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By A. M. Skov, L. F. Elkins

First response to large-scale water flooding in the fractured very low permeability Spraberry sand has led to a new unique cyclic operation. Capacity water injection is used to restore reservoir pressure. This is followed by marly months production without water irzjection and the cycle repeated. Expansion of the oil, rock and water during pressure decline expels part of the fluids but capillary forces hold much of the injected water in the rock. At least with reservoir pressure restored and with partial water flood development, field performance has proved this cyclic operation is capable of producing oil from the nzatrix rock at least 50 per cent faster and with lower water percentage than is imbibition of water at stable reservoir pressure. INTRODUCTION The Spraberry Field of West Texas presents unusual problems for both primary production and water flooding. Extensive interconnected vertical fractures in the fractional-md sandstone permitted recovery of oil on 160-acre well spacing, but they made capillary end effects dominant. Primary recovery by solution gas drive is less than 10 per cent of oil in place. The concept of displacement of oil from the sand matrix by capillary irnbibition of water has led to field techniques which promise greatly increased oil recovery. Free exchange of laboratory research, reservoir information and results of field pilot tests among the various companies has been very important in development of this technology. Five units covering a total of 170,000 acres have been formed for water flooding, and 10 other areas covering an additional 175,500 acres are in various stages of unitization. Part of the Driver Unit reaching fillup first has demonstrated very unusual waterflood behavior and indicated numerous operating problems that will develop within and among the various units. SPRABERRY ROCK AND PRIMARY PERFORMANCE The Spraberry, discovered in February, 1949, is a 1,000-ft section of sandstones, shales and limestones with two main oil productive members: a 10-15 ft sand near the top and a 10-15 ft sand near the base. In part of the field some thinner intermediate sands are oil productive, and others are water bearing. All sands have permeabilities of 1 md or less and porosities of 8-15 per cent. Ordinary core analysis and electric and radiation logs are ineffective in differentiating between oil productive and nonprcductive sands. Sands capable of containing producible oil are best identified by mercury injection capillary pressure measurement and, in some cases, by core water saturation. About 3,500 wells have been drilled in the 500,000-acre trend. Vertical fractures were observed in practically all Spraberry cores. Continuity and interconnection of fractures were confirmed by pressure interference among wells during early development.' Major fractures trend northeast-southwest as indicated by oriented cores and confirmed by five fluid injection tests, by analysis of the pressure transients observed during development,''' and by three interference tests in the Driver Unit Water Flood reported herein. Fracture spac- ing probably averages inches to a few feet. Spraberry wells typically produced 100-400 BOPD initially after hydrauLic fracture treatments. By 1962 oil production had declined to an average of 12 bbl/well/day, near the economic Limits of operation. Reservoir pressure had declined from 2,300 psi initially in the Upper Spraberry and 2,500 psi in the Lower Spraberry to 500-1,000 psi. Partial closing of the fractures with declining reservoir pressure is believed to be the cause of such low oil production rates at these relatively high reservoir pressures. Cumulative recovery of 208 million bbl of oil is 80 to 90 per cent of that recoverable by primary means. Performance of the entire reservoir is summarized in Fig. 1. IMBIBITION WATER FLOODING By 1952 reservoir performance indicated low primary recoveries. Most engineers, expecting serious channeling of injected fluids through the fractures, held little hope for secondary recovery. With its extensive background of research on the fundamentals of fluid flow within reservoir rocks, Atlantic's Research and Development Division on short notice in 1952 conceived that displacement of oil by capillary imbibition of water into the rock might significantly increase Spraberry recovery. Laboratory data reported by Brownscombe and Dyes scaled to probable reservoir conditions showed potential waterflood recovery equal to or greater than primary recovery with a 10-15 year flood life.= A pilot test using three 40-acre injection wells, one central producing well and 18 surrounding observation wells demonstrated technical feasibility of the process. Injection of 1.5 million bbl of water from November 1952 to August 1955 proved water entered the rock and displaced oil

By Richard W. Markley

A centralized online data acquisition system has been developed by the U.S. Bureau of Mines Pittsburgh Mining and Safety Research Center for rapidly digitizing, storing, and processing experimental signals originating up to 1100 feet away from a central computer. This system, which services seven laboratories, is currently based on a CDC System 17 1/- computer with 56K of semiconductor memory, four disk drives (one shared online with a CDC 1700), two magnetic tape drives, high-speed A/D hardware, and other input/output peripherals. The laboratories are linked to the central computer by 15-pair cables and signal conditioners and to the computer's communications controller by modems and current loops. The A/D throughput rate is approximately 30,000 samples per second (9 bit plus sign resolution) and permits scanning about 30 instruments once every millisecond for up to 100 seconds, being limited only by disk capacity. The laboratories serviced by this facility conduct explosions research and include such facilities as an Experimental Coal Mine Explosion Facility (45 channels), a Constant Volume Combustion Laboratory (4 channels), and a Simulated Coal Mine Laboratory (15 channels). Personnel support includes one systems analyst, two applications analysts, one operator, and a hardware technician. The system has performed adequately for burst-type data acquisition, but due to a lack of long-term reliability (24 hours) of the real-time multiprogramming operating system and unpredictable power failures, slow phenomena signals are generally digitized and stored offline. This latter data is input to the computer through peripherals such as a high-speed paper tape reader, or high-speed asynchronous communications ports. Processing of data is done either in real-time (as soon as data is collected) or in batch mode. Smaller batch jobs are run on this computer, and all others are transmitted by means of the system's high-speed UT 200 terminal simulator to a CDC-6000 series computer.

Jan 1, 1977

By A. W. Bitner, A. W. Asman

An analysis is made of three different types of section production units that represent the manner in which most of the nation's bituminous coal is produced. The general delays and production characteristics of these sections are presented along with a method for evaluating section performance based on actual and theoretical production characteristics. THE forerunner of the modern mechanical loading machine first entered the mines in 1890—a Stanley header with a conveyor. Since then progress has been substantial, both in the design and application of mechanized production units. Mechanization is almost a necessity for survival in the economy of today. In this paper an analysis is made of three types of sections, and a method for evaluating section performance based on present production characteristics and theoretical characteristics is presented. In mechanical loading mining sections the loading machine is the unit directly responsible for production. If the face preparation units provide a plentiful supply of properly prepared coal and the transportation system is coordinated and adequate, the loader will be idle a minimum of time. If either of the above do not perform adequately or other delays occur, the effect on production will be reflected in the performance of the loading machine. Therefore, attention is focused on the loading machine and factors that affect the overall performance of the production unit. Three complete mechanized production units are presented for analysis: A track section, a trackless section using battery-powered shuttle cars, and a trackless section using cable-reel shuttle cars. These particular sections were chosen for the following reasons: 1—The daily tonnage and mining conditions are approximately the same. 2— Production in each is 10 to 20 pct above the daily average. 3—The production characteristics and delays are average and typical. 4—They represent the manner in which the most of the nation's bituminous coal is produced. A. W. ASMAN, and A. W. BITNER, Members AIME, are Chief, and Research Assistant, respectively, Div. of Mining, The Pennsylvania State College, State College, Pa. Discussion on this paper, TP 3140F, may be sent to AIME by Oct. 31, 1951. Manuscript, Feb. 22, 1951. St. Louis Meeting, February 1951. Section A Fig. 1 is a layout for the track mining section showing the development to date, the projected plan and the cuts loaded on the shift studied. The seam mined averages 96 in. in thickness with a fireclay bottom and a roof of 10 in. of drawslate topped by sandstone. The mineability is considered good, and roof support is not a difficult problem. Two locomotives are used in the section to minimize the losses occurred in trip changing. The places are driven 20 ft wide, and the crosscuts are angled to permit fast tramming of the equipment. Table I lists the equipment and labor that make up the section. ANALYSIS Production Characteristics: The average loading rate for eight loading machines studied of this type is 1.81 tons per min. This one at 2.78 is considerably above average.

Jan 1, 1952

By A. E. Lee

THE Blackwell Zinc Co., Inc., a subsidiary of the American Metal Co., Ltd., operates a horizontal retort zinc smelter at Blackwell, Okla. The plant has 14 furnace blocks of 800 retorts each, fired with natural gas on a 48 hr cycle. Over 13,000 tons of zinc-bearing material, chiefly sulphide flotation concentrates, are treated monthly to produce slab zinc and high lead-cadmium fume. In 1942 a program of rebuilding and modernizing the smelter was started. By 1947 furnace smelting capacity had been increased to a point where roasting and sintering facilities were inadequate, and it was necessary to purchase oxidized materials to supplement sinter production. The seven 210 ft Ropp roasters and three 42 in. x 44 ft Dwight-Lloyd machines then in use had been in service at least 20 years and were in need of major rebuilding. Thus it was entirely practical to consider all new equipment and a change of method rather than rebuilding and repairing obsolete units. A study of the problem indicated that roasting as such could be eliminated and roasting and sintering accomplished in one step by a modification of the Robson process,' which had been used since the early 1930's by the National Smelting Co., Ltd., at their plants at Avonmouth, England, and Swansea Vale, South Wales. Francis P. Sinn, General Manager, Zinc Smelting Operations, The American Metal Co., Ltd., who was familiar with the practice in England, suggested the use of one large machine for the entire operation from concentrate to sinter. One step sintering appeared to best meet Blackwell's plant requirements and indicated substantial savings in labor, gas, coal, and repair costs. Choice of Machine Size The sinter machine size was set at 12x168 ft for a rated capacity of 540 tons per day. This tonnage, produced on a five day week, would meet the seven day requirements of the 14 furnace blocks. The one large machine was quoted at a lower cost than two or more 6 ft wide machines of similar total capacity. Further, the larger machine could be housed in a smaller structure and only one set of equipment for charge preparation and delivery and for disposal of sinter cake was needed. One machine on a five day week made possible a concentration of the skilled operating personnel and required less men than a plant including two or more machines and related equipment circuits. Fewer units of equipment meant less maintenance, and the two down days weekly allowed ample time to repair and, if necessary, to make up lost production. Experience had indicated better sintering quality and rates with larger masses of material, not only on wider machines, but also in deeper beds. The ratio of windbox perimeter to area for the 12x168 ft machine is 0.179, compared to 0.353 for a 6x102 ft machine and 0.617 for a 42 in. x 44 ft machine. This meant less air leakage with resulting fan power savings and less spoilage of charge along the pallet sides. Performance Initial operation of the new sinter plant was made in November 1951 and regular production attained late in December. The average product sinter output during 1952 and the first half of 1953 has been 18.2 tons per hr. The average for one month has been as high as 22.4 tons per hr. Considerable experimenting with varied operating conditions accounts in part for the below capacity — 24 tons per hr — average output, and work to further improve production rate continues. A typical sinter analyses is 66.0 pct Zn, 0.3 pct Pb, 0.1 pct Cd, 0.3 pct S, 8.0 pct Fe, 2.0 pct SiO,, 0.8 pct CaO, and 0.2 pct MgO. Use of this material has made possible increases in furnace burden and improved furnace operation over the former practice using sinter made from Ropp roasted concentrates. Better lead and cadmium elimination in sintering has permitted the furnace production of slab zinc lower in lead and cadmium. Anticipated economies of operation have largely been gained. The sinter plant is operated by seven men per 8 hr shift — one head operator, three equipment operators and three sweepers — plus one oiler on day shift only. While it has been necessary at times to operate seven days a week to produce the required sinter tonnage, the five day work week usually has been adequate. Consumption of natural gas for sinter bed ignition is 200,000 to 300,000 cu ft per day. Green Ore Sintering Practice The 30 to 31 pct sulphur content of the —200 mesh zinc concentrates is the fuel used to sinter the charge, no coal addition being required. In the feed to the machine, sufficient concentrates are added to crushed return sinter fines containing 0.3 to 0.5 pct sulphur to produce a charge averaging 5.0 to 6.5 pct sulphur. Since the return sinter used in Blackwell's practice is varied from — 1/2 to — 1/8 in., the actual sintering mixture of fine sinter and concentrates is somewhat higher in sulphur. The coarser sinter particles are too large to resinter and merely aid porosity in the sinter bed. The ratio of concentrates to return sinter in the charge ranges from about 1:4 to 1:5.5. Variations are based on the appearance of pried up bed sections, bed exit gas temperature trends, windbox suctions, and return sinter size. Sufficient sulphur must be used to obtain fritting of the charge into a soft sinter cake and to aid in the elimination of lead and cadmium. Excessive feed sulphur will result in partial slagging of the cake impairing porosity and prolonging sintering time.

Jan 1, 1954

By HILLARY W.

THAT colleges and technical schools constitute a vital factor in our industrial system is being realized more and more of late years. Consequently it is desirable that there should be a constant interchange of ideas between the 'school and the industries and that there should be a more intimate contact between the student and his future employer. Business and industry demand certain proficiencies and qualifications of the student and he, in turn, sees certain rewards and advantages in the industry. . In a meeting of this kind, whose primary purpose is to promote a greater intimacy between the students and those men who are active in the mining profession, it is quite fitting that each state his demnds upon the other in order to establish a common understanding. It is probable that a student, not being conversant with actual conditions in the industry, may be unfair in what he asks of his employer. Therefore criticism, constructive or other- wise, is not only accepted, but is invited.

Jan 1, 1930

By Ovid W. Eshbach

ENGINEERING education has been powerfully affected by the impact of war, just how powerfully can be better understood after considering the postwar problems regarding students, staff, and plant. In time of war no one will question the necessity of expediency of military training. With the cessation of hostilities, expediency gives way to the evolutionary process of strengthening engineering education as need is exemplified by experience. During the war, except for the Navy V-12 program, engineering education was at its lowest ebb of the century. Freshman enrollments were largely limited to those graduating from high school at the age of seventeen; and the upperclass, to those disqualified for active service. In most schools the experienced staff was either in service or government and industrial research. Many may never return to their former occupations. The most immediate problem is that of maintaining and building a staff to meet the enrollment of returning veterans. It is estimated that out of the eleven

Jan 1, 1945

By J. W. Mills

This paper's aim is to demonstrate, by reviewing findings and conclusions of earlier authors and through recording and interpreting the outcome of recent laboratory study of the ores, that the ores around the Gem stocks are metamorphosed equivalents of common siderite-sulfide ores far from the stocks, as was first proposed by Hershey (1912, 1913). That is, all the ores probably have the Precambrian age of 1250 million years reported by Long et al. (1960). Those near the Gem stocks, however, were extensively metamorphosed in Cretaceous time during the emplacement of stocks so their resemblance and relation to other veins in the district are camouflaged.

Jan 1, 1985

By Harry H. Power

WORK of the Committee on Education of the Petroleum Division has been under way for approximately-one year. Although some progress has been made, further activities of the Committee are necessary in order to discuss mutual problems more thoroughly by a unified group interested primarily in this field of specialization.

Jan 1, 1944

By Joseph W. Roe

MANY questions arising in the work of the mining engineer may be solved quickly and with sufficient accuracy by the methods of descriptive geometry; but, unfortunately, this subject is more often considered from a mathematical view-point than as an effective tool. for solving practical problems. Some of the principles involved are merged into the ordinary operations of mechanical drawing, and are used unconsciously by the engineer in his every-day work. The rest are stowed away on the book-shelf with his forgotten or rarely-used college text-books. One reason for this condition of "innocuous desuetude " may lie in the unfortunate and often cumbersome notation which it has been found necessary to introduce. If some of these principles can be recalled to the engineer's attention in terms of every-day use they may prove of practical bearing. Recently, in talking with several mining engineers, I used some of the drawing-room methods of a machine-designer, to the evident surprise of those around me. These men were perfectly familiar with the methods, but their application to mining-work had not occurred to them. At their suggestion the present paper is offered, not in any way as a treatise, but merely to suggest a certain point of view, in hope that it may lead others far more familiar with mining-problems to pursue the subject further. I. To FIND THE STRIKE. As the simplest and most fundamental problem, let it be required to find the strike of a vein when the location and elevation of three points on the outcrop are known. It will be assumed for the present that the vein is a plane.

Mar 1, 1910

By Hon. Tasker Oddie

DURING the closing days of the last Congress a resolution was passed, creating the Senate Com-mission of Gold and Silver Inquiry. The resolu-tion charges the Commission with the responsibility to investigate and report to the Congress on Jan. 1, 1924, upon the following subjects: 1. The causes of the continuing decrease in the production of gold and silver. 2. The causes of the depressed condition of the gold and silver industry in the United States. 3. The production, reduction, refining, transportation, mar-keting, sale, and uses of gold and silver in the United States and elsewhere. 4. The effect of the decreased production of gold and silver upon commerce, industry, exchange, and prices. The personnel of the Commission is as follows: Senators Pittman, Sterling, Goodling, Walsh and Oddie. At a meeting on May 8, H. N. Lawrie, a mining engi-neer and economist, was appointed as Assistant to the Commission. The present situation with respect to the gold and silver mining industries is well illustrated by the follow-ing data: The total world production of gold (in dollars) for 1915 was $468,724,918, and for 1921, $329,915,101; as shown by the reports of the U. S. Mint; and for the year 1922, $306,793,000, which is based oh a prelimi-nary estimate; this indicates a decrease of 34.5 per cent. between 1915 and 1922. The total world production of silver (in fine ounces) for 1915 was 178,850,000 oz.; for 1921, 175,268,234 oz., a decrease of 2 per cent.

Jan 6, 1923

INTRODUCTION The first installation of large, commercial, high gradient-high field cannister and matrix magnetic separators for removal of impurities from kaolin was made in 1973 (1). Since then the technology and equipment have been widely adopted for clay processing with about 12 units in commercial use. These new separators have filled a need, caught the imagination of many and become a technology worth fighting for. A fight has occurred, and a resolution on royalties for kaolin processing, at least, has been achieved. LIMITATIONS TO APPLICATIONS OF MAGNETIC SEPARATORS Other than the use of these magnets on kaolin clay, no other application has yet achieved widespread adoption. Dr. Iannicelli blames inertia, and1 would agree that it is a factor. There are other reasons too, and if they are examined, they may isolate problems that R&D can significantly assist in solving. I'd like to break the problems into two areas. Machine limitations - the mineral properties are there but performance is insufficient or uneconomic. Separation limitations - the mineral properties aren’t there, but the magnetic separation would perform well if the properties were there (size is right; concentration is right, etc).

Jan 1, 1979

By Thomas L. Kesler

I all of the 14 million tons of kaolin produced in Georgia through 1949 had been mined from a single deposit 20 ft thick, it would represent a mined-out area of less than 1 sq mile. This measure of depletion is in such strong contrast with the large size of the area shown in Fig. 1, from which most of the output has come, that there has developed an optimistic outlook concerning future supplies of kaolin equal in grade to that already mined. Dozens of mines are widely but not evenly distributed within this area, which consists mostly of parts of Twiggs, Wilkinson, and Washington counties. There are scarcely half a dozen kaolin mines elsewhere in the state that have been appreciably productive, although the areas in which they occur may have good possibilities. Most of the efforts to find new deposits, therefore, will be confined to the area shown in Fig. 1, for it is here that the industry has established its facilities, and prospecting is encouraged by relatively numerous outcrops and opened deposits of kaolin. The Ocmulgee and Oconee rivers drain the area. They and their main tributaries have flat, swampy floodplains covered with alluvium and for the most part thickly wooded. The divides between these streams are intricately dissected by the minor tributaries, which are spring-fed in steep-walled, cirque-like heads. Gullying and under-cutting are active along the streams but are partly controlled by unusually dense vegetation. The mean altitude is about 350 ft above sea level, and locally the relief ranges up to 200 ft. The area is near the inner margin of the Coastal Plain, and is underlain by Cretaceous and Tertiary formations. Its general location is shown in black in Fig. 1. The division between the Coastal Plain and the Piedmont plateau is actually a very sinuous line, the fall line, marking the extent to which erosion has stripped the Coastal Plain sediments from the southeastward-sloping surface of the crystalline rocks of the Piedmont. Cretaceous Host Formation The kaolin deposits, which are described in the succeeding section, occur sporadically in lenslike bodies in a thick series of poorly sorted clayey sands constituting the lowermost of the Upper Cretaceous formations, the Tuscaloosa. The basis for this correlation has been reviewed by Cooke.1 The same formation has been termed the Potomac group by Ladd2 and the Middendorf formation by Smith' in reports on the kaolin deposits. In another report, Veatch4 called the formation the Tuscaloosa but correlated it with the Lower Cretaceous. The Tuscaloosa in this area consists of fine to very coarse sands, commonly cross-bedded, which contain widely different proportions of white, pink, and yellow kaolin and considerable white mica. A few of the coarser beds contain quartz grains up to 3 in. in length, with bodies of pure white kaolin of equal size that appear to have been formed by the weathering of feldspar grains in place. In the kaolin-producing area, gravel and cobbles occur mainly at the base of the formation. Fig. 2 shows the relations of the Tuscaloosa and its kaolin deposits to the adjacent formations. Its base, on the eroded surface of the crystalline rocks, dips southeastward 50 to 60 ft to the mile, according to LaMoreaux.5 The upper surface of the Tuscaloosa is also an unconformity,

Jan 1, 1952

By J. J. Kramer, W. A. Tiller, G. F. Bolling

The temperatures of solid-liquid interfaces have been measured during the growth of Sn-Pb alloy crystals which exhibited a cellulur substructure. A simple descriptive theory was used in combination with this data and the other measurable growth variables to predict some features of the solute segregation such as the intercell excess concentration and the depth of cell grooves during freezing. The effective distribution coefficient at the tip of a cell, a, was predicted and experimentally found to vary in the range, 1 >a > k0. At the lower limit, the severe segregation that must arise between dendritic cells was substantiated by various observations such as the existence of a second Phase even for alloys of only 0.2 wt pct Pb. ThE cellular morphology of a solid-liquid interface is known to coincide with the formation of a zone of constitutional supercooling ahead of the interface during growth.' The occurrence of various cell structures, (two-dimensional cells, regular cells, dendritic cells), has been quantitatively investigated,'2,4 but the segregation of solute which arises as a consequence of this mode of growth has only been examined qualitatively. An indirect method of obtaining the solute concentration at the tip of a cell cap during solidification has been de-

Jan 1, 1963

YOU must know, my Messer Bernardino, that all things in this world made by art or produced by Nature are made only for their own specific purpose. If there should be any that perchance should fail therein, they would be useless and imperfect, and those are in a state of imperfection that should have it and have not yet arrived at it. Thus, in short, when you have dug out the ore with so much labor and extracted the metals, when you have made from copper (in addition to other works) guns that are ready for military service and have then put them on

Jan 1, 1942

By Francis C. Blake

Although the use of gaseous fuel in blast-furnaces has been often proposed, I hope the description of a very simple, yet practical and valuable, application of natural gas to the smelting of lead-ores and residues, at the works of the Pennsylvania Lead Company, will prove interesting. In May, 1886, directly after replacing the use of bituminous coal at the above works by that of natural gas, half-inch pipes from a branch gas-main were inserted directly into the tuyeres of a lead blast-furnace, and through these pipes gas was delivered into the furnace, with the air-blast at a pressure a little more than double that in the tuyere-pipes. At the same time the blast-pressure at the tuyeres was increased by an amount estimated to give a sufficient air-delivery when mixed with the gas-supply. The amount of gas delivered to the furnace is easily regulated by stop-cocks at each tuyere, and is under the immediate control of the furnace manager. Upon the introduction of gas into the tuyeres of the furnace the coke charged at the mouth was reduced 30 per cent., this being the amount of coke which I thought could be advantageously replaced by gas. This first estimate has proved to be very close to the working results, though probably the average gas-consumption corresponds to a little less than 30 per cent. of the former coke used. The proportion that we use varies, with the nature of the furnaceburden, between 20 and 40 per cent. of the total fuel. We have used 60 per cent. of gas; but there is difficulty in keeping a cool furnace-mouth when the proportion is so high. With some residues, notably metallic drosses containing some zinc, we have found it best not to use over 20 per cent. gaseous fuel. The percentage used with ore-charges has generally been higher than that used in smelting the higher-lead charges of residues from our refining works. It results from this use of natural gas that the temperature of the hearth is under almost immediate control, and, for this reason chiefly, a cleaner and more uniform slag can be run, and the furnaceworking can be made more nearly independent of the effects of atmospheric conditions or the variable moisture in the furnace-burden.

Jan 1, 1887

By L. R., McLeod

NO important changes in metallurgical practice are exhibited in the smelter that has been erected for treating the Morenci concentrate: the material is charged to reverberatory furnaces without roasting, and the matte subsequently blown in Peirce-Smith converters to separate the iron and sulphur from the copper. In fact the process is essentially the same, except for preliminary roasting of the concentrate, that was adopted in the new smelter that was built for the Arizona Copper Co. at Clifton, a few miles away, to treat Morenci concentrate just before the start of the first World War, and which went into service in October, 1913.

Jan 1, 1942

By C. Law McCabe, R. G. Hudson

The Knudsen cell has been employed to determine the free energy of formation of Mn7Cs in the temperature range 800" to 950°C. A value of 66,440 cal was found for hH°o for a-manganese. Measurements of the pressure of manganese over a mixed carbide, (Fe,Mn),C, points to a power relationship between aun7cs and N.4,. RECENTLY Kuo and Perssonl have reported that the carbide of manganese which is in equilibrium with graphite at temperatures up to 1100° C is Mn7Ca. There are no published data on the thermo-dynamic properties of this compound. In order to determine the stability of Mn7Ca, it appeared that, by obtaining the pressure of manganese above 8-manganese and also above Mn,C, in equilibrium with graphite, the free energy of formation of Mn7Ca from 8-manganese and graphite could be obtained. In addition, the vapor pressure of manganese, reported by Kelley From data of Bauer and Brunner,' is subject to some uncertainty and further determinations of the vapor pressure of manganese seemed warranted. In this investigation of the pressure of manganese vapor above pure manganese and also above the carbide of manganese in equilibrium with graphite the apparatus used is the Knudsen orifice cell. The same apparatus, experimental procedure, and method of calculating the pressure was used in this investigation as in one previously reported.~ Care was taken to insure that the cells were at constant weight before using them in a run. The manganese charged in the cell was CP grade powder, carbon free, obtained from the Fisher Scientific Co. A spectroscopic analysis of the manganese after appreciable amounts of it had vaporized from the Knudsen cell showed that no element was present in sufficient quantities to contribute to a weighable weight loss or to decrease the vapor pressure of manganese to any appreciable extent. The spectro-graphic analysis was 0.002 pct Cu, 0.05 pct Fe, 0.002 pct Pb, and 0.002 pct Ni. 8-manganesea is the allo-tropic form of manganese which was present in the cell at temperatures used in this investigation. The manganese carbide, Mn,Ca, was made in the following way: In a closed graphite cell manganese powder was added to graphite powder, which was made from graphite rods for spectrographic use. The manganese powder was the same as that described previously; 5 pct excess graphite was added over that required for the formation of Mn7C,. The mixture was heated in a closed graphite cell for approximately 20 hr at 1350°K under vacuum. X-ray analysis revealed that there was no manganese present after this treatment, but that the lines due to Mn,C, were present. In order to prove that there was no volatile carbide of manganese which was effusing out of the cell, the following experiment was performed: A graphite effusion cell containing graphite power, in excess of that to form Mn,C, of a desired amount, was brought to constant weight on heating at 1228°K. The required amount of manganese was accurately weighed and then added to the graphite effusion cell. The cell was placed in a vacuum at 1228°K for one week, which was the time calculated for the manganese to have effused completely, assuming instantaneous formation of Mn,C8. The cell was then weighed again. This experiment was carried out on two different occasions and both times the weight loss of the cell came within 1 pct of the weight of manganese originally charged minus the weight of manganese left in the cell, as determined by chemical analysis. These data are summarized in Table I. This agreement is considered to be within experimental error and is taken as proof that no carbide of manganese is volatile in this temperature range. It was established, by X-ray analysis, that Mn,C, formed before appreciable amounts of manganese vaporized from the metal powder which was charged. The identification of the carbide of manganese which was present in the Knudsen cell in equilibrium with graphite and manganese vapor was carried out by Kehsin Kuo at the University of Uppsala. He established that the authors' sample, which was submitted to him for analysis, contained the phase

Jan 1, 1958

By Leon Hart

THE nickel-chromium alloys of importance are those containing iron and those free from iron. The most important alloys containing iron, with regard to high tonnage, are the nickel-chromium steels. Straight nickel steel was introduced about the year 1889, but it was not until 1895, when it was found that the addition of chromium greatly increased the FIG. 1.-RESISTIVITY OF NICKEL-CHROMIUM-IRON ALLOYS. strength and resistance to shock, that nickel-chromium steels came into use. The three types of nickel-chromium steels developed at this time were: Type 1, containing 3.50 per -cent. nickel and 1.50 per cent. chromium; type 2, containing 2.00 per cent. nickel and 1.00 per cent. chromium; and type 3, containing 1.50 per cent. nickel and 0.50 per cent. chromium.

Jan 1, 1921

By Haakon Styri

In discussion of Dr. Fitterer's paper on electrolytic separation of slag inclusions, some results from experiments on electrolyzing high-carbon steels at the SKF Research Laboratory were given. l We had been working for a number of years on chemical methods of separating the inclusions but could not find any solvent that would dissolve the steel without attacking some of the inclusions, particularly the sulfides in which we were mostly interested at the time, nor any that would dissolve all sulfide or silica in filings as fine as 300 mesh without attacking the iron. Electrolytic methods had also been tried without any real progress until we learned from the Bureau of Mines about the use of the collodion membrane around the anode. Our early difficulties were to some extent different from those of the Bureau of Mines, perhaps because of experimenting on steels of higher carbon content, but most of our difficulties were of the same nature as those of the Bureau. Formation of large quantities of basic hydroxides was traced to the use of impure and oxidized ferrous sulfate. To protect from oxidation from the atmosphere during electrolysis, after purer chemicals were obtained, a thin layer, 54 in. or less, of molten paraffin was poured over the surface of the cathode liquid, where it solidified. It was found desirable also to hold the cathode chamber slightly acid by initial addition of 0.1 per cent acid (sulfuric or hydrochloric) to prevent precipitation of the hydroxide. This acidity would decrease gradually and the cathode chamber would become neutral before the end of the electrolyzing. The increase in acidity in the anode chamber during our early experiments had appeared to cause attack of the precipitated sulfides in the residue, which originally was analyzed by volumetric method for sulfur, and for this reason a 10 per cent sodium citrate solution was substituted for the sulfate in the anode chamber. With the use of the more reliable Eschka method for sulfur determination (as in coke), there was however no serious attack on the sulfides in the anode chamber with a variety of different liquids, as shown in Tables 2 and 4. The Eschka method gives a higher sulfur value than

Jan 1, 1933

By A. A. Jr. Smith, J. S. Smart

The controlled amounts of phosphorus, arsenic, sulphur or selenium found in commercial coppers perform a variety of highly useful functions. Indeed, a large segment of modern copper technology is essentially dependent upon the presence of one or more of these elements. Consequently, the literature contains many references to their effects but the scope is broad and has been only partly covered. New data are presented herewith directed toward a better understanding of the basic behavior of these elements in copper, with particular emphasis on the composition range o to 0.05 per cent. These data are a part of a general program of research on the effects of impurities on the properties of oxygen-bearing and oxygen-free copper, other portions of which have been reported previously. Schematically, the behavior of individual elements is determined from measurements of conductivity and softening temperature,'v2 and the binary alloys employed are synthesized from high-purity copper in order to eliminate interference from the effects of extraneous impurities. Alloys of selected composition were first prepared in the oxygen-free form by continuously casting the melts in the form of %-in. diameter rod. Oxygen was added subsequently to portions of the alloys, either by remelting or by diffusion at 8jo°C. from a surface scale. Test wires wcre drawn one B. and S. number per pass, using four 30-min. 600°C. anneals at 0.3125, 0.257, 0.204 and 0.162 in., and a final cold reduction of 75 per cent to 0.081 in. Oxygen-bearing slugs made by remelting nere hot-rolled to 4ia in.. drawn to 0.162 in., annealed for 30 min. at 6o0°C. and cold-drawn 75 per cent to 0.081 inch. The alloys containing phosphorus, having been compounded very early in the program, were prepared in the form of 3i6-in. rod, and processed to wire with only the last three intermediate anneals listed above, all of these having been conducted in commercial nitrogen. In addition, the conductivity anneals on these alloys were also performed in the same atmosphere, and the small amount of oxygen present as an impurity in the gas resulted in some loss of accuracy at temperatures of 700' to 8o0°C., as will be shown later. Subsequently, the anneals for all oxygen-free alloys were conducted in hydrogen to prevent oxidation, and purified nitrogen was employed only for oxygen-bearing samples. All conductivity anneals wcre of one hour duration followed by a rapid quench in 10 per cent HZSO*. Effect of Phosphorus The widespread use of phosphorus as a deoxidant has resulted in universal appreci-

Jan 1, 1946