75 oz. of gold per ton, free gold could rarely be seen by panning, but upon roasting a sample of the ore the gold became visible at once—a result which was discovered by chance and used to advantage later. In order to utilize the old mill to the best advantage, it was decided to use pan-amalgamation after roasting. The roasting, done in a lime-kiln, was similar to the ordinary " burning " operation. The roasted ore was trammed to the mill-bins and crushed by 10 stamps to pass a 30-mesh screen. The pulp was de-watered and fed to four 1-ton pans. My recollection is that upon starting the mill-work, the charge contained 1.5 lb. of copper sulphate and 5 per cent. of salt per ton. From the start the extraction was unsatisfactory and the loss of quicksilver was very large. Experiments were then carried out on a working scale. First, the quantity of copper sulphate was increased 4 oz. at a time; then it was reduced

Jan 1, 1910

By F. S. Pettit

The oxidation of Ni-3 to 25 wt pd Al alloys has been studied in 0. 1 atm of oxygen at temperatures between 900° and 1300°C. These alloys have been found to oxidize by three different mechanisms which depend on the temperature of- oxidation and the alloy composition. Two of the three mechanisms do not permit a continuous layer of Al,0, to be formed on the alloy surface and the oxidation rates are greater than that for pure nickel. The third mechanism results in the formation of an external A1203 scale and lke oxidation rates are about three orders of magnitude smaller than those for pure nickel. The minimum amount of aluminum required for the formation of external scales of A L,0, has been determined. NICKEL-base alloys are currently the main source of materials for use at elevated temperatures in gas turbine engines. These alloys are usually coated to obtain oxidation resistance. Coatings on nickel-base alloys are frequently formed by reaction of the alloy with aluminum whereby alloyed nickel aluminides are formed. The alloyed nickel aluminides provide protection to the nickel base alloy because external scales of A1203 (alumina) are formed during oxidation and mass transport through A120, is slow in comparison to mass transport through most other oxides. In view of the protective properties of A1203, it is important to know how much aluminum is required in these alloys in order to form external scales of AlzO,. The present paper is concerned with the oxidation kinetics and the oxidation mechanisms of Ni-A1 alloys and the minimum amount of aluminum required in these alloys for the formation of external scales of Alz03. THEORETICAL CONSIDERATIONS When a Ni-A1 alloy is heated in oxygen at elevated temperatures, the following reactions can take place on the surface of the alloy where the oxide phases are assumed to be virtually pure: These oxide phases are in the form of nuclei scattered over the surface of the alloy and, in view of their rapid formation, they need not be in equilibrium with the alloy. As the oxidation process continues, equilibrium between the alloy surface and the oxide phases is approached and the stability of the oxide nuclei is determined by the composition of the alloy at the alloy/oxide interface because of the following reactions: 3NiA1204 + 2A1 (alloy) = 4AlzO3 + 3Ni (alloy) [41 4Ni0 + 2Al (alloy) = NiA120, + 3Ni (alloy) [ 5 1 Application of the mass-action law to Eqs. [4J and [5J yields the following equilibrium conditions for these reactions: where aA1 and aNi are the activities of aluminum and nickel, are the standard free energies of formation of NiO, A1203, and NA1204, respectively, R is the gas constant, and T is the absolute temperature. If the composition of the alloy at the alloy/oxide interface is such that (akl/ahi) is greater than the equilibrium values defined by Eqs. [6] and [7], then Reactions (41 and [5] will go to the right as written. Conversely, if the alloy composition is such that the activity ratio (aLl,/aki) at the alloy/oxide interface is less than the equilibrium values, then Reactions [4] and [5] will proceed to the left. The equilibrium activity ratios in Eqs. [6] and 171 can be calculated since values for the standard free energies of formation of the oxide phases are available. Standard free energies of formation for NiO and A1203 have been tabulated by Elliott and ~leiser.' The standard free energy of formation for NiA1204 can be obtained from the data of Tretjakow and Schmalzried.' The results of these calculations are tabulated in Table I. Table I shows that the following inequality is valid over the temperature interval 900" to 1300°C: (Reaction [5]) (Reaction [4]) « 1and therefore the aluminum activity for these compositions can be taken as equal to the square root of the activity ratios (i.e., aNi = 1). If equilibrium is estab-

Jan 1, 1968

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members.) The following members have registered recently at the Headquarters of the Institute Seeley W. Mudd, Los Angeles, Cal. Charles Janin, San Francisco, Cal. Edgar Rickard, London, England. Donnel F. Hewett, Washington, D. C. L. Maurice Cockerell, Chihuahua, Mexico.

Jan 4, 1913

By Haydn H. Murray, Sam H. Patterson

The term "clay" is somewhat ambiguous un¬less specifically defined, because it is used in three ways: (1) as a diverse group of fine-¬grained minerals, (2) as a rock term, and (3) as a particle-size term. Actually, most persons using the term "clay" realize that it has several meanings, and in most instances they define it. As a rock term, clay is difficult to define be¬cause of the wide variety of materials that com¬pose it; therefore, the definition must be gen¬eral. Clay is a natural earthy, fine-grained ma¬terial composed largely of a group of crystalline minerals known as the clay minerals. These minerals are hydrous silicates composed mainly of silica, alumina, and water. Several of these minerals also contain appreciable quantities of iron, alkalies, and alkaline earths. Many defini¬tions state that a clay is plastic when wet. Most clay materials do have this property, but some clays are not plastic; for example, halloysite and flint clay. As a particle-size term, clay is used for the category that includes the smallest particles. The maximum-size particles in the clay-size grade are defined differently on various grade scales, Soil investigators and mineralogists gen¬erally use 2 micrometers as the maximum size, whereas the widely used scale by Wentworth (1922) defines clay as material finer than ap¬proximately 4 micrometers. Some authorities find it convenient to use the term "clay" for any fine-grained, natural, earthy, argillaceous material (Grim, 1968). When used this way, the term includes clay, shale, or ar¬gillite, and some argillaceous soils. Even though no standard definition of the term clay is accepted by geologists, agronomists, engineers, and others, the term is generally un¬derstood by those who use it. Clay is an abun¬dant natural raw material, and it has an amaz¬ing variety of uses and properties which will be discussed in this chapter. Clays rank among the leading industrial min¬erals in both tonnages produced and total value. Their importance is indicated in Table 1, which lists the 1970, 1971, and 1972 production and values according to the U.S. Bureau of Mines (Ampian, 1972). Adequate reliable statistical data on which to summarize world production of clay are un¬available; this paragraph outlines the world re¬quirements for clay only in a very general way. According to one estimate, the world bentonite production in 1972 was 3.5 million tons (Anon., 1973a), but in the authors' opinion it was prob¬ably at least 5 million tons. The total fuller's earth produced was at least 1.5 million tons and may have been as much as 2 million tons. The total world kaolin production in 1972 was more than 10 million tons. Approximately 7 million tons of this total was produced in only two regions-the Georgia-South Carolina kaolin belt in the United States and the Cornwall re¬gion, United Kingdom. The world's 1972 out¬put of ball clay, which is also produced pri¬marily in the United States and the United Kingdom, was approximately 1.5 million tons or perhaps a little more. The total world fire clay production in 1972 was probably about one and one-half to two times and the miscellaneous clay production three times the United States production. As industrial minerals, clays are a complex group that consists of several mineral commodi¬ties, each having somewhat different mineral¬ogy, geologic occurrence, technology, and uses. In this chapter these commodities are organized

Jan 1, 1975

By C. E. Lundin

The Ce-H system was investigated in the temperature range, 573° to 1023°K, and the pressure range, 10-3 to 630 Torr, as a function of 'composition up to 72 at. pct H. Families of isothermal arid isopleth curves were plotted from the pressure-terr~perature-composition relationships. From these curves the solubility relationships were determined for the system. The isopleths are analytically represented by equilibrium dissociation pressure equations. The relative partial molal enthalpzes and entropies of solution of hydvogen in the systerrz were calculated fronz the dissociation pressure equulions and are tabulated. The integral free energies, enthalpies, and entropies of mixing in the Ce-H system were determined from the relative partial quantities and are also tabulated. The standard free energy, enthelpy, and entvopy of reaction of the dihydride phase at kcal per kcal per mole H2, and ?S° = -34. 1 cal per deg mole H2, respectively. The equilibrium dissociation pressure equation in the two-phase region is: UNTIL recently very little was known of the detailed solubility and thermodynamic relationships of the Ce-H system. Two previous investigations1,2 are noteworthy. However, significant discrepancies and omissions exist on analyzing them. The work of Mulford and Holley1 on cerium did not clearly delineate the boundaries of the two-phase region, Cess - CeH2-x. The plateau partial pressures were not thoroughly defined and were considerably displaced in pressure compared to those from the work of Warf and Korst.2 These latter authors concentrated their studies primarily from 823° to 1023°K in the pressure range of 1 to 760 Torr. No data were determined to outline the regions of primary solid solubility and the hydride phase. Also the establishment of the plateau partial pressures was rather limited in scope. In neither work was a treatment conducted of the relative partial molal enthalpies and entropies of solution of hydrogen in the single-phase regions and the integral thermodynamic quantities of mixing throughout the system. Therefore, it was the objective of this research to determine the complete equilibrium solubility relationships and thermodynamic data for the system by pressure-temperature-composition studies. EXPERIMENTAL PROCEDURE The cerium metal for this study was donated by the Reno Metallurgy Research Center of the Bureau of Mines. Total impurity content was 0.13 pct with only 60 ppm O. The metal was checked metallographically and contained only minor amounts of second phase compared to cerium from other sources. Specimen preparation was done in a dry box flushed with argon gas. The surface of a small rectangular piece of cerium (about 0.2 g) was filed with a clean, mill file. Final weighing was done in a tared enclosed vial containing argon gas. The specimen was then loaded quickly into the reaction chamber which was purged several times with high-purity hydrogen gas and then allowed to pump to about 10-6 Torr. The furnace was heated to the reaction temperature and the run started. The equipment used to conduct the hydriding was a Sievert's-type apparatus. Basically it consisted of a source for pure hydrogen, a precision gas-measuring burette, a heated reaction chamber, a McLeod gage, and a mercury manometer. Pure hydrogen was supplied by the thermal decomposition of uranium hydride. The 100-ml precision gas burette was graduated to 0.1-ml divisions and was used to measure the quantity of gas and admit it to the chamber. The reaction chamber was a quartz tube. Prior to each run, the cerium specimen was wrapped in a tungsten foil capsule to prevent reaction of the cerium with the quartz. Control of the temperature was achieved within ±1°K. Pressures in the manometer range were measured to ±0.5 Torr and in the McLeod range (10-3 to 5 Torr) to ±3 pct. The compositions of hydrogen in cerium were calculated in terms of hydrogen to cerium atomic ratio. These compositions were estimated to be ±0.01 H/Ce ratio. The technique used to study the equilibrium pressure-temperature-composition relationships of the Ce-H system was to develop experimentally a family of isothermal curves of composition vs pressure. The range of pressure through which each isotherm was developed was from 10-9 to about 630 Torr in the temperature interval, 573° to 1023°K. RESULTS AND DISCUSSION The hydriding characteristics of cerium are iso-morphous with those of the elements of the light-rare-earth group (lanthanum, cerium, praseodymium, and neodymium) wherein the region from the dihydride to trihydride is continuously single phase.' The structure of this phase is fcc.3 The heavy rare earths form a trihydride,2 which is hcp, separated by a two-phase region from the fcc dihydride phase. The Ce-H system is represented by the family of experimental isotherms in Fig. 1. Due to the small scale required to draw the curves, the experimental points are omitted; however, a total of 240 experimental data points were taken to prepare these curves. The solubility relationships can be deduced therefrom. Three distinct regions of partial pressure and composition can be seen. The region of cerium solid solution is represented by the rapidly rising isotherms in the dilute composition range. In accordance with Gibbs Phase Rule only one solid phase, the cerium solid so-

Jan 1, 1967

By Irving Cadoff, Kurt Komarek, Edward Miller

Barium can be purified by equilibration with titanium. The melting point of barium was found to be 726.2° i 0.5 °C. The room-temperature lattice parameters of BaTe and Bask are 7.004 * 0.002A and 6.600 * 0.002A. Melting points for BaTe and Base were found to be 1510° * 30°C and 1830° ± 50°C, respectively. HIGH-purity barium and its compounds are difficult to prepare because of the reactivity of barium with the atmosphere and the large heats of formation of the compounds. Purification of barium by vacuum distillation,' and the preparation and properties of barium oxide2 and barium sulfide3 have been reported. However, little has been done on the homologous compounds barium selenide and telluride. PURIFICATION OF BARIUM Distilled barium obtained from King Laboratories was used as the starting material. The analysis supplied with the metal showed the presence of: 0.4 wt pct Sr, 0.001 pct Mg, 0.02 pct F, 0.003 pct Cu, 0.005 pct Na and less than 5 x 10-3 wt pct of any other metallic impurity. Analyses for oxygen and nitrogen were not available. Since there is evidence4 that any barium nitride present in the starting material may decompose on distillation producing nitrogen which can contaminate the distillate, further purification was performed. At elevated temperatures, any nitrogen and oxygen present in barium should be removed by reaction with titanium. Assuming that the solubility of oxygen in liquid barium is negligible near the melting point of barium, any oxygen present will be in the form of BaO. Removal of oxygen from molten barium is expressed by the equation: BaO(S)+ TixOy(S) = Ba(l)+ TixO(y+1)(s) where Ti,Oy and TixO(y+1) are solid solutions of oxygen in titanium. At 1000°C, the change in free energy for this reaction is negative for (y+1)/x +y+1) x (100) 17.5 at. pct O.5 Since reaction with commercially pure titanium (containing 0.07 wt pct oxygen) results in a free energy change for the reaction of -19 kcal per g-atom, slight solubility of oxygen in barium would not hinder the oxygen removal. Since comparable thermodynamic data are not available to permit calculation of the partition of nitrogen between liquid barium and titanium, a similar quantitative relationship cannot be obtained. However, on the basis of work by Kubaschewski and Dench,5 complete removal of nitrogen from liquid barium can be expected. Since the melting point of barium is depressed markedly by small additions of nitrogen,' the change in melting point during reaction of barium with titanium was used to follow the purification reaction. MELTING POINT OF BARIUM A 50-g sample of barium was sealed by arc welding under argon into an all titanium crucible provided with a thermocouple well. The melting point of the sample was determined by thermal analysis, using a Pt/Pt-10 pct Rh thermocouple which was calibrated according to National Bureau of Standards specification6. The crucible was then heated for 48 hr at 950°C in vacuum and the melting point redetermined. This procedure was repeated until three successive thermal analyses agreed within ±0.5oC, the limits of error of the analysis. The melting point increased from an initial value of 720.0°C to a final value of 726.2°C. Analysis on samples quenched from 950°C gave a solubility value of 0.004 wt. pct Ti. Assuming that the titanium-barium phase diagram is similar to those of titanium-magnesium7 and titanium-calcium,8 the solubility of titanium in liquid barium decreases with decreasing temperature. Therefore, the solubility of titanium in liquid barium should be less than 0.004 wt. pctat the melting point (726oC), and the effect of dissolved titanium on the melting point would be negligible. Addition of up to 3 wt pct Sr does not significantly change the melting point of barium,7 so that the effect of the 0.4 wt pct Sr in the starting material will also be negligible. The value of 726.2" ± 0.5C obtained for the melting point of barium can be compared .with a determination carried out by Keller and coworkers in low-carbon steel crucibles,' who obtained a value of 725± 1C, using barium purified by fractional distillation. The higher value obtained in the present investigation is indicative of the effectiveness of titanium in removing traces of nitrogen. PREPARATION OF BaTe AND Base The compounds were prepared by direct reaction

Jan 1, 1961

By Behram H. Wadia, Robert S. Lehto

A new metallurgical treatment for capturing as much of the values as possible from zinc refinery feed has been devised by personnel in Cerro de Pasco's Peruvian operation at La Oroya. Results from a pilot test illustrate that 50 metric tons of throughput can be maintained whereby substantially all the silver and copper report in the sponge iron while zinc and lead with indium and cadmium volatilize in the fume. This new technique named the Zileret (zinc leach residue treatment) process complements the electrolytic system used in the refinery so that all values in a zinc concentrate are economically recovered. In the system, dried zinc leach residue is pelletized with soluble zinc sulfate which already exists in the leach residue and a finely divided reducing agent such as anthracite coal. Upon heat addition, the loose anthracite in the charge maintains a reducing atmosphere while the free space above the charge has an oxidizing nature. When the charge reaches the reaction zone at about 1100°C, metals such as zinc, lead, cadmium and indium volatilize from the pellets, are oxidized in the upper kiln atmosphere, and are then carried in suspension as an oxide fume to the cooler and baghouse. The copper and silver content in their reduced forms, along with the iron, discharge from the kiln as a calcined product which is then cooled to below 130°C before being exposed to the air.

Jan 9, 1969

By R. G. Davies, P. Beardmore, T. L. Johnston

The flow stress of a series of Ni-Cr-A1 alloys consisting of a dispersion of y' (based on Ni3Al) in a rnatrix of nickel-base solid solution y has been measured at temperatures up to 950°C as a fwzction of the volume fraction of y'. At high temperatures the flow stress is controlled by the amount of Y' in the alloy, i.e., the higher the volume fraction of y', the greater is the flow stress. This simple relationship is not obeyed at low temperatures in so far as a peak in the flow stress-volume fraction relation occurs at about 25 pct y'. The variation in the mechanical properlies of these alloys as a function of both temperature and volume fraction of y' has been correlated with changes in distribution of both the dislocations and y'. The results are interpreted on the basis that at low temperatures the y matrix is strengthened significantly bv the presence of a hyperfine y' precipitate due to decomposition on cooling; at high temperatures the y matrix is a single phase of low strength. It is clearly recognized that the high temperature strength of most nickel-base superalloys depends upon a dispersion of the ordered fcc phase y', based on Ni3A1, in a fcc solid solution matrix y based on nickel. Although the volume fraction of y' varies widely from about 0.2 in Nimonic 80A to about 0.6 in Mar-M200, all such nickel-base alloys manifest an unusual insensi-tivity of the flow stress with respect to temperature. In Mar-M200 for example, the 0.2 pct flow stress remains essentially constant from room temperature to 750°C. The conclusion has been drawn1 that the characteristically low temperature dependence of the flow stress of y-y' nickel-base alloys is obtained when the state of dispersion of y' is such that dislocations are forced to cut through the y' particles at the onset of yielding. When the spacing between the y' particles is so large that the flow stress is controlled by dislocation bowing between particles, then the initial flow stress decreases progressively with an increase in temperature at a rate determined by changes in elastic properties. The same conclusion is inherent in the detailed, mechanistic model of the deformation process in commercial superalloys which has been developed by Copley and ear' in which the temperature independent flow stress is attributed primarily to the contribution of the antiphase boundary energy created in the y' particles during deformation. In this theory the temperature insensitivity of the flow stress is a reflection of the constant antiphase boundary energy as a function of temperature. An important microstructural parameter that is relevant to the explanations that have been suggested' to account for the temperature insensitivity of the flow stress is the volume fraction of y'. To vary the latter to any significant extent in a given commercial alloy is clearly difficult. However, it is possible in a relatively simple Ni-Al-Cr ternary system which manifests analogous microstructures in terms of the distribution of y' in y and contains specific alloys which have flow properties that depend on temperature in a manner quite similar to their more complex commercial counterparts. Hornbogen et . have studied precipitation phenomena and deformation mechanisms in such alloys but only where the y' volume fraction was small (less than 0.2) and the y' particle size varied from less than 100A up to a maximum of -1000A. In the present study, a series of alloys was prepared in which the volume percent of y' at 900°C was varied from 0 to 100 pct with the y' particle size (of the order 0.5 p) comparable to the sizes obtained in commercial superalloys. Particular attention has been given to the relationship between variations in the volume fraction and distribution of y' and the temperature dependence of the flow stress EXPERIMENTAL TECHNIQUES The Ni-Cr-Al system was selected because it is well characterized, bears a close relationship to commercial alloys, and offers the advantage of an extra degree of freedom over a binary system. In the present investigation, a series of alloys across the tie line between NisA1 and Ni3Cr (Ni3Cr is not an in-termetallic compound, the nomenclature is only used to designate the composition) were vacuum cast. The pseudobinary6 and the composition of the alloys used are shown in Fig. 1. It is important to note that the compositions of the y phase and the y' phase in the two-phase alloys was always the same. Alloy compositions were selected from the binary diagram, Fig. 1, in order that aging at 900°C would produce from 0 (100 pct y) to 100 pct y' by volume percent. (The size of the y' particles produced during the equilibrium aging treatment increased as the volume fraction of y' increased, ranging from about 0.2 p at low volume fractions up to about 0.8 p at the highest volume fraction.) The y' phase is based on the inter-metallic compound Ni,A1 which has the fcc LIZ type superlattice structure, and chromium substitutes for aluminum in the structure. The y phase is a disordered fcc solid solution. The alloys were heat treated at 1150°C for 2 hr, air cooled to room temperature, and finally annealed for 16 hr at 900°C. The rods were then centerless ground to 0.25 in. diam and cut into compression samples 0.5 in. long. The compression tests were made on an In-stron machine at a strain rate of 7 x 10"4 sec-'. A rapid heating radiant heat furnace was used which minimized the heating and temperature stabilization time to 10 min for the highest testing temperature. All the tests were stopped after 5 pct plastic strain.

Jan 1, 1970

By Grafton M. Thrasher

For the proper discussion of this subject it is necessary to incorporate in this paper the substance of part of an article published by me in Metallurgical and Chemical Engineering for January, 1915. Several years ago, while I was chief chemist for a malleable-iron company, it occurred to me that the mere regulation of silicon was not sufficient to produce the desired degree of chill. But only after repeatedly encountering this fact in both open-hearth and air-furnace, as well as cupola metal, was I led to regard variation in the total carbon as the principal cause of disturbance; and I resolved to determine the total carbon as well as the silicon in every heat, and by a carefully prepared test piece to gauge the approximate degree of chill. The test piece selected was a round plug, 2 in. in diameter and 12 in. long, cast on end

Jan 1, 1916

By Norman Weiss, H. W. Kaanta

CUSTOM ores reach across the New Mexican mesa to American Smelting & Refining Co.'s new lead-zinc mill at Deming. The influx of ores justified increasing mill capacity from 12,000 tons per month to 20,000 tons per month with the installation of a second milling section. Deming mill has met a complex material handling problem with the successful instrumentation of modern machinery and knowledge. A tight, compact plant does a big job with the aid of the latest ore moving equipment. Location and Layout The mill is located three miles northwest of Deming in the tumbleweed covered valley of the Mimbres River, 30 miles north of the Mexican border. Deming has a population of 4000 and is about halfway between Lordsburg and Las Cruces and 54 miles southeast of Silver City. The AT&SF and the SP railroads and U.S. Highways 70, 80, and 260, cut across the mesa to the town. Asarco mill station is east of the AT&SF single track, and north of Deming. The nearly level terrain is covered with fine sand supporting only yucca and tumbleweed. Compacted gravel at depth affords excellent foundation bearing. The climate is semi-arid, but the district is underlain by water-bearing strata. Tailing disposal space is plentiful. The Deming site appeared favorable because of easy rail and highway access, central location in a mining district, excellent climate, plentiful water supply, space for all present and future requirements, and proximity to a town. The milling plant is a 250-ft square. The rail spur forms the west side; sampling plant, fine-ore conveyor and bins are on the east; track hopper, primary conveyor, and crushing plant lie on the south; and the mill building completes the north side of the square. Construction The mill site was chosen and the land purchased in 1,946 and 1947. Design began in 1948, and Stearns-Roger Mfg. Co. of Denver started construction in June 1949 completing work in April 1950. Construction is steel and concrete throughout, with main concrete floors supported on cellular steel beams. The building is covered by galvanized corrugated iron, attached to the frame by welded Nelson studs, and made dust tight at the joints with roofing paper and asphalt sealing compound. Crushing and Sampling Custom ores, delivered to the mill by railroad cars or trucks, are weighed on arrival. A Robbins car shaker dumps the ore into a 100-ton capacity steel hopper. Adjacent is a 40-ton truck hopper. Three 36-in. Pioneer apron feeders supply ore from the receiving hoppers to a 36-in. conveyor which runs to the crushing plant. A tramp-iron detector protects the primary crusher except when handling magnetite containing ores. A 2 ½ -in. spaced grizzly precedes the primary Traylor 24x36 in. jaw crusher set at 4 in. A Symons 4-ft cone crusher in closed circuit with 48x78 in. Robbins Gyrex screen completes crushing to 5/8 in. The discharges of both crushers drop upon a common conveyor, which, after gaining sufficient elevation, transfers ore to a return conveyor. This return conveyor passes under a suspended magnet and over a magnetic head pulley to the Gyrex screen. Screen undersize is conveyed by a 20-in. belt to the sampling plant. Crushing rate varies from 60 to 90 tons per hour. Ores containing magnetite and pyrrhotite nullify the magnetic detector and overload the magnets

Jan 1, 1952