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By M. M. Wong, D. E. Couch, G. M. Martinez

The Bureau of Mines electrowon hafnium metal with an average oxygen content of' 150 ppm at 700°C from an electrolyte containing 27 wt pct LiCl, 62 wt pct RbCl, and 11 wt pct HfC14. The average anode and cathode current efficiencies were 90 pct at anode and initial cathode current densities of 86 amp per sq ft. Haf-nium metal with an average oxygen content of 440 ppm was electrowon at 800oC from an electrolyte containing 90 wt pct KC1 and 10 wt pct HfCl4. The average anode and cathode current efficiencies were similar to those obtained in the LiCL-RbCl-HfCl, electrolyte. The chlorine gas given off at the graphite anode was vented through either a silica or a graphite tube to prevent cell corrosion. THE current method for the commercial production of high-purity hafnium is the thermal decomposition of Hfl4.1 The iodide method is not adaptable to continuous process techniques. Nettle, Hiegel, and Baker2 studied the electrorefining of hafnium from hafnium sponge containing 800 ppm oxygen. They failed to obtain hafnium with 600 ppm oxygen in their initial deposits and obtained AEC specification for oxygen only after 75 pct of the soluble hafnium had been removed from the electrolyte. Calculations using their data indicated this was approximately 4 lb of hafnium. The electrolyte was then used to produce approximately 3 lb of hafnium with a low oxygen content. However, no data are shown concerning the amount of anode material initially used or what percent of it was dissolved, therefore, results are not suitable for evaluation of a continuous operation. In general, it was not possible to consistently obtain low oxygen content metal with the electrolytes described by Nettle, Hiegel, and Baker. Wong, Hiegel, and Martinez3 investigated the electrorefining process for hafnium and showed that even by strict control of electrolyte composition only relatively low oxygen reduction could be obtained. The oxygen contained in the hafnium anode material tended to transfer to the cathode deposit and only a limited purification was possible. Both the "iodide" and the "electrorefining" processes depend upon hafnium sponge as a starting material. The sponge is normally produced by magnesium reduction of HfC14 ' and does not meet AEC specifications for hafnium metal. Since only 30 pct of the anode feed could be utilized3 in the electrorefining cells, the Bureau of Mines developed an electrowinning process. HfC14 was used as the feed material for the electro-winning process described in this report. Many of the electrolytes used in the electrorefining studies3 ap- peared to be suitable carrier-electrolytes for HfC14. However, in the initial studies on electrowinning, it was desirable to use electrolytes that had low solidus temperatures and could be operated over a wide temperature range to investigate parameters of the process. Therefore, electrolytes containing LiC1, NaC1, KC1, RbC1, CsC1, and HfC14, in various combinations were explored. EQUIPMENT Chlorinator. Hafnium carbide was chlorinated to produce HfC14 in the batch-type chlorination shown in Fig. 1. Chlorination temperatures were measured with a thermocouple placed in the center of the HfC charge. A flow meter was used to monitor the helium and chlorine. The exhaust side of the silica chlorina-tor tube was equipped with a flask for collecting organic material released during the initial heating of the HfC. The temperature of an internal heater, which extended from the HfC14 condensing flask to the hot end of the chlorinator, was adjusted to prevent the HfC14 from condensing before entering the collection flask. Helium and excess chlorine were exhausted through the lid of the collection flask to an aqueous NaOH solution. Sublimer. Initial studies were conducted using a sublimer, Fig. 2, made by placing a 13/8-in. OD nickel thimble 11 in. long, inside a 11/2-in. ID nickel bell 12 in. long, and locking it in place. This unit was loaded with HfC14 and partially immersed in the molten electrolyte for sublimation directly into the electrolyte. In another sublimer shown in Fig. 3, the HfC14 was contained in a "resin reaction flask". Quartz wool, previously heated to 600aC, secured between two nickel wire screens, was placed just above the HfC14 powder. The lid contained a vacuum outlet, a gage, an argon inlet, and an air-cooled pipe for condensing the HfC14. This sublimer was evacuated and heated. The sublimation temperature was not critical and the sublimer operated satisfactorily at all temperatures between 250" and 350°C. Electrolytic Cell. The electrolyte chamber, Fig. 4, was made of mild steel 8-in. schedule 20 pipe, 30 in. long. The exterior was metallized with a Ni-Cr alloy. The electrolytes were contained in a 16 gage nickel or iron liner with a nickel heat shield on top. The cell was heated by a resistance furnace. A 21/2-in. ID by 25 in. long air lock was connected to one port of a two-port cell cover assembly through a slide valve. The cover assembly of the air lock was electrically insulated from the cell and was equipped with a rubber sleeve that provided for the passage of the cathode lead. This allowed the cathode deposits to be removed and a new nickel cathode to be introduced without allowing air to enter the cell. A tube-rod assembly was bolted to the other port on the cell cover assembly and was sealed by a packing seal. The tube-rod assembly consists of a graphite

Jan 1, 1970

By Thomas S. Carnahan

The mining property of the Utah Copper Co. is situated in the West Mountain mining district, Salt Lake County;Utah, in the Oquirrh Range of mountains. Geology In a general way the rock formation of the district consists of a series of beds of quartzite and limestone intruded by a body of monzonite porphyry roughly elliptical in shape, with an east-west axis over a mile in length and a north-south axis of about 3,000 ft. This porphyry intrusion, accompanied by strong mineralizing action and fracturing, resulted in the formation of orebodies in the adjacent sedimentary rocks, and was itself sufficiently mineralized to make it one vast orebody. The Utah Copper Co.'s mining property comprises within its boundaries practically the entire outcrop of the monzonite mass, of a commercial grade. Genesis of Porphyry Ore Following an intricate system of fracturing, mineral solutions circulated freely through the porphyry, depositing small quantities of copper and iron, and resulting in a considerable silicification of the monzonite. The quantity of copper originally deposited was undoubtedly too small to have ever given the porphyry a commercial value, had not secondary enrichment, due to the leaching of the copper from the surface of the mass and re-deposition in the sulphide zone, been active over a long period of years. A large portion of the leached material has probably been removed by erosion, but there still remains a blanket of leached and oxidized porphyry of varying thickness covering the sulphide ore, known as capping. Over certain sections of the orebody, this capping contains commercial quantities of copper carbonates, but most of it contains little or no copper.

Jan 1, 1916

By J. R. Kyte, L. A. Rapoport, R. J. Stanclift, S. C. Stephan

Experimental studies covering a wide range of core materials and fluid properties have been conducted to determine the mechanism of oil displacement by water in a partially gas-saturated porous medium. In all instances, the presence of a gas phase was found to have a beneficial effect in reducing residual oil saturations. The practical significance of this benefit is discussed, and a simplified procedure is outlined for evaluating the effects of free gas on water flooding by means of short core tests. INTRODUCTION In addition to oil and water, reservoirs subjected to water flooding frequently contain, also, a gas phase. Common engineering procedures account for the presence of this "free gas" only from the viewpoint of volumetric balance, implying that the only role of the gas consists of providing "fill up" space. It is usually visualized that during the initial stages of the water invasion, the oil, moving ahead of the water, displaces part of the gas and that subsequently the remaining portion of the gas phase is totally compressed and dissolved in the advancing oil bank. Thus, consideration of a two-phase, water-oil flooding mechanism supplies an adequate basis for predictions of oil recovery if the pressure build-up caused by the flood is sufficiently great, so as to reduce the free gas saturation to a negligible value in any portion of the reservoir by the time that portion is reached by the advancing flood water. In many in- stances, however, waterflooding operations are carried out when the reservoir pressure is still relatively high SO that the pressure build-up associated with the water flood may not result in complete dissipation of the gas phase. Under such circumstances it is necessary to ascertain whether or not the presence of free gas has an effect on waterflood behavior and, if so, to account for any such effect in the evaluation of field operations. The difficulties encountered in attempting to arrive at a comprehensive picture of the displacement mechanism of oil by water in the presence of free gas stem from the fact that most of the published data on this subject were obtained under conditions that were either not clearly representative of those existing in a reservoir or not sufficiently controlled to permit evaluation of the effects specifically caused by the gas phase. Some of the most precise data found in the literature were obtained in tests using a "static" gas phase created prior to each water flood by circulating oil through partly gas-saturated cores until a "trapped," residual gas saturation was established throughout the system.' Other investigations were conducted under more representative conditions where the gas phase was free to move during the water flood: but in most cases the results of these tests were obscured by auxiliary phenomena which arise from the compressibility and solubility of the gas and preclude quantitative conclusions.2,3,4 Prior to water flooding, a reservoir usually contains oil and gas, distributed in a manner in which both are free to move. Thus, the principal objective of the present studies was to determine the type of displacement mechanism occurring when water invades a porous medium containing oil and a "mobile" gas phase. Further-

Jan 1, 1957

By K. P. Wang

Under the Communist regime marked industrial progress has been achieved on the China mainland. Within a decade, the country has been transformed from an economy primarily agricultural to one bristling with industrial possibilities. The industrial capacity of Communist China is beginning to approach that of Japan and will probably surpass it by 1962, the last year of the Second Five-Year Plan. The slogan already is Beat the United Kingdom by 1972, a goal which most observers feel will be achieved ahead of schedule. During the early years of the industrialization program in Communist China, emphasis has been placed on basic goods; hence additional time will be needed to make large quantities of the more complicated products. However, regardless of the current stage of industrial development, it is apparent that the necessary forward momentum has been created. The many capital construction projects being brought into production and the additional projects being initiated confirm this observation. The accuracy of Communist China's industrial statistics can be questioned, but their order of magnitude is clear. To properly evaluate the industrial capability of the country, differentiation must be made between the absolute quantities that reflect overall strength and the per capita quantities that reflect living standards. While Communist China is well on the road to becoming a world power, its living standards will remain below European levels for many years to come.

Jan 8, 1960

By George Burgess

I. INTRODUCTION THE suggestion has often been made that it would be highly desirable, at least for certain grades of steel, to be able to control more certainly, by pyrometric measurement or otherwise, the temperatures of the operation of the open-hearth and other furnaces used in the manufacture of steel and iron. That the properties of the ingot and finally of the finished steel product are intimately related to the final temperatures attained by-the metal inn the furnace and to the temperature of casting, has been recognized by metallurgists for a long time, and this question has been very thoroughly treated, especially by Prof. Henry M. Howe, and by A. W. and H. Brearley.1 It is the object of this paper to demonstrate that in so war as casting temperatures of furnaces, steel ingots, and similar operations involving the temperatures of streams of iron and steel are concerned, well-known pyrometric methods s may be easily applied-if certain recently determined corrections are made and precautions taken-with a relatively high degree of accuracy. Greater but not insurmountable difficulties will be encountered in. the case of open-hearth furnace temperatures, while for" those of the converter type a ready solution does not seem practicable. It appears that certain essential data have always been lacking in reporting observations such as those of Le Chatelier in 1892. Thus the correction to be applied for the characteristic radiation-or emissivity¬has hitherto not been adequately taken into account nor the limitations of the several possible pyrometric methods clearly recognized.

Jan 2, 1917

By Richard B. Moore

The successful commercial production of helium during the last few years has added greatly to its scientific interest. When the quantity of an element available for experimental purposes increases within a few years by 200,000 per cent., both public and scientific interest in the element are greatly stimulated. Before the war, probably, there was not more than 10 or 15 cu. ft. of helium in existence. The larger part of this was owned by Prof. Kam-merlingh Onnes, and was used by him in connection with his low-temperature work at Leiden. By experimental work during the war and immediately afterwards, the Canadians, under Prof. J. C. McLennan, produced about 60,000 cu. ft. of helium of various grades of purity. Up to Dee. 1, 1921, when the plant at Fort Worth was shut down because of lack of funds, there had been produced during the experimental work by the U. S. Government, during the war and afterwards. 2,300,000 cu ft. of helium averaging between 92 and 95 per cent. purity. After the new appropriation was made in 1922, the production plant was again started and at the time of writing was making about 15,000 cu. ft. of helium a day. Only three of the five units were being operated because of the inability to get sufficient gas to run at full capacity. The gas supply is owned by two companies and on account of a disagreement between them, it has been possible for some time to get gas from only one. It is expected that when all five units are running steadily, the daily production will be between 30,000 and 40,000 cu. ft. of gas averaging from 93 to 95 per cent. purity. All three experimental plants used during the war have been shut down. The Air Reduction plant, using the Claude system, and the Linde

Jan 1, 1923

By Richard B. Moore

The successful commercial production of helium during the last few years has added greatly to its scientific interest. When the quantity of an element available for experimental purposes increases within a few years by 200,000 per cent., both public and scientific interest in the element are greatly stimulated. Before the war, probably, there was not more than 10 or 15 cu. ft. of helium in existence. The larger part of this was owned by Prof. Kam-merlingh Onnes, and was used by him in connection with his low-temperature work at Leiden. By experimental work during the war and immediately afterwards, the Canadians, under Prof. J. C. McLennan, produced about 60,000 cu. ft. of helium of various grades of purity. Up to Dee. 1, 1921, when the plant at Fort Worth was shut down because of lack of funds, there had been produced during the experimental work by the U. S. Government, during the war and afterwards. 2,300,000 cu ft. of helium averaging between 92 and 95 per cent. purity. After the new appropriation was made in 1922, the production plant was again started and at the time of writing was making about 15,000 cu. ft. of helium a day. Only three of the five units were being operated because of the inability to get sufficient gas to run at full capacity. The gas supply is owned by two companies and on account of a disagreement between them, it has been possible for some time to get gas from only one. It is expected that when all five units are running steadily, the daily production will be between 30,000 and 40,000 cu. ft. of gas averaging from 93 to 95 per cent. purity. All three experimental plants used during the war have been shut down. The Air Reduction plant, using the Claude system, and the Linde

Jan 1, 1923

By R. I. Jaffee, H. R. Ogden, D. J. Maykuth, W. L. Finlay

Titanium with up to 7.5 pct Al forms single-phase a alloys that are work hardening, not heat treatable, and ductile as welded. The high aluminum Y phase alloys are not usefully ductile, despite their low hardness, but they have excellent oxidation resistance and hot hardness. LITTLE has been published on the effect of aluminum on the mechanical properties of titanium, despite the fact that two of the first four commercial alloys released by titanium alloy producers contained aluminum as an important alloying ingredient. These were both a-ß type alloys, one containing 4 pct A1 and 4 pct Mn and the other containing 3 pct A1 and 5 pct Cr. However, neither of these alloys reflects the true alloying nature of aluminum, since each contains important amounts of the ß-stabilizing addition, manganese or chromium. In a previous publication on the constitution of Ti-A1 alloys,' the authors showed that aluminum had a high solubility in a titanium and was strongly a stabilizing in nature. About 25 wt pct A1 is soluble in a titanium at room temperature. With as little as 5 pct added aluminum, the a transus temperature is increased from 882" to 970°C, and the correspond- ing ß transus to 995°C. The first intermediate phase in the Ti-A1 system is the ordered face-centered tetragonal TiAl phase, which extends from 34 to 46 wt pct Al. The present paper presents hardness data over the entire titanium-rich region of the system, through the TiAl phase, and mechanical property data on the alloy range capable of being fabricated. Methods of Investigation The materials used and general preparation of alloys, as well as experimental techniques used in the investigation of Ti-A1 alloys, have been adequately described.' Briefly, the preparation consisted of arc-melting the desired amount of high purity aluminum (99.99 pct purity) and iodide titanium (maximum hardness 100 Vickers, as deposited) together on a water-cooled copper hearth under a partial pressure of argon. The resulting button ingot was of such form that it could be fabricated without further treatment. All work was done using ingots weighing 10 to 15 g, which were hot-rolled to strip form whenever possible. Tensile samples were 3.25 in. long, 0.5 in. wide, and 0.040 in. thick, with a reduced section 1.25 in. long by 0.250 in. wide. The gage length used was 1 in. Electrical strain gages mounted on the

Jan 1, 1954

By James E. York

The honor so fairly earned and so incompletely and tardily paid to Henry Cort, the inventor of the puddling-furnace and the rolling-mill, has been fully set forth by Mr. Charles H. Morgan,' and needs no further emphasis here. In view of the importance of the rolling-mill in the treat ment of iron and steel, the paucity of information concerning it is surprising. With the exception of a book, written about 35 years ago, by Peter Ritter von Tunner, an Honorary Member of this Institute, and of desultory articles on simple sections, which have appeared in technical journals, I know of no publication attempting to treat this subject, although volumes have been written on the scientific theory and technical manipulations involved in other branches of the iron- and steel-industry. This strange anomaly may be due to the fact that roll-turning cannot be called a scientific business. It does not ordinarily come within the range of an educated engineer; yet it cannot be performed by an ordinary mechanic. It demands some of the qualifications of an engineer, in designing, and those of a mechanic, in execution. The men who have followeci this trade have controlled the training of their successors. In many cases the technical knowledge required has

Jan 1, 1907

By H. I. Aaronson, C. Laird

Although the past results of X-ray experiments indicate that the broad faces of 0' plates are coherent with their matrix, dislocations lying in arrays have frequently been observed at these boundaries by transmission electron microscopy. Critical experiments employing the latter technique have been carried out in order to determine the origin of these dislocations. It is concluded that 8' plates are essentially coherent with the matrix at their broad faces throughout the aging temperature/time envelope studied. Virtually all of the dislocation arrays observed are deduced to have been formed by plastic deformation accompanying transformation. The proportion of dislocations arising from convexity of the plates is shown to be negligible by comparison with that from plastic deformation. At the higher aging temperatures, a[001] dislocations appeared in moderate numbers. These dislocations were traced directly, however, to the ledgewise dissolution of 0' occasioned by the formation nearby of 0 crystals. On the other hand, since there is a parametric difference normal to the broad faces of the ?' plates, mismatch dislocations do form at their edges. A previous conclusion that these dislocations have Burgers vectors of type a[001] was confirmed directly. The edges of 0' plates were observed to develop octagonal shapes when growing, but circular shapes during dissolution. 1 HIS paper presents the results of an investigation of the interfacial structures of plates of the transitional phase, 8', formed in an A1-4 pct Cu alloy. In a companion paper, Part 11, the effects of these structures upon the migration kinetics of a:?f boundaries are reported. This work is pa.rt of a general program designed to establish the basis of precipitate morphology. The present authors in Al-Ag,1 and whitton2 previously in U-C alloys, have used transmission electron microscopy to examine directly the vander Merwe3-6 networks of dislocations anticipated7 to compensate the small amount of lattice misfit normally founda at the broad faces of Widmanstatten plates. Since the broad faces of 0' plates are considered to be perfectly coherent with the corresponding habit planes in the a matrix,' no dislocations should be present at these faces. Many reports have been published, however, giving evidence to the contrary.10-18 The primary objective of this investigation was therefore to ascertain the nature of these dislocation structures. An attempt to do this is described in the first three sections of this paper. Inspection of the matching of the a and 8 ' lattices at the orientations of the 0:0' boundary corresponding to the edges of 0' plates raises the possibility that these edges may be made up of rather closely spaced edge- type misfit dislocations oriented so as to be sessile with respect to the lengthening or shortening of the plates. Since this structure should severely inhibit migration of the plate edges (Ref. 7, Part II), a situation not originally anticipated,' an experimental determination of the interfacial structure of the edges of 8' plates was clearly in order, and is reported in Section III. Those aspects of the experimental procedure applicable to both Parts I and I1 are presented in the next section. Specific procedures applicable to individual aspects of each investigation, and also the relevant surveys of the literature, are then individually reported in the appropriate sections. I) GENERAL EXPERIMENTAL PROCEDURE The material used in both parts of these studies was the same as that of a previous investigation:" strips of A1-3.93 pct Cu, 0.009 in. thick, prepared as before, solution-annealed at 548°C for 6 hr, and quenched. Details of subsequent aging, and in some cases deformation treatments, are given in the Experimental Procedure sections of the individual parts of both papers. Specimens of the heat-treated strips were electro-thinned as beforeLg and examined in a Philips EM 200 microscope equipped with a goniometer stage. A commercial hot stage, of the grid-heater type and capable of * 30-deg tilt about one axis in the plane of the specimen, was also used for kinetic studies. The usual precaution of calibrating for the additional heat supplied by the electron beam was taken.19 A 16-mm cine cam-I era mounted outside the viewing window was frequently used to record the transformations. Conventional selected-area diffraction and dark-field viewing techniques were used to identify the precipitates in the foils. Normal bright-field images corresponding to two-beam diffracting conditions or dark-field images were employed to characterize the dislocations observed at the interfaces of the precipitates. The application of these techniques to the study of an interphase boundary, and the interpretation of the images,20'21 has been fully described in a previous paper.'

Jan 1, 1969

By Herbert Clark Hoover, Lou Henry Hoover

We give the following brief notes on early works containing some reference to mineralogy, mining, or metallurgy, to indicate the literature available to Agricola and for historical notes bearing upon the subject. References to these works in the footnotes may be most easily consulted through the personal index. GREEK AUTHORS.-Only a very limited Greek literature upon subjects allied to mining or natural science survives. The whole of the material of technical interest could be , reproduced on less than twenty of these pages. Those of most importance are : Aristotle (384-322 B.c.), Theophrastus (371-288 B.c.), Diodorus Siculus (1st Century B.c.), Strabo (64 B.c.-25 A.D.), and Dioscorides (1st Century A.D.). Aristotle, apart from occasional mineralogical or metallurgical references in De Mirabilibus, is mostly of interest as the author of the Peripatetic theory of the elements and the relation of these to the origin of stones and metals. Agricola was, to a considerable measure, a follower of this school, and their views colour much of his writings. We, however, discuss elsewhere1 at what point he departed from them. Especially in De Ortu ct Causis does he quote largely from Aristotle's Meteorologica. Physica, and De Coelo on these subjects. There is a spurious work on stones attributed to Aristotle of some interest to mineralogists. It was probably the work of some Arab early in the Middle Ages.[ ]

Jan 1, 1950

By N. Albon, J. F. Miller, R. W. Coutant

The deposition of nickel from nickel carbonyl onto amorphous substrates has been studied, with attention being paid to the specific effects of the physical and chemical nature of the substrate and to the effect of oxygen on the crystal morphology. With substrates having microscratches or etch lines, nu-cleation was observed to occur preferentially at these surface features. Flame polishing of the substrate surfaces was found to remove any regularity in preferred nucleation sites. Nucleation was observed to occur less readily on substrates having relatively low surface energies, e.g., Teflon and carbon, than on materials having relatively high surface energies such as fused silica. At low oxygen concentrations [Ni(CO)4/O2 > 54 x 1031, apparently pure and well-formed nickel crystals were observed to nucleate and grow irrespective of the presence of oxygen. At higher concentrations of oxygen, a secondary growth process, dependent upon oxygen concentration and resulting in a gradual change in crystal morphology, was observed. It is concluded that the influence of oxygen on the nucleation and growth of nickel is determined by the relative kinetics of the various possible reactions, and that under the experimental conditions employed the 0-Ni interaction occurs at some nucleation or prenuclea-tion stage. THE purpose of the research on crystal nucleation in chemical vapor deposition as described in this paper has been twofold: 1) to examine some effects arising from the use of amorphous substrates, and 2) to study the specific effects of oxygen on the nucleation and growth of nickel in a nickel carbonyl-carbon monoxide system. The nickel-nickel carbonyl system was chosen for study for several reasons: 1) nickel films are of potential interest in electronic technology, and 2) the deposition can be carried out at moderate temperatures, thus making possible detailed study of the processes occurring and the use of a variety of substrate materials (including some which melt at relatively low temperatures). Fairly well-characterized chemical kinetics and a broad background of information are available on the py-rolysis reactions and on the mechanisms of Ni-O interactions. NUCLEATION AND GROWTH THEORY The theoretical background for the analysis of nucleation and growth by vapor deposition for a one-component system (physical vapor deposition) and the problems encountered therein have been reviewed by Hirth and pound.' More recently Mande12 has indicated the difficulties of applying such theory to chemical systems. One of the major problems involved is the possible multiplicity of chemical reactions and deposition routes. For example, those reactions which are probably of significance in a discussion of the pyrolytic deposition of nickel from nickel carbonyl under the conditions of the present experimental work are illustrated in Fig. 1. As is true with most cases of chemical deposition, many of the quantitative data necessary for a complete analysis of the system are either not available or not directly measurable. However, with the present system, sufficient data are available for a discussion of nucleation and growth on a qualitative basis. Classically, the rate of nucleation of a monatomic species being deposited from a vapor phase is given by

Jan 1, 1965

By D. S. Gleason, D. E. Severson, D. R. Skidmore

Pittsburg and Midway Coal Co. has modified the German Pott-Broche process, on which patents date back to 1927, to produce on a bench scale liquid products by solution hydrogenation of coal. A continuing program of lignite solution-hydro gena-tion experiments is directed toward investigating coal solution reactions, determining favorable conditions for the solution refining of lignite by the Pott-Broche process, and investigating some of the uses for the de-ashed product obtained from lignite The German Pott-Broche process1" on which patents date back to 1927, has been modified by the Pittsburg and Midway Coal Co., a Gulf Oil subsidiary, to produce on a bench scale liquid products by solution -hydrogena-tion of coal." The objectives of the present effort are to investigate coal solution reactions, to determine favorable conditions for the solution refining of lignite by the Pott-Broche process, and to investigate some of the uses for the de-ashed product obtained from lignite. This paper is a summary of results to date in a continuing program of lignite solution-hydrogenation experiments. The coal solution reaction program has several principal aims. The first of these is to determine whether lignite can be successfully dissolved in solvents that might be practical for commercial development. The second object is to determine whether the solvents function after successive cycles of use, recovery, and reuse. It seems necessary to the economics of a potential commercial process that the solvent be recycled. Third, it is desired to learn something about the distribution of the ash constituents between cake and filtrate. The extent of ash removal is important. The nature and quantity of mineral matter passing through the filter may determine end-use marketability. For certain use applications, trace quantities of certain minerals can be objectionable, e.g., titanium and vanadium must be very low in electrode carbon for aluminum production. The Solution Reaction The coal solution Process involves an extremely complex system of chemical reactions. An initial solvent such as anthracene oil is a mixture of hundreds of different compounds with a boiling range of roughly 500" to 750°F at atmospheric pressure. The coal macro-molecule is broken down by thermal decomposition and solvent action into myriads of different compounds, some the same as those comprising the solvent. This similarity in structures opens up the possibility of production and subsequent recovery of solvent. Some solvent is inevitably lost by reaction. Regeneration of solvent was not a problem in the early German Pott-Broche plant. The coal refinery was an integral part of a petroleum refinery complex and replacement solvent was readily available. A coal refinery using lignite, however, might be isolated from other hydrocarbon processing facilities and the regenerability of solvent could be vital to the economic success of the venture. Several structural features of the solvent molecules have been cited as important to the coal solution process.'. The first of these is aromaticity of the material, the second, ability to transfer hydrogen to another molecule, as for example the ability of tetralin to transfer hydrogen and be converted to naphthalene. Finally, the presence of hydroxyl groups on aromatic rings within the molecule, i.e., phenolic character, seems beneficial. Mixtures of pure compounds have been tried by various investigators. Mixtures of o-cresol, a phenolic substance, and tetralin were found to dissolve bituminous coal better than either substance alone.3 This maximum solubility was not found with lignite." Hydrogen contributes to the reaction by hydro-genolysis and by combining with free radicals and molecular "loose ends" to stabilize the compounds formed in coal depolymerization. High boiling point, and correspondingly high molecular weight, seems to be a property which improves solution potential for coal with a given type of compound.' The maceral components of the coal appear to have an important bearing on its ease of solution. The fusain portion is quite inert to solvent action, but the an-thraxylon material dissolves quite readily.3 The hydrogenation reaction can be improved by the use of a catalyst; commercial hydrogenation catalysts having been found effective. Although cost is involved in the use of catalyst and catalyst recovery, the resulting saving in time and perhaps lowered temperature or pressure might justify their use in the solution refining process and decrease the total process costs. Apparatus and Procedure The coal solution runs were made in a 1-gal stainless steel stirred autoclave. The autoclave was provided with thermocouple wells and a transducer to permit continuous recording of temperature and pressure. The autoclave stirrer was magnetically driven, eliminating the leakage inherent with a rotating pressure seal. For runs in which a catalyst was used, the catalyst in the form of beads was placed in a wire mesh container mounted on the stirrer shaft. A control system programmed the heatup and reaction cycle. The permissible heating rate was 5°F per min because of the need to minimize thermal stress in the autoclave body. The temperature was raised at that rate until the reaction temperature was attained and then the temperature was held constant for the desired length of time. The maximum temperature seldom exceeded the average run temperature by more than 15°F.

Jan 1, 1971

By C. Schlumberger, M. Schlumberger

The object of this paper is to clarify the idea, so important when exploring by potential methods, of the depth of investigation attainable by electrical measurements. After defining, with some precision, .the term "depth of investigation'' in geophysics, the authors show how it is possible to regulate this depth in potential methods and to obtain an 'electrical drilling" from surface observations. They consider also the difficulties encountered in deep measurements and indicate how it is possible to reach greater depths than those having an industrial interest. Depth of Investigation The term, depth of investigation, in its general sense, is easily understood. For instance, a driller who can pull cores from a depth of 2000 m. is capable of working, with accuracy, to that depth. By means of a properly placed drill, he may locate an orebody at a depth of 1999 m., however small this orebody may be. On the contrary, the term as used in geophysics requires precise elaboration. As a matter of fact, no geophysical method, irrespective of the physical property studied (density, magnetic permeability, conductivity), can discover a very small body at a great depth because, in practice, the physical parameter upon which such a geophysical method is based is never regular enough, throughout the ground, to distinguish the feeble anomaly caused by the small, deep-lying body from the numerous anomalies due to irregularities of the encasing terrains. Aside from this question of the ratio between the size of the body being hunted for and its depth of burial, a second factor plays its role in the possible depth of investigation; that is the difference, for the parameter under consideration, between the body and its surrounding material. The greater this difference, and the more homogeneous the encasing terrains, the greater is the possible depth of investigation. This being generally established for all geophysical methods, it is possible to distinguish two main classes of these methods, from this same point of view

Jan 1, 1932

By A. J. Lanea

INDUSTRIAL MEDICINE bids fair to become one of the most important and highly developed branches of medical science. Mining companies, even in remote districts, have developed large and efficient medical organizations that comprise the best types of physicians and surgeons. Not infrequently, however, company medical departments have been influenced too much by local conditions-including the compensation laws, which differ widely in the various states. The possibilities of industrial medicine are just beginning to be generally understood, and the variations in the organization and aims of medical departments of mining companies are no more pronounced than in industry as a whole. The industrial physician should be as much a part of the organization as any other official and he should know intimately the various types and phases of work in the plant and should look at his work from the viewpoint of the needs and requirements of his particular industry and company. He should not-be on the outside looking in, but on the inside, working hand in hand with the superintendent, manager, foremen, employment director, safety director, and anybody else with whom in his work he might associate. In any industry it is essential that the doctor be-familiar with working conditions. The mine doctor who never goes underground must remain ignorant of the factors causing many of the disorders he treats as well as miss the best opportunity of gaining the respect and cooperation of the men he. serves. If the mine doctor remains unfamiliar with underground working conditions he bars himself from valuable preventive medical work. It is estimated that the time lost by industrial workers, as a whole, because of illness is about four times as great as that lost because of accidents. While the effort to determine the responsibility of working conditions for illness is often futile, there is a wide field, both for study and practice, in the lessening of sickness among industrial workers. The first step in this direction must be a knowledge of the factors involved.

Jan 2, 1921

By G. G. Priest, B. E. Morgan

The production of oil and gas from wells is often seriously hindered by the compaction of solids in the perforations during the perforating process. To realize the full productive capacity of a well, it is necessary either to remove the plugging material from the perforations or to perforate in a manner which does not cause plugging of the perforations. The latter method can be accomplished by having a non-plugging fluid in the casing at the time the well is perforated. This paper describes the results of laboratory tests, perforating tests, and experimental field tests which demonstrate that certain emulsions serve effectively as non-plugging perforating fluids. The principal components of these emulsions are two liquids: an aqueous phase consisting of a solution of either sodium chloride or calcium chloride, and an oil phase consisting of diesel oil, tetrachloroethylene, or a combination of both. Small amounts of other agents which serve to stubilize the emulsions, to reduce the fluid loss, and to inhibit corrosion are also present. The density of the emulsions is controllable within the range of 7.5 to 12.5 lb/gal; no insoluble solids are present, the filtration rate is low, and the thermal stability is satisfactory at temperatures as high as 200°F. The corrosion of steel by these emulsions is negligible. Tests conducted under conditions which simulate the temperature and the pressure in an actual well demonstrate that these emulsions fulfill the requirements of a non-plugging perforating fluid. In addition, lirnited field experience furnishes evidence that these emulsions remain in position after they are spotted, that they are retained in the casing after the perforations are made, and that they are easily removed from the perforations when the well is opened for production. When the pressure in the borehole is greater than the formation pressure at the time a well is perforated, plugging of the perforations can be avoided by spotting an emulsion adjacent the interval to be perforated. This procedure should eliminate low well productivity caused by plugging the perforations. INTRODUCTION Nature of Problem The most widely used method for the completion of oil and gas wells is to set and cement casing through productive horizons, and then to obtain production by gun-perforating the section of casing opposite the desired interval. This method is gen- erally successful and it was thought at one time that those failures which did occur were due to insufficient penetration by the perforator. Despite recent improvements in perforators which assure ample penetration, unsatisfactory fluid production continues to be a problem. Evidently, the trouble comes from some other source. Recent results obtained by Allen and Worzel1 demonstrated that low fluid productivity may be caused by the perforating process and/or by the fluid in the wellbore at the time of shooting. They found that perforations are often completely plugged by debris from the perforator, pulverized sand from the formation, and compacted solids from the drilling mud when the pressure in the wellbore is greater than the pressure in the formation at the time of perforation. In some cases a differential pressure in excess of 400 psi was required to initiate flow into the well through these plugged perforations. The plugging of perforations by solids not only causes low productivity from wells, but it creates simultaneously other problems in the production of oil and gas. For example, when most of the perforations are plugged, high rates of flow must occur through the few perforations that are open. The resulting high pressure drop may cause production

Jan 1, 1958

By K. C. Li

TITANIUM, because of its high strength, weight ratio, and high melting point, became the metal of the jet age. Zirconium, because of its low neutron cross section and high corrosion resistance to hot water, became an integral part of the nuclear era. Since both metals are very similar chemically, more or less the same process is used for their production. The sudden rise of this new industry of titanium and zirconium seems to have caused some uncertainty as to the future development of processes for making these metals. Although zirconium was discovered in 1789 and titanium in 1790, it was not until 1945, six years after W. J. Kroll patented his process, that F, S. Wartman of the U. S. Bureau of Mines perfected the technique of producing ductile titanium, and it was not until 1946 that Kroll perfected the technique of producing ductile zirconium in commercial quantities. Since then the Government and private industry have spent millions of dollars each year constantly searching for new methods, with the hope that some day titanium can be produced as economically as aluminum and magnesium or as cheaply as stainless steel.

Jan 11, 1957

By Thomas R. Mager

An in.t!estigation has been made of the equilibrium conditions at 1200°C in the reaction between hydrogen sulfide gas and sulfur dissolved in Fe-Si alloys From this the equilibrium constant, activity coefficient, and activity of sulfur in solution were calculated. A number of studies of the equilibrium of sulfur with iron and iron alloys have given closely agreeing results from which the activity and free energy of the dissolved sulfur may be found. Sherman, El-vander, and chipman1 discussed the significant researches of dilute solutions of sulfur in liquid iron prior to 1950, and the results of this study indicated that the relationship between the ratio of PH2S/PH2 in the environment and the percentage of sulfur in solution is not a linear one. Morris and williams2 studied the equilibrium conditions in the reaction between hydrogen sulfide gas and sulfur dissolved in liquid iron and Fe-Si alloys, and reported that silicon dissolved in iron has a pronounced effect on the equilibrium conditions. They found that the activity of sulfur in iron is increased by the addition of silicon. At a silicon content of 4 pet the activity coefficient of sulfur was about twice that for sulfur dissolved in pure iron. Sherman and chipman3 investigated the chemical behavior of sulfur in liquid iron at 1600°C through the study of the equilibrium: H2 + S = H2S; K = PH2S/PH2 . 1/as [1] From the known equilibrium constant of the reaction between H2, H2S, and S and the experimental data, the activity of sulfur in the melt was determined. They found that the activity coefficient of sulfur defined as fs = as/%s is increased by silicon and decreased by manganese. Morris4 and Turkdogan5 also reported that manganese decreases the activity coefficient of sulfur in liquid iron and iron-base alloys. A recent technique of sulfur analysis developed by Kriege and wolfe6 of the Westinghouse Research Laboratories permits an accurate sulfur analysis of 0.5 * 0.2 ppm in the range of 0.1 to 3 ppm, whereas in the range of 3 to 50 ppm the accuracy is ±1 ppm. This technique of sulfur analysis was utilized in this experiment. Previous unpublished data reported that sulfur analysis by the combustion technique was not accurate below 20 ppm. EXPERIMENTAL PROCEDURE Five 5-lb ingots of high-purity Fe-Si were prepared. Three of these ingots were prepared without the addition of manganese but with a variation of silicon contents from 2 to 4 pet. The remaining two ingots contained 3 pet Si with the addition of manganese. Ingots were made at each of three silicon levels: 2, 3, and 4 pet. No alloys were made with less than 2 pet Si since below approximately 1.8 pet Si the binary alloy exhibits a to ? transformation. The two additional ingots of 3 pet Si-Fe were made at each of two manganese levels: 0.20 and 0.50 pet. To minimize the effects, if any, of impurities on the activity of sulfur on Si-Fe, the best metals available were used for melting. All ingots were vacuum-melted in magnesium oxide crucibles. After obtaining samples for chemical analyses, the ingots were processed. This consisted of hot rolling and subsequently cold rolling the alloys. Each ingot was hot-rolled at 1000°C, reheating between every pass to minimize grain growth. All heating was done in a protective argon atmosphere. The slabs were hot-rolled to strips 50 mils thick. After hot rolling, all the material was pickled to remove the scale formed on the surface of the strip during hot rolling. The material was then cold-rolled to 12-mil strips. Single strips of the material used in this experiment were hydrogen-annealed at 1200°C for 16 hr in an alumina tube. Chemical analyses of strips M-1, M-3, M-4, M-7, and M-8 are given in Table I. Sulfur, silicon, and manganese analyses were made from the millings from the cold-rolled 12-mil strips. The oxygen analyses were made from slugs of the as-cast material. The hydrogen sulfide used in these experiments was supplied from cylinders containing a mixture of argon and 1 pet hydrogen sulfide. The parts per million of hydrogen sulfide were determined from the analysis of the exit gas of the annealing furnace during each anneal. The flow rate of hydrogen was approximately 1 liter per min in all anneals. The

Jan 1, 1964

Edward K. Landis, Philadelphia, Pa.: In studying Mr. Thackray's paper it seemed that a critical comparison of the results from different methods therein reported would he of interest. For this purpose Table I. was constructed by grouping all determinations made by the same method, and the probable errors were calculated. In this table all chemists titrating with permanganate (A1, E, F, G and 0 of Mr. Thackray's paper) are classed under "Emmerton;" those titrating with nitric acid (C, J, S and Y) under " Handy; " those re Probable error of result: a, ±0.0008996; b, ±0.000694; c, ±0.00107; d, ±0.00115; e, ±0.000674; f, ±0.000473; g, ±0.003675; h, ±20.0007959; i,0.000.5098; k, ±0.0008303. Probable error of single determination: a, ±0.001989; b, ±0.001547; c, ±0.00214; d, ±0.0023;e, ±0.00116;f, ±0.000818;g, ±0.0019;h, ±0.00224; i, 40.00143; k, ±0.00234. The formula for calculating the probable error is 0.6745, where N (N— 1)' S is the sum of the squares of the differences from the mean and N is the number of determinations.

Jan 1, 1897

The regular activities of the Institute are financed mainly by income derived from members' dues, from advertising in MINING AND METALLURGY, and from the sale of publications to the public. In addition, collateral activities and special projects are financed each year by means of income from endowed funds controlled and administered by the Institute. In the aggregate, the principal sums of these endowments amount to more than $530,000. An active effort is being made to in¬crease the endowment funds of the Institute through a standing committee, of which H. T. Hamilton is chairman, and of which the other members are: W. H. Aldridge, George D. Barron, Cleveland E. Dodge, D. C. Jackling, Henry Krumb and J. V. W. Reynders. This committee feels that there exists a tremendous opportunity for the Institute to be of ever-growing service to the public, to the mineral industries, and to the profession. It welcomes suggestions as to names of men of means who are vitally interested in the mineral industries, and to whom the opportunity to make a contribution or bequest might appeal favorably if presented in the proper light by the committee.

Jan 1, 1944