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By Robert L. Llewellyn

Preparation of coal begins at the face in underground mines or in the pit with surface mines. Impurities in raw coal can be in the seam itself or in extraneous material taken in mining from the roof or bottom. Raw coal is prepared only to the extent that is necessary to make the product salable. Over 60% of all coal production is processed to some extent in cleaning plants. For underground mines the proportion cleaned is 72% as compared to 42% from surface and 15% from auger mines. Coal supplied for coking purposes is nearly all upgraded by washing, while for the largest market, electric power generation, a high proportion is shipped as a raw product with processing, in whole or in part, only as necessary when excess impurities are mined with the coal. This chapter will deal primarily with plants that process or wash coal to some extent and only incidently with mines shipping raw run-of-mine coal crushed to a top size of, usually, 2 to 4 in., with little, if any, other treatment. ECONOMICS OF COAL PREPARATION During the past decade, major changes have occurred affecting the market, profit, and long-rang planning of the coal industry. Mining companies have become "partners" with consumers at many new and some old mines, both for steam and metallurgical coals. Coal properties have become "assigned" tonnages at mutually agreed upon conditions and prices. Lower unit-train tariffs have been instrumental in helping coal markets to compete against oil and atomic energy. Cod prices for power plants are still on a Btu (British thermal unit) basis but with more emphasis on sulfur content. For metallurgical coal, the lower and medium volatile coals are in demand and the price rises, generally, as the volatile percentage is lower. Moisture affects the Btu value of coal almost the same as ash content, but dusty conditions during loading and unloading are no longer accept-

Jan 1, 1973

By M. E. Straumanis, J. -P. Krumme

In basic ([KOH + KCl] with a total polarity of 2) or acidic (2N H2SO4) electrolytes and at anodic current densities of more thun 2 to 4 ma per sq cnz, n-type GaAs single crystals of lozo resistivity preferentially dissol~je forming etch tunnels with triangular or civc~ilay cross sections and of a width between 0.5 arid 5 p. These etch tunnels are oriented along any one of the four possible (111) directions of GaAs. However, their growth occurs only in one direction of a given (111) whick apparently is determined by the atomic sequence Ga —As (and not the rezlerse) in respect to an individual valence bridge in the crystal. It is concluded from comparison with the cubic lattice structure of GaAs that the etch tunnels represent macroscopic evidence for the tetrahedral bonds and their polar properties. If the anodic current density is increased the tunnel fomation results in the development of a fibrous surface layer consisting of GaAs. The latter separates frorn the substrate (in an anodic s~irface disintegration process) by the growth pressure of an As,0, filnz forming in the interior of the fibrous layer, 100 to 200 µ under the surface, at more than about 50 ma per sq cni. The fibrous GaAs film has the same crystallographic orientation as the substvate and represents a skeleton of the original crystal. Since the etch-tunnel density in a separated GaAs layer is about 108 c?n-', and the etch tunnels develop only along (111) in a given polar direction, it is assurraed tlmt the dislocations have no influence on the growth of these tunnels. ElECTROLYTIC treatment of smooth surfaces of poly- and single-crystalline GaAs at high anodic current densities causes the formation of porous surface layers.' This phenomenon suggests comparison with effects being observed with magnesium,' indium,, gallium,4 and aluminum5 and known as "anodic disintegration". The purpose of the present paper is to explore and to explain the reasons for the formation of such surface layers on GaAs and, in particular, to investigate the influence of the lattice polarity of this III-V compound semiconductor in the (111) direction on the anodic dissolution behavior. GaAs SINGLE CRYSTALS For the experiments described below GaAs single crystals from the Monsanto Co., St. Louis, Mo., were used. Their impurity levels were below 1 ppm and their dopant levels between 1 and 100 ppm. They were grown in (111) using the Czochralski or the gradient-freeze technique. The crystals had n-type conductivity and electric resistivities between 1 and 5 ohm-cm. EXPERIMENTAL The GaAs single-crystal rods were cut perpendicularly to (111) into wafers of about 1 mm thickness using a wire-blade crystal slicer and an aqueous slurry of Sic or a diamond saw. The orientation of the faces of these wafers were checked by Laue back-reflection patterns. If there was a deviation from (111) the faces were abraded under a certain angle using grinding paper and distilled water. The damaged surface layer was removed from each crystal by chemical etching with a mixture of 1HF:1HNO3: 1H20 or 2HF:1HNO3:2HAc (glacial). {110) faces were obtained by mechanical cleavage, producing surfaces which did not require a further treatment. The GaAs wafers were mounted using "alligator" clamps instead of soldered electrical contacts.' Only the bare crystal surfaces were dipped into the electrolyte. The clamps were coated with insulating wax to prevent any contact with the electrolyte. The experiments were carried out in aqueous 2 N H2so4,' or in an aqueous solution of KOH and KCl1 (1 mole KOH + 1 mole KCl in 1000 cu cm solution). Anodic current densities up to several hundred ma per sq cm were applied for periods between 30 sec and 2 hr. For the purpose of investigating the initial steps of disintegration the anodic current density applied never exceeded 20 ma per sq cm. The films which partially separated from the anodic surfaces under high-field conditions were treated with KOH to further their detachment by dissolving the As2O3 formed. The washed and dried films were pasted to strips of filter paper, and Laue pictures were made. The back-reflection patterns obtained were compared with those of the original anode surface before and after anodic dissolution. Furthermore, space reciprocal lattices7 were constructed from asymmetric rotation crystal patternsa which permitted the determination of the crystallographic orientation of the detached films of the corrugated anodic surfaces. The disintegration products were identified from assymmetric powder patterns.8 The polarity of the {111) faces was determined by chemical etching with mixtures of 1HF:1H2O2(30 pct): 2H2O or 1HNO3:2H2O. Different patterns on each of two inverse (111) sides appeared.'-l8 The correlation of these patterns to the Ga{111) or the As(111) side has already been established by the use of light figures,18-20 by X-ray diffraction near the absorption edges of gallium and arsenic,'lmZ4 and by LEED measurements.25 The geometric structure of these surfaces and the interior of the anodically attacked crystals were observed and photographed with a high-power microscope using oil immersion objectives up to magnification of X1720.

Jan 1, 1968

By W. L. Fink, R. S. Archer

This paper describes results obtained on aluminum-beryllium alloys and aluminum-beryllium-copper alloys in the preparation of which aluminum of 99.95 per cent. purity was used. The constitution and structure of the high purity binary alloys are given. The aluminum-beryllium eutectic occurs at 0.87 per cent. beryllium and 645° C. The solid solubility of beryllium in aluminum at 631° C. is 0.05 per cent, beryllium, and at room temperature is less than 0.013 per cent. beryllium. The densities of the alloys are substantially the same as the values calculated on the assumption that the densities of the elements are not changed by alloying. All of the alloys age-harden at room temperature after a solution heat treatment, and the chill cast aluminum-beryllium-copper alloys age-harden at room temperature without a prior solution heat treatment. Hardness and tensile properties are given. Salt spray corrosion tests on sheet specimens are described. It is shown that beryllium docs not lower the corrosion resistance of aluminum to salt spray provided the alloy has received a solution heat treatment. Commercial Possibilities of Beryllium Alloys Beryllium has certain properties such as low density, high hardness, good corrosion resistance, low thermal expansion and fairly good electrical conductivity, which would indicate that it is worthy of consideration as an ingredient of light alloys. It was not until recently, however, that beryllium could be produced with sufficient ease to encourage research along this line. The production of beryllium by electrolysis from a fluoride bath has now developed to the stage where it could be used commercially if there were sufficient demand for the element. Claims made in certain newspapers and technical articles in regard to thc strength and corrosion resistance of thc aluminum-beryllium alloys are not justified by experimental results. Moreover, beryllium is an expensive metal ($200 a pound at the time this work was done) and, on account of the nature of its ore and the consequent difficulty of its extraction, it will in all probability continue to be a relatively expensive metal, although the cost would undoubtedly be a great deal less than $200 a

By Kazutami Imai

Effects of heavy metal ions on the growth and the activities of iron and sulfur oxidation of Thiobacillus ferrooxidans were investigated. Mercuric, silver, and stannous ions inhibited both of the growth and the iron- oxidizing enzyme system of the bacterium. On the other hand, uranyl ion inhibited the growth, but it gave almost no effect on the iron-oxidizing enzyme system. The inhibitory effect of uranyl sulfate on the growth of the bacterium is intensified on lowering the cultivating ' temperature from 28 ºC to 7 ºC. In the concentration of 10-3M, cadmium and copper ions inhibited colloidal sulfur-oxidizing activity of the cells 69 and 52 %, respectively, though they did not inhibit the iron-oxidizing activity at all in the concentration. On the contrary, stannous chloride did not givr any effect on the sulfur-oxidizing activity of the cells, though it inhibited the iron-oxidizing activity 55 % in the concentration of 10-3M. Several differences were observed among the cytochrome systems of cell-free extracts of the cells grown on iron and on sulfur.

Jan 1, 1976

By W. F. Campbell

One of the deepest coal operations today is the Springhill No. 2 mine of Cumberland Railway & Coal Co., subsidiary of Dominion Coal Co. Ltd. Mining is now conducted at a slope distance of 14,000 ft, with 4400 vertical ft of cover. The record of Springhill No. 2 can be said to contain the history of bumps in the Province of Nova Scotia. The Springhill coal field forms part of the Cumberland field of Carboniferous age. There are seven mineable fields in the area, numbered in the order they were discovered. Mining has been carried on in all but the No. 4 and 5 seams, but present operations are confined to the No. 2. Fig. 1 shows a vertical section through the seams. Opened in 1873, No. 2 mine was first worked from parallel slopes driven from the outcrop of No. 2 seam down to the 7700 level. As the mine went deeper, a two-place auxiliary slope was driven from the 6900 level to the present workings. A transfer level at the 7800 connects the main haulage with the auxiliary haulage slope. The No. 2 mine plan is shown in Figs. 2 and 3. The seam is bituminous, averaging 8.5 to 9 ft thick. There is a well defined parting 14 to 16 in. from the roof, and this roof coal is harder than the rest of the seam. Average pitch at the outcrop is 30°; at the 6500 level, 20°; at the 7900 level, 16°; and at the 13,800 level, 10°. Immediate roof and floor strata consist of beds of variable thicknesses of shales, grading to arenaceous shales to shaly sandstones to sandstones. A characteristic of the strata is the appearance and disappearance of sandstone bands, of considerable thickness, over distances of several hundred feet. MINE HISTORY Entrance to No. 2 mine is obtained by three parallel slopes, separated by 100-ft pillars except in the upper portion of the mine where the pillars are smaller. Main haulage levels were originally driven 600 ft apart for room and pillar extraction. A parallel drainage and intake airway was driven below each haulage level and a parallel return airway (counter level) above. Pillars 80 to 100 ft wide separated these two servicing entries from the center haulage level. Inclines up to 700 ft apart were driven off the levels up pitch to the upper levels, and at 40-ft centers level rooms 12 ft wide were driven off each side of the inclines, separated by crosscuts every 50 to 100 ft. The rooms were driven up to 350 ft or until they were holed into the room from the adjoining incline—a plan followed until the level reached its boundary. When the entire area between two levels had been divided into pillars, the pillars were extracted from the boundary back to the slope pillars. As depth of cover increased, mining conditions required larger pillars, and at the 3300 level, where NECESSARY PRECAUTIONS FOR MINING AT DEPTH In Room and Pillar Extraction: 1) Pillars must not be too small. 2) Pillar size must be uniform. 3) Extraction lines must be kept as straight and as uniform as possible. If they are irregular they should be brought back into line slowly. 4) Peninsulas of coal surrounded by gob must be avoided. 5) Pillars should not be disturbed after they have been formed. If it is necessary to increase the width of an opening, stripping or ribbing should be done gradually over a long distance. If increased width of openings is necessary at certain locations and can be anticipated, the openings should be widened during development. 6) Under no conditions should small pillars be left in the gob that would interfere with caving. In Long wall Operations: 1) Pillars formed during development for retreating longwalls should be uniform in size and shape. 2) Pillars should not be split after development, but if pillar splitting does become necessary it should not be carried out within the zone influenced by the working faces. 3) Width of levels should not be increased after the levels have been developed. If it does become necessary to widen a level it must be done gradually over a long distance by stripping or ribbing the coal ribs. 4) Extraction lines should remain uniform. If several walls are worked together—one behind the other—a uniform distance must be maintained between them and the wall faces must be kept as straight as possible. If the walls do get out of line, they must be brought back into line gradually to allow for a gradual change in the stress distribution over the area. 5) Stumps of coal, roof supports, etc. must not be allowed to remain in the gob to interfere with caving. 6) Midwalls should be built as rigidly as possible and properly maintained.

Jan 1, 1959

Boundary and general corrosio~z rates for higkpurity alutninum were ~rzeasured irz 16 pct HC1 at sJmllow penetrations (< 25 p). The rates for several high-angle random tilt boundaries, several [001] synzmetrical tilt boundaries, a 54-deg [010] twist, and a 15-deg randorn tw~st boundary were one-fourth to one-third higher than that of the (001) surface used as reference. Boundary attack was slower for 23 and 37-deg [001] tilt boundaries and a 16-deg [010] twist boundary. The corrosion rate for a (111) surface was roughly om-third higher than for (001) and was thus about as high as the corrosion rate of the fastest boundaries. The boundary attack did ?lot appear to parallel the variatiorz of boundavy energy. The signvicance of the anisotropy of corrosion was discussed.

Jan 1, 1966

By Francis Lucas

ANY metal which contains even a small percentage of aluminum possesses certain peculiarities of appearance and properties which are exhibited both when the metal is melted and after it solidifies. Pure aluminum, or an alloy containing a small proportion of aluminum, can be melted without flux-except for a layer of charcoal-because a film of aluminum oxide and metal forms at the surface of melted aluminum. Although very thin, this film is air-proof, and it prevents the metal underneath from oxidizing. This oxidized film does not move easily on account of its toughness and high surface tension. One very important point in connection with this process of still casting has not been strongly enough stressed, namely, that the same kind of surface film with the same peculiarities forms over the surface of all melted alloys that contain even a small proportion of aluminum. Experienced foundrymen know how desirable it is to cast aluminum under its "skin" or-under the surface of the film which tends to remain still. In the case of red copper, when in fusion, the surface shows pure copper only. This is due to the fact that liquid copper constantly absorbs the copper oxide which forms on the surface. By closely examining melting copper the oxide can be seen dissolving in the bath, and going into solution just as pulverized sugar dissolves in water. When copper is cast in the open, either in wire bars or cakes, the surface of metal exposed to the air is covered by a film of black, oxide that cannot be absorbed by the metal.

Jan 1, 1927

By John J. Egan, A. B. Kinzel, Walter Crafts

The demands of the petroleum and chemical industries for steels to be used in pressure vessels and similar structures at artificially low temperatures are continually increasing, and the writing of proper specifications with suitable tests becomes increasingly important. Likewise, the selection of suitable steels for such applications is of increasing concern to the metallurgist. It is generally recognized that highly alloyed steels of the austenitic stainless type retain their properties even at very low temperatures and represent the best technological solution of the low-temperature steel problem. However, in many instances less expensive carbon or low-alloy steels suitable for service within limited temperature ranges are available. The problem thus becomes one of defining the various factors involved in the production and fabrication of these less expensive steels and determining the temperature ranges in which their properties justify engineering application. Most of the applications involve welded structures, and the heat effect of welding as well as the nature of the weld metal are matters of prime concern. The first problem that the metallurgist faces is the determination of the type of test to be used as a criterion of the performance of the steel in low-temperature service. It has been generally recognized that the static properties of steel as determined in the ordinary tensile test undergo a gradual and relatively slight change as the temperature of test is lowered in the range of current interest; i.e., from room temperature to minus 120&apos; C. It is further generally recognized that the behavior of steel under impact involving notch sensitivity is definitely affected at the lower temperatures. While the major subject of this paper is the effect of grain-refining deoxidizers, of low-alloy additions and of welding on the low-temperature notched-bar impact properties, an inquiry into the general behavior of steel under low-temperature impact testing is included. This is a pertinent portion of the investigation and the results thereof are

Jan 1, 1937

By Francis Lucas

EACH year we gather in this auditorium to honor the memory of a . distinguished American metallurgist and educator. I cannot bring to you reminiscences of Prof. Henry Marion Howe as other lecturers have done. It was not my good fortune to enjoy the privilege of studying and ,working under his direction. As I have reflected on the published works of Professor Howe, it has seemed to me that his mind was trained on the nature of metals and on the mechanism which produced known but unexplained effects. He was interested in controlling and regulating the causes so as to produce specific effects, useful in serving mankind. I recall an afternoon in May, 1925, when, at the invitation of Mrs. Howe, I visited his former home, Green Peace at Bedford Hills, N. Y. The purpose of my visit was to receive at the hands of the widow -an engraving of Professor Howe, a reproduction of a painting from life. Mrs. Howe showed me his study. The walls of this large attractive room, brilliantly illuminated by the spring sunshine, were literally covered with the scrolls of honors and of decorations which had been conferred on Professor Howe by governments, academies, universities, societies and. institutions the world over. As we walked about the room, she pointed out the significance of each honor and recited a few details of each occasion. I sensed the pride with which Mrs. Howe, then in the late autumn of her life, told me of her husbands&apos; achievements, of his struggles, of his disappointments and of his successes. There was a surprisingly familiar note in the recital to which I was listening. I have found the same theme running as a disconnected thread through the written accounts of the lives of most men of science. We then went to the drawing room to chat for a few minutes before I said my farewells. As we seated ourselves, Mrs. Howe turned to me and asked: "Mr. Lucas, what of this great microscope of yours? Cannot it be applied to the study of disease? What a great blessing it would be if it could be directed to relieve the suffering of mankind."

Jan 1, 1931

By R. M. Brick

Segregation can occur only in cast alloys that solidify over a range of temperatures with a difference in composition of liquid and solid phases within this range (ignoring monotectic systems and chemical reactions as in rimming steels). Thus a pure binary eutectic alloy should show no segregation unless undercooling occurs for one of the solid constituents of the eutectic; e.g., chill-cast Al-I2 per cent Si alloys. The phasial condition implicitly described above—solidification over a range of temperatures with a compositional difference between solid and liquid—is found in nearly all solid solutions or combinations of solid solutions and eutec-tics, Metastable conditions of solidification of these types of alloys cause coring; i.e., a difference in composition between the center of a dendrite and its periphery. This composition gradient can be detected usually only by microscopic examination of etched structures; it is a "micro" effect. The gradient of more immediate industrial concern is that between the center of a cast section and the surface layers. This gross (macro) effect is usually deter-minable only by sampling of the casting at different points, with chemical analyses of each sample. If the compositional difference is of the same type as in coring, the first parts to freeze being enriched in higher-melting-point constituents, and vice versa, the effect is called normal segregation. When what is apparently the first part of the casting to solidify shows a higher concentration of low-melting-point constituents, the effect is called inverse segregation. These macro effects are quite separate from the micro effect, coring, yet the latter must be described first because it is an essential part of the picture. Coring Solid Solution, Ni-Cu The nickel-copper phase diagram is reproduced in Fig. Ia, in which the solid lines represent the equilibrium liquidus I, 3, 7 and solidus 2, 5, 8, and where the vertical I, 4: 8 represents a 55 per cent Cu alloy. Upon moderately rapid solidification, the first dendritic axes of composition 2 (see Fig. Ib) start to form at a temperature somewhat under I. Solidification continues by growth of the dendritic nuclei, but at temperature 4 the increment solidifying is of composition 5. The rapidity of this crystal growth prevents diffusion of nickel and copper atoms from adjusting the composition of the entire dendrite at 5, which it would be under equilibrium conditions. The average composition of a specific dendrite, or the entire solid phase, at temperature 4 might be that indicated

Jan 1, 1945

By Royal Jackman

Two comprehensive papers have appeared regarding the forms of copper that occur in smelter slags, one by Frank E. Lathe1 and the other by C. G. Maier and G. D. Van Arsdale.2 These authors comment on other published results and draw conclusions from their own investiga-tions. The development of X-ray examination of minerals and improve-ment in high-power microscopic methods make it possible today to get additional evidence by means that were not available to earlier investi-gators. The present work was confined to reverberatory slags obtained from five different plants. Some definite conclusions were reached regarding the forms of copper present in these slags. In most cases these agree with some of the findings of Maier and Van Arsdale but new methods of attack were used in the investigation.

Jan 1, 1933

By G. R. Fitterer

NONMETALLIC inclusions in steel have received much attention by metallurgists during the past few years. Many investigators have been emphatic in stating their belief that these impurities are the chief causes of steel failures, while others think that their effects are negligible. One of the main reasons that definite information on the effects of these impurities is lacking is that no reliable method has been developed for the exact determination of the amounts of these different impurities in steel. Some valuable new information has been brought out by a reliable method for nonmetallic inclusions which has been developed at the Pittsburgh Experiment Station of the U. S. Bureau of Mines, in cooperation with the Carnegie Institute of Technology and the Metallurgical Advisory Board. This procedure satisfactorily extracts some of the more common inclusions from steels, thus enabling the investigator to correlate steel failures with inclusion content. Although the data given herein are the first to be published on the subject of the electrolytic extraction method, the interest in the subject is evidenced by the fact that it is already being used by some 20 to 30 steel companies for their various purposes. Some of the comments received from these laboratories indicate that the method is highly satisfactory: the unfavorable comments, when traced to their sources, have been found to be based on some small mistake made in either installation or operation. The chief discrepancy seems to have occurred in attempts to apply the method to the extraction of inclusions from alloy steels. The procedure can be used only for the plain carbon steels and for such low alloy steels as those containing the usual amount of copper (0.2 to 0.3 per cent). Steels containing the carbide-forming alloys such as chromium, tungsten, etc., present far too many difficulties for the accurate determination of inclusions. Luckily, the iron and manganese carbides do not offer any difficulties and no contamination of the oxide-sulfide residue results. It is highly probable that some modification of the following

Jan 1, 1931

By Everette Lee DeGolyer

FIFTEEN thousand barrels of oil daily, the production of the United States 75 years ago, amounted to more than 90 per cent of world supply. Russia and Romania, neither of which produced as much as one thousand barrels daily, were the only other suppliers in substantial quantity. The adolescent oil industry of the United States, a dozen years old in 1871, was still confined to the Appalachian region. Wells were drilled by cable tools; many of them were "kicked down" by manpower with a spring pole; and depths were measured in hundreds rather than thousands of feet-a 1000-foot well was a deep well. Casing was an innovation, come into general use only a few years previously and still so new as to be subject to bitter patent litigation. Crude oil was packaged in wooden barrels and shipped by flat boat and barge on the creeks and rivers and by railroad. Such pipe lines as existed were only a few miles long. There were many refineries. Pittsburgh, Cleveland and the Atlantic seaboard were refining centers. Refineries were very small, however, and their operations consisted essentially in simple fractionation by distillation and treating for quality. The products in demand were burning oil or kerosene and lubricating oils. Oil was not yet used as fuel and gasoline was a nuisance to the refiner.

Jan 1, 1947

By Robert B. Kistler, Ward C. Smith

The borate industry is one of the few sectors of the mining and mineral-processing industry which the United States still dominates. Since about 1927, the United States has supplied over half of the world&apos;s total boron and borate raw materials, and many of the chemical derivatives as well. Chiefly responsible for this record are companies producing sodium borates from two large deposits in southern California, at Boron (Kramer) and Searles Lake. The sodium borates, or products derived from borax and borax-containing brines, are the preferred borates for industry because they are soluble in water and combine readily with most other chemicals. Calcium borates are required for certain end uses, and these are produced from smaller colemanite-ulexite-probertite bodies. Sodium-free borate compounds also are produced from boric acid, which can be manufactured from either sodium or nonsodium borate minerals. During the past hundred years, the use of boron compounds throughout the world has risen from a few tons per year to the equivalent of over a million tons of B2O3. Leadership in supplying borates shifted from country to country and from region to region during this period, generally as the result of the development of newly discovered deposits that were better in quality, more accessible, or more economically exploitable than previous sources (Table 1). Primary Products and End Uses The principal borate products offered by primary producers in the United States are listed in Table 2. In general, these products are utilized worldwide by almost all consumers, regardless of the original source of the primary borates, In the United States, the primary borates all originate in southern California. Colemanite is produced as crude or processed crude ore from the Death Valley area and is utilized by the fiber glass and ceramic industries without further treatment. Production from Searles Lake, CA is from brines that are processed in chemical plants where borax and other compounds are recovered and the principal borate products are produced. At Boron, CA, the world&apos;s leading producer is mining a deposit of mineral borax and operating a chemical refinery. The mineral borax is mined together with included clay, and refined borax or "10-mol" is one of the refinery products. The mineral and the chemical compound are identical, Na2B4O7 • 10H2O. In addition to ship¬ping all major refined borate products from [ ]

Jan 1, 1983

By J. W. Lacey, F. H. Brinkman, J. E. Faris

This paper presents an analysis of the high-pressure, gas-driven LPG-slug process, based on fluid flow tests in areal models. Two types of tests were made. One series was made in low-pressure models which permitted observation of fluid movement. Three completely misci-ble analog fluids were used. A second series of tests was made in high-pressure models using methane, propane and a light refined oil saturated with methane at room temperature and 1,550 psig. Under the test conditions of room temperature and a pressure level of 1,550 psig, the phase diagram for the fluids used is similar to those for many of the field systems where the process is considered for use. A method for using these laboratory data to calculate field performance of the process is outlined. As a result of this work, it is concluded that small banks of LPG (5 per cent HV or less) are not effective in increasing oil recovery in horizontal reservoirs. Znstead, where small banks are used, the driving gas quickly penetrates the LPG bank because of fingering and channeling; and from this point on, the process behaves essentially as an immiscible gas-injection project. The validity of this conclusion was substantiated by: (1) laboratory studies of the effect of rate, model size and mobility ratio on miscible displacement in areal models; and (2) calculation of field recovery, which compared closely with actual field recovery. INTRODUCTION Field applications and pilot tests of the gas-driven, LPG-bank, oil-recovery process are on the increase. Most of these tests are employing small banks (2% to 5 per cent hydrocarbon volume) of LPG, which is miscible with both the driving gas and the oil in place, in an effort to attain an effective yet economical miscible displacement of oil by gas. The expectation of miscible displacement with small banks is based on the concepts that: (1) lengths of solvent-oil mixed zones, measured during miscible displacements in long slim cores, are representative of those that will occur in the field; and (2) areal sweep efficiencies5 measured in electrolytic model studies are applicable to miscible displacement in reservoirs. Our experimental evidence indicates that the mixed-zone lengths and sweep efficiencies mentioned are not applicable to miscible displacement in reservoirs. In this paper we present an evaluation of the gas-driven, LPG-bank oil-recovery process based on fluid flow experiments in areal models. These results are used to predict the performance of a field pilot test of this process, and the results are compared with the actual test results. THE EFFECTIVENESS OF LPG BANKS The effectiveness of LPG banks of various sizes in accomplishing miscible displacement of oil by gas was determined by displacement tests in a model representing one-quarter of a confined five-spot pattern. The model, 12 X 12 X 1/4 in. in size, was packed uniformly with glass beads. It was operated at a pressure of 1,550 psig and at room temperature; the fluids used were methane, propane and refined oil saturated with methane at 1,550 psig. The saturated oil had a viscosity of 1.2 cp at room temperature. The results of these tests are shown in Fig. 1, where recovery is plotted as a function of the volume of fluid injected for: (1) an immiscible-gas drive with an oil-to-gas viscosity ratio of 85; (2) three sizes of LPG banks; and (3) two completely miscible displacements with mobility ratios of 85:1 and 10:1. (The miscible displacement data plotted are the averages of several tests.) The results show that a 2½ per cent bank of LPG does not increase oil recovery over that obtained by immiscible-gas drive. The 7 and 17 per cent banks are, respectively, about 30 and 50 per cent effective (with reference to the M = 85 miscible-displacement curve) in increasing oil recovery at the point where 2½ hydrocarbon volumes (HV) of fluid have been injected. The percentage effectiveness of the banks at a given volume of fluid injected is defined as Recovery by Bank — Recovery by Gas Drive Recovery by Miscible Recovery by Flooding Gas Drive We conclude from these results that banks of LPG smaller than about 5 per cent HV in an individual stratum will cause from little to no increase in oil recovery. This finding was substantiated by work in low-pressure models, which permitted visual observation of fluid movements. In these tests, three completely miscible fluids having the same viscosity ratios as those used in

By J. M. Ross

THE Homestake mine is situated in Whitewood mining district, in the northern Black Hills of South Dakota, in the city of Lead, Lawrence County. The entire property, comprising 557 lode claims with a total area of 3343 acres, is held under United States Patent. The older claims were 300 by 1500 ft. under local regulations, the newer ones 600 by 1500 ft. The Homestake was discovered April 9, 1876, by Moses and Fred Manuel, and Jake Harney, who were drawn into the northern hills, from the Custer placer district, by news of the discovery of rich placer deposits in Deadwood Gulch. They located a number of additional lode claims and, in a short time, the whole country was covered with locations. The Manuel brothers built an arrastre the following winter and took out $5000. The next year the Homestake lode was sold to Senator George Hearst and associates, who organized the Homestake Mining Co. Other companies were formed to exploit other groups of claims and at one time five companies were operating on this deposit, the Father DeSmet, the Deadwood-Terra, the Caledonia, the Highland, and. the Homestake Mining Co. These companies, however, have been merged into the Homestake Mining Company. The first stamp mill, known as the "Eighty Mill," commenced operation on July, 12, 1878, and production has been nearly continuous since that time.

Jan 2, 1925

By S. R. Titley

The recent emphasis placed upon the use of molybdenum as a geochemical indicator has stimulated considerable inquiry into the behavior of molybdenum in the zone of oxidation. This paper represents a summary of recent and continuing experimental work and calculations in an investigation of a portion of the system Mo-Fe-S-H20 and treats the stability of various iron and molybdenum compounds with respect to oxidation potential and pH. Using experimentally determined free energy values for ferrimolybdite, diagrams of the stability fields of this mineral have been calculated with respect to ilsemannite (?), molybdenite, pyrite and limonite. This theoretical approach is the one utilized by Garrels3&apos;4 in studies of the relationships of various minerals in the zone of oxidation. Use of this approach is particularly suited to the study of geochemistry in the zone of supergene processes because of the low temperatures, low pressures and other relatively easily determined and duplicated factors that exist in the near surface environment. Such a study of molybdenum, however, is complicated by several factors. One of these is the fact that the strong amphoteric behavior of molybdenum makes possible a wide variety of substances and complexes whose exact chemical natures are unknown. The second factor is the dearth of thermodynamic data for many of the simplest of the possible compounds and ions important to the study. For the purpose of this study, the problem of complexes has been approached through considering only the simpler possibilities realizing that the complexes and systems so treated may be gross oversimplifications. All the complexes considered, however, have been suggested in the chemical 2,7,9,12 or geologi-cal literature. EXPERIMENTAL WORK Studies of the behavior of molybdenum ions and ferrimolybdite have been carried out in aqueous sys- tems, and reactions have been followed by simultaneous measurement and recording of pH and oxidation potential. A major problem involved in this study was the long periods of time necessary for equilibrium to be established in some of the systems considered; in a few instances, these periods exceeded four weeks, that is, four weeks during which measured conditions changed continuously. Another problem, in some instances, was the indeterminate nature of the reactions that have taken place. Because of the tendency of molybdenum to complex, reactions which take place under some of the more extreme imposed conditions of oxidation and acidity or alkalinity are unknown. However, useful data for the present work were obtained from studies of the molybdate ion and ferrimolybdite between pH 2 and 8 and under only moderately oxidizing to nonoxidizing conditions. Instruments used in the experiments were a Hewlitt-Packard Model 412A VTVM, a modified Beckman Zeromatic pH Meter and two Varian model 11 recorders. pH was measured between glass and calomel electrodes and Eh was measured between calomel and platinum electrodes. Conditions of pH were varied with 1N H2SO4 and 1N NH4OH and 1N NaOH. Eh was varied with gaseous nitrogen, oxygen or aqueous H202. Ambient temperature was essentially uniform at 24ºC and was increased in the reaction vessel by the positioning of a magnetic stirrer whose temperature was sufficient to bring the temperature to 2S°C in the reaction. The temperatures of reaction did not vary more than 1/2ºfrom 25°C. Two reactions were investigated, the ferrimolybdite-limonite-water reaction and the reduction of molybdate ion. Studies of both reactions yielded useful data that were used in preparation of the Eh-pH diagrams. The traces of the reactions are shown on Fig. 1. Ferrimolybdite-Limonite- Water: Studies of this reaction involved analysis of the solution of ferrimolybdite and simultaneous formation of ferric hydroxide. The data are summarized on Fig. 1. In this reaction, equilibrium was attained at various pH&apos;s when coexistence of the two solid phases (ferrimolybdite and ferric hydroxide) was attained. At the proper pH, controlled by the amount of ferrimolybdite and thus the dissolved content of molybdate species, both phases were observed and reaction times to complete the transition were on the order of weeks. The reac-

Jan 1, 1963

By John R. Low

A number of cases of low-temperature, intergranu2ar brittle fracture of metals containing small amounts of certain impurities, have now been identified. Some degree of understanding of this phenomenon exists for the simpler binary systems of a metal and a single impurity, but the profound effects of other impurities and alloying elements in modifying this type of behavior remain unexplained. Current research in this area is reviewed and some of the newer techniques of investigation which should make possible a more quantitative study of the structure and composition of grain boundaries in impure metals are described. To indicate the subject matter of this lecture, we may begin by reviewing the experimental observations concerning low-temperature intergranular brittleness in impure metals, particularly those examples in which the embrittlement appears to result from what has been called "equilibrium grain boundary segregation."&apos; These are the systems in which it has been impossible, at least up to now, to detect the presence of any second phase film at the brittle interfaces. When second phase films are present they are usually readily detectable by fractographic methods, often appearing as epitaxial films in geometric or dendritic patterns. An example is shown in Fig. 1 for the case grain boundary carbides in a sensitized stainless steel which failed by intergranular brittle fracture at 78?k2 In contrast to this type of embrittlement there are numerous examples of low-temperature intergranular embrittlement in which the fractographs are essentially featureless, for example, that of an oxygen-embrittled iron shown in Fig. 2. The only second phase particles visible are the small, widely separated, round oxide particles typical of the bulk material. The fracture surface is extremely smooth and the fracture path appears to follow the intergranular interface without deviation. This type of fractograph also implies that crack propagation has occurred without plastic deformation at the crack tip, since localized slip or twinning ahead of the crack would be expected to distort the interface and be readily visible in the fractograph. Such indications are occasionally seen in these fractographs, but are not characteristic. A second example of this type of fractograph is shown in Fig. 3, which is from a temper-embrittled, carbon-free, Fe-Cr-Ni alloy containing Sb, broken at 1OO?C.3 The similarity to the oxygen embrittled iron case will be apparent. In the case of the temper embrittled Cr-Ni ferrite containing antimony, it is possible to remove the embrittlement by suitable thermal treatment. The grain boundaries may then be examined by thin film transmission in the electron microscope for the material in both the nonembrittled condition and in the embrittled condition. Two boundaries are shown in dark-field transmission in Fig. 4, one in the nonembrittled

Jan 1, 1970

By John D. Ridge

For mining geologists, the most important trends during 1962 have been the increased concentration of the exploratory activities of American mining companies in the United States and Canada and the greater use of the combined techniques of geology, geophysics and geochemistry in searches over larger areas for wider varieties of metals and minerals. The principal reasons for these changes in approach have been the deterioration of the political-economic climate in many areas of the globe of equal or greater geologic promise and the realization that modern exploration is most efficiently and economically conducted through the use of all available means of detecting ores in areas sufficiently large to raise to a maximum the chances of success. The attitude of certain major U.S. metal-producing companies can be shown by the officially ex- pressed positions of their principal officers. Early in 1962, Clyde E. Weed, Chairman of the Board of Anaconda, remarked that "because of unsettled conditions and disruptive influences in many of the copper-producing areas of the world, it is imperative that domestic copper-producing capacity be improved and made as efficient as possible in order to meet consumer demands at reasonably stable prices." In November, Robert G. Page, President of Phelps Dodge, pointed out that his company is not only concentrating most of its exploratory effort on this continent but is also increasing the number of metals for which it is searching. Frank R. Milliken, President of Kennecott, recently said that "most of our exploration money is going into the northern part of the Western Hemisphere."

Jan 2, 1963

On the following pages are abstracts of papers published by the Institute during the year 1934 as TECHNICAL PWLICATIONB, CONTRIBUTIONS, m bound volumes and in MINING AND METALLURGY. For abstracts of papers that appear In bound volumes in 1934 but that were published as TECHNICAL PWLICATIONS m 1932 or 1933, see the TRANSACTIONS for 1932 and the YEAR BOOK dated January, 1934. Many of the TECHNICAL PWLICATIONS have been reprinted In bound volumes Information regarding this disposition, and number of pages in each paper, may be found m the list beginning on page 92 Volume numbers are given as listed at the beginning of the index, page 99 The abstracts are grouped as follows:

Jan 1, 1935