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By Shiou-Chuan Sun

THE fact that coals of different ranks and even of the same rank differ greatly in their amenability to froth flotation is well known. In recognition of the need for an explanation of this phenomenon, two hypotheses have been suggested. Wilkins1 reported that the floatability of coals increased with an increase of the carbon content or rank. This postulate is handicapped by the fact that bituminous coals that possess moderate carbon contents are actually more floatable than anthracite coals that have high carbon contents, as shown in columns 6 and 9 of Table I. Taggart and his associates' implied that the difference of floatability between bituminous and anthracite coal was caused by the variation of carbon-hydrogen ratio. This is not applicable to the relative floatability of other coals and carbons. For example, column 11 of Table I shows that the carbon-hydrogen ratios of low-floating lignitic coal and non-floating animal charcoal are not only smaller than the moderate-floating anthracite coal, but are also similar to the high-floating bituminous coal. Furthermore, according to this hypothesis, high temperature coke-A (464), Ceylon graphite (1238), and lamp-black (357), all possessing extremely high carbon-hydrogen ratios, should be less floatable than other substances having much lower carbon- hydrogen ratios such as high volatile-B bituminous coal (11.9 to 22), anthracite coal (35.7 to 60.5), lignitic coal (15.6 to 33.6), and charcoal (13 to 26.2). However the former group is actually more floatable than the latter group.

Jan 1, 1954

By Alec M. Crowell, C. H. Thigpen

Continuing the increase in production of crude oil and condensate started in 1937, the oil fields of South Arkansas reached a 13-year peak with 26,570,704 bbl. for the year 1942. The stability of the production branch of the industry in the area is demonstrated by Fig. I, which reflects the fact that although the number of producing wells in the state has declined from 3280 in 1931 to 2957 at the end of 1942, total production has continuously increased since the beginning of 1937. This is because all fields discovered since Jan. I, 1937, have observed spacing patterns up to one well to each 160 surface acres, the dual completion of wells where there is more than one producing horizon Eight new pools were brought into production in South Arkansas during 1942 (Fig. 2) They increased the state's crude oil and condensate reserve by 121,000,000 bbl., bringing the total recoverable reserve figure to 450,000,000 bbl. (Table 3) as of Jan. I, 1943. Abandonment of wells in the stripper areas of the state increased by 32 per cent over the preceding year, there having been 142 wells permanently abandoned in 1942. For economic reasons 279 wells were temporarily shut down as of Dec. 31, 1942. A price increase may start these wells to pumping again and also be the incentive toward the commencing of several secondary recovery projects in the fields discovered between 1922 and 1937. There were 149 wells brought into production in 1942 as against 119 for the

Jan 1, 1943

By C. H. Thigpen, Alec M. Crowell

Continuing the increase in production of crude oil and condensate started in 1937, the oil fields of South Arkansas reached a 13-year peak with 26,570,704 bbl. for the year 1942. The stability of the production branch of the industry in the area is demonstrated by Fig. I, which reflects the fact that although the number of producing wells in the state has declined from 3280 in 1931 to 2957 at the end of 1942, total production has continuously increased since the beginning of 1937. This is because all fields discovered since Jan. I, 1937, have observed spacing patterns up to one well to each 160 surface acres, the dual completion of wells where there is more than one producing horizon Eight new pools were brought into production in South Arkansas during 1942 (Fig. 2) They increased the state's crude oil and condensate reserve by 121,000,000 bbl., bringing the total recoverable reserve figure to 450,000,000 bbl. (Table 3) as of Jan. I, 1943. Abandonment of wells in the stripper areas of the state increased by 32 per cent over the preceding year, there having been 142 wells permanently abandoned in 1942. For economic reasons 279 wells were temporarily shut down as of Dec. 31, 1942. A price increase may start these wells to pumping again and also be the incentive toward the commencing of several secondary recovery projects in the fields discovered between 1922 and 1937. There were 149 wells brought into production in 1942 as against 119 for the

Jan 1, 1943

By Charles A. Kliche

INTRODUCTION The Northern Great Plains Coal Province which occupies approximately 36.6 ha contains about one-half of the nation's total coal resources. About one million ha are underlain by coal that is considered to be mineable from the surface. The topography of the province is predominately plains, rolling hills, and some badland areas characterized by breaks or sharply eroded hills. Elevations range from about 1500 m above sea level on the west to about 600 m above sea level on the eastern boundary. The average slope of the ground is approximately 2 m per km. Streams in the province drain generally easterly and southeasterly (1). In the United States, the Northern Great Plains Province lies within the states of North Dakota, South Dakota, Montana, Wyoming, Nebraska, and Colorado. The coal within the province is located almost entirely in the states of North Dakota, Montana, and Wyoming. Although it is relatively low rank, the coal within the province encompasses a large portion of the total remaining U. S. reserves. The U. S. Geological Survey estimates the total remaining coal resources of the United States to be 2.6 trillion mt within 1000 m of the surface, and 2.9 trillion tons within 1830 m of the surface. Of this total, only about 177 billion mt are classified as reserves meaning that they are (1) known in location, quantity and quality from geologic evidence supported by engineering measurements, and (2) economically recoverable based on currently available technologies and current market value (2).

Jan 1, 1983

By C. C. Furnas

IT is well known that particles of different sizes are not distributed evenly throughout the average charge in an iron blast furnace. Just how great the disparity in particle size in different parts of a single plane in a furnace may be is indicated by the results of some recent investigations1 conducted by the Bureau of Mines on a furnace operating on Lake ores. The wide variations found in gas velocity, gas composition, and temperature from the periphery to the center of the upper charge column were caused by the great variation in particle size of the raw materials used and were also greatly influenced by the methods of charging. This paper summarizes the results of an investigation of the influence of different methods of charging and of the treatment of raw materials upon the size distribution of the solid particles in the blast furnace. A more complete report will appear later as a Bureau of Mines technical paper.

Jan 1, 1929

By AIME AIME

The Bulletin. The Bulletin of the Institute will be issued hereafter monthly instead of bi-monthly as heretofore. Among other reasons for this change, it is desired to effect thereby the earlier transmission to members of important papers, lists of candidates tin? membership, and other items of timely information. The New Haven Meeting. As already announced in special circular, the XCVIth meeting of the institute for the reading and discussion of papers will be held at New Haven, Conn., beginning Feb. 23, 1909. The Secretary of the Local Committee is Prof. J. D. Irving, Box D, Yale Station, New Haven. The program embraces visits to many interesting works in New Haven, Ansonia, Bridgeport, etc. The leading topics for discussion at the sessions will lie: The Conservation of Natural Resources; A Sea-Level Canal at Panama; and The Technical Education of Mining Engineers. But papers on other subjects also are announced. Lt is probable that a supplementary session of this meeting, will be held in New York City, at some time during March, 1909, as a joint session with other national engineering societies, for the farther discussion of the subject of The Conservation of Natural Resources. A Pacific Coast Meeting. It is now reasonably certain that the XCVIIth meeting will be held oil the Pacific Coast, including a. visit to the Exposition at Seattle, and various other points en. route going or coming, depending upon the route and program finally adopted. (lore definite information will be announced at the New Haven Meeting, or at the earliest possible date thereafter.

Jan 1, 1909

NEARLY one hundred members of the Mining and Metallurgical Society of America and friends of Professor Peele met at dinner at the Aldine Club, New York, on the evening of April 26, to take part in the ceremonies attending the presentation of the Society's annual gold medal. This had been awarded to Professor Peele by the Society in recognition of his laborious and painstaking work as Editor-in-chief of the monu-mental "Mining Engi-neers' Handbook. Carl A. Meissner acted as toastmaster. W. Y. Westervelt, a student and lifelong asso-ciate of Professor Peele, then recounted some of his friend's early exploits, be-ginning with his mining adventures in the paternal cellar, whereby the neces-sity for adequate ventilation was indelibly impressed on his mind. Graduating from the Columbia School of Mines in 1883, Robert Peele for several years followed the typical mining career, as assayer and superinten-dentatan outlying Colorado mine; mill foreman and assistant superintendent of the Silver King, in Ari-zona; in charge of a mine at Fairplay, Colo.; and superintendent for the Ore-gon Gold Mines Co., at Cornucopia. At intervals during this experience, he spent parts of four years on two mineral investigations m in Peru, Bolivia, Colombia, and Dutch Guiana. He i was called to Columbia as Adjunct Professor of Mining in 1892, and became Professor in 1904. During his sabattical leave in 1903 he travelled around the world, r stopping at some of the most important mining cen-ters, and in 1910 he renewed his acquaintance with South Africa and South America.

Jan 6, 1923

CORPORAL SHEPPARD B. GORDY Sheppard B. Gordy, a brief biography of whom was printed inn the January Bulletin, entered the employ of the Braden Copper Co. immediately on his graduation from the Sheffield Scientific School in 1912. He remained with this company four years, working up through the various grades to assistant foreman and foreman to one of the individual mines. The last year he was in its employ, he acted as general mine foreman. He was for a short time with the Chile Exploration Co. and then went with the Andes Exploration Co. (Anaconda) and remained with CORPORAL SHEPPARD B. GORDY. the latter, doing mine exploration and development work, until he sailed for home in June, 1918, to give a more personal and active service to his country in her need. He declined a tender of induction into an officers' training camp, at the urgent request of Professor McClelland supplemented by Mr. Potter, because they demonstrated to his satisfaction that he could give more valuable service to his country in helping out with the aircraft production. Being within the draft age, in order to carry out this plan, it was necessary for him to be called by his Local Board and sent to camp. This call came Aug. 26. Two weeks before that time lie had gone to Dayton, Ohio; to begin the study of aircraft production, and was sent by the Dayton Board to Camp Sherman, Chillicothe, Ohio, where he died of pneumonia on Oct. 9.

Jan 3, 1919

By H. Scott

Since Bohler discovered, in 1903, on cooling certain alloy steels, the phenomenon of a new and lower temperature transformation than the usual Ar 3-2-1 obtained by increasing the maximum temperature to which the material was heated, much has been published1 connecting this phenomenon with a large number of dissimilar steels of high alloy content. From the fact that the transformation divides itself, taking place at two widely separated temperatures, it has been called a "split transformation." The significant facts established by recent investigators2 are: that when the transformation occurs at the higher temperature Ar1, troostite or a decomposition product is formed, and that when the transformation occurs at the lower temperature Ar", the resulting structure is martensite. The terminology Ar' and Ar" adopted here is that of Portevin. Previous Investigations Reviewing the work on this subject published in a recent issue of Revue de Metallurgie and referring in particular to his statement that martensite is a solution of carbide in alpha iron, Le Chatelier says :4 "How then can a theory already 20 years old demand new investigations? The reason for it is that we have not succeeded in proving directly the real presence of the transformation of iron during the very short duration of the quenching. The fall of temperature takes place at the rate of several hundred degrees per second and the observation of

Jan 1, 1920

By John T. Crawford

Introduction Loading and hauling systems are evaluated in open pit mining for new properties, expanding existing operations, changing systems or equipment, and equipment replacement analysis. The objective of such evaluations is to determine the equipment needed to handle planned tonnages at the lowest cash flow cost. Cash flow costs are used to combine capital outlays with operating and maintenance costs. Leasing costs could be substituted for capital costs with appropriate modifications to calculation procedures. These modifications will not be covered. This chapter will describe methods of evaluating loading and hauling systems, concentrating on some of the more often raised questions concerning quantitative data. While the methods described are not the only ones in current use, they have a record of proven reliability. The shovel and haulage truck system is used In the examples because of its common use in open pit mines. In medium to large open pit mines, electric shovels and diesel-electric drive haulage trucks are normally used. The basic ideas presented in this chapter apply to all loading and hauling systems, with appropriate modifications. The process of performing a shovel and haulage truck evaluation can be time-consuming and tedious because of the quantity of data involved, but it is not particularly difficult. The examples used to Illustrate shovel and haulage truck evaluation are based on a hypothetical open pit mine operating 350 days per year producing 31 750- 000 t (35,000,000 st, 100,000 stpd) annually, of which 11 110 000 t ( 12,250,000 st, 35,000 stpd) are ore. Selection of the optimum shovel and haulage truck fleets will be shown. The principal sources of data for the examples or any other equipment evaluation are equipment manufacturers and actual operations. Whenever possible, actual operating experience should be used to verify estimates. The quantitative data presented herein are unrelated to a specific existing mining operation.

Jan 1, 1979

By Jackson R. Pellett

INTRODUCTION The Friedensville mine is situated in Upper Saucon Township, Le- high County, Pennsylvania, in the southern central part of the Allentown quadrangle of the United States Geological Survey, approximately 5 miles southeast of the City of Allentown and 4 miles south of the City of Bethlehem. Zinc was first discovered in the Friedensville area early in the 19th century and several mines were operating during the latter part of the century. Zinc oxide was produced in 1853 and zinc metal in 1859. All mining in the area ceased in 1893 chiefly because of an unfavorable economic situation caused by a severe ground water problem and competition from the higher grade ores in New Jersey. Property acquisition by the New Jersey Zinc Company began in 1899 and periodic exploratory drilling was carried on until 1940 when sufficient reserves were proved for development of a mine. Shaft sinking was undertaken in 1947 and, due to severe hydrologic conditions, was not completed until 1952. Production began in 1958 and today the mine is producing about 64,000 tons of zinc concentrate per annum. The concentrates are trucked to the Company's smelter at Palmerton, Pennsylvania, approximately 30 miles north of Friedensville. The mine also produces from its mill tailings industrial and agricultural grades of limestone for commercial markets.

Jan 1, 1970

By W. C. Ellis, M. E. Fine

INTRODUCTION IN the iron-cobalt system there are several property-composition relationships of theoretical importance. The alloys are ferromagnetic exhibiting a maximum saturation at approximately 33 at. pct cobalt;1 the interatomic distances at room temperature show large positive deviations from Vegard's rule;2 and in the region of 50 at. pct cobalt there is an order-disorder transition which has a large effect on other properties. The thermal expansion data for the system have been reported3,4.5,6 only from room temperature to 100°C, and for this temperature range a minimum in coefficient in the region of 50 at. pct cobalt is well established. 3,4,6 This paper reports the expansion properties in the iron-cobalt system for temperatures from 30 to 850°C, shows the correlation with other physical properties, and proposes an explanation for the interrelation. EXPERIMENTAL PROCEDURE The thermal expansivities of iron-cobalt alloys in 10 pct steps in composition were determined from 30 to about 850°C. The major series of alloys was prepared by induction melting from Armco iron and cobalt rondelles with the addition of about 0.6 wt pct manganese. This series was supplemented by three compositions: high purity electrolytic iron, high purity electrolytic cobalt, and an alloy of 52.1 wt pct cobalt prepared from the high purity electrolytic iron and electrolytic cobalt by vacuum-melting. The compositions of both series of alloys are given in Table I. The specimens for measurement were prepared from the cast ingots by first hot-swaging followed in most instances by cold-swaging to 0.180-in. diam rod. Some alloys in the region of 50 pct cobalt, because of inherent cold-brittleness, were swaged hot to the final diameter. The expansion specimens were approximately 2 ½ in. long with flat-ground and polished ends. Before measurement they were annealed in hydrogen for r hr at 900°C. In the apparatus used for the thermal expansivity measurements (Fig I), a modification of that designed by Hidnert and Sweeney,7 the differential expansion between the specimen and vitreous silica was measured by a dial micrometer reading to 0.001 mm. An invar fixture supported the dial gauge, and this fixture, in turn, was connected to a split invar collar which supported the outer silica tube. A pyrex "T" was placed over the outer silica tube and was sealed to the invar collar by Apiezon Q sealing compound. A movable hollow vitreous silica rod which rested on top of the test specimen slid through a flexible rubber diaphragm cemented to the top of the pyrex "T." The specimen rested on a vitreous silica pedestal fused into the outer tube and was kept centered by a silica sleeve. A non-oxidizing atmosphere was obtained by admitting hydrogen into the

Jan 1, 1948

By George M. Fowler, F. E. Gregory, William M. Agar, Joseph P. Lyden

The fact that most of the zinc-lead ores of the Tri-State district are associated with abundant chert in the Boone formation has led us to give much consideration to the manner of occurrence of the chert throughout the formation and to its relationship to the structural and other geologic features having bearing upon the sulfide mineralization. Necessarily the question of the source and the manner of deposition of the chert has come up in the course of these studies. We do not pretend to have arrived at the answer to all the questions regarding the chert. However, we have made a very large number of field observations, which present certain facts about the chert in this district that may be worth elaboration. Whatever theories may be drawn upon to explain the presence and distribution of the chert must necessarily be capable of reconciliation to these facts. The more important theories that have been presented are briefly summarized, and some of them discussed, in this paper. This paper is in three distinct parts, each complete in itself, wherein is recorded the evidence gained from three separate methods of attack. In an earlier paper,(3)‡ we briefly described the chert and its relation-ship to the ore deposits. Chertification, as used in this paper, means the replacement of limestone by introduced silicic acid. It is a common phenomenon in many widely distributed limestones. The products of chertification may be chert, cotton rock, or tripoli, depending upon the extent to which the replacement has been carried. Chertification is used instead of silicifica-tion in order to reserve the latter for the siliceous emanations so common in connection with the sulfide ore deposits of this and many other districts. Broadly, it is meant to include all silicification in this district prior to the introduction of the jasperoid, the latter being contemporaneous with the ore-bearing solutions.

Jan 1, 1935

By William M. Agar, F. E. Gregory, Joseph P. Lyden, George M. Fowler

The fact that most of the zinc-lead ores of the Tri-State district are associated with abundant chert in the Boone formation has led us to give much consideration to the manner of occurrence of the chert throughout the formation and to its relationship to the structural and other geologic features having bearing upon the sulfide mineralization. Necessarily the question of the source and the manner of deposition of the chert has come up in the course of these studies. We do not pretend to have arrived at the answer to all the questions regarding the chert. However, we have made a very large number of field observations, which present certain facts about the chert in this district that may be worth elaboration. Whatever theories may be drawn upon to explain the presence and distribution of the chert must necessarily be capable of reconciliation to these facts. The more important theories that have been presented are briefly summarized, and some of them discussed, in this paper. This paper is in three distinct parts, each complete in itself, wherein is recorded the evidence gained from three separate methods of attack. In an earlier paper,(3)‡ we briefly described the chert and its relation-ship to the ore deposits. Chertification, as used in this paper, means the replacement of limestone by introduced silicic acid. It is a common phenomenon in many widely distributed limestones. The products of chertification may be chert, cotton rock, or tripoli, depending upon the extent to which the replacement has been carried. Chertification is used instead of silicifica-tion in order to reserve the latter for the siliceous emanations so common in connection with the sulfide ore deposits of this and many other districts. Broadly, it is meant to include all silicification in this district prior to the introduction of the jasperoid, the latter being contemporaneous with the ore-bearing solutions.

Jan 1, 1935

The fact that most of the zinc-lead ores of the Tri-State district are associated with abundant chert in the Boone formation has led us to give much consideration to the manner of occurrence of the chert throughout the formation and to its relationship to the structural and other geologic features having bearing upon the sulfide mineralization. Necessarily the question of the source and the manner of deposition of the chert has come up in the course of these studies. We do not pretend to have arrived at the answer to all the questions regarding the chert. However, we have made a very large number of field observations, which present certain facts about the chert in this district that may be worth elaboration. Whatever theories may be drawn upon to explain the presence and distribution of the chert must necessarily be capable of reconciliation to these facts. The more important theories that have been presented are briefly summarized, and some of them discussed, in this paper. This paper is in three distinct parts, each complete in itself, wherein is recorded the evidence gained from three separate methods of attack. In an earlier paper,(3)‡ we briefly described the chert and its relation-ship to the ore deposits. Chertification, as used in this paper, means the replacement of limestone by introduced silicic acid. It is a common phenomenon in many widely distributed limestones. The products of chertification may be chert, cotton rock, or tripoli, depending upon the extent to which the replacement has been carried. Chertification is used instead of silicifica-tion in order to reserve the latter for the siliceous emanations so common in connection with the sulfide ore deposits of this and many other districts. Broadly, it is meant to include all silicification in this district prior to the introduction of the jasperoid, the latter being contemporaneous with the ore-bearing solutions.

Jan 1, 1935

By F. E. Gregory, George M. Fowler, William M. Agar, Joseph P. Lyden

The fact that most of the zinc-lead ores of the Tri-State district are associated with abundant chert in the Boone formation has led us to give much consideration to the manner of occurrence of the chert throughout the formation and to its relationship to the structural and other geologic features having bearing upon the sulfide mineralization. Necessarily the question of the source and the manner of deposition of the chert has come up in the course of these studies. We do not pretend to have arrived at the answer to all the questions regarding the chert. However, we have made a very large number of field observations, which present certain facts about the chert in this district that may be worth elaboration. Whatever theories may be drawn upon to explain the presence and distribution of the chert must necessarily be capable of reconciliation to these facts. The more important theories that have been presented are briefly summarized, and some of them discussed, in this paper. This paper is in three distinct parts, each complete in itself, wherein is recorded the evidence gained from three separate methods of attack. In an earlier paper,(3)‡ we briefly described the chert and its relation-ship to the ore deposits. Chertification, as used in this paper, means the replacement of limestone by introduced silicic acid. It is a common phenomenon in many widely distributed limestones. The products of chertification may be chert, cotton rock, or tripoli, depending upon the extent to which the replacement has been carried. Chertification is used instead of silicifica-tion in order to reserve the latter for the siliceous emanations so common in connection with the sulfide ore deposits of this and many other districts. Broadly, it is meant to include all silicification in this district prior to the introduction of the jasperoid, the latter being contemporaneous with the ore-bearing solutions.

Jan 1, 1935

By A. H. Bromly

THE small agricultural village of Santa Barbara, in the State of Guanajuato, has been the center of spasmodic tin-mining operations during recent years. The deposits, so far as I know, are unique, and a few brief notes may be of interest. Santa Barbara, about 12 miles west of San Felipe station on the Mexican National Railway, and at an elevation of 2,400 m. above sea-level, is situated in a flat valley extending east and west, and bounded north and south by broken rugged bills rising about 330 m. above the general level of the valley. Tin-mining operations have been conducted-at the Queensland mine, near this village. A small concentrating-mill was erected and attempts were made to smelt the ore in reverberatory furnaces. The country-rock of the district for many miles is rhyolite of great thickness. There are some local variations due to differences in cooling, or subsequent alteration or impregnation; but throughout the whole district the principal constituents of the rocks remain the same, viz., free silica, orthoclase-feldspar and sanidine. The latter is especially marled. The crevice and joints of the rock are frequently filled with calcedonic and opalescent quartz. The ore-formation at the Queensland mine is of an unusual nature, consisting of cracks in the rhyolite which have been filled with clay. This phenomenon is largely developed over a width of from 80 to 100 m., in which the principal fissuring follows an approximate direction of north and south. The av¬erage clip ranges between 70 to 80 degrees. Some of the fissures bold sufficiently true for a time to afford the impression that they are clue to dynamic causes, or earth-movement. This may be true of some of the north by south fissures; but considering

Jul 1, 1905

By Yuri D. Tretyakov, Robert A. Rapp

The stoichiometry ranges ofNiOl+y and LiFe,O,-d were established by high-temperatwe electrochemical meas7rements in a stabilized-zirconia electrolyte cell. The results were consistent with doubly ionized cation vacancies in NiO,+y and interstitial lithium or iron ions in . The defect structure of the ternary ferrite was derived from the consideration of equilibration with respect to oxygen between the solid and the gas phase. The absolute magnitudes of defect concentrations were calculated. Pavtial molar enthalpies of oxygen in the compounds were calculated and interpreted in terms of the enthalpy of defect formation in these crystals. NICKEL oxide (NiO,,?) is a metal-deficient, p-type, extrinsic semiconductor whose properties are consistent with a structural model based on the presence of cation vacancies as the predominant ionic defect at sufficiently high temperatures and oxygen activities. A survey of previously reported conductivity studies and the presentation of some more recent conductivity measurements will be given in a later paper.' The absolute magnitude of the equilibrium vacancy concentration in NiO has been reported from combined conductivity and thermogravimetric data of ' However, disagreement exists concerning the state of ionization of the nickel vacancies in NiO. Some authors3-' have proposed that the predominant defects in NiO are singly ionized nickel vacancies and positive holes (h') formed by the reaction where, accorhng to the notation of Kroger and Vink,6'7 Oq represents an oxygen ion on its normal lattice site. Other authors"27E have proposed that doubly ionized nickel vacancies (V{i ) and positive holes are predominant and are formed by the reaction One purpose of the present investigation was to establish the nature of the predominant defect in NiO,+? as well as its equilibrium concentration and thermo-dynamic properties at elevated temperatures and known oxygen activities. To accomplish this purpose, the coulometric titration of oxygen into and out of NiO was accomplished using a galvanic cell involving the calcia-stabilized zirconia electrolyte. The ternary oxide, lithium ferrite (LiFe50,-6) is ferromagnetic and has the inverse spinel structure LiFe,O,-d Thus, in the ideal stoichiometric XY204 lattice, Fe3 ions occupy one-eighth of the tetrahedral (A) sites, and i' and Fe3' ions share at random one-half of the octahedral (B) sites within the fcc sublattice of oxygen ions.g The structure and thermodynamics of the spinel structures have been comprehensively decribed.'-' A recent compilation of literature for lithium ferrite is also available. 15 Oxygen-excess LiFe50sis not expected to exist because both i' and 17e3& ions are in their highest normal valency states (positive hole formation is not favorable). As will be discussed, equilibration of the ferrite crystal with oxygen of a surrounding gaseous phase will result in the introduction of equilibrium concentrations of ionic and electronic defects. In the Results and Discussion section a defect model for LiFe50,-d is proposed. This defect model is tested by high-temperature coulometric titration experiments. EXPERIMENT The oxygen activities in nonstoichiometric NiOl+, (and also LiFe,O,-d) were measured by means of coulometric titration with the high-temperature galvanic cell The critical characteristic of a suitable experimental cell is the complete isolation of the phase to be investigated in a minimum sized chamber which is free from extraneous sources and sinks for oxygen (leakage). Then oxygen is only admitted to the chamber or removed from it in known amounts by coulometric titration, which involves the passage of oxygen ions through the solid electrolyte with electrochemical oxidation and reduction reactions at the platinum contacts to the electrolyte. The experimental cell is shown in Fig. 1. The cap of the cell was the tip from a closed-end alumina tube, which was found to be leak-free from a helium leak-detector test. This alumina cap was about 1.2 cm OD and about 1.5 cm high. A Zircoa calcia-stabilized zirconia tablet (crucible lid) of 1.5 cm diam and 0.3 cm thickness served as the solid electrolyte. A Pyrex ring of about 0.1 cm thickness was placed between the electrolyte and the cap. The electrolyte tablet was painted with platinum paste on the entire outer face and on that part of the inner face which would be within the enclosure; these electrodes were further prepared by heating in air at 1000°C for 2 hr. Nickel oxide powder, listed as 99.999 pct pure, was purchased from Leico Industries, Inc. Pills of the NiO were cold-pressed and sintered at 1050°C for 3 hr in a platinum crucible. This poorly sintered NiO was crushed, and chunks were wrapped in 52-mesh Pt gauze (to catalyze the solid-gas exchange) for place-

Jan 1, 1970

By E. O. Wagner, V. F. Parry

This paper summarizes investigations during 1949 on three pilot plants for drying low-rank fine cool by entrainment in hot gases. Detailed operating results on processing seven coals having moisture ranging from 24 to 62 pct, formulas and data for calculating performance of large units, and general conclusions on the problem of drying fine coal are presented.

Jan 1, 1950

By K. A. Svanstrom, W. R. Opie

Problems associated with deposition of titanium infused chloride baths using TiCl4 as a feed material are reviewed. A potentially workable cell design using Alumdum diaphragms is discussed. Problems inherent to diaphragm-type cells are emphasized and experiments described which led to the development of a cell without a diaphragm. INVESTIGATORS assigned the problem of developing a commercial electrolytic process for making titanium metal have found that they are faced with the difficulty of overtaking rapidly improving magnesium and -sodium reduction processes. The ultimate goal must be a simple process that can be conducted with low-cost raw materials in equipment that is inexpensive to build and operate. This paper deals with some work of a preliminary nature conducted by personnel of the Research Laboratories, National Lead Co., Titanium Division. Many others have reported on the general subject of depositing titanium from fused salt electrolytes. A partial bibliography is attached. PRIMARY CONCEPTS Anyone attempting to deposit titanium metal from fused chloride electrolytes using TiC14 as a source material is faced with at least the following problems: 1) Getting the titanium into solution in the bath. 2) Controlling oxidation and reduction reactions associated with multiple valency of titanium, which result in low electrical efficiency. a) Prevention of dichloride oxidizing to trichloride and trichloride to tetrachloride at the anode. b) Prevention of trichloride from being reduced only to dichloride at the cathode. 3) Prevention of metal formation away from the cathode thru disproportionation of titanium dichloride to satisfy the equilibrium. 3 TiCl2 == 2 TiCl3 Ti [I] 4) Protection of reduced chlorides in the bath from reaction with oxygen from the bath container or air. 5) Removing from the bath the deposited metal formed without allowing it to become contaminated with oxygen or nitrogen. 6) Selecting cell materials of construction which will not contaminate the metal product or cause cell inefficiencies. EARLY EXPERIMENTS The initial attempts made to electrodeposit titanium from fused chloride baths using TiCl4 as a source material indicated that TiCl4 was essentially insoluble in molten chlorides of alkali and alkaline earth metals. If, however, the TiCl4 was introduced close to a nickel cathode some metal could be formed and appreciable quantities of reduced chlorides would be present. These reduced chlorides reacted with any oxygen present in the atmosphere above the bath and would also diffuse quickly to the anode (graphite) where they would react with chlorine and be evolved as TiCl4. The net electrolytic efficiency of such a cell is essentially nil. The TiCl4 evolves from the anode at almost the same rate that it is introduced in the vicinity of the cathode although a small amount of titanium metal can be formed on the walls of the cathodic pipe. It becomes apparent from the operation of such a cell that: metal can be deposited on the cathode, although of small particle size and a nonadherent nature, and when reduced chlorides are present in the electrolyte, TiCl4 can be absorbed, probably by the following reactions: TiCl4 + TiC12 - 2 TiCl3 [21 2 TiCl3 + 2 faradays - 2 TiC12 + C12 [31 DIAPHRAGM CELLS These facts encouraged the development of cells containing diaphragms to prevent migration of reduced chlorides from the cathode area to the anode. Small-scale cells for process development are described by Alpert, Schultz, and Sullivan.20 A larger brick-lined cell incorporating internal heating by passing ac through the bath is shown in

Jan 1, 1960