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By R. G. Mallon, R. L. Braun

Primary copper-sulfide ore deposits that are well below the water table can be chemically mined by in-situ high-pressure leaching. The leaching is accomplished by pumping oxygen gas into the bottom of a large underground flooded column of rubblized ore. Part of the injected oxygen dissolves under the high hydrostatic pressure in the column. With a high enough injection rate, the excess oxygen gas induces a convective circulation of oxygenated solution within the rubble column, which transports dissolved oxygen throughout the system. At elevated temperatures, this results in a relatively rapid dissolution of the copper minerals. A method of calculating the leaching rates is presented. The calculation is done by means of a finite-difference computer code that couples all of the processes relating to copper leaching, convective circulation, and the injection, dissolution, and consumption of oxygen. Results of the calculation for a typical case show that over 70% of the copper can be extracted in less than six years with good efficiency in oxygen utilization.

Jan 1, 1976

By C. D. Rugen

GROUND raw material as fed to the cement kiln generally is a mixture of two to four components, each of which may have widely varying physical and grindability characteristics. Chemically similar materials found in the same or different deposits may also differ appreciably in physical properties, depending on their crystalline structure. The calcareous or principal cement raw material may vary from a soft chalky limestone or friable cement rock at one plant to a hard limestone or oyster shell at another plant. Argillaceous materials include clays, shales and granulated slag. Siliceous and/or iron-bearing material, including sand, iron ore and cinders, may also be required in addition for certain types of mixes. Frequently differences in grindability characteristics are not given the attention they deserve in comparing grinding results at one plant with those at another or in selecting suitable circuits or equipment. Many types of crushing and grinding units are used, with numerous open and closed circuit arrangements. Both wet and dry processes are used successfully. When rebuilding or installing a new grinding department, the choice of process or circuit in some cases may be dictated by the nature of the materials being ground but in other cases it may be the result of good salesmanship or a compromise. An over-all evaluation of wet process vs. dry process grinding should not be made without considering the effects on all other producing departments in the plant. In general, the more recent grinding installations, both wet and dry, have employed closed circuits, but many older open circuits are still in successful operation. In our experience, closed-circuit raw grinding pays, because of lower power consumption and less operating labor per ton of product. However, some dry open-circuit mills with improved equipment and operating methods compare favorably in performance with dry closed-circuit units. CHARACTER OF GROUND RAW MIX (KILN FEED) Grinding in the cement plant in general requires a considerably finer product than in most ore-grinding operations. A distinction between fineness of kiln feed and of cement may be made in that kiln feed preferably should be ground to a limiting size, whereas finished cement should include a range of size fractions including sufficient fine flours to give a product with satisfactory physical qualities. Grinding raw mix for kiln feed therefore is more comparable to ore grinding, although the limiting size is smaller. Most kiln feeds are ground from 85 to 95 per cent passing 200-mesh, depending on mix composition. Some cement chemists believe that raw materials cannot be too fine, since finer particles theoretically combine more readily and intimately in the kiln. However, there are certain definite practical objections to extremely fine kiln feed, such as loss of kiln dust, unstable material flow through the kiln and greater difficulty in control of chemical composition due to dust loss, and the disproportion of fines from the more easily ground component. Our

Jan 1, 1945

By Sanai Nakabe

Japanese wartime economy demanded domestic cobalt production. This paper describes a process operated for two years at the Besshi mine and smelter on extremely low grade (0.1 pct Co) pyrite concentrates obtained from copper ore. 'The steps in the process were roasting, leaching, precipitation, reduction fusion to crude cobalt, and finally refining by electrolysis to 99+ pct. COBALT ore deposits in Japan are all small and of poor grade. In the past, a small amount of cobalt has been produced from the best portions of a few of these deposits, and very little production is expected in the future. In addition to these lean cobalt ores, cobalt is present in the cupriferous pyrite which is fairly abundant although of low grade, as is shown in Table I. Considerable cobalt is expected from these deposits because of their extent. Cobalt cannot be exclusively recovered economically from ore of this type; however, if means could be devised to recover it as a byproduct of copper production, a fairly large production at reasonable cost could be expected from Japanese sources. It was along this line that the research work was done. Selection of Suitable Process The process for extracting cobalt differs from ore to ore according to their composition. The difficulty in cobalt metallurgy arises from the fact that chemically cobalt resembles many such common metals as Mn, Fe, Ni, Cu, and Zn, associated with it in the ores. In the present case the most serious difficulties were: 1—Extremely low grade ore, 0.1 pct Co. 2—The large proportion of iron accompanying cobalt and its close similarity in chemical behavior. 3—The fairly large proportion of zinc and manganese and their chemical similarity to cobalt. The recovery of cobalt oxide as a byproduct of the hydrometallurgy of copper had been attempted in Japan but was stopped after a short period because it proved uneconomical. The literature disclosed no method for the recovery of cobalt from cobaltiferous copper pyrite and it was therefore necessary to devise a new process. The following basic principles were considered in selecting the process: 1—A major alteration in copper production methods should not be necessary. 2—The first step should be the extraction of cobalt leaving the large quantity of iron unaffected. For this purpose wet metallurgy would be preferred.

Jan 1, 1952

By F. L. Bosqui

A. L. BlomFIeld, Denver, Col. (communication to the Secretary.*) — Mr. Caldecott says on p. 67: "The Dorr thickener shown, while a useful device when crushing with cyanide solution for removing surplus solution from slime pulp prior to air-lift agitation or vacuum filtration, is not adapted to effect as complete a separation of water from settled slime as the ordinary intermittent settlement and decantation." This statement might have passed muster in this country several years ago when. the Dorr thickener was a new device, but its use in hundreds of mills in the United States has demonstrated that as thick a product is being discharged from it as was obtained from the intermittent settling which it has supplanted. • It is interesting to note that recent investigation, especially the work of 11. 6. Coe and G. H. Cleveilger,' in the March Bulletin of the Institute, under the title: Laboratory Method for Determining the Capacities of Slime Settling Tanks, has developed the general theory of settlement and explains the results obtained in practice. Just as free settlement is a function of surface area, so thickening after the zone of free settlement is passed is a function of time. The time required is obtained by the capacity or volume provided in the settler for this thickening zone. Each pulp is a problem in itself, both in regard to free settlement and to time required to reach a commercially finished thickness. Some pulps require 48 hr. and more to reach a density of 40 per cent. solids; others no coarser to the screen test reach a density of 65 per cent.' solids in a fraction of that time. In thickening any pulp a point is reached where the increase in density is so slow as to be commercially unprofitable. When any part of the pulp has reached this point it should pass on for treatment—its place in the thickener should be occupied by pulp which has not yet reached the commercial limit. By doing this the whole volume of the settling tank is kept in active use. Thus the continuous thickener keeps the whole tank at work to its commercial limit, while the intermittent settler has much of its volume occupied at times by pulp which is either quite finished thickening or at least thickened past the commercial point. The mechanical efficiency of the continuous thickener can be the only argument for limiting this statement. In my own experience I have never

Jan 1, 1916

By M. W. Hayward

THE object of this paper is to record and tabulate the data and field observations obtained by the writers and their associates during 10 years of intensive study of lead-zinc deposits in the Cretaceous limestone areas in Northern Mexico, particularly in mines owned by the Cia Minera de Peñoles, S. A. At the El Paso meeting of the Institute in October, 1930, J. G. Barry made the suggestion that a committee be appointed to correlate the ideas and theories which have been put forth by the numerous engineers and geologists who, during recent years, have made a study of the ore deposits in the area under consideration. The first step in a work of this nature would be to record all of the observed facts, and these facts would have to be accepted by those who attempted to formulate a theory of ore deposition. It is with this idea in mind that the writers have described as accurately as possible the actual, observed facts pertaining to the occurrence of the lead-zinc ores in dolomites or dolomitic horizons. By most writers the term "dolomite" is loosely used to designate magnesium-bearing limestones, regardless of the percentage of MgO present. Since no true dolomites exist in the areas to be described, we shall also loosely use the terms dolomite or dolomitic limestone to desig-nate those beds having a magnesia content of 5 per cent MgO or more. For a number of years the writers have been impressed with the fact that in areas where dolomite beds occur a large percentage of the lead ore is found in these beds, in spite of the fact that such beds may be overlain or underlain by pure limestone, which one would assume to be just as favorable for replacement as the dolomite, if not more so on account of its being more soluble in acid solutions than the dolomite. It is true that in some limestone areas, such as the Erupcion-Ahumada districts, Chihuahua, and Providencia, Zacatecas, where no dolomite beds have been found, large tonnages of lead ores have been mined. We venture to predict, however, that had there been dolomitic beds in these areas, the

Jan 1, 1932

By Carl H. Beal

The most important factors that should be given consideration in the valuation of oil lands are: (1) the amount of oil the property will produce; (2) the amount of money this oil will bring (based upon the future prices of oil); (3) development and production costs; (4) the rate of interest on the investment; (5) the retirement or amortization of invested capital; and (6) the salvage or "scrap" value of the equipment when the property is exhausted. These factors are of varying importance and some of them may not enter all valuation problems, but most of them should be given consideration in any valuation even though only a rough estimate of the value of the property is desired. The value of a property may be changed over night by the completion of important test wells, by the sudden water flooding, or by a change in the price of oil. The best a petroleum engineer can give is the value of the property under the conditions existing at the time the appraisal is made with a fair forecast of future action of the wells and of the price of oil. Our experience in the scientific valuation of oil lands is not broad and there is very little published information on the subject; it, therefore, becomes necessary in studying such problems to form comparisons with the factors involved in the valuation of mines—the closest parallel. One of the reasons for the lack of substantial progress in oil-land valuation methods has been the necessity of making an estimate of the future production of the oil property to be valued. Oil men and accountants have not generally conceded that such estimates could be made with any degree of accuracy. It has been shown, however, in several recent publications that with certain data available reasonably close estimates can be made. The accuracy of an appraisal depends chiefly on the accuracy of the estimates of future production and of the future price of oil. The accuracy of the former is sometimes necessarily based on geological inferences. Geology is not an exact science and geological data in connection with oil production cannot always be mathematically evaluated.

Jan 1, 1921

By J. S. Johnson, W. C. McCulloch

ALL phases of plant operation must be synchronized so that the number of interruptions in the flow of material may be reduced to a minimum. In the majority of plants operating under a labor agreement, time lost during the operating shift cannot be made up with overtime. With the work week restricted to 35 hr., the ratio of productive time to total time justifies extra effort in keeping the plant operating at capacity during the productive shift. This does not apply when central plants with adequate storage are operated by multiple shifts. In such installations the problems become similar to those of any factory or mill where added units parallel circuits, or excess capacity serve to maintain the average production during intervals of maintenance shutdown. These plants, by special agreement, may run continuously, barring mechanical interruptions. The control of plant operation is in those procedures that are practiced to obtain from the run-of-mine product a high recovery of clean coal products to meet adopted trade standards and consumer specifications at the lowest possible cost. Correlation of all factors for continuous operation requires more than mechanical perfection in the plant. The run-of-mine coal must be delivered to the preparation plant without delays and the clean coal and refuse products taken away. Power supply and water requirements must be adequate. Signal systems must be established for emergency stops and to facilitate resumption of coal flow. ORGANIZATION Probably the most important item for successful operation of a preparation plant is a capable organization interconnected with the mine organization. A typical organization chart for companies operating in the Pennsylvania anthracite region is shown in Fig. 1. The breaker foreman is in direct contact with the plant preparation operation and reports to the outside foreman, who, in turn, reports to

Jan 1, 1943

By Orville R. Lyons

THE Russellton preparation plant of Republic Steel Corp., located north of Pittsburgh, Pa., prepares 3 1/2x0-in. Thick-Freeport coal by means of a 13-ft 6-in. diam Chance cone and 16 No. 7 Deister tables. The plant feed ranges between 370 and 410 tons per hr, of which approximately 31 pct is ¼x0-in. size, and the plant reject ranges between 14 and 16 pct of the feed. The 3½xY4-in. washed coal, the cone product, is dewatered and desanded by a double-deck Parrish-type shaking screen 46 ft long and 7 ft wide. The 1¼x¼-in. portion is further dewatered by two 4x12-ft single-deck vibrating screens. The ¼x0-in. washed coal from the tables is distributed to three 54x70 in. Bird centrifuges. The dewatered centrifuge product is combined with the product of the de-watering screens prior to loading into railroad cars. During the early part of 1951 complaints were received from officials at Republic's coke ovens concerning the moisture content of Russellton washed coal. The records revealed that during the first half of 1951 the shipped washed coal moisture averaged

Jan 1, 1954

By Mark Malamphy

MOST igneous rocks, and particularly those of the basic type, con-tain relatively high percentages of magnetite and other iron oxides, which give them moderately high magnetic susceptibilities and make them responsible for an important percentage of the magnetic anom-alies observed during the course of geophysical surveys by the mag-netic method. The irregular form and high susceptibility of the igneous rocks make them readily polarizable and the position and strength of the magnetic poles formed are not always explicable by theoretical calculations of anomalies due to certain assumed forms in the normal magnetic field of the area under study. During the last four years our field work has permitted us to make detailed observations of anomalies due to igneous rocks in all the states of south Brazil. The form and position of the igneous rock at some places were fairly accurately known, which made it possible to calculate theoretical anomalies and compare them with the observed data. Some of the data we obtained have been published and additional cases are now awaiting publication. In this paper, we will present a few specific cases where the geology is moderately well known and which we believe to be of considerable value as representing typical magnetic anomalies in the south magnetic hemisphere, where the inclination of the magnetic field is very low. Although the vertical intensity is negative in the Southern Hemis-phere, we have adopted the convention of plotting increase in intensity (negative) as a positive anomaly; i.e., above the x axis. This conven-tion facilitates comparison with anomalies in the north.

Jan 1, 1936

By R. F. Mehl, C. S. Barrett, A. H. Geisler

THE complicated nature of the property changes that accompany age-hardening has made it necessary to reconsider and to elaborate the simple dispersion theory.1 It has been apparent for some time that more direct information is needed concerning the atomic mechanism of precipitation from solid solution if the theory of age-hardening is to be developed past a purely qualitative stage.‡ Fortunately, in recent years information has been developed which allows us to trace in detail the lattice changes accompanying the process of precipitation from solid solution. This information relates chiefly to the sequence of the several stages of lattice alteration by which the matrix lattice is transformed to the equilibrium precipitate lattice, and permits reasonable inferences to be drawn concerning the states of internal strain that accompany these stages. This information is most complete for the solid solution of copper in aluminum. The equilibrium precipitate is the ?' phase," CuA12." This forms in plates, parallel to the {100} matrix planes. The atom pattern and atom spacing on the plane in ?' lying parallel to this plane are roughly similar to those opposite it in the matrix.' The formation of ?', however, is preceded by the formation of a transition lattice ?', which again lies parallel to the matrix {100} plane, but in this case the matching of atom pattern and spacing across the matrix-precipitate interface is nearly perfect; thus there is lattice coherency across the interface and the interface is a plane of separation in only a very limited sense.4-8 Particles of ?' may be recognized microscopically and form a well-defined Widmanstätten figure.* The ?' lattice is recognized by the occurrence of diffraction lines on powder photograms or of spots on Laue photograms which may be analyzed in the usual ways to determine the lattice type and the lattice spacings. Very recent research 6.7,1 has shown, however, that streaks occur on the Laue photogram at an earlier point in time during the aging process. These streaks have been attributed to a preferential clustering of copper atoms into small platelike elements of only a few atoms in thickness and a few hundred atoms in diameter, probably of the composition of "CuA12," which may be designated as Guinier-Preston zones or aggregates.1 It is difficult if not impossible to determine the lattice type and lattice spacing in these aggregates. It is possible1 that these aggregates are in fact merely ?' in a high state of dispersion; the inclination to argue this is strong, as we shall see later. Never-

Jan 1, 1941

By J. G. EVANS

It is with a certain amount of trepidation that a man considers gathering his family of six, traveling across a continent, two oceans and a sea, and going to live in a foreign land. But "pioneering" is still possible, and a nation is "foreign" only until one has lived in it. We've had eight years of pleasant experiences in South Africa on which to base that contention. It was in January 1938 that my brother first extolled the virtues of South Africa to us, and just three months and a thousand small problems later my wife, two daughters, three sons and I were boarding a ship in New York, bound for Cape- town. We arrived in May, and within a week had found a furnished home with beautiful lawns, tennis, court, a garden, and everything needed for family comfort. The children were soon located in school, and I settled down to the task of entering the importing business, as had been my original intention. The importing business started out slowly but was coming along nicely when on Sept. 3, 1939 the war started in Europe and a declaration of war by the Union of South Africa was made on the following day. With the declaration came import and export controls. In fact we were controlled completely out of business in one stroke. Liquidating the business, I went to Johannesburg intending to find work in one of the mines. Government health and safety regulations require that all underground mine employees have a red ticket from the Miners Phthisis Bureau certifying that they are not susceptible to silicosis, the scourge of the Witwatersrand gold mining industry. I made application to the Bureau, completed a form covering my whole past life, and was given a complete physical examination. The following day I was startled to find that I had not only been refused a red ticket but had been classified with a green ticket which for- ever bars one from working underground in any scheduled mine in the country, and all this in spite

Jan 1, 1949

By Nicholas J. Grant, Joseph T. Blucher

High-purity aluminum and an Al-10 pet Zn alloy zvere tested in axial fatigue from 80" to 900oF, at struzn vales of 5 and 150 pct per min, at a strain amplitude of 1 pcl. Cycles to failure were recorded as well as the load per cycle during the entive test. Several grain sizes were examined in each material. Examination was made of modes of deformation, initiation and growlh of' cracks, and vecovery mechanisms such as srbgrain formation and boundary migration. Strain rate effects on cycles to failure are first observed ahoi'e 50O0F, the highev vate vesulting in longer lije. Crack initiclion at room temperature may be truns-or iutercrystalline but fructures are transcrystalline. Abore 600'F, crack iniliation and growth ave largely inlercvystalline. Boundary wzigratiotz to 45-deg positions is observed above 70Oo F, and fractrrves are a combination of grain bol~ndary voids and cvacks. It is only in recent years that studies of deformation and fracture which prevail in fatigue at elevated temperatures have attracted significant attention.' Of such studies considerably less attention was given to high strain-low strain rate fatigue. Moreover, the majority of high-temperature fatigue studies were performed at conventional machine speeds (1000 to 10,000 cpm). As it is well-demonstrated in uniaxial creep-rupture series, at high strain rates, even at high temperatures, metals undergo work hardening with little or no attendant recovery or recrystallization thus the nature of deformation and fracture which is observed is similar to that encountered at lower temperatures.'-" Thus, for example, fatigue testing of a stainless steel at 750°F does not involve high-temperature deformation processes,2 and might more correctly be termed "fatigue testing at an elevated temperature". It was the purpose of this work to study deformation and fracture in fatigue as a function of low strain rates and temperature, selecting conditions which would result in grain boundary sliding, migration, fold and subgrain formation, and intercrystalline cracking in high-purity aluminum and a high-purity A1- 10 pct Zn alloy. Grain size was an additional variable. Extensive studies of the deformation and fracture behavior of these aluminum materials in simple creep had been done in the authors' laboratory, and were to serve as a basis of comparison for the observed effects in fatigue:'-'' the range of the creep test temperatures was 80° to 1150oF. MATERIALS AND EXPERIMENTAL PROCEDURE The compositions of the 99.99 pct pure A1 and the A1-10 pct Zn alloy are shown in Table I. Button-head specimens, with a liberal fillet, of 0.20 in. diam and of gage length 0.40 in. were machined from wrought bar stock. The ratio of 2:l gage length to diameter was selected after preliminary tests showed that a shorter length gave a shorter life, probably due to end effects, and after evidence of buckling in longer gage length specimens. After machining, the specimens were chemically polished to remove the worked outer layer, and were subsequently heat-treated to stabilize the selected grain sizes. Both the high-purity aluminum and the A1-10 pct Zn alloy were heat-treated to produce grain diameters of approximately 0.5 and 2 mm in each case. These grain sizes are referred to in the text as fine and coarse grain, respectively. One lot of the high-purity aluminum was heat-treated to produce a still coarser grain size in which the cross section was occupied by 2 to 3 grains. This structure is referred to as very coarsegrained. After heat treatment, the specimens were again electropolished. To avoid complications of both stress and strain gradients in the cross section of the specimen, a hydraulic, axial fatigue machine was designed and built. A button-head specimen, 1/2 in. diam at the head, was firmly gripped in a split-type holder free of any play in the grips. The test temperatures varied from 80" to 900°F. The strain amplitude in all of the reported tests was 1 pct for a total strain amplitude of 2 pct. The strain range was set by precision micrometers and measured by a precision dial gage. Constant strain rates of 5 and 150 pct per min were selected so that high-temperature type deformation and fracture would occur in the higher-temperature tests5,6 The strains and strain rates must be regarded as nominal values because they are based on the original specimen dimensions, which changed significantly as a result of necking and crack propagation, as can be observed from Fig. 8. For the elevated-temperature tests, a thermocouple was inserted into a well in the head of the specimen; the selected temperatures could be maintained with less than ± 5oF fluctuation during the entire test. To avoid changes in grain size before the test, specimens were heated to the test temperature in less than 15 min; similarly, they were cooled to room temperature after fracture with an air blast to avoid or minimize recovery or recrystallization. During the fatigue tests, load vs strain curves were recorded by a strain gage load cell for each fatigue cycle. In addition, the maximum values of load amplitude were recorded for the entire test.

Jan 1, 1968

By Hiland G. Batcheller

HISTORY shows that the nation which makes the most steel is the most likely to win wars. Today the course of war shows that the nations which get there first with the most steel of the right kind will be the ones to win. Not only the most steel, mind you, but the right kind. Adequate production, which was enough for victory before the days of totally mechanized warfare of 1943, must now be accompanied by still better quality as well as more effective distribution. Further, both production and distribution must be flexible enough to permit rapid shifts from one weapon to another for use in varying elements in varying geographical areas. Thus the problem of making enough steel of the right kind at the right time in the face of changing requirements dictated by experience has been and will remain highly complex. This does riot permit us to ease our restrictions on nonessential use. War is a complex business, like the job of making steel for war. Each time we solve one problem, another pops its head up. Yet we are making some progress.

Jan 1, 1943

By Charles M. Ryder

In presenting this paper to the Institute I beg to mention, first, the results which I have obtained and the apparatus which I have employed, and to follow this with a brief description of the steps by which I hare perfected this process. My present mode of testing is as follows: I obtain, either from the furnace or from the finished product in any stage in which it may chance to be, a small test-piece, usually about 3/4 of an inch square by 3 1/2 inches in length. I place this test-piece upon the poles of an ordinary electro-magnet, for about one minute, and thus magnetize it to its extreme limit. I then place it upon an indicator (which I will shortly describe), on which indicator there is already placed a piece of steel of similar form which has been magnetized in the same manner, the percentage of carbon of this second piece being definitely known. I then, by means of a scale, which forms part of the indicator, marked in degrees of carbonization, read the exact percentage of carbon contained in the piece under examination. My apparatus consists of an ordinary electro-magnet, connected with a suitable battery of moderate power, by which I magnetize the pieces as before described, and of an indicator which consists of a magnetic needle suitably mounted or suspended, so that it is free to deviate a few degrees only from the zero point, and having a rest, which is used to check the vibrations when in use, and to support its weight when not in use. At a right angle to the natural position of the needle I have a scale about 3 feet long, the zero point of which coincides with the natural position of the needle. This scale is marked in each direction from the zero point in degrees of carbonization. The marking of the scale is in accordance with the following rule: Taking the carbonization of the steel as a basis, I maintain the same proportion between the squares of the distances on the scale as exists between the percentages of carbon in the steel, for instance, if .08 of

By Charles M. Ryder

IN presenting this paper to the Institute I beg to mention, first, the results which I have obtained and the apparatus which I have employed, and to follow this with a brief description of the steps by which I have perfected this process. My present mode of testing is as follows : I obtain, either from the furnace or from the finished product in any stage in which it may chance to be, a small test-piece, usually about 4 of an inch square by 3 1/2 inches in length. I place this test-piece upon the poles of an ordinary electro-magnet, for about one minute, and thus magnetize it to its extreme limit. I then place it upon an indicator (which I will shortly describe), on which indicator there is already placed a piece of steel of similar form which has been magnetized in the same manner, the percentage of carbon of this second piece being definitely known. I then, by means of a scale, which forms part of the indicator, marked in degrees of carbonization, read the exact percentage of carbon contained in the piece under examination. My apparatus consists of an ordinary electro-magnet, connected with a suitable battery of moderate power, by which I magnetize the pieces as before described, and of an indicator which consists of a magnetic needle suitably mounted or suspended, so that it is free to deviate a few degrees only from the zero point, and having a rest, which is used to check the vibrations when in use, and to support its weight when not in use. At a right angle to the natural position of the needle I have a scale about 3 feet long, the zero point of which coincides with the natural position of the needle. This scale is marked in each direction from the zero point in degrees of carbonization. The marking of the scale is in accordance with the following rule: Taking the carbonization of the steel as a basis, I maintain the same proportion between the squares of the distances on the scale as exists between the percentages of carbon in the steel, for instance, if .08 of

Jan 1, 1877

By W. S. Stahmann, F. W. Bowdish

Previously published experimental data showing that both collectable and non-collectable sulfide films may be formed on chrysocolla were analysed, and chemical mechanisms were proposed for the formation of the films. A special technique was developed by which the quantity of sulfur adsorbed was determined for samples sulfidized under different conditions of pH and soluble sulfide concentration. The data on sulfur adsorption were used together with the expression for the equilibrium constant for the proposed reaction to indicate the validity of the chemical mechanism theory. A recent paper 1 about contact angle studies on chrysocolla reported the effects of pH value and sodium sulfide concentration during sulfidization upon the character of the surfaces produced. In each experiment the surface of a specimen of chrysocolla was prepared by grinding it with fine abrasive and washing it in tap water. The specimen was then placed in the sulfidizing solution for 10 min, rinsed in tap water, treated for 15 min in a solution containing 30 mg of potassium amyl xanthate per liter, rinsed in distilled water, and tested for air adhesion in a contact angle apparatus. The results, when plotted as in Fig. 1, showed an island representing conditions giving air adherent or collectable surfaces surrounded by conditions giving non-collectable surfaces. Particular interest may be attached to the region of non-collectability to the right of and above the island in Fig. 1, and to the boundry curve separating these two regions. It is apparent that at any pH from 4.0 to 6.0, where a collectable surface may be produced, a sufficient increase in the sulfide concentration results in a non-collectable surface. Thus it appears that too much soluble sulfide has a depressing effect upon the mineral, just as it has in sulfide flotation. This paper presents some speculations regarding the chemical mechanisms by which the collectable and non-collectable sulfide films may be formed and reports on a physical-chemical study intended to support these speculations. THEORETICAL CONSIDERATIONS The experimental results presented in the previous paper were analysed in several ways in an attempt to understand better the chemical mechanisms involved. For several points on the boundary to the right of the region of contact in Fig. 1, molar concentrations of H+, OH-, HS-, and S= ions, as well as various ion concentration products, were calculated. Following the reasoning of Wark and Cox, 2,3 no single kind of ions may be credited with causing depression of the surface because none of them have a constant con-

Jan 1, 1968

By Mayumi Someno, Kazuhiro Goto, Masahiro Kawakami

The apparent rates of decarburization of liquid alloys of Fe-C, Fe-C-S, Ni-C, and Co-C systems and the rate of oxidation of solid graphite with pure carbon dioxide gas and with gas mixtures of carbon monoxide and carbon dioxide have been measured in the temperature range of 1000° to 1600°C. The cotnposition of carbon dioxide and carbon monoxide gas at the reaction surface has been measured by oxygen concentration cells with the ZrO,-CaO solid electrolyte. 1) The apparent rates of the carbon removal are essentially the same for all the cases of solid graphite, Fe-C, Fe-C-S, Ni-C, and Co-C systems under the same experimental conditions. 2) The apparent rates are independent of the carbon content in the high carbon concentration range but very much affected by the flow rate and the gas composition of the CO-CO2 reactant gas mixture. The ratio of the gas consumed by the reaction to the total quantity of the supplied gas is very large under the present experi~nental conditions. 3) There is a concentration gradient of' carbon dioxide in the vicinity of the reaction surface and the content of CO, becomes extremely small at the reaction surface. 4) A large time fluc-tuation of the gas composition was observed. This jluctuation implies the presence of unstable flow in the gas phase in the vicinity of the reaction surface. THE decarburization of molten steel by an oxidizing gas or by slag may be one of the most important chemical reactions in steelmaking processes. Nevertheless, the kinetics of this heterogeneous chemical reaction do not seem to be well-solved even with the previous studies. Although the conditions for the reaction in steelmaking processes are quite different from those in the laboratory scale, some critical experiments may give information on the mechanism of the decarburization. From the previous work,'-' it is known that the rate of the decarburization is independent of the carbon content in liquid iron with more than about 0.2 wt pct C when the oxidizing gases are supplied to the surface of liquid Fe-C alloys on a laboratory scale. Two rate-controlling steps have been proposed for the decarburization of liquid iron with the high carbon content: one is the surface reaction control proposed by Swisher and Turkdogan;' the other is that the rate is controlled by the gaseous diffusion through the gaseous stagnant layer. proposed by Baker. Warner, and Jenkins.7 and also by .Ito and Sano.2 In the present study, some experiments have been carried out for the evaluation of these rate-controlling steps in the decarburization of liquid iron with high carbon content. The apparent rate of decarburization of liquid iron has been compared with the rates of carbon removal of liquid Ni-C, Co-C, and solid graphite under the same experimental conditions. The composition of carbon dioxide and carbon monoxide gas at the reaction surface has been measured by oxygen concentration cells. I) EXPERIMENTAL PROCEDURE Fig. 1 shows the schematic diagram of the reaction chamber. Solid graphite and liquid metals were contained in an alumina or magnesia crucible of 32 mm ID and 35 mm in height. The samples were heated by high-frequency induction and the temperature was measured by the calibrated optical pyrometer. The temperature was held constant to within 10°C. The re-actant gases were supplied to the surface of the samples through the quartz tube of 8.0 mm ID. The distance from the end of the quartz tube to the surface was 20 mm. The block of high-purity graphite was cut and shaped to the inner profile of the crucible. The height of the shaped graphite was 18 mm, which corresponded to the depth of the liquid iron of 100 g. About 100 g of Fe-C alloy (4.20 to 4.40 pct C), Ni-C alloy (1.84 pct C), Co-C alloy (1.85 pct C), and Fe-C-s alloy (4.35 pct c, 0.5 or 1.0 pct S) were melted in the crucible. The reactant gases were pure CO, and gas mixtures of CO-CO,: the flow rates were controlled by capillary flowmeters with bleeders.

Jan 1, 1970

By George H. Eldridge

The existence of phosphate of lime within the State of Florida has been known for over a decade; but until the spring of 1887, the extent and value of its deposit.;, possibly with one exception, were unsuspected. In that year Col. T. S. Moorehead, induced by a statement made by Mr. J. F. Le Baron, examined the gravels of the Peace river, recognized the importance of the deposits, acquired such tracts as were regarded as desirable, and established the pebble-phosphate industry, making his first shipment in May, 1888, to the Scott Manufacturing Company, of Atlanta, Ga. The establishment of the pebble-phosphate industry upon Peace river was followed, a year later, by the discovery in Marion county of an entirely different class of phosphate, now commonly known as hard-rock phosphate. This discovery was made early in June, 1889, by Mr. Albertus Voght, in a well which he was sinking upon his place near the site of the present town of Donnellon, about 20 miles southwest of Ocala. To it, more than to any other cause, is due the rapid and remarkable development of the present great industry of the State. It was, however, Mr. John F. Dunn, of Ocala, who turned to advantage the accidental discovery of Mr. Voght. After acquiring a knowledge as to the chemical composition and value of the material, Mr. Dunn and hid associates purchased several thousand acres of land and organized the Dunnellon Phosphate Company for active operations. From Dunnellon as a center, prospecting rapidly extended in all directions, until at the present day important mines have been opened over a well-defined tract more than 200 miles long and about 6 miles wide. This tract lies par-

Jan 1, 1893

By W. L. Phillips

Stress-strain curves were obtained for single crystals of 70 pct Ag-30 pct Zn tested in tension and shear. Samples tested in tension and shear had comparable resolved shear stresses and stress-strain curves. The {111} <110> slip system was observed. It zoas found that the9.e is a barrier to slip in both latent close -packed directions and that the magnitude of these barriers is proportional to prior strain during easy glide. It was observed that cross-slip in tension and shear was most frequent in crystals with an initial orientation near <100> "Oershoot" zoas observed in tension. The amount of this "overshoot" was independent of initial orientation. AN idealized concept of plastic deformation indicates that a single crystal should yield at some stress that is dependent on crystal perfection and it should then continue to deform plastically by the process of easy glide which is characterized by a linear stress-strain curve and a low coefficient, d/dy, of work hardening. Hexagonal metal crystals generally conform to this ideal concept of laminar flow. In fcc metals the range of easy glide is always restricted in magnitude and it is strongly dependent on orientation, composition, crystal size, shape, surface preparation, and temperature. Since one of the principal differences between the two crystal systems, both of which deform by slip on close packed planes, is the existence of latent slip planes in the fcc crystals, it has been proposed that the transition from easy glide to turbulent flow, characterized by rapid linear hardening, is due to slip on secondary planes intersecting the primary plane.ls Several theories have been proposed to explain the linear hardening and parabolic stages of the stress -strain curve.6"10 The easy-glide region is the least understood of the three stages. The stress-strain characteristics of Cu-Zn, which shows a long easy-glide region, have been extensively investigated."-" In light of recent ideas on dislocations, cross-slip, effect of solute atoms, and stacking fault energy, it was felt that the certain features of this earlier work might be compared with another alloy, Ag-30 pct Zn, which also exhibits a long easy-glide region. Tension and shear stress at room temperatures were employed. The results obtained, together with some interpretation of the observations, are described below. EXPERIMENTAL PROCEDURE The silver and zinc used for mixing the alloys were 99.99 pct pure. The two components were weighed to within 0.1 pct of the weights required fo the alloy composition. They were then placed in a closed graphite mold and the mold and contents were heated in 100°C stages from 500&apos; to 900°C with sufficient time and vigorous agitation at each stage provided to dissolve the silver. The crucible was then heated to 1150°C and agitated violently before being quenched in oil. The resulting alloy rod was machined free of sur face defects and then placed in a graphite mold designed for growing single crystals. The graphite mold was closed with a graphite plug and was encased in a pyrex glass tube which was connected to a vacuum system. The tube and mold assembly were placed in a furnace; the tube was evacuated and the furnace was rapidly heated to a temperature sufficient for fusing and sealing the glass. The glass-encased evacuated mold and contents were then lowered through a vertical furnace. The top section of the furnace was held at 100 °C above the melting point of the alloy. The lowering rate was 1.5 in. per hr. The tension specimens were 1/4 in. diam; the shear specimens were 1/2 in. diam. These specimens were then removed from the mold, etched, and chemically polished with hot (60°C) Chase etch reagent (Crz03-4.0 g, NH4C1-7.5 g, NHOs-150 cc, HzS04-52 cc, and Hz0 to make 1 liter). In preparation for tensile testing, the specimens were carefully machined to a diameter of about 0.200 in. to permit a gage length of 6 in., annealed for 16 hr at 800&apos; to reduce coring, and then cleaned and polished. A modified Bausch-type shear apparatus which has been described previously18 were employed. The gage length was 1/8 in. This shear apparatus was placed in an Instron tensile testing machine. EXPERIMENTAL RESULTS A) Tension. Several specimens were extended at room temperature to determine the effect of initial orientation on the stress-strain curves of Ag-30 pct Zn. The initial orientation and the resolved shear stress supported by the active slip system at various total strains are plotted in Fig. 1. The critical resolved shear stress, t,, initial rate of work hardening, d/dy, and length of the easy-glide region are independent of orientation. The arrival at the symmetry line is shown by an arrow in Fig. 1. During the easy-glide region of the stress-strain

Jan 1, 1963

By Rex B. McLellan

A simple model for dilute interslitial solid solutions is set up which enables a solubility equation for the equilibrium between the solid solution and the gaseous solute to be deduced. This solubility equation is used to estimate the partial thermody -namic functions of Ag-O and Fe-N dilute interstitial solid solutions from the measured equilibrium between these solutions and the gas phase. It is shown that the partial excess entropy of the solute atom in solution is a vibrational entropy which is due Principally to the oscillation of the interstitial atom and does not arise from electronic or elastic interaction between the solute atoms and solvent matrix. In this work measurements of the equilibrium between dilute solid interstitial solutions and a gaseous phase are used to deduce the important thermody-namic functions of the solid solution with the aid of a theoretical solubility equation formulated from a knowledge of the thermodynamic functions of the gas and a simple model for the solid solution. The quantity of principal interest which is deduced from the equilibrium data is the change in vibrational entropy occurring when a solute atom (u) is placed in an interstial site in the solvent (u) lattice. This paper forms part of a more general study in which the properties of condensed phases are deduced from measurements of the equilibrium between the condensed phase and a gas. Previous investigations have dealt with the equilibrium between krypton and liquid metals,&apos; a pure metal and its vapor,&apos; and dilute substitutional alloys and the vapor,3 and the subject has been popularly reviewed by McLellan.4 In the latter investigation3 the vapor pressures of very dilute Cu-Ag and Cu-Au alloys were measured with a Knudsen cell technique over a large range of temperatures and the analysis of the vapor-pressure data showed that the relative partial excess entropies were large and positive [ds= -Sudk = 30 for Au-Ag alloys and 150 for Cu-Au alloys; these values should be compared to unity, the value assumed for these exponentials in the quasi-chemical theory of solutions]. For many interstitial solutions experimental data is available for the equilibrium between the solution and a gaseous phase, and this can be used to deduce the vibrational entropies of the solute atoms in solution. The general method employed is to calculate the chemical potential of the solute atoms in the gas and equate this to pi, the chemical potential of solute atoms in the solid, which is deduced from a simple model set up for the dilute interstitial solution (in which the solute atoms act as bound oscillators in interstitial sites). This enables a theoretical solubility equation to be set up. In the case of Ag-O and Fe-N solid solutions the solubility c, is found to vary with temperature according to a relation of the type, where PU2 is the pressure of the O2 or Np molecules. Essentially, the theoretical solubility equation enables the parameter A(T), which gives the vibration entropy, and the parameter AH, which gives the energy of solution of a solute atom, to be estimated from the measured variation of solubility with temperature. The solutions treated are dilute enough to enable solute-solute interactions to be neglected so that the partial energy and excess entropy of solution E, and GS are not functions of composition and the configurational entropy is that of a random solution. Large positive values have been found for sxSu this quantity has not been given sufficient consideration in recent work on interstitial solutions and it is felt that the partial thermodynamic quantities of very dilute solutions should be understood before the thermodynamics of concentrated solutions can be fully appreciated. EXPERIMENTAL DATA 1) The Silver-Oxygen System. The measurements of Steacie and Johnson,= using silver foils, indicate that there is a pronounced minimum in the solubility vs temperature curve for O-Ag solutions. Eichenauer and Miiller6 have recently redetermined the solubility of oxygen in silver using a method developed in the investigation of metal-hydrogen systems.7 The solubility determinations were carried out on compact specimens of differing shapes and sizes and the results indicate a much lower solubility than was obtained by Steacie and Johnson with no minimum at 400°C. Subsidiary experiments showed that the erroneous results of Steacie and

Jan 1, 1964