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E. A. Loria (Product Metallurgical Engineer, Crucible Steel Co. of America, Pittsburgh)—In this interesting paper, our introductory work was quoted. We would like to call attention to our sequel paper on the experimental determination of oxygen in cupola-melted cast iron,20 which was not mentioned. Vacuum-fusion oxygen values (as well as hydrogen and nitrogen) were reported for nine heats of cast iron melted in the Battelle 10-in. cupola under normal operating practice and under oxidizing conditions. The oxygen analyses ranged from 12 to 68 pprn compared to the author's computed range of 10 to 80 ppm. The average amount of oxygen found in our irons was about 20 pprn and changes in the silicon content of the iron from 1.32 to 2.35 pct had no consistent effect on the oxygen content of the iron. The gas determination specimens were poured in split steel molds that produced a clean pin, 3/8 in. diam and 2 in. long. Because freezing was almost instantaneous, the pins were entirely white iron (nongraphitic). In the early stages of the investigation, the pins were transferred to a mercury-filled trap system immediately after pouring. This was done to collect gas evolved between pouring and analysis. However, it was found that during storage for 4 weeks gas evolution was negligible. Because the vacuum-fusion analysis was usually completed within 4 days of pouring, pins from later heats were not stored in the mercury-trap system. We found some evidence that cast iron picks up oxygen during long storage, because of rusting. Earlier work by the British Cast Iron Research Association has shown that cast irons may be stored for a long time without significant change in their oxygen content. The practical significance of this study (and our own) would be in the improvement of cast-iron quality. Has the author investigated this aspect and reached any conclusions on the effect of oxygen on the mechanical properties of cast iron? The second phase of our study was to determine the properties of the test bars poured simultaneously with the gas analysis specimens. We realize that there may be complicating factors attendant in this procedure.21 Results from many test specimens measuring chill depth, transverse flexure and deflection strength, spiral fluidity, and sensitivity to hardness of gray irons ranging from 12 to 68 pprn oxygen showed that the lowering of transverse strength was the only significant undesirable effect of high oxygen content. A statistical study of the chill test results21 showed that the iron containing 22 to 46 pprn oxygen had forced chill depths that were 2/32 in. below the expected value from their composition, and irons containing less than 16 ppm oxygen had forced chill depths averaging 1/32 in. greater than the expected chill depth. Higher oxygen contents, within the range of 12 to 68 pprn did not increase forced chill depth. With the wedge tests, there was a good linear relationship between carbon equivalent of the irons and their chill depth. The results indicated that oxygen contents below 50 ppm in the iron did not affect chill depth. With 50 to 70 ppm oxygen in the iron, oxygen appeared to have a slight graphitizing tendency. These results are in disagreement with the common belief in gray iron foundries that "oxidized irons" produce high chill depths. It would be appreciated if the author would comment on this subject. Gustaf Ostberg (author's reply)—In Fig. 1 the legend of line I should read 2 pct C, 1 pct Si. The author wishes to thank Mr. Loria for calling attention to his later work, which was published after the present paper was concluded. The range of oxygen contents quoted seems to agree well with the author's values. The lack of response to variations in silicon content is probably due to the fact that the oxygen content in most cases was below the saturation level. The absence of temperature dependence, even in the case of saturation, is understandable if the difficulty in formation and escape of the deoxidation products is taken into account.

Jan 1, 1960

By Ralph Sherman

THE remarkable increase in the distribution of the small underfeed stoker for use in furnaces and boilers in small industrial plants, apartment houses and homes has brought producers and distributors of bituminous coal to consider the problem of which coals and which sizes are best suited to this market. Many papers have also appeared, mostly in the trade journals, discussing the problem of the combustion of various coals and various sizes of coal in small stokers. Much difference of opinion has been apparent in these articles; due often, it would appear, to a mis-understanding of the fundamentals of the process of combustion in the stoker fuel bed. During the past year and a half, a program of research has been conducted at Battelle Memorial Institute: (1) On the process of combus-tion in the fuel bed of the small stoker, sponsored by Battelle Memorial Institute, and (2) on the relation of the characteristics of bituminous coals to their performance on small underfeed stokers, sponsored by Bituminous Coal Research, Inc. As a result of this program of research, two publica-tions have been made, one1 dealing with the problem of clinker formation, and the other2 with the relation of the size of the coal fed to the stoker hopper to that of the coal that reaches the retort to be burned. The experimental research on the relation of size to the performance of the coal is being actively continued. A publication of Bituminous Coal Research, Inc. presenting the data obtained on the performance of several sizes of four typical bituminous coals will appear shortly. Because of the early appearance of that publication, the present paper includes few numerical data. The purpose of this paper is to follow the coal from the hopper through the furnace with a discussion of the various actions that occur, in the hope that it will lead to a clearer understanding of the relation of the type of coal, the size of coal, and other characteristics, to the performance. The authors do not pretend to have obtained the answers to all the complex questions involved; many unanswered questions will be proposed on which future research work is planned.

Jan 1, 1936

By Ralph J. Schilthuis, William Hurst

The nature of the forces that are important in producing the oil in the East Texas field and the manner in which these forces are affected by the rate of production have always been problems of outstanding interest. These questions are of great interest to the industry as a whole on account of the economic importance of the East Texas field and to the engineers in particular on account of the unique character and behavior of the field. Subsurface pressure data throughout the field have been collected systematically, so that a quite complete history of the reservoir pressures has been kept as the field has been developed and produced. Subsurface samples of the oil and gas have been taken and these have been examined to obtain data on the physical properties of the reservoir fluids under the actual conditions of temperature and pressure. All of these data have been valuable because they have afforded the basis for a careful study of the means by which the oil is produced. It is the purpose of this discussion first to point out several of the important facts revealed by the data mentioned and then to describe studies that have been made concerning the interpretation of these facts. Reservoir Pressure Data and Properties of Oil The reservoir pressure data on the East Texas field have shown conclusively that the pressures are readily affected by changes in the rate at which the field is produced. This can well be seen in Fig. 1, where the average reservoir pressures obtained from time to time are plotted with the daily production rates and the cumulative production of the field. It is noted that the average reservoir pressure has declined irregularly, depending upon the rate of production, from the estimated original value of 1625 Ib. per sq. in. to the value of 1228 lb. per sq. in. observed for Aug. 11,1934. The decline in pressure has been more rapid at the higher rates of production than at the lower rates. In contrast, the average reservoir pressure has increased, on several occasions, upon reduction of the withdrawal rate from a high value to a lower value. The reservoir pressure data have also shown that a definite gradient in pressure has existed across the field from west to east since the begin-

Jan 1, 1935

The first mention of the mining and use of coal in the Pittsburgh district refers to the mine under Duquesne Heights that furnished coal for the garrison at the fort at Pittsburgh in 1760. Coal had been dug and used as fuel just outside of Brownsville, Fayette county, in 1759, but this was not a regular mine as the opening was in an outcropping. Maps of Ohio in 1770 showed "Cole Mines" at various points. The Penns purchased all the coal south of Kittanning in southwestern Pennsylvania from the Chiefs of the Six Nations for a reported price of $10,000. During the Revolution, coal from Herron Hill, Mincrsville, and Coal Hill, all within the present city limits, was used in Pittsburgh. There is today one custom pit opened in Coal Hill (Duquesne Heights). The first steam engine was set up in Pittsburgh in 1794 and used coal as fuel. The first mine in the Youghiogheny gas district was opened in 1796. In 1803, the first shipment of coal by water was made from Pittsburgh down the Ohio river and landed at Philadelphia, where it sold for approximately $9.50 per ton. The mines along the Monongahela were naturally the first to be opened. With the completion of locks and dams in 1844, permitting slack-water navigation, the industry began to thrive. The No. 8 field of Ohio and the Fairmont region of northern West Virginia were opened in the period 1840 to 1855. From that time on there has been a continuous development of the coal rcsources of this district, until at present productive capacity is enough to supply 30 per cent. of the country's needs of bituminous coal. The original method of working the Pittsburgh seam was to drive under cover at some easily accessible point on the outcrop with a single entry, usually 1½ yd. wide. Rooms or gangways were turned to the right and left from this entry and ventilation was usually poor and inade-

Jan 1, 1927

By H. J. Polta, R. W. Michelson

Discounted cash flow analysis is commonly used to evaluate the profit making potential of a business venture. The same method can be used to analyze the effects of varying physical and economic conditions upon the real cost of supplying a mineral commodity. If a fixed rate of return on a capital investment is specified, and the flow of cash, discounted at that rate, is just adequate to repay the investment over the life of the venture, the net present value of the venture is zero. At this condition it is possible to evaluate the unit cost of producing the mineral. It will be exactly equal to the selling price required to calculate a zero present value. Increasing a particular cost factor will not always increase the cost of supply by the same amount. For example, in iron production from magnetic taconite, an increased cost per ton associated with beneficiation would be integrated into the discounted cash flow model along with local, State, and Federal taxes, depletion and depreciation allowances, resultant increased unit recoveries, and all of the other related component cost factors. Rather than adding to the cost, the factor may have a positive, instead of a negative, effect on the discounted cash flow and cause a decreased cost of supply. This value can be determined by a computer model which iterates the necessary selling price until the net present value is essentially zero. The discounted cash flow evaluation model lends itself particularly well to an application of the Monte Carlo simulation method for calculating a probability distribution of iron unit cost resulting from the probability distributions of the component cost factors.

Jan 1, 1969

By Henry G. Granger

It still rains in the Choco! I well remember one evening a dozen years ago, while traveling toward the town of Negua in a small champa or dug-out canoe, the rain fell so heavily that I had to work my hardest to bail out the water with a large totuma or gourd in order to keep the canoe afloat, the native boatman meanwhile plying his paddle in the stern. If any one thinks bailing is easy work, let him scoop out a quart or more at a stroke, 40 times a minute for half an hour, and I venture that he will change his opinion. These small canoes required only one paddler to make the 3 miles an hour which is the standard rate of aquatic progress on the Choco. Another time, on the Atrato river, about six o'clock in the afternoon, the rain fell so heavily that an empty gourd, 9 in. in diameter and 4.5 deep, was filled to the brim in 90 sec., timed by a watch. Such downpours are typical, but unless caught in one it is not specially noticed. These downpours seldom last more than an hour, and frequently cover only a limited area, occasionally falling on one bank of a river and not on the other. During the night-time, the rain, if gentle, will usually last until dawn, and sometimes an intermittent drizzle will keep up all day as well, although, as a rule, it rarely rains during the day. The rise of the rivers, due to the rain-fall, varies from a few inches to several feet. One night in August, 1899, the spuds of the dredge Margaret, operating on the Atrato river, showed a rise of 16 ft., and for 3 days thereafter occurred the greatest flood known in that district for 32 years. The dredge had all three spuds down, and the 2-yd. shovel dragging 011 the bottom. A 0.75-in. cable fast to a stout tree, 700 ft. away, stretched tight

Jan 1, 1909

By W. J. Reagan

The problem of increasing output and decreasing percentage of rejections is a vital one in the manufacture of steel of any kind. The making of basic open-hearth steel for use in rolled steel wheels, tires for locomotive and car wheels, and forgings of various kinds, is a highly specialized industry. The increase in weight of railway rolling stock of all kinds, and the high speed that the public demands of transportation facilities, make it imperative that steel for use in this class of material shall be of the highest quality obtainable. During the past few years it has been the writer's good fortune to have opportunity to study the defects in basic open-hearth steel, and also the results obtained by various changes in open-hearth practice, on such defects. The opportunity for study and the details available are rarely found in the manufacture of steel of any kind. It seems reasonable to assume that many of the results determined here can be applied to the production of steel of other types with a decided improvement in quality, a decrease in the percentage of rejections and an increase in output. All of the material described is basic open-hearth steel with the following range of analysis: carbon, 0.50 to 0.85 per cent.; phosphorus and sulfur, 0.04 max.; silicon, 0.15 to 0.35; manganese, 0.50 to 0.75. All of this material is bottom-cast, therefore tapping and pouring temperatures are higher than in top-cast production. Ingots used in this type of work are of standard length with varying diameters. The ingot is known as duodecagonal, or twelve-sided. The standard body length is 88 in. and the hot top length, 14 in. Fig. 1 shows a typical ingot of this type. The diameter varies from 13 to 30 in. Ingots for special forgings, which cannot be made in molds of standard size, are made in molds of various sizes and designs. These ingots are sliced cold, into blocks of various lengths, depending upon the weight of the forging to be made. Fig. 2 shows the ingot after coming from the slicing lathe. Jusf sufficient metal remains between blocks to hold the ingot in one piece while it is being removed from the lathe; then steel wedges are inserted between the blocks and the blocks are broken apart. This affords abundant opportunity for inspection, as the interior of the

Jan 1, 1930

By Joseph B. Umpleby

The oil industry is at the parting of the ways in relating fundamental engineering concepts to legal interpretations and field practices. The old concept, based on an erroneous analogy to wild game, that oil and gas are migratory substances and belong to him who reduces them to possession regardless of their point of origin in the reservoir, has come to be quite generally recognized as the basis of many of the serious ills and extravagances of the industry. The chain of consequences resulting from this erroneous conception has been traced elsewhere and need not be recounted here. The important problem at this stage in the development of the industry, when laws are being revised by legislative action and modified by court decisions; when added powers are being exercised by voluntary committees and official regulatory bodies; and when the need for control of output has forced itself to the forefront, is to see to it that new law and action are based on sound engineering concepts. Reservoir Energy Common Property Since the study of gas instituted by the Marland committee of the American Petroleum Institute in 1927, a great mass of information has accumulated concerning the function of gas in the development and production of oil. This wealth of data leads to the conclusion that every oil pool contains three resources: Oil, gas and reservoir energy. I take it that the central problem of this symposium is the ownership of these three resources and that "source" and "utilization" are involved because of their bearing on ownership through the demands of equity and conservation. In order to facilitate the discussion, permit me to state categorically, that: The oil and gas in a particular tract should belong to the owners of the mineral rights in that particular tract, but the reservoir energy should be common property of all owners of mineral rights in the pool I take it that apportionment of oil and gas among owners according to the relative amounts that exist in place in their respective tracts is

Jan 1, 1933

By G. Y. Chin, W. F. Hosford

It has long been recognized that, for a crystal to undergo an arbitrary shape change by crystallographic shear, at least five independent shear systems must be activated. Taylor1 analyzed the deformation of fcc crystals by {111}<110> slip and showed that the principle of minimum work could be used to determine which combination of slip systems might act to produce a given shape change. Later Bishop and Hi112 attacked the same problem by first identifying the state of stress which could physically activate five or more {111)(110) systems simultaneously and then invoking the principle of maximum virtual work to determine which combination would act for a given shape change. Taylor&apos;s general approach has been used to calculate the active slip systems and the relative strengths during axisymmetric flow of cubic crystals with other deformation modes, including {112}<111> slip3 and {111}<112> twinning.&apos; It is the purpose of this note to identify the stress states capable of activating simultaneously five or more of these systems. {111}<112> Twinning. The {111}<112> systems are defined in Table I and illustrated in Fig. 1. The sense of the shears are those for twinning in fcc crystals. The shear stress on any system may be written in terms of the stress components expressed relative to the 1,2,3 cube axes. For example, the stress For five or more of the systems ij to be activated simultaneously, it is necessary that Tij/T be equal to unity in at least five of the expressions [3], while Tij < T for the remainder. (These restrictions assume that the same shear stress T is required to activate each system and that the shear stress on any system cannot exceed that for its activation.) The discrete values of the stress components A through H which can satisfy these restrictions are listed in Table II together with the values of Tij/T for all systems. It may be noted that Tij/ T is not necessarily zero on all nonactive systems as found by Bishop and Hill for <110> {111} slip. In fact, for the case of twinning Tij/T may reach negative values as large as -2 for shear stress in the reverse direction, Table 11. This means that, if those stress states are to be valid, the shear stress to activate reverse twinning must be greater than twice that for forward twinning. Such stress states are probably valid in view of the directionality of the twinning process. There has been no documentation of reverse twinning thus far. It may be noted that the stress states fall into four classes, which may simultaneously activate eight, six, six, and five twin systems respectively. These solutions may be applied to the {112}(111)

Jan 1, 1970

By William P. Blake

It is scarcely necessary to point out the important functions of water in the mining operations of man, especially in the State of California, where sluicing and hydraulic mining have been practiced on such a grand scale as to arouse the opposition of the agricultural interests. But the role which water and ice have played in mining or excavating on their own account is not so apparent. The alluvions of existing rivers, and the higher gravel-beds left by ancient streams, are doubtless the result of running water; but how far these gravelly materials owe their origin primarily as rocky debris and fragments of veins to glacial erosion, it is difficult .to determine. Yet we see on every side in our higher mountains unmistakable evidences of the cutting, crushing and eroding effects of glacial ice. We note that mountain-summits have been reduced in height and shaped into rounded and dome-like summits. We know that the general contour of the hills of New England, of the Highlands of the Hudson, and of the mountains of northern New Jersey, is due to glacial carving. The same is true of the Laurentian hills of Canada and of the mountains of all northern regions. And we recognize in the vast deposits of so-called " drift," which are spread out over the surface of the northern States, the chips and debris from the glacial workshops. Thus we cannot avoid the conclusion that there was an enormous amount of cutting and excavating in glacial times, and that vast quantities of veinmaterial and of ores and metals must have been liberated by ice-action.

Jan 1, 1900

By Charles H. Jacoby

In 1774 a Swedish chemist, C. W. Schule, first recognized manganese as an element. That same year Schule&apos;s associate, J. G. Gahn, isolated the element manganese for the first time. In 1856 the Bessemer process of steelmaking gave birth to the economic importance of manganese. Later, in 1882, Robert Hadfield discovered high manganese steels. Although the primary use of manganese is in the ferroalloy industry, two additional important uses for manganese are making chemicals and dry cell batteries. Manganese is also vital to plant and animal life. Various chemical compounds of manganese are used in fertilizers, feeds, glass manufacture, paints, varnishes, and for numerous medicinal and chemical purposes. For the study of industrial minerals and rocks, only the chemical and battery grade material is of- concern, but for the sake of comparison, metallurgical aspects are included in this presentation. Although currently the world&apos;s largest consumer of manganese, the United States is producing only minor amounts of ore at the present time. This is due primarily to the fact that although huge deposits of manganese occur within our borders, all are of such low grade as to be economically unfeasible to mine. For many years various government agencies and segments of private industry have devoted sizable sums of money and time in an attempt to upgrade ores from the various deposits, and also in an attempt to recover manganese from blast furnace slags. In view of current world prices, and the quantity of high grade material available, there is little likelihood that any of these approaches will be found to be economically feasible in the near future. Geology and Mineralogy Mineralogy There are over one hundred minerals that contain manganese. These minerals vary from those with compositions that are predominantly manganese to those having only minor percentages. [Chemical Mineral Composition % Mn Hausmannite Mn304 72 Polianite MnO2, 63.1 Pyrolusite MnO24 60-63 Cryptomelane KR8O16R (R=Mn) Variable PsilomelaneBa Mn Mn8O16 (OH).45-60 CoronaditePb R8O16R (R=Mn) Variable Hollandite Ba R8O16R (R=Mn) Variable Manganite Mn2O3•H20 62 Braunite 3 Mn2O3•MnSiO3 62 Tephroite 2 MnO•SiO2 54.3 Rhodochrosite MnCO3 47 Rhodonite MnSiO3 42 Spessartite 3 MnO•AI2O3•3SIO2 33.3 WadHydrous Mn OxidesVariable Franklinite(Fe Mn Zn)O(Fe Mn)sO3 Variable Asbolan Cobaltiferous wad Variable AlabanditeMnS63.14] Geology From a geological standpoint most manganese deposits are complex. In general, it can be said that all primary deposits of manganese are carbonates or silicates. The most productive and profitable have been those of sedimentary origin and residual concentrations. Examples of these residual types of deposits are associated with the metamorphosed lodes of Madhya, Pradesh, India, and the lateritic deposits of Orissa and Bihar, India; nodules in the residual clays of the Philippine Islands, US southern Appalachians and Arkansas, Ghana, and Brazil. Sedimentary manganese deposits are best exemplified by the Nikopol district of Russia and the Tchiatouri area of Georgia, USSR. Hydrothermal replacements are characterized by the rhodochrosite deposits of Butte and Phillipsburg, MT. In general, the hydrothermal type deposit has not resulted in any large tonnages being produced, but may have given

Jan 1, 1983

By N. Marusov, D. K. Lowe, J. C. Karp

This paper considers, from an engineering viewpoint, several factors involved in creating, designing and locating horizontal barriers for controlling water coning. This is an effort to consolidate new concepts with previous information so that a reasonable selection of barrier materials, dimensions and vertical position can be made. Coning theories previously developed are briefly reviewed and an effort i,s made to reduce the results of coning-theory calculations to a point where routine calculations can be made with a desk calculator. It is expected that these simplified calculations will give usable predictions of the amounts of improvement attainable with barriers of various dimensions. Apparatus and procedures used for testing the suitability of commercial cements are described and test results are presented. INTRODUCTION Just about as soon as the phenomenon of water coning was recognized as an oilfield problem, there were suggestions that the production of water coning could be controlled or completely suppressed by means of horizontal barriers. It was also suggested that natural barriers such as shale streaks were helpful in restricting bottom-water production. The implication was that wells not having the benefit of continuous shale streaks to suppress bottom waters should, in some way, be supplied with an artificial barrier. With regard to the selection of barrier materials, there are many references which give the merits of liquid barriers.&apos;,&apos; These liquids include surface-active agents," recipitates&apos; and emu1sions. There is no real need to review the merits of these materials again. This paper deals with the use of solid barriers which could be made from various cements. The two major restrictions placed on these barrier cements are that (1) they must be commercially available in large quantities, and (2) they must be applicable by means of standard tools and equipment with techniques that have been fully developed and are in general use at the present time. A schematic drawing of a horizontal barrier in a reservoir is shown in Fig. 1. Two maximum stable water cones are illustrated-—-one for the wellbore diameter and the other for a barrier. A maximum stable cone is one that has attained its maximum volume at the critical production rate and is on the threshold of producing water. The volume displaced by each water cone and the rise in water table are indications of the amount of water-free oil produced. Corrections for porosity, connate water and residual oil, of course, must be applied. The water-oil interface which defines a maximum stable cone is called a free surface. It is a surface over which the pressure is constant. This free surface has the shape of a limiting streamline at and below which there is no movement or transport. The shape of the water cone describes the pressure drop in the reservoir. The effect of a completely impermeable barrier on the cone shape is essentially the same as extending the wellbore out to the barrier radius. The placement of a horizontal barrier requires that a horizontal fracture be created using a single-point entry technique. Two methods may be employed for filling this fracture. One method consists of propping the fracture before filling with cement. The other consists of fracturing with fracture fluid, then immediately following with cement

By Linn Bradley, W. W. Strong, H. D. Egbert

Marked differences of opinion have been expressed by engineers interested in cleaning iron blast-furnace gases for use in hot-blast stoves and under boilers, in reference to the advantages of a hot-dry method over a cold-wet method. One point at issue involves the sensible heat energy in the moisture contained in the gas. Some advocates of the cold-wet methods claim that the condensation and resultant removal of the greater portion of this contained moisture by wet scrubbing, spraying or similar methods, results in a saving of some of this sensible heat energy, by reason of the fact that water vapor has a high capacity for sensible heat energy and may carry from the exit of a hot-blast stove, for example, more heat units than are sacrificed or lost when the gas is cleaned by this cold-wet method. Other advantages claimed for the latter method are: That gas burns more readily when it is free from moisture in any form; that because gas is made denser by cooling and removing the moisture it has a higher calorific value than hot gas carrying moisture; and that higher flame temperatures are obtained when the gas is cleaned by the cold-wet method. A search through the available literature fails to disclose any extensive calculations or records of conditions obtained in practice, bearing upon these phases of gas cleaning. This paper deals with these problems from the standpoint of the economy of using a gas of higher flame temperatures, of improved stove design, and of economy in the gas-cleaning department. Calculations have been made which show that by cleaning the gases by a cold-wet method the sensible heat energy of the blast-furnace gases is greatly reduced; and, in general, this loss of heat energy is far greater than that lost from the stoves or boilers due to the sensible heat capacity of the water vapor if carried away by the exit gases. By making use of the

Jan 1, 1917

By N. Tiner

In an article on magnesium and its alloys, Gann and Winston! stated that manganese has a limited solubility in the liquid state. W. Schmidt2 showed a diagram according to Joseph Ruhrmann indicating that the solubility of manganese in liquid magnesium falls from about 2.65 per cent at 790°C. to about 0.5 per cent at 675°C. The curve was extrapolated to show zero solubility at the melting point of pure magnesium (Fig. I). This work suggested that at the lowest manganese contents it was not possible to detect either a eutectic or the formation of a solid solution, so that manganese was stated to be present in the structure as large individual crystals. Two years after the presentation of, these results, Gann3 brought evidence to show that some manganese is capable of dissolving to form a solid solution, any excess of manganese present then assuming chiefly the form of small blue-gray particles scattered throughout the primary magnesium crystals, occasionally in clusters but seldom at the boundaries. He presented micrographs of cast alloys containing 0.1, 0.4 and 1.0 per cent manganese that show a small amount of coring around the individual particles due to solid solution, and indicate that the location of the manganese particles is closely associated with the original dendritic structure of the primary crystallization. He also pointed out that the amount of manganese that can be dissolved in magnesium depends on the amount of other alloying elements present, the effect of the second alloying element being to decrease the amount of manganese retained in the alloy. E. Schmid and G. Siebe14 have determined the solid solubility of manganese and its variation with temperature by means of precision X-ray diffraction measurements. They found that the solubility is 3.4 per cent at 645°C. and decreases to practically zero at 200°C. It is apparent that the X-ray diffraction measurements of Schmid and Siebel are not in agreement with the results of Ruhrmann as presented by Schmidt. This disagreement, and also the lack of data on magnesium-aluminum-manganese and magnesium-zinc-manganese systems, led the author to the present investigation, to determine accurately the liquid solubility of manganese and its variation with temperature. Experimental Method The experimental method for making solubility determinations consists of saturating the molten magnesium or the alloys with manganese at various temperatures and analyzing the dip samples taken from these melts. Melting is carried out in a cylindrical steel pot heated by an electric resistance furnace. The pot had a metallic outside coating to protect the steel against oxidation, and a graphite inside lining to prevent the contamination of the melt by prolonged contact with iron. The inside diameter of the pot was 4 in. and the depth 12 inches.

Jan 1, 1945

By W. W. Smeltzer

The linear formation rates of wustite films have been determined over the temperature range 590° to 1030°C using a vacuum microbalance technique. These rates are dependent directly on the partial pressure of carbon dioxide, Activation energies for film and scale formation in carbon dioxide and oxygen atmospheres are equivalent to either the dissociation energies of carbon dioxide and oxygen, or the activation energy for the diffusion of cation vacancies in wustite. Of the metals, iron is the most widely used basic constituent of durable alloys despite its intrinsic property of converting at a relatively rapid rate to the oxides from which it is derived. This property has accounted partially for many investigations on the oxidation of iron at low and high temperatures. Interpretation of the results have been complicated by formation of multilayers containing the various oxide phases. To aid in elucidation of the oxidation kinetics, measurements have been carried out in this investigation on the growth of the wustite surface layer. There are several studies directly related to the objective of this investigation. The growth of multilayer scales has been demonstrated to be diffusion controlled in oxygen at atmospheric pressure over the temperature range 450" to 1200°C by Davies, Simnad, and Birchenall.&apos; To gain an insight into the diffusion mechanism, Himmel, Mehl, and ~irchenall&apos; determined the self-diffusion coefficients of iron in wustite, magnetite, and hematite. These results were used to evaluate the oxidation rates of iron and its oxides, taking as a basis the theoretical parabolic rate equation developed by Wagner., The evaluations were compared to experimental data and were shown to provide essential confirmation of this theory. Fischbeck, Neundeubel, and salzer4 have demonstrated that the oxidation of iron in carbon dioxide and other atmospheres at high temperature obeys a linear relationship. Because the Arrhenius temperature coefficients of the reaction rate constants changed at the A, point they concluded that the passage of iron into the oxide controlled the reaction. This viewpoint has been accepted by Benard and ~albot&apos; to explain the occurrence of linear rates in oxygen before the onset of diffusion-controlled parabolic oxidation. This basic premise of a rate-controlling reaction at the iron/oxide interface has been questioned recently by Hauffe and Pfeiffer.&apos; Since the formation of wustite may follow a linear or parabolic relationship depending on the pressure of the gaseous re-actant, they propose that linear oxidation is determined by a chemisorption reaction while parabolic oxidation is controlled by diffusion. As confirmation of this viewpoint, Hauffe and pfeiffer6 and Pfeiffer and ~aubmeyer&apos; have established that the linear scaling constants of wustite formation at 1000°C in carbon-dioxide or low-pressure oxygen atmospheres

Jan 1, 1961

By H. L. Riley, B. W. Gandrud

A froth flotation unit was added to the DeBardeleben Coal Corporation&apos;s Empire washer at Empire, Alabama, in the fall Of I94O following an investigation of possible ways and means of recovering coal values from settling-tank overflow or slurry. Officials of the DeBardeleben corporation hoped that some practical and reasonably economical way could be found for recovering fine coal from overflow water, although there had as yet been very little progress along this line in the Alabama coal fields. The Bureau of Mines was asked to cooperate in the project through its Southern Experiment Station, at University, Alabama. This paper presents a brief description of the process and the installation that resulted from the investigation of the overflow water or slurry problem at the Empire mine. The experimental data include&apos; as a Part of this Paper were obtained during the course of the investigation in 1940 Since that time, however, the flotation unit has been running more or less continuously without significant operational changes and is still Performing pretty much in accordance with the data obtained in 1940. Flowsheet at Empire and Type of Coal Treated The Empire mine is developed on the Black Creek bed near the the border of the Warrior field. The coal in this bed is extremely low-ash and although there is an almost complete absence of bone coal and partings, the bed is so thin that, with mechanized mining, a high percentage of rock from roof and floor inevitably gets into the run-of-mine coal. The thickness of the Black Creek bed throughout the part of the Warrior field in which it is mined extensively is rarely over 30 in. and probably would average about 25 in, the coal is of the high-volatile A rank and of excellent quality, but as a result of admixture of roof and floor material, the run-of-mine product usually contains I ; to 20 pct rock by weight. he following is a proximate analysis on an "as-received " basis of a typical seam sample from the Empire mine:&apos; moisture, 3.0 pet; volatile, 34.6 fixed carbon 58.3; ash, 4.1 This sample shelved 15,070 Btu per pound and 0.9 pct sulphur on a moisture-and-ash-free basis. In the Empire preparation plant the lump sizes above 3 in. are removed and hand-picked on a Marcus conveying Screen, the 3 to ? -in. size is removed by vibrating screens and washed in two Montgomery single-cell jigs, and the ?-in. to o slack is cleaned on four diagonal

Jan 1, 1949

By H. C. Fiedler

The solubility of sulfur in Si-Fe was determined by the metallographic examination of heat-treated and quenched samples. In the absence of manganese, the solubility in 3.1 pct Si-Fe was found to be about 0.010 pct at 1000o C, 0.015 pct at 11000C, and 0.020 pct at 1150°C, which is substatntially less than hitherto reported. Increasing the silicon content was found to decrease the solubility of sulfur, which is consistent with the increase in the activity coefficient of sulfur with increasing silicon content that has been reported for Fe-Si alloys. Manganese additions were studied in alloys containing 3.1 pct Si and between 0.013 and 0.015 pct S. At low manganese levels the solubility product of manganese sulfide was found to be lower than previously reported. THE solubility of sulfur in pure polycrystalline iron has been reported by Rosenquist and Dunicz1 and by Turkdogan et al.2 Samples were equilibrated in atmospheres containing different ratios of H2S/H2. Both groups of investigators found a solubility limit in y iron of 0.013 pct at 1000oC and 0.031 pct at 1200°C. In addition, Rosenquist and Dunicz1 found a solubility limit in a iron of 0.020 pct at 900°C. Ainslie, Hoffman, and seybolt3 found significantly higher sulfur contents in polycrystalline iron samples than in single-crystal samples after heating at 890°C in a sealed tube containing a mixture of powdered iron and FeS made with s35. Whereas the single crystals contained 0.013 and 0.016 pct S (± 0.005 pct), the polycrystalline samples contained between 0.016 and 0.026 pct S. Autoradiographs suggested that the excess sulfur in the polycrystalline samples was due to the segregation of sulfur in solution at grain boundaries. Ainslie and seybolt4 have reported on the solubility of sulfur in 3 pct Si-Fe. Their samples were sealed in capsules containing hydrogen and sufficient sulfur as cobalt sulfide to saturate the sample. After heat treating, the sulfur-rich phase on the surface was removed by abrading, and the sulfur content of the sample was taken as the equilibrium value for that temperature. Before the equilibrating heat treatment, the samples were heated to 1300°C to coarsen the grains. The resulting grain size, which was about 3/18 in. in diam, was considered sufficiently large to preclude a sensible increase in sulfur solubility due to grain boundary segregation. They reported the solubility to be 0.029 pct at 900oC, 0.063 pct at 1000oC, 0.076 pct at 1100°C, 0.122 pct at 1200°C, and 0.098 pct at 1300°C.

Jan 1, 1968

By Ihor A. Kunasz

Introduction Lithium minerals occur predominantly in pegmatites which contain mineral assemblages derived from the crystallization of postmagmatic fluids or from the metasomatic action by residual pegmatitic fluids. They have been the traditional sources of raw materials for ceramic and chemical industries. With the discovery of Searles Lake, brines became new sources of lithium. Indeed, the 1960s may well be referred to as the "brine decade" because several brine bodies of significant economic importance were discovered. In the United States, the brines of Clayton Valley, Nevada, are presently exploited by Foote Mineral Co. The brines of the Great Salt Lake of Utah, the Smackover formation, and the Imperial Valley geothermal field, have been defined as important resources of lithium. In South America, new occurrences have been identified in Bolivia and Argentina. At the Salar de Atacama, Chile, new production capacity is scheduled for 1984. Following the termination of the AEC purchase program in 1959, several companies such as Maywood Chemical Co., American Lithium Chemicals, and Quebec Lithium Corp. were forced to close their operations. Nevertheless, with the development of new applications in glass ceramics, air conditioning systems, synthetic rubber, and metallurgy (aluminum potlines), the lithium industry grew steadily, and with the potential application of lithium metal in batteries and nuclear reactors, a healthy growth can be foreseen. New products and new applications are likely to stimulate exploration for expanded, reserves as well as the search for new sources from which lithium could be extracted economically. Geochemistry of Lithium Lithium is the third element in the periodic table. It is the lightest of all the metals, having an atomic weight of 6.938, an ionic radius of 0.68Å and a charge of +1. The geochemistry of lithium has been extensively studied and has been summarized by Rankama and Sahama (1950), Goldschmidt (1937), and Hortsman (1957). The distribution of lithium in igneous rocks is controlled by its size and its charge, and by the (MgO+FeO) / Li2O ratio. In the early stages of crystallization of a magma, that ratio is very large. Consequently, both magnesium and iron are removed by ferromagnesian minerals in preference to lithium which is then concentrated in the residual magma. This results in an enrichment of lithium in silicic rocks and pegmatites (Strock, 1936). Pegmatites are coarse-grained igneous rocks formed by the crystallization of postmagmatic fluids. Minerals within pegmatites may also form by metasomatism (Jahns, 1955). Genetically, the pegmatites are associated with neighboring intrusives. Mineralogically, granitic pegmatites contain feldspar, quartz, and mica as the main constituents and a variety of exotic elements such as lithium, beryllium, tantalum, tin, and cesium, which may or may not occur in economically significant concentrations. Detailed studies by numerous investigators (Cameron et al., 1949, 1954; Hanley et al., 1950; Jahns, 1953, 1955; Page et al., 1953) indicate that pegmatites often exhibit an internal zonal arrangement, with each zone containing a specific suite of minerals. The lithium minerals are usually found in the intermediate zones, and although as many as 13 zones have been recognized by Cameron, et al. (1949), a complete zonal arrangement is rarely found. Zoning of pegmatite bodies has also been observed on a regional basis. The regionally zoned pegmatite sequences exhibit mineral assemblages and complexity according to their re-

Jan 1, 1983

By B. H. Caudle, R. L. Slobod, E. R. Brownscombe

An earlier publication has discussed three methods lor obtaining relative permeability data on small core sample-: and the apparatus and technique for the capillary pressure displacement method. This paper describes the apparatus and technique for the solution gas and the dynamic displacement methods and presents a routine procedure for obtaining oil-gas and water-oil relative permeability data. Theoretical and experimental considerations are presented to show that the end effect commonly associated with the dynamic flow mechanism is extremely small where constant rates are employed in the flowing phase. An effect of flow rate on relative permeabilities obtained by the dynamic system is found only when gas is one of the flowing phases and this effect is ascribed to a form of channeling in the capillary system. The apparatus and procedure* used to obtain relative permeability data with three phases flowing are described and some preliminary results of the use of this method are shown. INTRODUCTION In a previous publication from this laboratory there appeared a brief discussion of the concepts behind three basic methods for obtaining relative permeability data.&apos; These three methods were called the capillary pressure displacement method. the solution gas displacement method, and the dy. namic displacement method — the names being suggestive of the type of process used for obtaining the desired saturation prior to making the permeability measurements. In the same publication, the apparatus and technique for the capillary pressure displacement method were described and some typical results obtained by this method were presented. This paper will present: 1. The routine procedure used to obtain complete relative permeabilitv data (In small core samples with two phasec flowing; 2. The experimental techniques for the solution gas and dynamic displacement methods for obtaining relative permeability data; 3. The results of some studies on the mechanism of fluid flow through consolidated porous media; and, 4. The preliminary results on the determination of relative permeability for a system in which three phases are flowing. TECHNIQUE AND APPARATUS FOR THE DETERMINATION OF RELATIVE PERMEABILITY WITH TWO PHASES FLOWING In order to obtain relative permeability data on a small core sample which will describe the various phases of reservoir depletion. it is necessary that the methods used duplicate, as closely as possible, the various mechanisms involved in rescbrvoir depletion. It is important that. in any type of relative permedbility determination. the core be originally at virgin reservoir conditions with respect to the fluids within the pore *paces. (for example. oil used to displace water from core until connate water saturation estahlished). and that the subsequent saturation changes in the core be analagous to tile reservoir depletion mechanism for which the data are to he used. PROCEDURE OF DETERMINING RELATIVE PERMEABILITY DATA WITH TWO PHASES FLOWING A standardized procedure has been set up for obtaining relative permeability data and other information on small core samples. This procedure essentially consists of 11 steps as shown below: 1. Determination of tile capillary pressure curve.&apos;! This information is used to help select samples for relative permeability determinations and to charactrrize. in general. the pore size distribution of the sample. 2. Determination of the specific permeabilities to air, oil. and water. These values are those on which the relative pern~eahility calculations are based. 3. Reduction of the core to connate water by an oil drive using the high speed centrifuge. 1. Determination of the critical gas saturation value and the associated relative permeability to oil by the solution gas drive method. 5. Determination of the relative permeabilities to oil and gab in the region where both phases are flowing by the capillary presqure method. 6. Reduction of the sample to residual oil in the centrifuge by an air drive. and the determination of the relative permeability to gas at this point.

Jan 1, 1951

By R. L. Slobod, B. H. Caudle, E. R. Brownscombe

An earlier publication has discussed three methods lor obtaining relative permeability data on small core sample-: and the apparatus and technique for the capillary pressure displacement method. This paper describes the apparatus and technique for the solution gas and the dynamic displacement methods and presents a routine procedure for obtaining oil-gas and water-oil relative permeability data. Theoretical and experimental considerations are presented to show that the end effect commonly associated with the dynamic flow mechanism is extremely small where constant rates are employed in the flowing phase. An effect of flow rate on relative permeabilities obtained by the dynamic system is found only when gas is one of the flowing phases and this effect is ascribed to a form of channeling in the capillary system. The apparatus and procedure* used to obtain relative permeability data with three phases flowing are described and some preliminary results of the use of this method are shown. INTRODUCTION In a previous publication from this laboratory there appeared a brief discussion of the concepts behind three basic methods for obtaining relative permeability data.&apos; These three methods were called the capillary pressure displacement method. the solution gas displacement method, and the dy. namic displacement method — the names being suggestive of the type of process used for obtaining the desired saturation prior to making the permeability measurements. In the same publication, the apparatus and technique for the capillary pressure displacement method were described and some typical results obtained by this method were presented. This paper will present: 1. The routine procedure used to obtain complete relative permeabilitv data (In small core samples with two phasec flowing; 2. The experimental techniques for the solution gas and dynamic displacement methods for obtaining relative permeability data; 3. The results of some studies on the mechanism of fluid flow through consolidated porous media; and, 4. The preliminary results on the determination of relative permeability for a system in which three phases are flowing. TECHNIQUE AND APPARATUS FOR THE DETERMINATION OF RELATIVE PERMEABILITY WITH TWO PHASES FLOWING In order to obtain relative permeability data on a small core sample which will describe the various phases of reservoir depletion. it is necessary that the methods used duplicate, as closely as possible, the various mechanisms involved in rescbrvoir depletion. It is important that. in any type of relative permedbility determination. the core be originally at virgin reservoir conditions with respect to the fluids within the pore *paces. (for example. oil used to displace water from core until connate water saturation estahlished). and that the subsequent saturation changes in the core be analagous to tile reservoir depletion mechanism for which the data are to he used. PROCEDURE OF DETERMINING RELATIVE PERMEABILITY DATA WITH TWO PHASES FLOWING A standardized procedure has been set up for obtaining relative permeability data and other information on small core samples. This procedure essentially consists of 11 steps as shown below: 1. Determination of tile capillary pressure curve.&apos;! This information is used to help select samples for relative permeability determinations and to charactrrize. in general. the pore size distribution of the sample. 2. Determination of the specific permeabilities to air, oil. and water. These values are those on which the relative pern~eahility calculations are based. 3. Reduction of the core to connate water by an oil drive using the high speed centrifuge. 1. Determination of the critical gas saturation value and the associated relative permeability to oil by the solution gas drive method. 5. Determination of the relative permeabilities to oil and gab in the region where both phases are flowing by the capillary presqure method. 6. Reduction of the sample to residual oil in the centrifuge by an air drive. and the determination of the relative permeability to gas at this point.

Jan 1, 1951