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By E. Gybbon Spilsbury

In the course of the persistent and rapid advance of our country towards the goal she has set for herself, of commercial and manufacturing supremacy, there stand out certain periods or cycles of prosperity or depression, succeeding one another with a comparative regularity as to their ultimate trend, but of varying lengths and intensities. I might compare this course to that of a railroad between two points at different levels, with intervening mountain ranges and valleys, the up-grades climbing towards the final upper terminal of prosperity, while the down-grades retard the ascent, and tend to return to the valleys below. Just at the present time we are evidently at the bottom of one of these valleys, and, before starting to climb the next divide, it may be prudent for us to look into the condition of our rolling-stock, and especially into that of our brakes, and see what the experience of our downward journey has taught us, and whether we are properly equipped for the new upward advance which now lies before us. Probably no previous period of the same duration has produced in all branches of mining and metallurgy improvements SO many and so various as have the last ten or twelve years. Not that they have brought forth any such startling and revo-

Jan 1, 1898

By S. C. Sun, John A. L. Campbell

The surface properties exhibited by bituminous coal and bituminous coal lithotypes were ascertained by using streaming potential techniques. The electro kinetic prop-erties wereascertainederties of bituminous coal were found to be similar to those of anthracite. The principle electrokinetic properties of the coal and lithotypes, zero-points-of-charge (ZPC), and potential determining ions, were established. The effects of indifferent electrolytes, hydronium and hydroxyl ion sources, and polyvalent ions (cationic and anionic) were also evaluated. Location of the ZPC's with respect to pH is discussed in terms of chemical and mineralogical composition of the respective surfaces. To account for the observed electrokinetic phenomena, a generalized surface model and adsorption mechanism are proposed. Surface-dependent processes, such as froth flotation and flocculation, are important or potentially important techniques for combating some of the current major problems in coal preparation. In order to correctly apply or improve a surface-dependent process, it is of paramount importance to understand the interfacial phenomenon, especially the double layer properties, exhibited by the solid. The specific objective of this research was to determine the properties of the bituminous coal/liquid interface by an electrokinetic method, streaming potential, and to relate the findings, wherever possible, to the existing unit operations of froth flotation and floccula-tion tion. The electrokinetic properties of both the whole coal and its lithotypes were investigated. As part of the total investigation, the role played in the double layer by the reagents commonly employed in the surface dependent process was also established.' These data will be presented at a later date. Experimental Procedures The coal samples used in this research and their designations are listed in Table 1. The classical description of humic coal lithotypes as developed by Stopes" was used for the delineation of the lithotype samples. The samples were taken from the working face of a producing deep mine of the Pittsburgh seam in the area of Ellsworth, Pa. To avoid oxidation, only freshly exposed areas were sampled. The normal precautions against contamination were also exercised. Two types of samples were taken, specimens rich in a particular lithotype and a representative channel sample. The latter sample was prepared for analyses by grinding it to —35 mesh. It was screened repeatedly during the grinding to provide the largest amount of 35 x 48-mesh (standard Tyler sieves) material possible. The screened fraction was passed over a magnet and then washed several times with distilled water and finally with conductivity water. The resulting sample now termed "whole coal" was stored under conductivity water in a glass bottle. Pure lithotypes were obtained from the lithotype concentrates by hand picking, and were processed in the same manner as the representative sample. Maceral analyses, employing standard petrographic procedures," were performed on the lithotype samples to determine the purity of the samples. The results are presented in Table 2. Reflectance measurements of the vitrinites and fusinites are also reported in this table. Proximate and ultimate analyses of the samples are given in Tables 3 and 4. The electrokinetic properties of the coal samples were determined by streaming potential methods.'-' All of the chemicals used in the investigation were reagent grade (Baker analyzed). The conductivity water was prepared by doubly distilling the water in a pyrex Yoe-type still and passing the distillate through a mixed bed ion exchange column. Results In general, the electrokinetic properties of the investigated bituminous coal were found to be similar to the results of a previous study of anthracite by Camp-bell bell5 and are in accord with the suppositions of Brown." The zeta potentials of the coal and all the lithotypes were found to be negative in conductivity water. Jowett? in a study of slime coatings on coal also found bituminous coal to exhibit a negative surface. Fig. 1 shows that the negative charges, at neutral pH's, for both fusain and the gangue are very small, almost zero, while at the same pH, vitrain has the largest negative charge, almost 30 mv. Durain has a negative charge of 17.5 mv. The determination of the affect of pH on the charge of the coal surfaces revealed that hydronium and hydroxyl ions apparently behave as potential determining ions; however, they do not appear to be potential determining for the gangue. These results are illustrated in Fig. 1. As the pH of the solution was decreased, hydronium ions were adsorbed, causing the surface of the coal to reverse polarity and become

Jan 1, 1971

By C. B. E. Douglas

The following analysis was stimulated by a previous article on evaluation of the water problem at Eureka, Nev., which describes a method using formulas especially devised to calculate flow potential of extensive aquifers characterized by relatively even porosity and permeability throughout. The present discussion submits that the method was unsuitable for solving the kind of problem occurring at Eureka, where the amount of water available, rather than the flow potential, may have been the vital factor. IN an interesting article on evaluation of the water problem at Eureka, Nev.,1 W. T. Stuart describes how a difficult water problem, or one phase of it, may be evaluated by means of a small scale test. Test data are plotted by a method rendering, under certain conditions, a straight-line graph that can be projected to show how much the water table will be lowered by pumping at any specified rate for a given time. A formula is then used to determine the size of opening, or extent of workings, necessary to provide sufficient inflow to enable pumping to be maintained at that rate. At first glance this might seem the answer to a miner's prayer, but a word of caution is in order. It may not be the whole answer. Moreover, results obtained by the method described are reliable only for conditions approximating those assumed. Even where conditions do not meet this requirement, however, it may be possible to draw helpful inferences from the results, perhaps enough to facilitate another approach to evaluation of a problem. The two formulas Mr. Stuart used, the Theis formula and the one developed from it by Cooper and Jacob, were given field checks a number of years ago in valley alluvials by the Water Supply Div. of the U. S. Geological Survey and found to be reliable when the aquifer is very large in horizontal extent and sufficiently isotropic for the test well and observation wells to be in material of the same average permeability as the saturated part of the aquifer as a whole." Extensive valley alluvials, sands, and gravels can be evaluated in this way, and there are even cases in which the method could apply to porous limestones, such as flat beds of very large areal extent that have been submerged below the water table after extensive weathering. These are sometimes prolific sources of water for towns and industries. It is necessary for them to have been above the water table for some geologically long period of time in a fairly humid climate before submergence because the necessary high porosity and permeability, and large reservoir capacity, are the result of weathering, that is, of solution by the carbonic acid (H,CO3) in rainwater formed by the absorption of CO, from the air by raindrops, and this dissolving action must cease when all the H2CO3 has been consumed by re- action with the carbonate to form the more soluble bicarbonate. Consequently this weathering process is largely restricted to a zone that does not extend much below the water level, and submergence is necessary after the weathering to provide large reservoir capacity and good hydraulic continuity. On the other hand, water courses tend to form along faults and fractures in limestone, and to become enlarged by solution, well below water level when, as often happens, fresh meteoric water is circulated rapidly through them to considerable depth by hydrostatic pressure, as through an inverted syphon. Although the reservoir capacity of such water courses is relatively small they may extend far enough to tap more prolific sources. Cavities, and sometimes caves of considerable size, are found in limestones where the acid formed by the oxidation of sulphides has attacked them. This action can take place as deep below water level as surface water is carried by syphonic or artesian circulation, because the oxygen it carries in solution will not be consumed until it reacts with some reducing agent, such as a sulphide. Moreover, the formation of acid and solution of limestone in this way is not confined to the immediate vicinity of the sulphide. Oxidation of pyrite, for example, results in formation of acid in several successive stages, each taking place as more oxygen becomes available, as by the accession of fresh water into the circulation at some place beyond the sulphides. When the acid thus formed attacks the limestone, CO, is liberated and the ultimate effect of the complete oxidation of one unit of pyrite will be the removal of six times its volume of limestone as the sulphate and bicarbonate, both of which are relatively soluble. The reaction may be continued or renewed along a water course far from the site of the sulphides, where the small electric potential produced by contact with the limestone helped to start the reaction. Mr. Stuart refers2 0 caves in the old mining area in the block of Eldorado limestone southwest of the Ruby Hill fault at Eureka, Nev., and to the cavities encountered in drillholes in the downthrown block on the other side of the fault. Although he interprets these cavities as evidence that this formation was sufficiently isotropic (evenly porous and permeable) to give reliable results by the method he describes, they may, in fact, be entirely local conditions. There is reason to think they were probably formed

Jan 1, 1956

By Larry G. Hayes

Development of the Bowers-Campbell zinc deposit, located in the Shenandoah Valley two miles northwest of Timberville, Va., was commenced in 1956 by the Tri-State Zinc Co. The occurrence of lead-zinc mineralization in this area has been known for many years, but the first serious exploration program was initiated in 1951 by the geologic staff of Tri-State Zinc Co. Ordovician dolomites. The deposit is approximately 700 ft long, 100 ft wide, and 475 ft thick. Its projected plan has an elongated ovoid shape, where- as the profile appears boot-shaped with the upper portion outcropping. Vertical cross sections show the lense as having been thrust-faulted along certain bedding planes. The movement along these bedding thrusts varies greatly and in one case, has offset the deposit so as to divide it into an upper and lower orebody. The breccia lense strikes parallel to the N 34" E strike of enclosing strata.

Jan 9, 1960

By Robert L. Bates

Definition An industrial mineral, says the Glossary of Geology, is "any rock, mineral, or other naturally occurring substance of economic value, exclusive of metallic ores, mineral fuels, and gemstones; one of the nonmetallics." Probably most geologists and engineers would accept this simple and straightforward definition, at least as a general statement. On analysis, however, certain anomalies crop up. For example, it may be considered arbitrary to include industrial diamond and corundum and to exclude their precious varieties, gem diamond and sapphire. So the present volume has a section on gems and gem materials, in spite of the definition. Another problem arises when we try to define precisely what is metallic and what is nonmetallic. Bauxite and ilmenite certainly qualify as metallic ores, but both are also raw materials of important nonmetallic substances; hence they are included in the book, A third anomaly is that, by common consent of geologists, engineers, mineral economists, and others concerned, the term industrial minerals may include not only rocks and minerals but also certain manufactured products like cement and lime, and even mixed groups of natural and artificial products, such as abrasives and refractories. Thus the central realm of the industrial minerals is clear enough, but its boundaries tend to be indefinable. Since a definition that allowed for every irregularity in the outer fringes would be excessively unwieldy, the one quoted above may be considered satisfactory. The expression industrial minerals is commonly equated with nonmetallics, and with the somewhat more precise phrase industrial minerals and rocks as in the title of this book. Characteristics of the Field The industrial minerals as broadly interpreted are a highly diverse group of materials; indeed, we may say paradoxically that diversity is about all they have in common. At one end of the spectrum are ordinary earth materials such as gravel and crushed stone, with a value of perhaps $3 per st; at the opposite end are industrial diamonds, which sell (by the carat) at the rate of roughly $18,000,000 per st. Neither the metals nor the fuels, and few if any categories of manufactured products, include items that differ in value by more than six orders of magnitude. Most gravel and stone are of no value unless close to a market; diamonds and other exotic substances possess such unique and desirable properties that their occurrence in remote corners of the earth is no deterrent to their use. The broad range of industrial minerals falls between these extremes of unit value and place value. The industrial minerals penetrate the entire fabric of modern industrialized society, from such fundamental operations as drilling for oil and smelting iron ore to the manufacture of virtually the whole array of consumer products. There is no industrial-minerals industry; there are many industries. The simple term field is convenient as an all-inclusive expression. An industry is considered to belong in the industrial-minerals field if its operations consist of extraction and processing, but not manufacturing. Thus the mining and beneficiation of feldspar is a mineral industry, but the manufacture of ceramic products is not. In the cement and lime industries, processing merges into manufacture, and the line is less distinct. It disappears altogether in a plant that extracts salt as artificial brines, and makes sodium and chlorine chemicals, all under the same roof. An aspect of some industrial minerals that differentiates them from the metals is that their physical properties carry over into ultimate use of the product. Such minerals as mica, asbes-

Jan 1, 1983

By P. E. Schauer

During the initial nine-year deple-tion of the McKamie-Patton pool gas-condensate reservoir, the pressure behavior and fluid analyses indicated pressure maintenance by gas injection would be attractive relative to continued pressure depletion. As a result, a gas cycling program was inaugurated in Aug., 1949, which has since maintained reservoir pressure. In order to evaluate the benefits of this program, the recoveries for natural depletion and for cycling followed by blowdown were determined by calculating the fractional balance of the molar quantities of vapor and liquid remaining in the reservoir and produced at the surface for various stages of depletion. The results of the investigation show theoretical ultimate recovery due to the cycling program will be 42 per cent greater than would be realized under pressure depletion type operation. INTRODUCTION The benefits of gas injection pressure maintenance programs in condensate reservoirs have been recognized and qualitatively described in several papers1-8 during the past 15 years. Some of these papers also describe methods for calculating the increased recovery realized from cycling; however, as a rule, hypothetical reservoirs were used as examples".'.. This paper presents an evaluation of the pressure maintenance program for the McKamie-Patton condensate reservoir and includes a description of the fractional balance method employed to determine the benefits. Reservoir Development and Characteristics The McKamie-Patton pool, Lafayette County, Ark., was opened in June, 1940, with production obtained from the oolitic Smackover lime at a depth of approximately 9,300 ft. The structure is an anticline 8 miles long by 1 to 2 miles wide, and is one of many productive Smackover structures in Southern Arkansas. Of predominant importance is the condensate-bearing gas cap portion of the reservoir, which covers approximately 4,000 acres, attains a maximum thickness of some 200 ft, and has an average thickness of 90 ft. Development of the cap was accomplished with 21 wells drilled on 160 acre spacing. An isopach map of the cap is shown in Fig. 1. In addition, an oil rim is present along most of the periphery of the pool. Production practice includes field separation of black oil, and a high pressure gathering system which carries total well stream from gas cap wells to a plant where condensate is separated and the gas is processed for recovery of natural gasoline, butane, and propane. Since the gas contains appreciable hydrogen sulfide, it is removed by amine contact, after which free sulfur is produced by the Claus process. Core analyses from 1,767 gas cap formation samples averaged 14.2 per cent porosity and 379 md dry air permeability. Connate water was restored on seven samples of gas cap rock by air-brine capillary techniques, from which the interpreted water saturation averaged 28.17 per cent. During the early life of the field, it was believed the recovery mechanism, based on several of the other regional Smackover reservoirs, might be a natural water drive. However, subsequent production and pressure history revealed that the gas cap would not be produced by water drive, but would behave as a closed reservoir. In this respect, during the nine-year period of natural depletion from initial production to Aug., 1949, the cap production of 84.3 billion

Jan 1, 1958

By J. T. Hayward

Studies of the forces and conditions governing the recovery of petroleum from natural reservoirs indicate that a low gas-oil ratio increases ultimate recovery, retards the encroachment of water and tends to reduce lifting costs. Methods for controlling and reducing gas-oil ratios in producing wells consequently have been given considerable attention during the past few years. However, during this same period, the production from wells in nearly all fields has been fixed by proration agreements and it is the opinion of the writer that where a well is required to produce steadily at a predetermined rate, less than its "potential" or maximum capacity, the gas-oil ratio will depend only upon the rate of production, and will be independent of the method of production and of the design of equipment in the well. If no change in the rate of production is contemplated, efforts directed to improving the gas-oil ratio by altering the diameter of the flow string, changing the position of the choke, assisting the flow with gas-lift or pump, etc., will be unsuccessful. This viewpoint is not new. It was presented by H. N. Marsh and B. H. Robinson in 1929,' but it has not been generally accepted. Although engineers believe that the rate of withdrawal and not the equip ment used governs the water-oil ratio, a similar opinion regarding the gas-oil ratio is not so commonly admitted. The rates of flow of oil and gas into the base of an oil well depend upon the following conditions: 1. The characterist-ics of the oil and gas. 2. The characteristics of the underground reservoir. 3. Temperature and pressure conditions in the reservoir. 4. The back-pressure held against the face of the sand. In operating a well, the only one of these conditions over which control may be exercised through operating procedure and the use of equipment above the sand is the back-pressure at the face of the sand. Strictly speaking, the back-pressure varies over the face of the sand, owing

Jan 1, 1932

By Alexander Sutulov

The Western industrial nations are facing today what can be defined as a gradual takeover of their investments in the developing world and more importantly, they are beginning to feel approaching problems with their adequate raw materials supply. This puts them into a strategically hazardous situation, which years ago would probably have been solved by conventional wars. However, the present political and military situation, and particularly the development of nuclear arms, makes such confrontations almost impossible or at least extremely dangerous. Thus other peaceful and more pragmatic solutions should be sought. This is particularly important because the present supply-demand situation in raw materials has a very strong political and ideological background. In the ultimate analysis there are two economic systems, that of free enterprise and the other of the collective or socialistic ownership. Both are competing for world domination, and it seems that both are eager to prove their advantages to the yet uncommitted Third World, which commands the great majority of the human race and a large part of its natural resources.

Jan 7, 1974

By E. W. Krampert

The oil industry was very active in Wyoming in 1936, in contrast to the several quiet years preceding. Production for the year again increased about 7 per cent, following an 8 per cent increase in 1935. During the year, 85 oil wells were completed, compared to 55 in 1935. Three gas wells were completed in 1936, and three in 1935. At the end of the year 45 wells were drilling, as compared to 55 drilling at the end of 1935. Two new oil fields and one new gas field were discovered in Wyoming during the year. In the year 1936 Wyoming produced 14,475,431 bbl. of oil, a gain of 1,001,081 bbl. over the 1935 figure of 13,474,350. This increase, in the main, was due to the taking of light oil from the newly developed Sundance sand pool at Lance Creek, and from the new fields, Quealy and Medicine Bow, which contributed their first production this year. Most of the other old fields either were partly shut in in competition with the new fields, or showed a normal decline. This was especially noticeable in the black-oil fields, where production had been slowly but steadily increasing for a number of years. During 1936 black-oil production decreased approximately 100,000 bbl. as compared to 1935. The only black-oil field to show marked increase was Garland, which managed to take the market from less favorably located fields. The production of Wyoming in 1936 was 11,358,757 bbl. of light oil and 3,116,674 bbl. of black oil. Salt Creek, with a production of 6,015,000 bbl., is still the largest single oil-producing field, accounting for 42 per cent of the year's total production. Lance Creek, an old field, with newly developed production in the Sundance sand, reached second place this year for the first time in its history, with a production of 1,878,486 bbl. Lance Creek production will almost equal that of Salt Creek in 1937, if the present rate of production is maintained during the coming year. Oregon Basin, a large black-oil field, held second place in 1935, but owing to a greatly lessened demand for its production, dropped back to third place in 1936. This was in part due to greatly increased light oil available, and in part to the greater supply of black oil available at

Jan 1, 1937

While the production of this state has not realized the early hopes that this coal would replace eastern coal on the Pacific Coast, it has been steady though small. Nearly all of the tonnages given are from Goodyear's, The Coal Mines of the Western Coast of the U. s., a carefully com- piled and accurate account of the development of the industry along the Pacific. [ ]

Jan 1, 1942

By R. W. Waterfill

MANY existing ore deposits of valuable metals have been worked out in their upper surface levels and the continued productivity of these mines is dependent on their extension to greater depths in the earth. The maximum depths at present reached are about 6000 to 8000 ft. below the surface, with no evidence of an impoverished ore vein. These mines are widely distributed; some of the best known are in South Africa, Brazil, India and in the western sections of the United States. Among the factors which increase the difficulty of working these mines at increasing depths are hoisting, rock pressure and temperature. The manner and effectiveness with which these problems arc met will, no doubt, determine in a large measure the ultimate depths to which any mine can be profitably worked. The most critical of these three factors at present is the increase in temperature with depth. The high temperature and humidity in many of these mines at present are severely detrimental to the health of the workers and greatly hamper their efficiency. Some have almost reached a condition in which the human system cannot survive. The problems involved in the cooling and ventilation of mines have all been ably analyzed and presented in previous articles. For this reason, only a résumé of conditions affecting the cooling and conditioning of deep and hot mines will be given in this paper before attention is directed to possible methods of improving atmospheric conditions in the working levels. Physiological Effects of Temperature, Humidity and Air Motion Many data on the physiological effects of different atmospheric conditions on the human system have been compiled and published through the combined efforts of the American Society of Heating and Ventilating Engineers, the U. S. Bureau of Mines and U. S. Public Health Service. These data were not primarily developed around the conditions existing in deep mines, but the upper temperature limits of the investigations extend into, and are applicable to, mine atmospheric conditions. While the exact values of the standard comfort conditions, established for persons of such habits as those employed in detecting the different degrees of comfort, might not produce identical effects upon persons inured to

Jan 1, 1929

By A. S. Rhea

SALT-WATER disposal in the East Texas field by means of injection into the Woodbine sand is a relatively new procedure. The purpose of this paper is to present what has been accomplished to date in this field, with-out detailed discussion of other means of disposal, such as surface impound-ing for evaporation or release into surface streams. Subsurface disposal of salt water is still in an experimental stage in the East Texas field, and, though water can be injected into the Woodbine sand, the economic problem is not as yet solved. As past experience has been that fields producing from the Woodbine formation produce large quantities of salt water, it was assumed early in development of East Texas that it would be necessary to dispose of a tremendous quantity of salt water in the later periods of production. There has been a gradual increase in the amount of salt water pro-duced in the field, until at present it is about 200,000 bbl. per day from approximately 4400 wells. It is only natural to expect an increase in the number of wells producing water, as well as the amount of water produced in the future, and it has been estimated that if present practices con-tinue the production of salt water may ultimately be as much as 700,-000 bbl. per day. The Woodbine sand is found in the East Texas field at an average depth of 3650 ft. The oil-bearing portion of the sand lies between the depths of 3050 ft. below sea level, on the east edge of the field, and 3320 ft. below sea level on the west, which depth was the estimated original average oil-water contact. The Woodbine sand under the field has the form of a broad tilted wedge pinching out on the eastern side of the field and dipping gently into the East Texas Basin toward the west. The Woodbine sand in the East Texas field has an average porosity of approximately 25 per cent and is highly permeable, the average being about 1300 millidarcys.

Jan 1, 1940

By Robert D. Pehlke, Robert G. Blossey

The solubility of nitrogen in liquid cobalt and a number of dilute cobalt alloys Was measured in the temperature range 1550" to 1700°C at nitrogen pressures to 1 atm. At 1600°C and 1 atm nitrogen pressure, the solubility in pure cobalt is 0.0047 wt pct [3.8 cu cm (stp) per 100 g Co]. The standard free- energy change for the solution reaction 1/2 N,(g) = gout pct in Co) is iF - 10,000 + 5.24 T cal per g atom N. The alloying elements Cv, Cu, Mo, Nb, Tu, W, and V increase the nitrogen solubility, while Al, Fe, Ni, and Si decrease the nitrogen solubility. THE solubility of nitrogen in cobalt was studied previously by Sieverts, Busch and Dodd,2 and Schenck, Frohberg, and Graf.3 Sieverts investigated the solution below the melting point of cobalt, and Busch and Dodd worked with the liquid metal; however, neither study found any solubility for nitrogen in cobalt. Schenck et al, reported a solubility of 0.005 wt pct N in cobalt at 1600°C. Seagle et al. 4 reported residual nitrogen in cobalt after electron-beam melting, although no reasons were ventured for the presence of this interstitial impurity. This investigation was undertaken to clarify these inconsistencies, and to provide additional data on atomic interactions in dilute metallic solution. EXPERIMENTAL PROCEDURE This study was well-suited to the Sieverts' method, which has not changed significantly since its introduction by Sieverts. 5 The apparatus was of the same design as that described by Humbert and Elliott, 6 with a reaction bulb similar to that reported by Weinstein and Elliott. 7 The buret was not water-jacketed, but the measured gas volumes were corrected for small changes in room temperature. The melt temperature was measured by a disappear ing-filament optical pyrometer sighted through a prism onto the melt surface. Temperature calibration was made based on a measurement of the melting point of pure cobalt taken as 1495°C. The difference between the reciprocal of the observed and the true temperatures was assumed to be a constant, neglecting the changes in emissivity with small additions of alloying elements. The total error in gas-volume measurement caused by accuracy limitations in reading the mercury level in the buret, variation in ambient temperature, and variation in melt temperature was about 0.5 cu cm. This represents approximately 10 pct of the total solubility, and is a larger relative error than in previous studies6-' because of the small nitrogen solubilities encountered in the present investigation. The source and purity of the materials used are listed in Table IA. Recrystallized alumina crucibles were used throughout the investigation. Examination of the crucibles after solidification of the melts showed no reaction or penetration. Alloying of the cobalt melt was accomplished with the dropping technique described by Humbert. 6 The investigation was started using cobalt from African Metals Corp. in shot form, but this material was not of sufficient purity and did not yield consistent solubility results. Sherritt Gordon Mines Ltd. cobalt was then used throughout the investigation. In experiments involving alloying elements which could react with oxygen dissolved in the melt, the cobalt was further refined by annealing at 1400°C in a dry-hydrogen atmosphere. This treatment, described by Woolley and Pehlke, 8 markedly reduced the oxygen content. The oxygen and nitrogen analyses of the cobalt used in this study are presented in Table IB. RESULTS Hot Volume. The hot volume was measured prior to each run and was 50 to 55 cu cm (stp) at 1600°C. It increased linearly with increasing pressure and decreasing melt temperature. Pure Cobalt. Measurements of the solubility of nitrogen in pure cobalt and the temperature coefficient of solubility are summarized in Table 11. At 1600°C and 1 atm nitrogen pressure, the solubility was found

Jan 1, 1967

By Sidney G. Parker, Jack E. Pinnell

Cubic ZnSe crystals have been grown with HCl, HBr, and I, as chemical transport reagents. The growth of large, well faceted crystals is in the order HCl < HBr < I, with some produced by I, transport being 1 cm on an edge. ZnSe:I crystals showed no strain in cross polarized light and were homogeneous as determined by electron microprobe. These ZnSe:I crystals had a mobility at 25°C of about 300 sq cm per v-sec and contained 103 dislocations per sq cm; further, these crystals were pure cubic and showed both photolumi-nescence and photo conductance. Doping was attempted during crystal growth. ZnS and Zn (S,Se) crystals were also grown by I, transport. ZnSe crystals have been grown by most of the common techniques.1"6 Of these, chemical vapor transport as developed by Kaldis2 showed promise of producing high perfection, cubic ZnSe. With chemical transport, crystals can be grown far below the transition temperature for conversion of cubic to hexagonal structure. A small temperature gradient between source and growth region tends to allow near equilibrium growth, which should lead to good crystalline perfection. Because it is necessary to form volatile compounds, halogens or their compounds are extensively used as transport agents. HCl, HBr, and I, were compared as transport agents for growth of ZnSe crystals. Doping during crystal growth was attempted. ZnS and ZnSxSe1-x crystals were also grown by chemical transport. Electrical and optical properties of the crystals were examined. EXPERIMENTAL Fig. 1 is a sketch of the growth apparatus, which was a modification of Kaldis&apos;. A quartz rod which butted against the seed crystal served as a heat sink to promote growth only on the seed. Initially, crystal growth was attempted with ZnSe prepared by wet chemical methods. Because such a material contained oxides and selenates, HC1 reacted with these oxygen compounds to form H2O and no ZnSe transport occurred. Further, this ZnSe contained about 10 ppm Cu plus other impurities. High purity ZnSe, containing small amounts or no oxygen compounds, was prepared by reaction of H2Se with zinc vapors at 600° to 800°C in an atmosphere of palladium diffused H2.7 The ZnSe thus produced was usually copper free and contained only 1 ppm by weight of magnesium as determined by emission spectrographic analysis. G.E.&apos;s electronic grade ZnS, which had about 10 ppm metallic impurities, was used without further treatment. ZnS-ZnSe charges were prepared by mixing the two compounds together, then sintering 24 hr at 1100°C in an H2S ambient. The gases, HBr and HC1, were commercial grade, of 99.9 pct purity, while the I2 was 99.999 pct pure. The single crystal seeds with (111) faces for growth were mechanically held in place by sealing the outer quartz tube to the growth tube. After the charge was introduced, the system was outgassed at l0-5 torr while heated to 500°C. The desired quantities of transport reagents were then sealed off in the system, which had been cooled to 25°C. The growth tubes were inserted into a furnace with the desired temperature and thermal gradient. The system was allowed to cool for 1 to 12 hr from growth temperatures of about 850" to 25°C. The tubes remained stationary during crystal growth. HCl CHEMICAL TRANSPORT GROWTH Preliminary runs with HC1 had a temperature gradient of 100° to 200°C and no seed or heat sink. Only small crystals were obtained in these experiments as

Jan 1, 1970

By G. P. de Forest, G. O. Hiers

The object of the experiments reported in this paper is to determine the eutectic composition of copper and tin and to determine the location of the part of the liquidus line immediately above the eutectic composition in copper. Three methods were used in the investigation: (1) the method of dissolving copper in a bath of molten tin at constant temperature, with the idea that when the bath was saturated with copper its copper content, by analysis, together with the temperature at which the saturation took place would locate a point on the liquidus line; (2) the method of the differential cooling curves, and (3) the method of microscopic examination. This paper is principally concerned with the results of the last two methods mentioned. The results of the first method, that of dissolving copper in molten tin, did not agree with the results of Miller,&apos; by the same method, nor with the results of other investigators by other methods, nor yet with the results of the cooling-curve experiments and microscopic examination reported here. Solution of Copper in Molten Tin To determine the amount of copper that would be dissolved by molten tin at a given constant temperature the apparatus shown in Fig. 1 was used. It consists of a cast-iron pot a, 6 in. deep and 8 in. dia., well cleaned inside and dressed with graphite. This pot, which holds 15 lb. of tin, g, rests on a hot plate b with resistance winding c. The thermocouple d leads to a Wilson-Maeulen temperature regulator for maintaining the temperahre at the heating coils at a fixed temperature to within ±5°C. There is a shallow bath of solder e on the top of the hot plate to improve the thermal contact between the plate and the pot. An insulating jacket f of asbestos prevents the irregular radiation of heat from the apparatus. The copper stirrer h slowly rotates in, and is dissolved by the bath of molten tin g. This bath is protected from excessive oxidation by a layer of charcoal j. The stirrer h is fixed to the lower end of the iron tube k, which is so mounted that it can be driven by a motor with reducing gear. The temperature of the bath is indicated

Jan 1, 1930

By E. T. Turkdogan, L. J. Martonik, R. J. Fruehan

Electrochemical measuretnents of the solid oxide electrolyte galvanic cells CY-Cr2O3 I ZrO2 (CaO) 1 O (in Fe alloy) CY-Cr2O3 I Tho2 (Y2O3)I O en Fe alloy) have been made at 1600°C (2912°F) in order to test the Performance of such cells at liquid steel temperatures. The oxygen pvobe (cell) consists of a disk of ZrO2 (CaO) or Tho2 (Y2O3) electrolyte fused at one end of a silica tube filled with a mixture of Cr-Cr2O3 which is the reference electrode. Upon immersion in liquid steel, the electromotive force readings achieve a steady value within a few seconds, and remain steady for 30 win or more. The perforwzance of the probes has been tested using Fe-O, Fe-Si-O, Fe-Cr-O, Fe-V-O, and Fe-Al-O alloys; the oxygen contents of liquid steel derived from the measured electromotive forces are in satisfactory agreement with those determined by arulysis. Use of the probe in the deoxi-datiorz of steel, in laboratory experiments, is discussed. The results indicate that there is insignificant electronic conductivity in ZrO2(CuO) at oxygen activities down to those corresponding to 10 ppm in steel. At lower oxygen activities, probes tipped with ThOn (Y2O3) disks perform satisfactorily at oxygen activities down to 1 ppm O or less. THE key to the control of deoxidation of steel is a sensing device to measure rapidly the concentration of oxygen in liquid steel in the furnace, ladle or tun-dish at any desired stage of deoxidation. The analysis of the cast steel by the neutron-activation or vacuum-fusion method gives total oxygen as oxide and silicate inclusions. This analysis is important for guidance to steel cleanliness; however, such a postmortem is of little value in the control of deoxidation of liquid steel. At the General Meeting of the American Iron and Steel Institute in New York, 1968, Turkdogan and Fruehan&apos; presented a paper on the preliminary results of the work done in this laboratory on rapid determination of oxygen in steel by an oxygen probe. Details of the work done in this laboratory leading to the development of a galvanic cell for the determination of oxygen in liquid steel, and the results of the tests made are given in this paper. It was through Wagner&apos;s contributions, since the early Thirties, to the physical chemistry of semiconductors in general that it ultimately became possible to construct galvanic cells for application at high temperatures. In 1957, Kiukkola and wagner2 successfully demonstrated the use of several solid electrolytes in measuring the free energies of several chemical reactions, in particular, the use of lime-stabilized zir-conia in high-temperature oxidation reactions. Starting 7 years later, a number of papers appeared in the technical literature3-&apos; demonstrating possible applicability of galvanic cells for the determination of oxygen in liquid steel. In the earliest work, Japanese investigators3j4 experimented with various types of reference electrodes, e.g., graphite-saturated liquid iron at 1 atm CO or Ni-NiO mixtures; the results obtained, though promising, were not of sufficient accuracy. Except for the work of Baker and West,6 all other investigators5,7,8 showed that ZrO2(CaO) electrolyte could be used for this purpose. The main part of the galvanic cell used by Fischer and ~ckermann&apos; and by schwerdtfeger7 (the latter work was done in this laboratory), consisted of a ZrO2(CaO) tube, -1 cm ID, closed at one end, with a platinum contact wire fixed mechanically inside the closed end. The tube was flushed with a gas of known oxygen partial pressure, e.g., air, CO-CO2 or H2-CO2 mixtures; gas along with the platinum lead wire served as the reference electrode. The oxygen contents derived from measured electromotive forces agreed reasonably well with the oxygen contents determined by vacuum-fusion analysis. It is evident from recent investigations that the electromotive force technique using a solid oxide electrolyte is fundamentally well suited for the determination of oxygen in liquid steel. However, it is equally clear that the cell arrangement of the type as commonly used is in need of considerable improvement, as it exhibits several shortcomings for industrial and even laboratory use. 1) Because of its size, the zirconia tube, though stabilized, has a poor resistance to thermal shock. 2) Fine pores and microcracks, which are invariably present in zirconia tubes, are detrimental to the satisfactory operation of the cell, particularly when gas reference electrodes are used. 3) Air or carbon dioxide reference electrodes give rise to high electromotive force readings; as a result, the determination of oxygen in steel becomes less accurate. For higher accuracy, the oxygen partial pressure of the reference electrode should be in the range similar to that of oxygen in steel. 4) Even in laboratory experiments, difficulties are experienced when flushing the tube with gases and maintaining the proper gas flow rate. Fischer and Ackermann,&apos; who used air as the reference electrode, reported that when the flow rate was too low, furnace gases would leak into the electrolyte tube, therefore lowering the oxygen potential and measured electromotive force. The required flow rate in order to avoid leakage depended on the tightness of the electrolyte tube which varied with different tubes, thus making it difficult to predict in advance the required flow rate. However, if the flow rate is too high the inside wall of the electrolyte tube would be cooler than the wall

Jan 1, 1970

By J. L. Lytton, T. E. Tietz

The recovery of flour stress of recrylstallized are-cast molyhdenum after 10 pet prestrain at 150°C was studied for recovery temperatures of 725o 801o and 901oC. The yield phenomenon observed after recovery was such that the yield drop diminished and disappeared as recovery proceeded. A fractional flow-stress recovery parameter fr, was developed and it was shown that, independent of recovery ternperatzwe, equal f, values of about 0.16 produced superposition of stress-strain curves except for the initial yield phenomenon. The activation energy for low degrees oj recovery was found to he 32,600 cal per mole, in close agreement with a reported valzie for difjzdsion of carbon in molybdenum. For values of fr greater than about 0.15 where recovery was thought to predominate over strain aging, the activation energy varied from 43,600 to 82,500 cal per mole and increased with increasing recovery and recovery temperature. A 10 pet pre-strain shifted the ductile-brittle transition temperature, as indicated by tensile elongation, from 10°C. to about -22"C. A 100-hr recovery anneal at 801oC was shown to shift the transition temperature to about —5oC, the major shift occurring during the first hour of recovery. ThE recovery of cold-worked metals is accompanied by changes in the arrangement of the dislocations generated during cold work. In recent years, the use of transmission electron microscopy has allowed direct observation of some of the dislocation configurations formed, such as "tangles", networks, cells, subboundaries, and loops. These observations have recently been reviewed by Keh and Weissmann.&apos; Accordingly, some understanding has been gained concerning the nature of the dislocation rearrangements involved. The relationship between recovery and the decrease of mechanical strength, however, has only recently been explored. Previous efforts of the authors were directed toward investigating the decrease of tensile flow stress of aluminum and Al-1 pet Mg during recovery2 and the effects of concurrent elastic and plastic strain on the flow-stress recovery of aluminum.3 In addition, an investigation of the effect of four different solute additions on the tensile flow-stress recovery of aluminum has been made.4 Many important metals, however, have the bee crystal structure, e.g., iron, molybdenum, tungsten, vanadium, columbium, tantalum, and chromium. These metals might be expected to behave differently during recovery from those with other crystal structures for two reasons. First, the previous and present investigations of aluminum and its alloys have shown that tensile flow-stress recovery is strongly affected by foreign atoms in the lattice. In the bee metals, interstitial impurities are usually present and might be expected to have various effects upon both flow behavior and recovery. For example, heterogeneous yielding might occur during prestraining. The diffusion of these interstitials can also relock dislocations during recovery so that a yield point might be obtained upon restraining (strain aging). Second, some of the bee metals (e.g., iron, molybdenum, and tungsten) undergo the familiar structure-sensitive ductility transition and exhibit brittle fracture at suitably low temperatures. It is of considerable interest to determine the effects of recovery on the transition temperature of such metals. The purpose of the present investigation was to extend our knowledge of flow-stress recovery to the bee metals and to study the effects of recovery on the ductile-brittle transition temperature. Unalloyed recrystallized are-cast molybdenum was chosen as a test material, since it exhibits a well-defined ductility transition near room temperature. As in the previous studies, the degree of recovery was measured in terms of the decrease of tensile flow stress. Prestraining and restraining were carried out at 150°C to avoid the possibility of brittle fracture. EXPERIMENTAL PROCEDURE The are-cast molybdenum sheet used in this investigation was obtained from the Climax Molybdenum Co. of Michigan. It was 0.060 in. thick by 10

Jan 1, 1964

By Charles H. White

METHODS in colorimetry are based on the assumption that the intensity of the color of a definite volume of solution is directly proportional to the quantity of the color-producing substance&apos; present. In the preparation and examination of colored solutions there are three ways in which the depth of color may be varied. These variables are; (1) the quantity of the coloring matter, (2) the quantity of the solvent, or the dilution, and (3) the thickness or depth of that portion of the solution examined. With these three variables as a basis, three general methods in colorimetry have been devised, all of which have been used in the determination of carbon in steel. In the first method, the quantity of the solution is kept the same for both the unknown steel and the standard, and the sections compared are of equal thickness, while the quantity of the standard is varied until the color obtained is of the same intensity as that produced by a definite quantity of the unknown steel. In laboratories where this method is used there is pre¬pared and kept for permanent use a series of solutions with varying amounts of the standard, representing the percentages of carbon from the lowest to the highest demanded in that laboratory. These standard solutions are kept in bottles, or test-tubes of equal diameter, and are arranged in series from the faintest to the most intense color, so that it is a simple matter to find the place of the unknown steel in the series, when the solution is of a definite volume and is contained in a tube of the same diameter as the standard tubes. In the second method, equal quantities of the standard and of the unknown steel are dissolved, the standard is diluted to a definite volume, and the solution of the unknown steel is di-

Sep 1, 1906

By Rudolph G. Wuerker

MUCH descriptive matter has appeared on the subject of suspension roof supports, or roof bolting, as it is more commonly called. The widespread introduction of roof bolting into coal mines and metal mines is truly phenomenal. Mine operators were quick to recognize the advantages of supporting wide openings without hindrance to machine maneuverability and ventilation. Although suspension roof support has long been installed at St. Joseph Lead Co. mines in southeast Missouri,&apos;" its application to coal mining presented new problems, such as proper anchorage and bearing for the bolts, bolt diameter, and spacing of bolts. After continuous testing and experimenting at the mines, standard roof-bolting materials were determined.&apos;!&apos; The study reported in this paper is not concerned with such details as bolt diameter, which may be considered already solved in practice. In the tests discussed here, small models patterned on actual bolts were found to function in the same way and as satisfactorily as their prototypes. The aim of these tests was rather to investigate the influence of roof-bolting systems on the stress distribution around mine openings and to study the fracture patterns obtained in actual testing. Little was found about this in the literature, as testing of suspension roof methods and quantitative measurements are only now coming to the fore. Several suggestions and actual measurements have been made to evaluate critically the functioning of roof bolting systems, single roof bolts, and parts thereof. Outstanding among them is Bucky&apos;s outline of structural model tests.&apos;" Since none of the suggested testing equipment was available, however, for the experiments discussed below, a different approach was chosen. The response of a mine roof under stress has often been compared to that of a beam. The slow coming down and bending through of beam or plate-like banks of shale, sandstone, or top coal is a familiar occurrence, extensively cited in the literature." It was felt that testing of roof-bolt systems installed in a concrete beam which was loaded in bending would be a fair approximation of the behavior of a mine roof underground. Another school of thought considers the roof behavior over an underground opening in connection with the stress distribution all around a circular or rectangular opening. This is more accurate, and leads to the concept of a dome-shaped zone of material destroyed under tensile stress. This is likewise a common sight in unsupported roadways where the continuous fall of roof results in what has been called the natural outline of roof fracture. This theory could not be tested and is treated separately in Appendix B. It is important to note that according to both assumptions the immediate roof fails in tension; the use of a beam in these tests, therefore, should give information valid for either of the two theories. With the testing equipment at hand it was possible to load concrete beams 6xlx0.5 ft under two-point loading, giving an equal bending moment over the center part in which the model bolts were installed. A comparison was made of the ultimate loads needed to break plain beams and beams in which roof bolts were installed. Arrangements were made with: 1—plain beams; 2—bolts with plate washers, some with holes drilled at 90" angles and others with holes drilled at 45" angles; 3—bolts with channel irons underneath; 4—bolts in holes filled afterward with cement; and 5—bolts anchored in a stronger stratum. The foregoing arrangement is made in order of increasing strength, as assumed from the theory of reinforced concrete. Likewise, laminated beams with wooden model bolts and with combinations of the foregoing set-ups were tested. All in all, 21 experiments were made out of the much greater number of combinations possible. There were, too, some trial tests. Enough observations from this limited number were made to interpret the behavior of mine roof, supported by various types of suspension bolts, at fracture. In present-day concepts, which have been proved by mathematical derivations and stress analyses, any opening driven underground will change the distribution and magnitude of the stresses existing around it. It does not matter whether the stresses become visible, as in rocks whose strength is less than the forces acting upon them, or whether they are invisible, as in the gangways lacking evidence of rock pressure. In this latter case the rocks can withstand changes in stress-distribution. To consider the mine roof as a beam, there are, with transversal loading, tensile stresses in the lower fiber and compressive stresses in the upper layers above the neutral axis of the beam. Beams of brittle material such as rock and concrete fail exactly as shown in Fig. 1. Nearly all model beams showed the same fracture pattern as that of a tension crack. The influence of support, by roof bolting or conventional

Jan 1, 1954

By Allen D. Gorrison

EFFORT to develop fundamental quantitative information and improved technique in the production of petroleum has long been faced with difficulties of a particularly evasive nature, owing to a combination of circumstances. In the first place, petroleum comes from far below the ground, out of sight, so that information derived from indirect observations must be extrapolated to reservoir conditions. If one does not force the analogy too far, the petroleum engineer may be said to be somewhat in the position of the astronomer. The actual phenomena which he wishes to observe in detail appear at a place so deep in the earth?s crust that personal observations and direct experiments are impossible.

Jan 1, 1942