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By Alex Boozenny

The results of potential measurements between 1) a titaniurn electrode in NaCl-TiCl, melts and a graphite-cizlorine reference electrode and 2) a titanium electrode in NaC1-Nu "melts and a graphite-chlorine reference electrode show that the following relationship expresses the equilibrium relationship between the TiCl, and the dissolved metallic sodium concentrations, expressed in mole fraction units, in dilute NaCl welts at 850°C. The results of potential measurenments between a graphite electrode in NaCl-TiCl, melts that were saturated with TiCl, and a graphite-chlorine reference electrode, when combined with the standard free energy data given in literature, gave the following expression for the equilibrium relationship between the TiCl, and TiCl, concentrations, expressed in mole fraction units, in dilute NaCl melts at 850°C. These relationships are for melts in equilibrium with pure titanium. In impure systems, less sodiurn and more TiCI, can be copresent with a given concentration of TiCl,. AFTER 10 years of existence, the titanium metal industry still relies on the original Kroll and the sodium reduction processes for the only important means of converting titanium-bearing ores to titanium metal via production of titanium tetrachloride as an intermediate. Through years of modification and development these two processes have evolved to a point where any further major economic advances in the field of titanium metal production must be achieved through implementation of processes which are distinct departures from simple magnesium or sodium reduction of titanium tetrachloride. Concurrently with the refinement of the Kroll and sodium reduction processes, industries and government have sponsored research and development in the field of producing titanium by electrolysis of oxides,' carbides,' and halides3'4 in fused salt media. However, the incomplete understanding of the physical chemistry of fused salt systems has in many cases hindered the development of promising new titanium production processes to the point where they will have a clear advantage over the processes presently employed. Fortunately the volume of information on fused salt physical and electrochemistry is increasing at an accelerating pace. The first approaches tbward investigating the electrochemical behavior of fused salt systems have been the measurements of equilibrium potentials of metals immersed in melts containing their halides.' Some work on the kinetics of fused salt electrochemical processes has been reported.'09" Some descriptions of the structural composition of fused salt systems are also available. The work described herein is a continuation of the study of metal electrode potentials in fused salts. Specifically, this contribution to the growing store of fused salt chemistry information presents a description of the equilibrium relationships between the concentrations of titanium dichloride, titanium trichloride, and metallic sodium in fused sodium chloride. The investigation of the titanium dichloride-titanium trichloride equilibrium relationships is not completely new. Kellog and Krye and Melgren and opie15 have presented the results of chemical analysis of salts containing titanium chlorides. Flengas and lngrahaml' have published the results of an investigation of these equilibrium relationships obtained by measurement of electrode potentials in a fused NaCl-KC1 mixture. The investigation described herein differed from that of Flengas and Ingraham principally in the use of straight NaCl as the solvent in place of the more costly and more difficult to purify mixture. This investigation was conducted in three parts. First, the equilibrium potentials of titanium in sodium chloride containing known concentrations of titanium dichloride were measured. A graphite-chlorine electrode was employed as reference. Second, the equilibrium potentials of titanium immersed in sodium chloride containing known concentrations of elemental sodium were measured. Third, the equilibrium potentials of graphite immersed in titanium tetrachloride-saturated sodium chloride containing known concentrations of titanium trichloride were measured. The results of these three related investigations are presented in the above order. The results are combined with the thermodynamic properties of titanium chlorides and sodium chloride, obtained from literature, to give the titanium dichloride-titanium trichloride-elemental sodium equilibrium concentration relationships. In the test, whenever a melt contains titanium chlorides in predominantly divalent form, the melt

Jan 1, 1962

By E. E. Thurlow

The Geology Div. of Northern Pacific Railway Co. has adapted to its exploration efforts field procedures for geochemical sampling and semi-quantitative analysis which have been developed through research by the U. S. Geological Survey. The sampling is done in conjunction with reconnaissance geologic mapping on aerial photographs or during field checking of maps which have been prepared largely by photo-geologic interpretation. Stream sediment or soil samples are taken and readily soluble combined heavy metals are extracted with ammonium citrate followed by colorimetric titration with dithizone at the sample site. The effectiveness of this approach has been demonstrated both in positive and negative results, thereby assisting in the elimination of large areas of land from further immediate attention and in providing targets for followup exploration. An occa sional sample is submitted for spectrographic analysis as a check on the possible presence of other elements of economic significance. Field laboratory procedures are also being implemented for determining molybdenum, mercury, and other metals which may be valuable in themselves or useful as pathfinder elements in outlining mineralized areas. A lead-zinc occurrence in Oregon and a copper deposit in Montana were readily detected and outlined by stream sediment and soil sampling and a heavy metal anomaly that lacks obvious interpretation has been found in northwestern Montana. Detailed mapping and additional sampling are followed by other exploration techniques if warranted. Northern Pacific's program of reconnaissance mineral evaluation of company-owned lands and adjoining areas was outlined in a paper presented at the American Mining Congress meeting in Las Vegas four years ago. That report included policies and procedures with respect to mineral development on Railway Co. lands and may be referred to for information on these matters.1 In a sense this paper is a progress report on the use of geochemical prospecting in Northern Pacific's continuing mineral evaluation program. At this time there are positive results but as yet there is no real success story in the form of a minable ore body. GEOCHEMICAL PROSPECTING PROCEDURES The decision to use geochemistry as a reconnaissance exploration tool must be followed by research into sampling and analytical methods and into the interpretation of results. Various analytical methods were tried and evaluated by the Geology Div., including hot and cold acid extraction with and without fusion of the sample, panning and magnetic separation followed by dithizone testing of the magnetite, and cold aqueous extraction of metallic ions followed by indicator tests. Samples were first sent to the laboratory for analysis; later field laboratories were established and now virtually all testing is done at the sample site. It was concluded that, where applicable, the quickest dependable methods for reconnaissance use are the dithizone field tests for readily extractable heavy metals. This involves the simultaneous treatment of a sample, usually of soil or stream sediment, with two immiscible liquids; one a cold aqueous extractant (ammonium citrate) and the other a solution of dithizone in toluene or xylene.2 Dithizone is a colorimetric indicator that reacts quantitatively with copper, lead, zinc, and several other metals to form colored complexes in organic solvents. Results may be expressed in ml of 0.001 pct dithizone that are required to reach the blue end point, or calibration of the test results can be carried out with standard solutions of zinc; conversion factors would then be expressed in ppm, zinc equivalent. Calibration of dithizone solution with zinc standards indicates that 1 ml of 0.001 pct dithizone is equivalent to approximately 0.25 ppm of zinc. An authoritative report on dithizone field tests authored by H. E. Hawkes in the June-July 1963 issue of Economic Geology* states "The appeal of these techniques has been the simplicity and speed of the determinations as compared with more tedious laboratory determinations of trace metals in weathered rocks, soils, or plant materials. This obvious appeal, however, has often been more than matched by misuse of the method in such a manner that the results are

Jan 1, 1964

By John V. Beall

They let the whole world know again that not only could we do it, but we make it look easy. The great crews before Scott, Irwin and Worden of Apollo 15 have all blended warm humor, informality and dexterity to put on a good show: but it keeps getting better and the last one was the best. Scott's rendition of Galileo's experiment using a hammer and a feather--not just any feather, but a falcon feather after the name of the LEM-was priceless. One generation of school kids will never forget that lesson. The final touch was in the "would-you-believe''" category, Now if English astronauts had been performing the mission, the sign-off would have been typically low key. Something like; "well its tea time, chaps; we'll have to toddle along." Apollo 15 surprised and thrilled spectators by blasting off to the Air Force song "Off we go into the wild blue yonder" and leaving a camera behind to photograph their own ascent. Now that is what we call showmanship. There is another aspect to our space show and that is that it cost billions of dollars to put on. With that kind of backing, the world for an audience and in the face of grave personal risk, one would expect the space explorers to be all business. Instead they did their jobs with limpid buoyancy. Our older readers will recall and contrast a movie of the thirties and the tense atmosphere when they had to talk that kid up there (Franchot Tone) down through the zero ceiling. A feat of considerably less difficulty than docking LEM. but nevertheless the gut tightening drama was absent in the latter event. In another example, few of us can visualize reporting back after a business mission to one of the old barons such as J. P. Morgan in any but the most sedate and business-like terms. In fact we don't have to go that far back, as we can think of a few pepper-pot bosses we have had to whom one always played it straight.

Jan 1, 1971

By Richard D. Divine

In the Parkes process of extracting precious metals from lead, zinc is added to the molten lead containing gold, silver, copper, and some antimony. These metals, with the exception of antimony, form an alloy with the zinc by reason of their greater affinity for it than for the lead, and this alloy, being lighter than lead, rises to the top, carrying the precious metals with it, whence it can be removed by skimming. These skimmings are further treated for the separation of the zinc therefrom, and the recovery of the precious metals, the zinc being driven off by heat and again used for another operation. In addition to the zinc that combines with the silver, etc., a certain amount is necessary to saturate the lead, and it is therefore necessary to treat the desilverized lead to free it from this residual zinc. TO do this it is heated again in a reverberatory furnace and air or steam is blown through it. This oxidizes the zinc together with a small amount of lead and antimony, leaving the lead free from zinc and antimony, and forming oxides of these metals, which rise to the top and are skimmed off. This process relates to the separation of the metals in these oxides or skimmings. The skimmings are cooled, crushed, and mixed with carbonate of soda and pulverized oil coke. The mixture is heated in a reverberatory furnace on a bath of lead, to about 1,000" C. The metals are reduced by the coke, the lead and antimony go into the lead bath, while the zinc is volatilized and burned to oxide. This impure oxide is at the present time treated at Omaha by the Hall process of electrical precipitation, making a very pure metallic zinc. It can also be very easily refined by the old Schnabel process of using ammonia and carbon dioxide as a solvent. It seems to be in an ideal form for this purpose, and very few changes from the original method are required to obtain the zinc oxide practically C. P., leaving the lead and antimony as residues. There has been considerable difference of opinion regarding the effect

Jan 1, 1915

By Herbert W. Huse

Nitrogen, and its compounds, unique among the materials described in this volume, is absolutely essential to the existence of the human race. Almost all minerals are important and the absence of any one of them would be sorely felt; but nitrogen is an integral part of the cycle of life itself. Man cannot live without nitrogen which, as an inert gas, composes the major part of the air he breathes; as compounds, nourishes the vegetation which he eats; and, as protein, forms a part of his very flesh and blood. Nature originally provided man with a vast reserve of usable nitrogen compounds in the form of fertile soil. She constantly replenishes the supply by "fixing" nitrogen in the air at the estimated rate of 400,000,000 tons per year (an insignificant 6 lb per acre) during electrical storms. She has also placed certain microorganisms in the soil which are able to "fix" nitrogen and convert it into forms which plants can use. Legumes like cow peas, soy beans, clover, and alfalfa have extraordinary roots which serve as stimulating hosts to these bacteria which, in turn, nourish the plant. By plowing in all or part of such crops, their above-average nitrogen content can be returned to the soil for other more useful crops. The mechanism for this recycle is supplied by "denitrifying" bacteria which attack the dead plant tissue and liberate nitrogen and ammonia. However, since one crop of grain, sugar beets, potatoes, tomatoes, etc., takes out a major portion of the nitrogen which a plowed-in legume crop can supply, this method of fertilization is obviously inadequate. Drastic intervention by man has become necessary to support the ever-growing population of the world.9,15,20 Old civilizations with a high population density, such as the Chinese, were able to exist for centuries by carefully tilling the soil, rotating crops, and returning to the soil all the nitrogen in vegetable wastes plus human and animal excreta. But the lack of a means for augmenting their supply of nitrogen placed a ceiling on further development and kept the mass of the population in a chronic state of undernourishment, frequently punctuated by famine. Nitrogen plays another important role in the life of mankind. In the form of explosives, nitrogen helps to wrest from the earth many materials needed for our material well-being. Also, in the form of explosives and propellants, nitrogen increased the destructiveness of wars to a point only exceeded by the fantastic power of atomic energy. Man's first really effective efforts to improve his position with respect to nitrogen began in the 18th Century with the mining of sodium nitrate. By the late 1880's this had become a big industry serving a large part of the world. In the late 1890's nitrogen, in the form of ammonia, was being recovered from coke-oven operations. In 1900 nitrogen, in the form of nitric oxide, was being obtained from the air by an electric-arc process. About 1904 another "fixation" process based on the reaction of nitrogen with calcium carbide to form cyanamide was commercialized. By 1913 the Haber-Bosch process of "fixing" atmospheric nitrogen by reacting it with hydrogen to produce synthetic ammonia was successfully applied on a large scale, first in Germany and then throughout the industrial areas of the world.9 All the above methods of obtaining nitrogen compounds are still in use and, between them, they assure mankind of adequate supplies for all time. While this fortunate situation is not unique amongst industrial raw materials, all too few of man's needs are so well in hand.

Jan 1, 1960

By P. M. Blair

This paper presents numerical solutions of the equations describing the imbibition of water and the countercurrent flow of oil in porous rocks. The imbibition process is of practical importance in recovering oil from heterogeneous formations and has been studied principally by experimental means. Calculations were made for imbibition of water into both linear and radial systems. Imbibition in the linear systems was allowed to take place through one open, or permeable, face of the porous medium studied. ln the radial system, water was imbibed inward from the outer radius. The effects on rate of imbibition of varying the capillary pressure and relative permeability curves, oil viscosity and the initial water saturation were computed. For each case studied, the rate of water imbibition and the saturation and pressure profiles were calculated as functions of time. The results of these calculations indicate that, for the porous medium studied, the time required to imbibe a fixed volume of water of a certain viscosity is approximately proportional to the square root of the viscosity of the reservoir oil whenever the oil viscosity is greater than the water viscosity. Results are also presented illustrating the effects on rate of imbibition of the other variables studied. INTRODUCTION The process of imbibition, or spontaneous flow of fluids in porous media under the influence of capillary pressure gradients, occurs wherever there exist in permeable rock capillary pressure gradients which are not exactly balanced by opposing pressure gradients (such as those resulting from the influence of gravity). The importance of such capillary movement in the displacement of oil by water or gas was recognized in early investigations and described by Leverett, Lewis and True in 1942.1 Methods advanced by these authors for studying the process using dynamically scaled models were rendered more general and flexible by the research of later workers.2"4 The influence of capillary forces in laboratory water floods has also been discussed by several authors.6 While imbibition plays a very important role in the recovery of oil from normal reservoirs, Brownscombe and Dyes7 pointed out that imbibition might be the dominant displacement process in water flooding reservoirs characterized by drastic variations in permeability, such as in fractured-matrix reservoirs. In water-wet, fractured-matrix reservoirs, water will be imbibed from fractures into the matrix with a countercurrent expulsion of oil into the fractures. If the imbibition occurs at a sufficiently rapid rate, a very successful water flood can result; if the imbibition proceeds slowly the project might not be economically attractive. Scaled-model studies have demonstrated the vital importance of imbibition in secondary recovery in fractured reservoirs. It is therefore important in the evaluation of waterflooding prospects to develop a thorough understanding of the quantitative relationships of the factors which control the rapidity of capillary imbibition. The imbibition process serves reservoir engineers in still another important way by providing a technique for studying the wettability of reservoir core samples. Such experiments are usually conducted by observing the rate of expulsion of oil or water from core samples submerged in the appropriate fluid. Several papers have been 'published on the experimental techniques involved?? Although Handy has recently published a method for calculating capillary pressures from experiments with gas-saturated cores, it has not yet been possible to deduce quantitative information regarding water-oil relative permeability and capillary pressure characteristics of the rock from the experimental results. Thus a technique is needed for studying the quantitative dependence of imbibition rate on oil and water viscosity, initial water saturation, relative permeability-saturation, and capillary pressure-saturation relations. The development of such information, including saturation and pressure profiles by laboratory experiments, would be very difficult. However, recent advances in the applica-

Jan 1, 1965

By J. N. Butler, R. J. Morris

A series of organic collectors has been developed which successfully float synthetic secondary uranium minerals, such as autunite, carnotite, and torbernite. Recoveries up to 97 pct have been obtained. With cleaning of rougher concentrates, ratios of concentration as high as 15:1 are possible on head assays of 0.10 to 0.50 pct U 3 O 8. Additions of certain base metal salts aid in recovery and materially increase the rate of flotation and selectivity of the collectors for the synthetic minerals. Flotation tests on natural uranium minerals have not yet equaled results obtained on the synthetics, although these collectors do give better results than conventional collectors for nonsulfide minerals. RAPID increase in mining and milling uranium ores during the past seven years and the discovery of large tonnages of uranium-bearing material too low in grade to stand the cost of leaching have developed considerable interest in possible methods for beneficiating these marginal ores. Such ores are generally classed as those containing less than 0.10 pct U3O8. Development of a beneficiation method that would give both high recovery and high ratio of concentration would also make possible the beneficiation of higher grade ores and would provide higher grades of feed to existing leaching plants. Although considerable research and testing on physical or physico-chemical beneficiation of domestic uranium ores has been done in the past, to the best knowledge of the authors only a single application of physical beneficiation is now in operation on a commercial scale. Flotation has been attempted on the basis of mineral association rather than by direct concentration of the contained uranium minerals. Flotation studies conducted on this project on certain ores gave recoveries of 60 to 70 pct of the uranium by the use of conventional flotation agents such as oleic acid, but ratios of concentration were in the order of 1.5:1 to 2.5:1. Subsequent cleaning to upgrade the concentrates rapidly increased losses in the cleaner tailings, which were not later refloated in the rougher flotation. Selection of Collector: In selecting desirable organic collectors for these oxide systems, a thorough study was made of the relationship between structural characteristics and collector activity by an examination of the behavior of a number of different functional arrangements present in a variety of organic molecules, (see Fig. 1). It is generally accepted that a collector must have a relatively long-chain hydrocarbon radical and a chemically reactive elec-trophilic center. Such a requirement could be met by a large number of compounds, but steric effects at the uranium mineral surface, solubility, compat-ability with aqueous systems, air avidity, bond strength at the mineral surface, interfacial concentration of the collector, and diffusion rate of the formed complex from the air-water interface eliminated many as unsuitable for this purpose. Preliminary investigations were completed of possible collector designs consisting of aliphatic and aromatic hydrocarbon radicals attached to stable combinations of nitrogen, oxygen, sulfur, and halogen electrophilic centers, Fig. 1.Tests were made to determine melting point spans, solubility of mineral-collector combinations in various solvents, reactions with soluble uranium salts, contact angles, and floatability by semi-quantitative beaker methods.' Contact angle determinations were not too useful because of the fine particle sizes of available mineral samples. From the foregoing study it appeared that nitrogen-sulfur electrophilic centers coupled with straight-chain saturated alkyl hydrocarbon radicals would hold the most promise for floating secondary uranium minerals. As the dithiocarbamate compounds can be made to combine these attributes they were selected for further study. The dithiocarbamates form a parallel structure to the xanthates, with the fortuitous exchange of

Jan 1, 1957

By Sam N. Dewitt, Albert S. Trube

This paper presents a discussion of the pressure maintenance operations which were begun in the New Hope Field. Franklin County. Texas. in 1944. The project has required the injection of extraneous waters at depths from 7.300 to 8.000 ft with intake well-head pressures up to 4.000 psi in three different reservoirs — the Bacon. Hill. and Pittsburg. Records of oil and water production. water injection and the GOR have been kept for each reservoir and reservoir pressures were taken at regular intervals. These data indicate that the Bacon Reservoir had no apparent water encroachment up to the time of water injection. However. the Pittsburg and Hill reservoirs had some natural water influx hut not sufficient to prevent pressures from declining below the bubble point. The Bacon and Hill reservoirs responded almost immediately to water injection. while the Pittsburg which is the least permeable. has shown good pressure response only since .August, 1948. The principle objective of the project has been to increase ultimate recovery. Success of the project to date also has resulted in reduced lifting costs. Esti- mates based on the initial water breakthrough patterns indicate that the primary objective of substantial additional recovery will he accomplished, and there is a possibility that the original estimates elf oil recovery with pres-sure maintenance will he exceeded. INTRODUCTION This pressure maintenance project was one of the earliest primary pressure maintenance programs to he attempted on a multiple zone field. There are three producing reservoirs into which water is being injected for the purpose of maintaining pressure and increasing the ultimate recovery- from each. This paper is limited in scope to al1 account of the development of the project. the pressure production relationship prior to the injection of water and the effect of water injection on the producing reservoirs. Also discussed are the nature of the injection system and the indicated results on initial water break-through in the Bacon Reservoir. FIELD CONDITIONS The New Hope Field, which is located about 12 miles northeast of Winusboro, Franklin County, Texas, is an elongated symmetrical anticline containing four known oil reservoirs. The reservoirs are of the Trinity group of the Comanchean or Lower Cretaceous period and are found in Table I. The oil productive portion of each reservoir is not present in all of the producing wells because their areas and positions vary with respect to one another. Fig. 1 shows the relative position of the four reservoirs and illusIrate? how some wells could penetrate all four, while others are restricted to three. two. or perhaps one. depending on structural location. The first three reservoirs contain undersaturated oil. The deepest. the Elledge, has a primary gas cap. Although this reservoir covers a considerable area of the field. it has a very thin section and a low order of permeability. Elledge producing wells have generally been characterized by an early increase in GOR, making it necessary to recomplete them in other reservoirs. (At present. one well is completed in the Elledge. which is still producing.) Because of the difficulties en-countered in producing oil from this reservoir. and the small quantity of oil actually present. future attempts at producing it will probably be on a salvage basis during the later life of the program. For this reason, the remainder of this report will be confined to a discussion of the Bacon, Hill and pius-burg reservoirs.

Jan 1, 1950

By James L. Poole

INTRODUCTION Companies in the mining industry are subjected at times to currency exchange rate risks and interest rate risks. The former occurs any time a firm deals in more than one currency. The latter occurs anytime a firm is financing itself with borrowings that have a floating interest rate (although a fixed rate can be a problem at times). FOREIGN EXCHANGE RISKS There are two general reasons why exchange rate risks (FX risk) can occur: First, a firm may be building a mine or plant in another country where financing for the plan is denominated in funds other than the country hosting the plant. For example, if a Canadian firm is building a smelter in another country which is being financed with Canadian dollars, the C$100 million for labor, which must be paid in the local currency, has subjected the firm to a C$100 million FX exposure risk. If after the cost estimates were made the local currency appreciates 30% against the Canadian dollar, the cost of labor has increased to C$130 million. (Of course, the local currency could also devalue during this period making the labor cost component less than estimated.) The other reason exchange rate risk arises is due to the fact that the costs of production in one country producing minerals may be incurred in one currency while the production is sold in another currency, such as coal being exported from Canada to Japan under contracts denominated in Yen. In this example, the Canadian firm is exporting coal to Japan and being paid in yen in 30 days at a contract price of 100 Y per ton. Furthermore, assume that the mining firm anticipates a depreciation of the yen against the Canadian dollar of 5% in the next 30 days. Therefore, the mining firm stands to lose 5% of the value of its shipment in a month's time not including carrying costs. In both cases, the mining company risks an adverse change in the exchange rate, that is, the currency the company holds may decrease in value relative to the other currency. There are a number of ways to mitigate the exposure to foreign exchange which can be utilized by the mining company. Optimally, a company should try to match all their inflows and all their outflows in the same currency. For example, if a Canadian firm has mining costs and debt service costs both denominated in Canadian dollars then 100% of their receipts would need to be in Canadian dollars. If a Canadian firm has 70% of its cash outflows in Canadian dollars and 30% of its cash outflow in American dollars in the form of a loan amortization then their receipts would need to be 70% in Canadian dollars and 30% in U.S. dollars. This general principle of matching cash receipts and cash costs in the same currency works fine in a perfect world but what of the real world when these cannot be matched? In actual practice, however, the financial markets have developed a number of ways in which foreign exchange risks can he managed or reduced. FORWARD MARKETS One method is to use the forward markets which are made on a world-wide basis by the commerical banks for foreign exchange. If a firm wanted to lock in the current exchange rate for the receipt of a foreign currency at some point in the future, they could do so by contracting on the forward market with a bank selling that foreign currency at the current rate at the future date. For example, assume that a Canadian firm is exporting coal to Japan which would pay yen in 90 days. If a firm wanted to lock in today's exchange rate they could contract with a bank to sell on the forward market yen in 90 days. When the yen was received the contract would be executed by selling the yen to the bank and receiving the previously agreed upon number of Canadian dollars. Generally speaking, the forward market can be used to sell forward about 12 months. The costs of selling (or buying) forward

Jan 1, 1985

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 A. Romero-Juarez

This paper is concerned with the effect of propping-agent concentration on flow capacity of a fracture in the case in which there is embedment of the propping agent. Previous published studies have shown definitely that there is a relationship between fracture flow capacity and prop ping-agent concentration, and it has been shown that the theoretical results are confirmed by laboratory experiments. The problem of directly finding sand concentration for maximum flow capacity of a sand-propped fracture is solved, and formulas and charts are given to obtain this concentration under various conditions of effective overburden pressure, medium sand-grain diameter and rock properties. It is shown that, for the same effective overburden pressure and the same rock characteristics, optimum sand concentration in pounds per gallon does not depend on medium sand diameter. For conditions met in bydraulic fracturing operations, it is found that sand concentration in grains per square inch for maximum flow capacity varies within a wide range of values; this indicates the convenience of using data of fracturing pressure and rock characteristics for calculating sand concentration in order to achieve the best results in fracture treatments. INTRODUCTION It has been pointed out in the published literature1 that one important factor controls the success of a hydraulic fracturing operation — the propping of the fracture. The main effect of the propping agent is to hold the fracture open by means of the reaction forces that oppose the pressure due to the overburden. It is assumed in this paper that the propping agent is sand, that the grains are spherical and uniform in size, and that this sand is distributed in a monolayer in the fracture. The existence of a sand concentration value for maximum fracture flow capacity has been recognized since the publication of one of the first studies on the subject.2 In the reference cited, flow capacity was assumed to be proportional to the cube of the fracture volume per square inch not filled by sand. The obtained experimental curves relating to flow capacity and sand concentration had the same appearance as the curves obtained with the afore-mentioned assumption. Recent work3 has shown that fracture permeability, in the case of a monolayer, can be calculated accurately by means of a modified Kozeny-Cacman equation; thus, it can be shown that fracture pqmeability is a function of free volume in the fracture and of the rock and sand wet surfaces. The flow capacity of a fracture is dependent on the permeability of the fracture and on the fracture width. If all excessive quantity of sand is present in the fracture, its width may be large but its permeability i:; low due to the greater flow resistance; too few grains of sand per square inch are present in the fracture, sand embedment in the rock is greater and the width becomes small enough to appreciably decrease the rate of flow. To determine optimum conditions of flow, therefore, it is necessary to know the dependence of fracture width on density or concentration of propping agent. This relation is given in a study4 in which the approach to embedment is similar to the one made in a penetration hardness test of metal. With the equacions presented by Darin and Huitt,3 the number of sand grains per square inch that results in maxirnum fracture capacity can be determined graphically by plotting fracture capacity vs sand concentration. Since the relationship between fracture capacity and sand concentration may be considered known, one is led to formulate the analytical problem of directly determining sand concentration for maximum fracture flow capacity, in order to study the effect of the various quantities that come into the process. The solution of this problem appears to be interesting both from the viewpoint of fluid mechanics and from the practical viewpoint of oil production in hydraulic fracturing treatments. EQUATION FOR FRACTURE FLOW CAPACITY It can be shown3 that the fracture flow capacity of a monolayer is given by the following expression,

By Edwin A. Rides

HISTORICAL ORIGIN OF THE EXPORT CREDIT AGENCIES Almost since the inception of international commerce sellers, having manufactured and/or sold and shipped goods to an overseas buyer, have been obliged to accept the risk that they will not be paid for one reason or another. There are many reasons why payment may not be forthcoming, for example, the goods may be lost at sea, or rejected by the buyer or the buyer nay simply not be creditworthy. These risks were brought into sharp relief as international trading became more sophisticated and the practice of giving credit to buyers gathered momentum. Inevitably enterprises sprang up which offered same mitigation of this exposure, accepting houses and later confirming houses and banks were prepared to assure acceptable credit risks an behalf of the seller, usually by discounting trade paper, and for many years the market ticked over reasonably satisfactorily. However, after the 1914-18 War international trade was at an extremely low ebb and its inherent risks were accentuated to a point where they were often commercially unacceptable. Yet a healthy and vigorous international market was indispensable to recovery of the world economy and a number of governments, led by the United Kingdom, perceived a need to offer their exporters a comprehensive form of insurance, particularly to facilitate the extension of credit to foreign buyers. In the United Kingdom the Export Credits Guarantee Department (ECGD) was set up to encourage trade through the provision of export credit insurance. Over the ensuing years others followed suit and now most of the developed trading nations and many developing nations have similar agencies. PRESENT DAY IDLE OF THE EXPORT CREDIT AGENCIES (ECAS ) Traditionally then the BA's role was to encourage trade through the provision to exporters of insurance against the risks of non-payment by overseas buyers of their goods and services. However, during the 1970's the manufacturing industries of most of the developed nations found themselves facing severe competition for business, particularly in the developing world. As a result the more aggressive ECA's began to introduce ancillary forms of cover designed to reduce exporters' risks outside of the credit field. For instance, most of the European agencies now have a form of cover against foreign exchange risks here contracts are denominated in currencies other than that of the exporter's country. Most of the agencies also provide cover to exporters against the risk of unfair calling of bid, advance payment, performance bonds etc and in certain countries, where high inflation rates were endemic, a form of cover against cost escalation. In certain circumstances it is also possible for an exporter to obtain cover against losses arising as a result of the involvency of a partner in a consortium or joint venture. These are all forms of insurance but, also during the 1970's, many of the national export credit programmes took a major step away from their original raison d'etre by facilitating the provision of preferential financing terns for the acquisition of capital equipment by an overseas buyer. This new line of business quickly became an important ingredient of major export financing packages and, as we shall see later, turned out to be extremely costly for the countries providing it.

Jan 1, 1985

By Jim F. Lemons

INTRODUCTION A nickel doesn't buy much anymore. That's even true in the cost of recovering nickel -- the commodity. A 5[C] per pound (11 [c] per kilogram) increase in the nickel price won't cover a 10-percent increase in fuel costs for processing laterite ores, nor will it cover a 10- percent increase in wages for recovering nickel from a sulphide ore. It won't even cover a 5- percent increase in the capital cost necessary to mine and process ocean nodules. The basis for this statement and a quantitative analysis of the variations in costs to recover nickel from different types of nickel ores will be discussed in this paper. During the early part of the 1970's, the interest in nickel and its potential development was shifting from Canada to the Pacific Basin area. Canadian growth rate was slowing and each additional increase in nickel capacity was very expensive (Argall, G.O., 1970). Laterite ores were attractive to developers since they were easy to mine at a low labor cost, and technologies were being developed that would allow the recovery of nickel in marketable forms (Mohide, T.P., Warden, C.L., Mason, J.D., 1977). During the last decade, new laterite production was achieved in the Philippines and Botswana, and a significant increase in production from Indonesia and New Caledonia occurred. However, recent reports on nickel identify numerous problems plaguing the industry, i.e., high energy costs that are forcing shutdowns (INCO, 1980), (Mohide, T.P., Warden, C.L., Mason, J.D., 1977), high Canadian sulphide mining labor costs (Anon., 1976), and rapid inflation of nickel capital costs (Anon., 1981b). No definitive study has been made to determine how sensitive the total cost of production is to rising energy, labor, or capital costs, or to identify to what extent increased byproduct revenues could be used to offset these production costs. The purpose of this paper is to quantify the effects of increases in energy, labor, capital costs, and by-product credits on the future cost of production from nickel reserves and/or resources. METHODOLOGY OF ANALYSIS In order to evaluate the sensitivity of nickel production costs to changes in energy, labor, and capital costs, and in byproduct revenues, an analysis was made of existing and proposed nickel operations, their costs, and their sensitivity to change. The data for these analyses were obtained from numerous sources including international govern¬ment and university publications, professional journals, company reports, private communications, U.S. Bureau of Mines contracts, and estimates by Bureau of Mines personnel. These data were collected, in part, as an ongoing effort of the U.S. Bureau of Mines Minerals Availability System (MAS) to systematically measure and classify identified mineral resources according to their respective extraction technologies, economics, and commercial availability. The MAS Program is currently evaluating the present and potential availability of nickel to the United States in relation to mining, beneficiation, smelting, refining, leaching, transportation, infrastructure, environment, land use, labor, productivity, technology efficiencies, operating capacities, deposit life, and political factors. As a summary of this data, the following briefly describes nickel ore types as each relates to energy, labor, capital, and byproducts. Sulphide Operations Nickel is currently available from sulphide deposits. Roughly 55 percent of the current world nickel production in market economy countries is from sulphide ores, although only about 20 percent of the known land-based nickel reserves and/or resources are sulphides (INCO, 1981). In 1979, the Western World sulphide reserves were estimated at about 9.2 million metric tons of nickel (Little, A.D., 1979). Sulphide ores are typically mined underground, thus resulting in high mining costs; however, these ores can often be upgraded by flotation prior to final nickel recovery and require about one-third of the energy required to recover nickel from laterites (Anon., 1981c). In addition, nickel in sulphide ores may be associated with economically recoverable byproducts, which include copper, cobalt, gold, silver, and other precious metals. Laterite Operations Forty-five percent of current nickel production is from laterite deposits. Laterite deposits account for 80 percent of the known land-based nickel reserves and/or resources (INCO, 1981). In 1979, the Western World laterite reserves were estimated at over 35 million metric tons of nickel (Little, A.D., 1979). Nickeliferrous laterites are residual soils formed by weathering, typically under tropical or near tropical conditions. They can be easily mined by open-cut methods, but generally cannot be beneficiated; thus, recovery of nickel must entail processing of the total mined ore. Usually, these ores have high moisture content (20 to 30 percent by weight) that result in additional fuel costs to dry the ore. Nickel silicates, garnierites, are, processed by pyrometallurgical methods; limonite nickel oxides are normally leached. Byproduct cobalt is not recovered from most ferronickel operations, and is only recovered to a limited extent from many leach operations.

Jan 1, 1982

By J. R. Hauber, N. R. Borch

A study uras made on the creep behavior of cast and extruded SR grade beryllium. It is shown that, for stresses below about 1000 psi in the temperature range 760" to 85o° c, the creep behatior is nearly exactly described by the Nabarro-Herring mechanism. The activation energy is apparently that for self-diffusion, 42 2 kcal per mole, below 1000 psi, but it rises to 88.6' kcal per mole at higher stresses. The slress exponent is 4.5 at the higher stresses. Tertiary creep in this material is clearly related to void formation apparently caused by grain boundary sliding. BERYLLIUM is becoming an increasingly important technological material. A search of the literature has revealed a lack of fundamental studies on the creep of beryllium. This investigation was therefore undertaken to gain insight into the creep behavior of this material. EXPERIMENTAL PROCEDURE Tensile creep samples were prepared from cast and extruded SR grade beryllium. The vendor's chemical analysis of the beryllium tested is shown in Table I. The test specimens were machined as shown in Fig. 1 from i -in.-diam rods. The machined creep specimens were annealed to remove surface damage and to establish a variation in grain size. The heat treatments and their resulting grain diameters are shown in Table 11. The average grain diameters were determined by the intercept method. True average grain diameters were estimated by multiplying the measured average grain diameters by 1.5.' The creep tests were performed at temperatures from 700" to 850°C in a vacuum of 105 Torr or better in a tantalum-element resistance furnace. Loads were applied by an Instron testing machine such that the stress was held constant to within 20 psi. The test temperature was measured by thermocouples on the sample. With one exception the deviation from the desired test temperature was 2"C, and in that case the deviation was 4"C. Elongations were measured by an extensometer within the vacuum chamber which was fastened to the creep specimens at the grooves in the grip ends, as shown in Fig. 1. The precision of measurement of elongation was 1 X loe4 in. The creep tests were begun only after thermal equilibrium had been established in the sample and the extensometer to insure that there was no strain rate component due to transient thermal effects. Two kinds of creep experiments were performed. First, at constant grain size, the effects of varying stress and temperature were studied. In the second set of experiments, the temperature was held constant and the grain size was varied. The activation energy for creep was determined by varying the temperature at constant stress, as described by orn, during the first set of experiments. The variable grain size experiments revealed that creep at low stress apparently occurred by the abarro-errin' mechanism. In all of the creep tests, the stress was held constant only until sufficient strain had occurred to accurately determine the creep rate. The stress was then raised to a new value and the new creep rate determined. This process was reported until tertiary creep occurred. In this manner several data points were obtained from each specimen. The assumption was made that the structure was not changing appreciably between the incremental stress levels. This was verified by reducing stresses to previously tested levels and comparing the creep rates with the creep rates obtained at the lower strains. The re-producibility was within experimental error over strains on the order of 1 pct. EXPERIMENTAL RESULTS A typical series of creep tests is shown in Fig. 2. Primary creep was not observed in any test. Transient creep, which we define as creep rates that are nonlinear with time, was not observed for any change in stress except where tertiary creep occurred. The absence of both primary and transient creep has been previously reported for hot-pressed powder beryllium.= The data for the creep behavior at constant grain size are summarized in Fig. 3. The data show two distinctly different stress dependencies. At stresses below about 1000 psi, in the equation:

Jan 1, 1969

By Gram Curtis

The apparatus described below for the handling of plates upon their delivery from the rolls, embodies features believed to be of interest to those contemplating the building of new plate-mills, and also to such owners of existing mills as may be considering the improvement of their works. The points to which attention is called are the small space required for the finishing-end of the mill, and consequently the very moderate size of the building for the amount of plates handled; the directness and ease of manipulation, and therefore the mall amount of labor required; the distribution of plates; the facilities and time allowed for their cooling. These, together with other features of detail and general arrangement scarcely less important, will become apparent when the descriptions and illustrations herewith given are understood. As these devices deal with the finishing of the plates only, they may be added to any plate-train when the floor-space and the building are large enough to permit their introduction; and it will be obvious that the features of this method, more or less modified, are applicable to any existing mill. Figs. 1 and 2 show a three-high 32-and 19- by 120-inch Lauth mill, with hydraulic lifting-tables, served by four heating-furnaces, with hydraulic cranes for charging and drawing. Upon leaving the rolls, the plate is allowed to rest with its forward edge projecting somewhat beyond the end of the catcher's table. Here it is seized by the automatic tongs, A, suspended from a buggy travelling in the overhead trough, B, and actuated by the hydraulic cylinder, C. These tongs are operated by a boy, who stands several feet from the heated plate, and controls the long light handle, D, shown in the plan, Fig. I. His duty is merely to advance the tongs by means of .the hydrulic cylinder, C, to raise or

Jan 1, 1892

By Eugene McAuliffe

THE Coal Division undertook its most ambitious program this year at the New York meeting, with six full' sessions and a luncheon on Monday which had a record attendance and at which the newly elected officers for the Division were announced. Eugene McAuliffe, president of the Union Pacific Coal Co., Omaha, Neb., was unanimously selected as Chairman; J. B. Morrow, preparation manager of the Pittsburgh Coal Co., as Vice-Chairman; and H. E. Nold, Ohio State University, Secretary. During the past year two new and interesting activities were conducted by the Division directed at stimulating the interest of junior and student members. Reports were presented at the luncheon meeting by the chairmen of these commit¬tees. J. B. Morrow. chairman of the paper prize awards, and H. N. Eavenson reported on the work of the mining machinery manufacturers fellowship, the work on which was completed the first of the year. Several excellent papers are expected from these two groups for the next meeting of the Division to be held in Pittsburgh some time in the fall. The regular six-session program was filled from start to finish with interesting papers and much discussion, but unfortunately not enough time for the latter. The papers covered the field of prospecting, mining methods, preparation, utilization, mechanization, and safety, and all through the program we were constantly reminded of the value and need of research in the coal industry.

Jan 1, 1936

By J. Szekely, Robert J. Fisher

A formulation is Presented and solutions are given for the problem of transient heat conduction in a sphere that undergoes a spatially uniform radiative heat exchange with its environment. The solutions were obtained by the numerical integration of the appropriate Partial differential equation and are Presented in a graphical form by Plotting a dimensionless average temperature against the Fourier number with the radiation number as a paranreter, for various initial sphere and environment temperatures. In addition to these numerical results asymptotic analytical solutions are also given. PROBLEMS involving the transient heating or cooling of droplets and particles frequently arise and are of importance in metallurgical operations. Spray refining, vacuum degassing, high-temperature gas-solid reaction systems, and pebble heaters are but few of the numerous examples that may be quoted. The practical interest in these problems from a design or operational point of view is to evaluate the change in the particle temperature with the time given its physical properties, initial temperature, and that of the environment. At the high temperatures encountered the principal mode of heat transfer between the particles and their environment is by thermal radiation; in case of vacuum degassing due to the very low thermal conductivity of the gas space the convec-tive components are negligible and radiation is the only heat transfer mechanism. Although much work has been done on transient heat conduction problems, the special class mentioned here, in which thermal radiation is specified at the bounding surface, received little attention to date. One contributory factor to this situation may be the nonlinearity of the radiation term in temperature, which in general precludes the use of analytical techniques and requires numerical or analog solution of the appropriate differential equations. In fact the only solutions of general nature that are available at present pertain to semi-infinite media and slabs.'-3 The work on which the paper reports forms part of a program aimed at the theoretical and experimental study of transient radiative heat exchange between particles and their environment. The purpose of the present paper is to develop a formulation and solutions to the problem of transient heat conduction in a sphere that undergoes a spatially uniform radiative heat exchange with its surroundings. The solutions, obtained by the numerical integration of the appropriate differential equations, will be presented graphically, by plotting dimensionless parame- ters covering the range of variables relevant to metallurgical interests, thus affording a ready reference for design calculations. In addition to these results, approximate analytical solutions are also given which represent asymptotes, corresponding to extreme values of the variables mentioned. FORMULATION Consider a spherical particle of radius, a, initially at uniform temperature, Ti (T measured on the absolute scale), having a thermal conductivity, k, density, , specific heat, C, and thermal diffusivity, a. At time = 0 let this particle be exposed to an environment which is at a temperature T, and subsequently let there be a purely radiative heat exchange between the particle and the environment resulting in a spatially uniform heat flux at the surface. If in addition to the above we make the assumptions that the sphere is a gray body radiator, homogeneous, isotropic, and opaque, and that the physical properties are independent of temperature, conservation of heat in the sphere may be written as follows: The boundary condition contained in Eq. [3] states that the initial temperature of the sphere is considered uniform, equalling Ti, whereas Eq. [4] is readily obtained from symmetry considerations. Eq. [5] expresses the continuity of the heat flux at the surface of the sphere, or in other words the condition that the rate of heat exchange between the sur-

Jan 1, 1969

By Brown, R. W., G. H. Neill, R. G. Loper

All facets of ball sealer behavior must be known and understood to design for their optimum use in well treatments. The down-hole factors including the inertial forces, drag forces and holding forces have been discussed. Equations have been developed and presented for these forces. The use of these equations in this process will contribute to the most efficient use of an economical and proven ball sealer process. The urocedure presented has been used to successfully analyze field results indicating problems involving the use of ball sealers. These problems have been isolated and corrected in future treatments by using the procedure presented to revise the perforating program, the injection rate, the design of ball sealer stages and/or the type and size of ball sealers. The procedure presented also indicates that dislodgement of ball sealers occurs primarily in ultra slim-hole completions. INTRODUCTION The perforation sealing process has been proven highly successful and economical since it was introduced to the oil and gas industry in early 1956.' Since it has proved so successful in multistage fracture treatments at a much lower cost than conventional packers, the ball sealer process has become a byword in well completions.' Not only has it changed the design of fracture treatments, it has changed the concepts of selectively perforating and has greatly aided the success of the single-point and limited-entry techniques." Yet with all the advantages, there are still facets of ball sealer behavior that are not widely recognized. These must be known and understood to better design and execute the optimum ball sealer treatment. The down-hole behavior of ball sealers is influenced by a number of factors including an "inertial force", a "drag force" and a "holding force". These are considered in two phases—the initial seating of the ball and the forces tending to unseat the ball after contact has been made (see Fig. 1). This paper presents a theoretical study of these factors and formulas for predicting their influence. The authors acknowledge the fact that the flow equations presented herein describe the behavior of Newtonian fluids and do not cover the so-called power-law fluids. The assumptions made, however, are reasonable and well within practical limitations of the conditions encountered during field application. For example, it is assumed that the perforations are round with a discharge coefficient of 0.82. While this may not be exactly true, it has been verified within practical field limitations.' The discharge coefficient would not vary significantly even if the perforation size or configuration varied pronouncedly. The approach of assuming uniform perforation size is not as strained as it might first appear. Normally, a perforator contains charges equally spaced with the same number in each vertical (or horizontal) plane. If the perforating gun is not centralized, the holes in one plane will be smaller than average, while the holes in opposing planes will tend to be larger than average. The net result is that the two effects tend to balance. FACTORS AFFECTING CONTACT WITH PERFORATlON Ball sealers are injected into well treating fluids for the purpose of contacting and sealing those perforations which are accepting the fluid flow. The efficiency of the sealers is primarily influenced by: (1) the velocity of the balls down the pipe, and (2) the fluid velocity through the perforations. To divert the sealer to the perforation, the inertial force of the ball must be overcome by the drag force created by the fluid velocity through the perforation. BALL VELOCITY The final, or stable, velocity of the ball is the sum of the actual fall velocity and the fluid velocity. This will be

William Kelly, Vulcan, Mich.:—In the northern part of Bedford county, Pa., the county immediately south of Huntingdon, the Clinton measures appear along the eastern slope of Tussey mountain near its base. The only iron-ore bed that has been worked is in the upper part of the formation. Along the mountain this seam has a dip of more than 60°. At the outcrop the ore is soft and rich, but with depth it passes often abruptly into an almost pure limestone similar to that described by Dr. Rutledge. The soft ore extends deeper in the cross-gullies than it does under the higher gound between the depressions. The slates adjoining the rich ore have been weathered, but where in juxtaposition to lean ore and limestone they are hard. The alteration of the ore-bed is evidently the result of the conditions of drainage in quite recent geo-

Jan 1, 1910

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