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By R. P. Olsen, A. K. Schellinger

Molten silicate salts, the important industrial byproducts termed "slags," are known to be electrolytic conductors at furnace temperatures. This property is due to their partial dissociation into ions with the ion kind and size being closely related to the slag composition. Ionic conductance, in liquids, is a function of the viscosity, which in turn is a function of the temperature. It could be anticipated, therefore, that a semi-log plot of conductivity vs. reciprocal absolute temperature might yield a straight line, in the case of molten silicates and salts. As liquids, the viscosity of these slags should follow the Shepard1 relationship: log viscosity = A/T + B Then, if the resistance of the molten slag is directly proportional to the viscosity: log Rs = A/T + B Resistance measurements of molten halide salts,2 and silicate salts34 by various investigators have, indeed, shown this straight line relationship between resistance and temperature. A further relationship between the conductivity versus the degree of ioni-zation, the size of the ions, and the slag composition is, also, to be expected. Large ions, and fewer ions, would move more slowly in a potential field and could not carry as much current as smaller, more numerous, and mobile, ions. Conductivity, therefore, would be smaller in the presence of such large ions and higher slag viscosities. The conductivity-composition relationship is of considerable interest in the case of the industrial slags produced in iron blast furnaces, and non-ferrous smelting furnaces. These slags usually approximate three component systems with several minor components as impurities. At least one of the major components is commonly purchased for the sole purpose of rendering the slag less viscous at a reasonable furnace temperature. Should the conductivity be related rather directly to the concentration of such a purchased slag component (that is, CaO) instrumental measurement and control at the furnace might be possible. Modern tele-metric control methods in aqueous chemical process industries are often based on the property of conductivity of solutions, and its variation with composition. Investigators3 of the phenomenon of electrical conductivity in molten blast furnace slags have established that these systems show lines of equal conductivity on their ternary diagrams at one temperature level. These isocon-ductivity lines form closed contours on the diagrams, and at times, minimum areas occur at which these contours are essentially closed down to a point. The conductivity reading at such a point, at one temperature , would, of course, locate one on the diagram, and give the slag composition. Research in this field is understandably scanty. The reactive nature of

Jan 1, 1950

By Henry S. Burnholz, Charles Y. Clayton, Francis B. Foley

This work was first undertaken for the U. S. Bureau of Mines, in 1919-20, by C. E. Julihn, superintendent of the station at Minneapolis. Learning of the interest, in this subject, of B. F. Tillson, of the New Jersey Zinc Co., Mr. Julihn and Mr. Foley went to Franklin, N. J., and discussed the matter with him. A conference in Chicago, in November, 1920, was attended by Dr. F. G. Cottrell, who was then Director of the Bureau of Mines, and representatives of the Bureau of Mines and of the hlissouri School of Mines and Metallurgy; at this time a cooperative plan of work was agreed upon by the Bureau of Mines and the Missouri School of Mines. In February, 1921, Mr. 'Tillson arranged a conference on this subject at the time of the annual meeting of the American Institute of Mining and Metallurgical Engineers, at which several technical papers were presented. In a paper, the Breakage and Heat Treatment of Hock Drill Stcels, he suggested a program that might be carried out in connection with the investigation of the problem. At this conference Mr. Manning, former Director of the Bureau of Mines, suggested the formation of an advisory committee to the Bureaus of Mines and of Standards for prosecution of this investigation. On Feb. 20, 1922, a secoud conference in New York, at the time of the annual meeting of the American Institute of mlining and Metallurgical Engineers, was attended by representatives of various technical societies. At this meeting, the report of Nov. 20, 1921, of the Chiefs of Divisions of Metallurgy of the Bureaus of Mines and of Standards, was discussed and it was agreed: 1. That the survey recommended by the two bureaus should be undertaken, which survey would have for its object the ascertaining of the present status of the practice of the heat treatment of drill steels, the extent to which the breakage occurs, etc.; and 2. That a report should be presented, of the findings of those who made the survey, to the Advisory Board to the Bureaus of Mines and of Standards. The Bureau of Standards assigned $4000 to the prosecution 01 a three-months' survey, which was carried out in April, May, and June, 1922, of about sixty mines

Jan 1, 1923

By Charles Y. Clayton, Henry S. Burnholz, Francis B. Foley

This work was first undertaken for the U. S. Bureau of Mines, in 1919-20, by C. E. Julihn, superintendent of the station at Minneapolis. Learning of the interest, in this subject, of B. F. Tillson, of the New Jersey Zinc Co., Mr. Julihn and Mr. Foley went to Franklin, N. J., and discussed the matter with him. A conference in Chicago, in November, 1920, was attended by Dr. F. G. Cottrell, who was then Director of the Bureau of Mines, and representatives of the Bureau of Mines and of the hlissouri School of Mines and Metallurgy; at this time a cooperative plan of work was agreed upon by the Bureau of Mines and the Missouri School of Mines. In February, 1921, Mr. 'Tillson arranged a conference on this subject at the time of the annual meeting of the American Institute of Mining and Metallurgical Engineers, at which several technical papers were presented. In a paper, the Breakage and Heat Treatment of Hock Drill Stcels, he suggested a program that might be carried out in connection with the investigation of the problem. At this conference Mr. Manning, former Director of the Bureau of Mines, suggested the formation of an advisory committee to the Bureaus of Mines and of Standards for prosecution of this investigation. On Feb. 20, 1922, a secoud conference in New York, at the time of the annual meeting of the American Institute of mlining and Metallurgical Engineers, was attended by representatives of various technical societies. At this meeting, the report of Nov. 20, 1921, of the Chiefs of Divisions of Metallurgy of the Bureaus of Mines and of Standards, was discussed and it was agreed: 1. That the survey recommended by the two bureaus should be undertaken, which survey would have for its object the ascertaining of the present status of the practice of the heat treatment of drill steels, the extent to which the breakage occurs, etc.; and 2. That a report should be presented, of the findings of those who made the survey, to the Advisory Board to the Bureaus of Mines and of Standards. The Bureau of Standards assigned $4000 to the prosecution 01 a three-months' survey, which was carried out in April, May, and June, 1922, of about sixty mines

Jan 1, 1923

By B. Blumenthal

THE present investigation was planned as a survey of the lead-rich portion of the ternary lead-antimony-silver system by thermal analysis. Since, however, a rigorous application of the conventional thermal analytical method is time consuming, an attempt was made to speed up the investigation by reducing the time required for a single thermal analysis. This was done by increasing the rate of cooling to 12° to 18°C. per minute. Since such a rate does not permit even an approach to equilibrium conditions, the melt was stirred vigorously by a stirrer operating at the high rate of 665 r.p.m. This proved to be effective in obtaining cooling curves with distinct points of arrest and of excellent reproducibility, which satisfactorily compare with those obtained at a rate of 1° to 2°C. per min. with or without slow stirring (Fig. 1). By this method the lead-rich end of the lead-antimony system and a series of ternary alloys in sections parallel to the lead-antimony side of the ternary system were investigated and it was observed that the two branches of the' liquidus curve of the .binary alloys did not intersect at the eutectic temperature. An equivalent effect was observed in the ternary system. The eutectic temperature of the binary lead-antimony system was found to be 252.0°C., which confirms the recent investigation by Pellini and Rhines,1 who determined the eutectic temperature to be 251.5°C. The observation that the curves of primary crystallization of the lead-antimony system do not intersect at the eutectic temperature was previously made by Dean.2 Dean explains the phenomenon by assuming the existence of a compound Sb4Pb. He felt that super-cooling was not the cause of the phenomena because he was unable to influence them by inoculation. The X-ray investigation by Solomon and Morris-Jones,3. the metallographic investigations by Stead,4 Charpy,5 Gontermann,6 and Dean, Zickrick and Nix,7 and the numerous investigations of physical properties, definitely disprove the occurrence of any compound. The work of Dean was not confirmed by Broniewski and Sliwoski,8 whose experiments did not show any irregularity and who report a eutectic composition of 13 per cent antimony and a eutectic temperature of 250° to 252°C. at a rate of cooling of about 6°C. per min. Abel, Redlich and Adler9 then report a eutectic composition of 12.1 per cent upon reviewing the previous, publications and adding a few of their own cooling curves. In 1934 Quadrat and Jiriste10 found from careful analyses of the bottom portion of slowly cooled hypereutectic melts that the eutectic contains only 11,4 to 11.5 per cent antimony. (Previous analyses by Stead4 in 1881 gave 13 per cent:) Weaver," however, reported in 1935 that cooling curves indi-

Jan 1, 1943

By R. B. Gilmore

It has been the custom of the Railroad Commission of Texas to hold hearings each month with respect to existence and imminence of waste of oil and gas in Texas and its prevention, and to issue orders restricting the production of oil to the reasonable market demands and allocating production to the various fields in Texas. The practice of designating the actual days during the month on which wells are to be shut down was discontinued in the order for November 1942, and orders issued thereafter contain only the number of shut-in and producing days for the month. Orders issued by the Railroad Commission are divided into two main subdivisions, the first a general shutdown order of all oil wells in the various fields in Texas, and second, the exception of certain fields to this general order. Table I shows the producing days for all of the fields in Texas for 1944 under the first of these classifications : The fields that have producing schedules varying from the general order may be divided roughly into three subdivisions, as follows: Table 2 shows the producing days for certain fields that were prorated as a group throughout 1944. Other fields which were occasionally included with this group were also prorated under the general order and by special orders. The producing days for these irregular fields are shown in Table 4. In Table 3 are listed fields that were exempted from any shutdown days during December 1944, the majority retaining this exception throughout 1944. Certain fields included in the general order were added to this group on the first day of the month shown.

Jan 1, 1945

By L. Grånäs, B. Aronsson

In a recent study of Fe-Si alloys Walter and Koch' observed pairs of dislocations in Fe-6.25 pct Si crystals rolled to reductions of 10 pct and subsequently annealed for 1 hr at 650°C. They interpreted these pairs as being due to stacking faults. From the spacing of the dislocations a stacking-fault energy of 15 to 19 ergs per sq cm was calculated. These authors did not pay any attention to the order -disorder phenomena in Fe-Si alloys. It is the purpose of this communication to report some preliminary results from a study of ordering and its influence on the plastic deformation of Fe-6.0 pct Si alloys. Our results suggest that the dislocation pairs observed by Walter and Koch may have been due to long-range order rather than to stacking faults. The alloys used in this investigation were prepared from pure electrolytic iron and silicon and were melted in argon. After hot working, strip tensile specimens were machined to a gage length of 70 mm and a thickness of 1 mm. The specimens were heat- treated for 2 hr at 1000°C, furnace-cooled, and subsequently deformed 2 pct in tension at 400°C. The strain rate was 5.6 X lo-' sec-'. Thin foils of the deformed specimens were prepared by means of the Bollman technique and examined in a Siemens Elmis-kop I at an accelerating voltage of 100 kv. In the Fe-Si system long-range ordering occurs at a silicon content of about 6 pct Si. In our alloys evidence for ordering is given by selected-area diffraction patterns which show extra reflections consistent with a super lattice of the D0 9 type. In addition, the dislocation arrangement in deformed specimens indicates that long-range order is present. A typical mi-crophotograph of a thin foil is shown in Fig. l. The dislocations are usually straight and parallel and laying in distinct directions. In the commonly observed (111) zone the projections of the dislocations are close to (113) and (oil). Observation of the image position indicates that the two dislocations in a pair have the same Burgers vector and hence constitute a superlattice dislocation.~ According to theory3 a superlattice dislocation in the DO3 structure consists of four ordinary dislocations connected by two types of antiphase boundaries as shown in Fig. 2. In our specimens only two dislocations in each pair have been observed, Fig. 1. The problem is to decide whether the area between these is a NN or a NNN antiphase boundary. Dark-field images using the (200) reflexion (the indices are defined with respect to the DO3-type superlattice) can

Jan 1, 1968

By Wei-Kao Lu

A general rate equation is derived for gas -solid reactions in metallurgical processes by considering the contributions of chemical reaction at inter-phase boundaries and diffusion through the solid product layer simultaneously. This equation takes care of the whole range continuously from purely diffusion control to purely chemical reaction control. The parabolic law,' McKewan's equationa derived with the assumption of interface area control and the equation derived by Kawasaki et al. with the assumption of purely diffusion control are found as the limiting cases of the corresponding forms of the general rate equation. Many metallurgical processes involving gas-solid reactions have been extensively studied. The common examples of these processes include the reduction of oxides to metallic products, the roasting of sulfides to oxides or chlorides and the oxidation of metals. Gas-solid reactions consist of at least two kinds of steps; one involves the transport of reactant and product to and from the reaction zone and the other is the chemical reaction taking place at the interphase boundaries. In the limiting cases one or the other of the above mentioned steps will be much slower than the other and is then rate controlling. For example, the oxidation of metals is diffusion controlled and obeys the parabolic law.' On the other hand, if the diffusion rate is much larger than the chemical reaction rate then it will be controlled by the chemical reaction rate. This latter case occurs for the reduction of iron oxides studied by McKewan. If the rate of diffusion and of the chemical reaction have the same order of magnitude, a more detailed analysis is necessary. Thus at the beginning of the reaction when the solid and gaseous reactants are in direct contact, the reaction should be chemical reaction rate controlled as no diffusion process is involved. At the other extreme as the reaction zone moves further into the solid, the diffusion distance becomes greater and the diffusion rate continuously decreases. Eventually, therefore, for a sufficiently large sample the rate must become diffusion controlled. As the transition from one controlling step to the other must be continuous, we cannot describe this transition period by either of the two limiting cases. In this paper the author attempts to derive a general rate equation for gas-solid reaction systems. This is effected by considering the rates of diffusion and chemical reaction simultaneously from the state of pure diffusion control to pure chemical reaction control. I) DERIVATION The system under consideration is made of at least three phases, namely the gaseous one, the solid reactant, and the solid product as shown in Fig. 1. The notations are listed at the end of the paper. The mass transfer process involves the diffusion of reactants and products across the solid product layer. It is reasonable to consider that no chemical reaction will take place in the solid product layer with respect to both gaseous reactant and product. For the characteristics of local equilibrium of the system, the diffusion process is really in a quasi-steady-state. It will be proved in the following paragraphs. Then we can invoke the law of conservation of mass valid for all chemical species passing through the layer. The solid reactant sphere has an initial radius, ro, after a fraction of completeness of the reaction, the unreacted core has a radius ri, where r, is in the solid product region. Let Cg be the activity of gaseous reactant in the

Jan 1, 1963

By E. G. Leonardon, C. Schlumberger, M. Schlumberger

The authors give a definition of the various types of corrosion that may affect a metallic conductor buried in the ground, namely: 1. The metallic conductor may be attacked by the surrounding soil. This phenomenon is purely local and is called by them soil corrosiveness. 2. The metallic conductor may connect two regions of the ground when the electrolytes have a different composition. An electrical current will then be generated and certain zones of the conductor will be oxidized. This is autogalvanic corrosion. 3. Stray current may flow in the ground and enter the conductor in certain sections and leave it in others, thus causing oxidization in certain zones; this is electrolytic corrosion. The soil corrosiveness has been studied extensively by the United States Bureau of Standards and the authors give a summary of the work carried out and results obtained along this line. In autogalvanic corrosion it has been shown, by the investigation of buried pipes, that the zones of corrosion are associated with the zones of egress of the electric current (anodic zones). The location of these zones can be determined by measuring at the surface of the ground the difference of potential that exists along the path of the pipe. This work is performed easily and quickly with the apparatus invented by the authors for the exploration of conductive orebodies. The problem of electrolytic corrosion is a difficult one because it is a question of stray current which may vary in direction and intemsity at every instant. Therefore the components of the electrical field must be known at a given station and compared with the components of the clectrical field at another station, at the same moment. This is achieved by a rccording apparatus that will register the variations of the intensity of the electrlc current along two rectangular directions, during several minutes

Jan 1, 1934

By A. G. Metcalfe, Koeneman

A study of the structure of chemically deposited nickel by Goldenstein, Rostoker, Scpssberger, and Gutzeit has been reported recently. In this work it was shown that the nickel deposit produced by the catalytic nickel-reduction process was an amorphous solid. Crystallization occurred at elevated temperatures when the original powder pattern which showed only a diffuse ring with a d-spacing of 2.01A became sharp, revealing nickel and nickel-phosphide lines. The phosphide was indexed provision%lly on a tetragonal lattice of parameters a = 9.01A and c = 4.42A, which is in reasonable agreement with the structure of Ni3P proposed by No-wotny and Henglein.3 The transformation from the amorphous to the solid state occurs abruptly (e.g., after 7 min holding at 400°C) with the evolution of considerably more than 1000 cal per gm-mole. A more detailed analysis of these effects requires a knowledge of the solubility of phosphorus in nickel. Konstanti-now3 mapped out the phase diagram in 1908 but did not determine the solid solubility. The eutectic was placed at 11 pct P and 880°C. The purity of typical catalytic nickel deposits is very high.' Spectrographic analysis for heavier elements showed only trace amounts of aluminum, calcium, iron, magnesium, lead, and silicon. The term "strace" is a qualitative definition for less than 0.1 pct and probably less than 0.01 pct. Analysis for the interstitial elements yielded 0.04 pct C, 0.0023 pct 0, 0.0005 pct N, and 0.0016 pct H. Some of this material with 7.5 pct P was used in the present work. EXPERIMENTAL METHODS Alloys were prepared from carbonyl-nickel shot and a master composition containing 7.5 pct P. Cold-crucible, nonconsumable-arc melting was used.

Jan 1, 1959

By G. A. Vissac, R. G. Minet, N. E. Sylvander

R. G. Minet—The authors' description of the remarkable progress made in the last few years in applying the fluidized solids technique to the problem of lignite drying and carbonization clearly demonstrates that engineering techniques available today may make many processes practical and profitable which a few years ago were considered otherwise. As pointed out in the article, the future of the carbonization step hinges on the value and utilization of low temperature tar. On paper, at any rate, this tar looks like a valuable raw material for the chemical industry to use. Some 50 to 60 pct may be converted to pitch for electrodes, roofing, road tars, and other valuable products; the 25 to 30 pct tar acids could conceivably form a basis for a new low cost resin or plastic of the phenolformalde-hyde type. Yet these materials are so new and dissimilar from available sources that much work must be undertaken by the chemical industry before they will be accepted. Now that the work of Dr. Perry and his colleagues has made a large supply of low temperature tar a real possibility, I would expect the chemical industry to accelerate its work in this field. On the basis of certain data available in the literature it appears possible to produce a more aromatic tar, although in smaller yield, by operating at temperatures in the range of 1300" to 1500°F. Operating a fluidized bed process for lignite at these conditions should be technically possible, at least, and could produce a tar having more familiar characteristics. I wonder if Dr. Parry would care to comment on such a possibility. Incidentally, in our own work on carbonizing coking coals in fluidized beds, using Ohio, Pennsylvania, and West Virginia high volatile bituminous coals, we have obtained yields which agree with the correlation given for tar yields vs moisture and ash-free volatile Btu. Our data are slightly under the line, but certainly in the range of the correlation. We have also obtained evidence in support of the authors' statement as to the effect of air on the process. In our pilot plant all the heat required for carbonizing is released by internal combustion of char in the fluidized bed in normal operation. We are also equipped to obtain all carbonization heat by external electric heaters on the shell of the carbonizer while introducing only an inert gas to the process. We note no difference in tar yield or characteristics between the two operations. In the case of the gas, however, it appears that some hydrogen is consumed by the air combustion. We would be interested in hearing in a little more detail about the hot dust and char handling problems at Sandow. Have the authors found char subject to spontaneous combustion? Have they ever tried a coking coal in their pilot plant? V. F. Parry (author's reply)—Production of a more aromatic tar by operation of the carbonizer at 1300" to 1500°F does not appear to be economical. 1) The capacity of a reactor operating at 1500°F would be 30 to 50 pct less than the capacity at 932 °F and the cost of processing would increase materially. 2) The cracking of tar vapors in a reactor requires appreciable time to complete the reactions and it is doubtful that considering the very short time of residence of tar vapors within the reactor (4 to 10 sec after evolution) the basic character of the tar would be changed significantly. This is indicated from the data reported in Table XIV. 3) General studies have shown that it is advisable to operate at the minimum temperature to produce the maximum tar and minimum gas. 4) Operating problems and the maintenance of vessels and reactors, and the hazards of handling hot char, increase with the temperature of carbonization. It is technically possible to operate at temperatures as high as 1500°F, but in my opinion it is not economical or desirable. We believe that the primary tar must be won in the simplest way and then processed alone to change its character for production of desired products. It is interesting to have confirmation of our observations on the reaction of air with the products of carbonization. The major reaction is with the char, fol-

Jan 1, 1957

By Frederic P. Dewey

By the old method of determining platinum in ores and bullion, the silver-alloy first obtained in the regular course of assay is parted in strong sulphuric acid and the residual metal weighed. This is re-alloyed with silver by a second cupellation and parted in nitric acid, the residual metal being again weighed. Any difference shown between the two weighings is assumed to be, and is called, platinum. Sometimes it is SO, and if any considerable amount of platinum be present, there will be a decided difference between the two weighings; but a slight difference is no real evidence whatever of the presence of platinum. On the other hand, the second weight may equal or possibly exceed the first, even when traces of platinum are present. Again, other members of the platinum group may go into solution in nitric acid more or less. If present, these would be called platinum and escape detection. The method does not provide any direct tests whatever as to the presence or absence of platinum. It is often indecisive, and sometimes gives erroneous results. It is, therefore, quite unsatisfactory. Being called upon many times to determine platinum in a wide variety of materials, particularly when present in very small amounts, I have realized the disadvantages and defects of this old method. In an article on the solubility of gold in nitric acid,' I have briefly outlined a method of gathering a little gold out of a solution containing much silver, which furnishes the basis of

Jan 1, 1913

By Eben E. Olcott

The Mine.—For some years attention has been drawn to the copper deposits of the Appalachian range of mountains, and especially to those in that portion crossing the corners of Virginia, North Carolina, and Tennessee. Certain it is that in many places in this locality available deposits of copper await the miner, and one after another are being opened and worked. The parts of these three States alluded to are but sparsely settled, and communications are insufficient to meet the demand for transportation. Railroads are wanted, as the existing wagon roads are unfitted for heavy hauling; these circumstances increase very much the difficulties in the way of mining enterprises. Notwithstanding this, the success of some of the mines of this section is an established fact, and Ducktown has for some years held a high rank among the copper-producing localities of the United States. of all these deposits, however, none is more interesting or more deserving of attention than the one now under consideration. The works of the Ore Knob Copper Company have been energetically pushed forward, since the reopening of the mine, in the spring of 1873, by Mr. J. E. Clayt,on, the superintendent and one of the chief owners of the property, and if one thing more than another can insure success it is the combination in this gentleman of rare business capabilities with the deepest personal interest in the prosperity of the undertaking. The copper vein at Ore Knob* is a clearly defined fissure traversing the gneissic rocks of Pre-silurian age in a direction 61' east of north.

By M. Muskat, R. D. Wyckoff

The general problem of the simultaneous movement of water and oil in a connected sand is of considerable practical interest from two points of view. First, there is the situation usually described as "edge-water encroachment." Here the water in the sands contiguous to and flanking the oil sand begins to enter the latter as the oil is removed and the reservoir pressure declines. The physical questions involved concern an understanding of the mechanism of the advance of the water and its control, so as to aid the oil recovery rather than to hinder it. In so far as the entry of the water into the oil sand means at least the partial replacement of the oil from the region of the encroachment by the advancing water, it is quite appropriate to consider this type of situation as one of natural water-flooding. For the present discussion, however, we are primarily interested in the problem of artificial flooding. Here the water is deliberately injected into the oil sand with the intention of displacing the oil and removing it through prearranged output wells. For the practical development of such a procedure rather large areas are included in the flooding program and the injection and output wells are arranged in regular patterns or networks, which are felt to be most favorable for a high oil recovery. Although remarkable success has already been obtained in such flooding programs, especially in the Bradford field of Pennsylvania, essentially by the application of the lessons of practical engineering experience, a more thorough physical analysis of the problem appeared to offer promise of leading to results of some interest and value. Another phase of the problem, which stimulated both the experimental and mathematical analysis, is that it is susceptible in large measure to empirical field tests. It, is in itself but an example and illustration of the general theory of the flow of dead (gas-free) liquids through porous media, in which the authors have been interested for the last several years. From the point of view of its applicability to actual petroleum technology problems, however, water-flooding is a particularly favorable

Jan 1, 1934

By A. D. Schwope, L. R. Jackson, A. M. Hall

IN the course of an extensive investigation of the comparative properties of several types of copper, data were obtained on the cold working and subsequent recovery and recrystallization of the copper. In this paper, relations between the degree of cold work and the course of recrystallization are developed. In particular, it is shown that the course of recrystallization over long periods of time and at low temperatures can be predicted with reasonable accuracy from short-time high-temperature recrystallization data. MATERIALS USED IN THE INVESTIGATION Three types of copper were used in this investigation; these were tough pitch, OFHC, and OFHC copper with 15 oz per ton of silver added identified herein as Lots C, D, and F, respectively. The material was supplied by the American Metal Co. Ltd., and processed by the Rome Cable Co. The analyses of the three types of copper are given in Table 1. Originally, it started as wire bars 4 X 4 X 54 in. These bars were heated to 871°C in air and hot rolled to 3/8 in. rod. This rod was cold drawn to 0.204 in. rod (70 pct reduction) in three passes and annealed at 427°C for 4 hrs. A portion of the 3/8 in. rod was saved for more detailed cold-drawing experiments. Starting with the annealed 0.204 in. rod, hard-drawn wires were produced by cold drawing to 0.081 in. wire in 7 passes (84.4 pct reduction in area). Half-hard wires were made by cold drawing the 0.204 in. rod to 0.102 in. wire, (75 pct reduction) in 6 passes and annealing at 427°C for 4 hrs. This annealed wire was then drawn to 0.081 in. wire, (37.1 pct reduction) in 2 passes. Square rod was made by hot rolling wire bars to 9/16 in, rod in 8 passes. This rod was then cold drawn to 0.445 in.-diam rod and annealed for 3 1/2 hrs at 538°C. It was then cold drawn to 0.325 in. rod and again annealed at 538°C for 3 1/2 hrs. Hard square rods were then made by cold rolling this material to 0.257 X 0.257 in. rod, a reduction in area of 20.5 pct. Half-hard square rods were made by cold rolling to 0.268 X 0.268 in. square, annealing for 332 hrs at 538°C and cold rolling to 0.257 X 0.257 in., a reduction of 8.5 pct. Soft wire or rod was made from all types of copper by annealing the hard-drawn material at 343°C for 3 hrs in steam. The grain size of the annealed 0.081 in. wire varied slightly among the three lots: from 0.015-0.025 mm in the silver-bearing OFHC to 0.035-0.045 mm in the OFHC copper. The annealed 0.257 in. wires were more uniform in grain size, averaging about 0.035-0.045 mm. Representative structures are shown in Fig I. EFFECT OF COLD DRAWING AND TENSILE STRAIN ON STRENGTH OF COPPER Conventional tensile tests were performed on the three types of copper in the various degrees of hardness described above. Results of these tests are tabulated in Table 2. The results in Table 2 are

Jan 1, 1947

By William P. Blake

The occurrence of enormous masses of pure copper has given the mining district of Lake Superior worldwide reputation. The first masses brought from there excited great attention, and directed the notice of the mining world to the few particular mines from which they were taken. It may not now be generally known that nearly all the veins which are worked, and which cut across the trap ridge, contain mass copper, and that large masses are continually being raised from them. The largest continuous mass which has been taken out was probably that from the Minnesota, in 1857, which is variously stated as weighing 420 tons and 470 tons. Its length was about 45 feet, its breadth or height 22 feet, and its greatest thickness 8 feet. All such masses are very irregular and ragged in their form and thickness, thinning out generally from a foot to a few inches, and straggling through the vein until they connect with other large masses. This was the character of a mass found in the Phœnix Mine, one of the oldest on the lake, which mass altogether weighed some 600 tons. But this was really a series of masses more or less connected by strings of metal, yet no one large part of it weighed, singly, over 200 tons. A similar series of masses, weighing about 600 tons, was extracted from the Miunesota. Some of the Phœnix masses were four to five feet thick of solid copper. The Cliff Mine has yielded masses weighing from 100 to 150 tons in one piece. One of 40 tons was taken out this year, besides numerous blocks weighing from 1 to 8 tons. This mine and the Central are now yielding mass copper in abundance. It is, bf course, impossible to pick, or drill, or to break out such huge masses of solid metal when they are found, by drifting upon the course of the vein. The method of extraction is as follows: The miner picks out or excavates a narrow passage or chamber upon one side of the mass, laying it bare as far as possible over its whole surface. It is usually firmly held by its close union with the veinstuff, or by its irregular projections above, below, and at the end. If it cannot then be dislodged by levers, the excavation of a chamber is commenced behind the mass, and this excavation is made large enough to receive from 5 to 20 or more kegs of powder. In one

By Ajoy K. Ghose

INTRODUCTION Longwall mining made its debut in Indian coal mining scene around 1900. Despite this headstart, the application of the method has been slow and halting. Currently, there are some 16 operating longwall faces only in different Indian coalfields contributing to perhaps less than 3 percent of the total underground coal production. Ambitious plans for expansion of longwall mining notwithstanding, apprehensions on the cavability of Indian coalmeasure roof rocks and some unsavoury experiences with face collapses in caved longwalla have impeded wider adoption of the technique. Between 1960 and 1983, some 41 caved longwall faces were worked in Jharia, Raniganj, Karanpura and Korba Coalfields in India, of which 6 faces reportedly had collapsed(1). The first powered support longwall face was started in August 1978 at Monidih colliery which marked a major step forward in the introduction of advanced technological system in Indian coal industry. This paper attempts to analyse critically the experiences with longwall ground control in caved longwall faces in India. Experiences from powered support faces at Monidih, Dhemomain and Pathakhera are synthesized to provide an appraisal of the present status of caved longwall faces under the Indian coalmeasure roofs, which thus far have been characterised as “massive”. The geotechnical site factors at the powered support faces are evaluated and conclusions drawn on the pre-assessment of caving characteristics and support resistance required at the faces.

Jan 1, 1984

By P. B. Baxendell, R. Thomas

Work on the calculation of vertical two-phase flow gradients by Cia. Shell de Venezuela has been based mainly on the "energy-loss" method proposed by Poett-mann and Carpenter in 1952. The "energy-loss-factor" correlation proposed by Poettmann and Carpenter was based on relatively low-rate flow data. This correlation proved inapplicable to high-rate flow conditions. In an attempt to establish a satisfactory correlation for high rates, a series of experiments was carried out at rates up to 5,000 BID in Cia. Shell de Venezuela's La Paz field in Venezuela, using tubing strings fitted with electronic surface-recording pressure elements. As a result of these experiments a correlation between energy-loss factor and mass flow rate was established which is believed to be applicable to a wide range of conduit sizes and crude types at high flow rates (e.g., above 900 BID for 27/8-in. OD tubing). It is anticipated that the resulting gradient calculations will have an accuracy of the order of % 5 per cent. At lower flow rates the energy-loss factor cannot be considered as constant for any mass rate of flow, but varies with the free gas in place and the mixture velocity. No satisfactory correlating parameter was obtained. As a practical compromise for low flow rates, a modification of the curve proposed by Poettmann and Carpenter was used. In practice this was found to give gradient accuracies of approxirnately ± 10 per cent clown to flow rates as low as 300 B/D in 27/8-in. tubing. INTRODUCTION Production operations in Cia. Shell de Venezuela's light- and medium-crude fields are principally concerned with high-rate flowing or gas-lift wells. Under these conditions the analysis of well performance, the selection of production strings and the design of gas-lift installations are vitally dependent on an accurate knowledge of the pressure gradients involved in vertical two-phase flow. Initially, attempts were made to establish the gradients empirically as done by Gilbert,' but the results were not reliable due to scarcity of data over a full range of rates and gas-oil ratios. Several methods of calculation based on energy-balance considerations were attempted, but the computations were cumbersome and the results cliscouraging. In 1952 a paper was published by Poettmann and Carpenter' which proposed a new approach. Their method was also based on an energy-balance equation. but it was original in that no attempt was made to evaluate the various components making up the total energy losses. Instead, they proposed a form of analysis which assumed that all the significant energy losses for mutiphase flow could be correlated in a form similar to that of the Fanning equation for frictional 1osses in single-phase flow. They then derived an empirical relationship linking measurable field data with a factor which, when applied to the standard form of the Fanning equation, would enable the energy losses to be determined. The basic method was applied in Venezuela to the problem of annular flow gradients in the La Paz and Mara fields" This involved establishing a new energy-loss-factor correlation to cover high flow rates and, also, some adaptation of the method to permit mechanized calculation using punch-card machines. The final result was 1 set of gradient curves for La Paz and Mara conditions which proved to be surprisingly accurate. With the encouraging results of the annular flow calculations, several attempts were made to obtain a corresponding set of curves for tubing flow. Here, unfortunately, little progress could be made. The original correlation of Poettmann and Carpenter was based on rather 1imited data derived from low-rate observations in 23/8- and 27/8-in. OD tubing. It did not cover the higher range of production rates, and extrapolation proved unsuccessful. A new correlation covering high flow rates was required, but this proved to be extremely difficult to establish since tubing flow pressure measurements at high rates did not exist—due to the difficulty of running pressure bombs against high-velocity flow. The necessity for reliable tubing flow data increased with the development of the new concessions in Lake Maracaibo, where high-rate tubing flow from depths of 10,500 ft became routine. Thus. it was decided to set up a full-scale test to establish a reliable energy-loss factor for tubing flow conditions. A La. Paz field light-oil producer with a potential of approximately 12,000 B/D on annular flow was chosen. To obtain full pressure gradients, a special tubing string was installed which was equipped with electronic surface-recording pressure measuring devices,

By B. E. Lindsly

The withdrawal of gas and/or oil in appreciable quantity from a natural oil reservoir causes the pressure within the reservoir to diminish, and if the oil is completely saturated with gas, this dissolved gas begins to evolve from solution. The liberation of gas from solution in oil causes the oil to change in several ways, the principal changes being: (1) reduction in volume or "shrinkage"; (2) increase in specific gravity (decrease in degrees A.P.I.); (3) decrease of energy in the oil; (4) increased viscosity; (5) increased surface tension. As the writer's investigations have been concerned more with the first three items than with changes in viscosity and surface tension the following discussion relates particularly to the volumetric shrinkage of the oil, to the increased specific gravity, and to the decreased energy in the oil, each caused by the liberalion of dissolved gas. One of the most surprising facts that have developed in the study of high-pressure well-head and "bottom-hole" samples is the great reduction in volume that occurs in some oils when the naturally dissolved gas is liberated. High-pressure samples taken from well heads in the Oklahoma City, Kettleman Hills and Ventura, Calif., fields decreased in volume from 11.2 to 40.5 per cent when the dissolved gas was liberated in reducing the pressure on the sample to atmospheric. The amount of shrinkage an oil undergoes when gas is liberated depends upon the quantity of gas liberated and also upon its composition. A given volume of the heavier gases, propane and butane for example, will occupy more space in the oil than an equal volume of methane. The reason for this probably is that the molecules of the heavier gases are larger than those of the lighter gases. When gases are not in solution, and particularly when they are at low pressures, the distance between the gas molecules is so much greater than the dimensions of the molecules themselves that the mere size of the molecules has little effect upon the space occupied by the gas, Avogadro's hypothesis, which in effect states that all gases under the same conditions have the same number of molecules per unit volume, relates to this phenomenon. The fact that the heavier gases occupy more space than the lighter gases in the oil, and

Jan 1, 1934

By George A. Packard

The experiments here described were made under my supervision while temporarily acting as head of the Department of Metallurgy at the Missouri School of Mines, at Rolla. The work was done by Messrs. W. E. Brown, W. C. Richards, and F. L. L. Wilson, and the description of the results forms a portion of a thesis presented for the degree of Bachelor of Science. These results are submitted because I have seen no description of the application of pot-roasting to the treatment of a copper-concentrate. This work followed that already described in the discussion of the Lime-Roasting of a Galena-Concentrate,' and was similarly occasioned by the lack of a furnace of the reverberatory type in which the copper-concentrates could be smelted. The material for the tests was a mixture of three lots available. The first consisted of 8-mm. ,jig-concentrates and the second of 0.5-mm. table-concentrates, from the San Juan district, Colo. Both contained pyrite, chalcopyrite, and galena. The third was a lot of copper-ore, found in the laboratory, which had been crushed through 8-mm. screen, and had at some previous time, before the laboratory roasting-furnace was torn down, received a partial roasting. The analyses of these ores are given in Table I. In order to determine the applicability of pot-roasting as to each lot of ore, and the effect of varying proportions of lime, six preliminary tests were made in a " size N " Battersea crucible, 9 in. high by 6 in. in diameter at top, with a 5/8-in. hole bored through the bottom. The crucible was set in the upturned elbow of a 2-in. pipe, the joint being luted with clay; and air was obtained from a receiver supplied by a compressor. The

Jan 1, 1908

By A. Simkovich, R. W. Lindsay

The possibility of using sodium sulfide slags to remove copper from ferrous alloys has been investigated by Jordan1 and by Langenberg.2, 3 In these studies, such slags were determined to be capable of removing copper and sulfur from the melt. The present work represents additional effort to clarify the effects of temperature on copper removal. The experiments were performed in a 17-lb induction furnace. Graphite crucibles contained the melts and kept the baths saturated with carbon. Temperatures were measured with a calibrated optical pyrometer and were controlled by manipulation of power input to the furnace. Estimated accuracy of temperatures in this investigation is ± 10°C (18°F) for measurements prior to slag additions, and + 20°C (36°F) after slag formation. The procedure consisted of melting 800 g of electrolytic iron. During this step, powdered graphite covered the exposed iron surface. After a predetermined temperature was reached, copper shot was added. A sample of the molten alloy for chemical analysis was then aspirated into a silica sheath. Next, a slag-forming mixture of sodium sulfite and graphite was added instantaneously to the melt. The sodium sulfite amounted to one-tenth the charge weight of iron; sufficient graphite was added to combine with oxygen in the sodium sulfite, assuming formation of carbon monoxide and reduction of the sulfite to sulfide. Subsequent to the slag addition, the molten alloy was sampled periodically, with the exception of heat A in which no intervening samples were taken between the slag addition and the end of the run. The iron was poured into a graphite mold, and the ingots sectioned and drilled for samples. Results of selected heats are presented in Table I. Analyses of samples drawn from the iron prior to slag addition are listed under zero time. Two samples from heat D were reported with copper contents greater than the initial concentration in the bath. Owing to the gradual but complete disappearance of slag during this heat, it is believed copper momentarily became more concentrated in the upper portion of the bath while reverting from the slag. This is the region from which samples were drawn. It should be noted that analysis of the ingot was equal to the copper content at the time of slag addition. The terminal temperatures of heats D and E, and the initial sulfur content of heat A are also to be noted. Because of the large temperature drop which occurred when slag was formed in heat D, power input to the furnace was increased in heat E after the slag addition, causing a higher terminal temperature. In heat A, the initial sulfur concentration was relatively high as compared to heats B through E owing to contamination by some slag remaining in the crucible from a previous heat. It is evident from Table I that copper was removed at the onset of slag formation. Roughly 30 pct of the copper was taken into the slag, with the exception of heat D, which had approximately 50 pct removed. For a comparatively short time of slag-metal contact, it appears that no gain is to be made in copper removal through use of high or low temperatures. If the slag initially formed remains in contact with the iron for an extended period, temperature has a marked effect upon copper removal, as can be seen by studying results for the two extremes in temperature. At about 1425°C, the copper level remained relatively constant after the initial removal by the slag. However, in the region of 1670°C, a definite reversion of copper occurred. Reversion was incomplete in heat D, and complete in heat E. The final temperatures of heats D and E differed by about 75°C. This temperature difference is thought to be the reason for only partial copper reversion in heat D. It is believed the effects of temperature noted above are related to the evolution of a white fume, which appeared in every run except heat A. (In the case of heat A, the fume was practically indiscernible.) After each slag addition, a yellow flame formed for about 5 sec. When the flame subsided, a white fume appeared. Upon contact with surrounding cooler surfaces, this fume deposited as a white solid. In the experiments made at 1425°C, evolution of fume continued unchanged to the end of the runs. However, heats D and E exhibited a different behavior. A very noticeable decrease in fume evolution from heat D was observed. Furthermore, this heat had much less slag remaining than did runs A through C when the experiments were terminated. No slag remained at the end of heat E; evolution of fume from this heat ceased prior to pouring. Spec-trographic analysis of the white deposit indicated sodium to be the major metallic element, with the maximum concentration of iron and copper as 0.1 and 0.01 pct, respectively. It is supposed the white fume observed in these experiments is principally sodium oxide (Na2O), formed by oxidation of sodium in the slag and subsequent sublimation. (Sodium oxide is a white to gray substance in the solid state; at 1275oC, it sublimes.4) According to this mechanism, elevated temperatures would accelerate removal of sodium from the slag, sulfur pickup by the

Jan 1, 1961