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By Edward Keller

THE ASSAY FOR COPPER. SOMEONE some time ago remarked that some chemists still insist on telling us how to determine copper by the electrolytic method. The. writer must confess that he believes that everything is not known definitely as yet as to how the exact amount of copper is determined in such material as purest commercial electrolytic copper. Some of us are not yet convinced that the pure copper atom is at all times deposited from an acid solution and that no oxygen or hydrogen will, under certain conditions, accompany it. Difficulties with impurer material are frequent, but erroneous results are not always apparent, since these do not speak so readily for themselves as those in the first case. By this is meant that if a chemist finds 100 per cent. of copper in electrolytic copper it is pretty certain that he perceives the result to be wrong, while if he finds 0.1 per cent. of copper too much in a very impure material he is far more likely to be unconscious of his error. These, in a wide experience, are frequent happenings and the writer has always looked with interest to publications on this subject. In turn, he :feels justified in giving to others a few of his own observations. Up to a few years ago there were two methods of electrolytic copper assay in technical use, which had in common, that the amount of copper deposited on the cathode did not exceed 2 g., and they differed in that, for the one a large sample 1 (20 to 80 g.) was taken from the general sample by a splitting device, dissolved, and from the solution a small portion (to contain 1 or 2, g. of copper) measured out for the electrolytic deposition; in the other Method the copper was determined, generally in 1-g. portions of the separated coarse and fine portions of the sample, all of which passed -a 16 or 20-mesh screen, being accomplished by a 40-mesh screen,

Jan 8, 1913

By Ernest Lilley

WHILE American scientific literature contains much information upon geologic conditions controlling the production of oil in Rumania, copper in Chile, and other fuel and metallic resources in many foreign countries, it is singularly lacking in data about the nonmetallics outside of the United States. Thus, though the United States is the outstanding market for European high-quality refined kaolin, and for the chinaware, porcelain, and other products of the European ceramics industries, Amer-ican literature contains only the briefest references to the deposits from which the raw kaolin utilized is obtained. To the writer, to whom has come in the past year .the opportunity of visiting a number of these deposits personally, they have proved of extreme interest both com-mercially and geologically. It is the latter phase that is discussed in this paper. The older and now largely crystalline rock areas of France, Germany, ;end other parts of western Europe contain numerous pegmatite dikes of which the upper portions have been subjected to surface weathering and kaolinization in much the same way as those of the eastern portion of the United States. Like the latter, the European pegmatite kaolins have long been known for their freedom from iron and other impurities offensive to the china and porcelain manufacturer. Unfortunately, they are also, like the American deposits, individually of small size and noted for their high costs of production. Deposits of sedimentary clay similar in many respects to the high-quality sedimentary kaolins of Georgia and South Carolina are known and worked, notably in southern Germany and in the Newton Abbott district of Devon and Dorset. in England. In general, their relationship to the parent rock from which they were derived is more evident than in the United States and the individual deposits are of smaller areal extent and less regular in outline.

Jan 1, 1932

By F. L. Bosqui

Discussion of the paper of F.* L. Bosqui, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 101, May, 1915, pp. 997 to 1033. SIDNEY J. JENNINGS, New York, N. Y.-I notice Mr. Bosqui says that zinc dust can be used profitably. I had occasion recently to try to ship some zinc deist to South Africa, owing to the. high price of zinc in the last six or eight months and the difficulty in getting zinc sheets We were informed that the steamship companies in England refused to accept zinc dust for shipment through the tropics on the score that it was an explosive mixture. C. W. MERRILL, San Francisco, Cal.-In the early days zinc dust was packed in wooden casks. The steamers at that time were very chary of transporting it. It was put on the deck in the wooden casks, and if the zinc dust got wet it exploded. Since that time we have used hermetically sealed cases, in which case there is no risk whatever in its transportation.. This rule of the steamship companies is perhaps another sample of their ultra-conservativeness. HENNEN JENNINGS, Washington, D. C.-Unfortunately, I have not yet read Mr. Bosqui's paper, but believing it might interest you to know something of the beginning of the cyanide process on the Rand, I will speak briefly as to my own knowledge and experience of the early initiation of this process in South Africa. I took the position of consulting engineer of H., Eckstein, the parent firm of H. Eckstein & Co., and a branch of the firm of Wernher, Belt ,C Co., at Johannesburg, in December, 1889, and at that time the Robinson Co. managed by them was the premier company of the fields. Up to this date plate amalgamation and catchment of a small percentage of concentrates by blankets, and in a few instances Frue vanners, were the main gold-saving devices used and had obtained an extraction' of only about 65 per cent of the gold contents of the ore. Also at that time the orebodies were seen to be changing from oxidized deposits to pyritic at varying depths from 50 ft. to 300 ft. below the surface, and uneasiness was felt as to future recovery. The deepest exploitation at any of the mines was not much below 300 ft.

Jan 12, 1915

By G. H. Clevenger

(Continuing the discussion of the paper of James Johnston, presented at the New York meeting, February, 1914, and printed in Bulletin No. 85, January, 1914, pp. 107 to 133.) This paper cannot fail of being of great interest and value to all who are interested in the cyanide process, on account of the important developments which it records. Mr. Johnston is to be commended for the large amount of detail which he gives, and the company and its management for permitting the publication of data of this character, which while of great value to others could well be considered private property. It might be discussed from a number of standpoints: First, as an example of recent practice in mill and cyanide plant construction; second, the mill practice; third, the cyanide practice; and fourth, the new features in cyanide treatment involved. Perhaps a more vivid way of expressing it would be : First, the equipment or tools with which the various operations are carried on, are they the best and most efficient which could have been selected for their respective uses; and, second, is the best use in every case made of these tools? It may be well inquired is the highest possible recovery of silver made at the lowest cost per ounce recovered? For after all, the making of the greatest ultimate profit is inseparably associated with successful metallurgical practice; there must therefore be at all times a careful balance maintained between recovery and cost of obtaining it. I wish to call attention in a very general way to the equipment used and to an anticipation of questions which are bound to arise in this connection. However, the. bulk of my discussion will be confined to the presentation of certain additional data, together with a more or less general discussion showing the line of development which leads up to the present practice and .the applicability of certain features of it to similar problems elsewhere. There are a number of vital points of broad general interest involved in Nipissing low-grade practice upon which metallurgists will by no means be agreed to which I wish to call particular attention in the hope that it will lead to the presentation of data y others of practice in other districts which will' assist in reconciling this divergence of opinion.

Jan 7, 1914

By F. A. Champion

The work described in this paper was carried out in the Research Laboratories of the British Aluminium Company Ltd., under the general direction of A. G. C. Gwyer, Scientific Manager of the Company. In considering the effect of stress?corrosion conditions on metals, or the failure of metal through stress corrosion, it is evidently advisable to adopt a clear definition of the meaning of those phrases. There appears to be general agreement that stress-corrosion conditions may be defined as the continuous application of static stress to a metal while it is exposed to corrosive conditions, but recognition of the occurrence of true stress-corrosion in a metal is often a difficult matter giving rise to some confusion. For the purpose of this paper stress corrosion in a metal is defined as the acceleration of corrosion by the application of static stress. On this view it is necessary to test a metal not merely under stress-corrosion conditions, but also under the same corrosion conditions without the simultaneous application of stress, if the liability of the metal to stress corrosion is to be assessed. Failure of a metal under stress-corrosion conditions is sometimes quoted as evidence of stress corrosion (for example, by Althof(1)2), but this evidence is totally inadequate if the above definition is

Jan 1, 1945

By Edward Judd

THE old Cerro de Pasco smelter at La Fundicion, near Tinahuarea, 9 miles. from the Cerro de Pasco. mines and at an elevation of 14,300 ft., has now been replaced by a thoroughly modern smelting plant at Oroya, the junction point of the company's private railroad with the Central Railway, of Peru. This site has the advantages of being closer to the Morochoca mines, as well as nearer to the port of Callao, and at the same time is 2000 ft. lower in elevation, which benefits not only the cost of transportation but also the tech-nical operation of blast furnaces , and converters. The Oroya smelter was designed with the idea of .smelting about 2500 tons of. ore per day, but having in mind the possibility of increasing its capacity, all departments of the plant can be extended within reasonable -limits; for instance, if it is found that reverber-atory smelting is cheapest, taking into consideration the cost of fine crushing and fuel, it is possible to extend the roaster and reverberatory plants accordingly. The ore handling system is modern, consisting of belt conveyors, reclaiming machines, and electrically driven calcine cars, all requiring the minimum of labor. Waste heat from the reverberatory furnaces is utilized in boilers for the production of power to operate the plant, and the power house is equipped with condensing units to obtain the highest economy. Shop installations for the making of all repairs required for the smelter are unusually complete, includ-ing iron foundry, steel foundry, forging and machine shops, carpenter and pattern shops, and an electrical shop. There is also a plant for the production of all clay and silica refractory brick used in the furnaces; this is situated on the smelter site and is conveniently arranged for receiving raw materials and delivering finished brick to the several departments of the smelter. The laboratory is in a wing. of the general office, which is a two-story brick structure, situated on the smel-ter site.

Jan 10, 1923

By J. B. Wagstaff, R. A. Buchanan, J. F. Elliott

High speed photography through blast-furnace tuyeres showed coke particles moving rapidly. Model studies showed a raceway was formed and gave quantitative results which were correlated with actual blast furnaces. Another study showed the similarity between hanging and the flooding of a packed column. This was explored by models. THE combustion zone before the tuyere in an iron blast furnace is a vital region because here are generated: 1—most of the gases on which the furnace depends to carry out its basic operation of reducing iron ore to the metallic state, and 2—the major fraction of the heat required in the nearby regions of the furnace for the various reduction reactions, the fusion of the slag, and the melting of the iron. Since the greater part of the coke is consumed in this region, the descent of the burden must be greatly affected by the characteristics of the tuyere zone. This region then would seem to be a profitable field for study. Fortunately, a view into this important zone is available to the operator through the tuyere peep sight. Here he sees relatively dark pieces of coke "dancing" in the blast. What he sees is of considerable help in interpreting the behavior of the furnace at a given time but the very rapidly moving particles and the intense radiation obscures what is happening very deep in the zone. This investigation was initiated in the hope that a better understanding of the combustion region could be obtained by using a high speed camera with a maximum speed of 3000 frames per sec. It seemed the best practical method of "slowing down" this characteristically violent action within the highly luminous field. Model studies and tuyere probing also have been used to aid in explaining the observed phenomena. Above the combustion zone, but below the fusion zone, there is probably a region in which the coke is comparatively stationary. Here are zones in which the gases must flow up through the granular bed counter to descending liquid slag and metal. There is no easy way to observe this zone in a blast furnace, but model studies have been of some help in explaining the nature of the zone and the laws governing the flow of the fluids involved. The whole problem is difficult and involved and any approach to a complete solution may require long investigation. This preliminary report has been written, therefore, because it is believed that appreciable progress has already been made that would be of interest to others. Tuyere Studies, Chemistry and Kinetics It is well known from the early work of Kinney and coworkers1,2 that combustion of carbon before the tuyeres appears to occur in two zones: Zone A: C + O, = CO2; AH77°F. = — 14,108 Btu per lb of carbon [I] Zone B: CO2 + C = 2CO; H77°F = + 6,183 Btu per lb of carbon [2] Zone A (Fig. 1) is close to the tip of the tuyere and zone B is somewhat farther back; there being a transition region in which both reactions occur. It is interesting to estimate the rate at which coke is burned before a tuyere with a wind rate of 90,000 cfm in a modern furnace having 18 tuyeres. Approximately 0.55 lb of carbon is consumed by eq 1 per tuyere per sec. A like amount disappears by eq 2 for a total consumption of 1.11 Ib per sec per tuyere. Assuming the coke is 85 pct C and has a bulk density of 30 lb per cu ft, this figure can be converted to a total of 1.30 lb of coke with a bulk volume of 0.043 cu ft disappearing per sec per tuyere. At the temperatures prevailing in the combustion zone (according to Kozlovich,³ he maximum is about 3400°F), the rate at which carbon is con-

Jan 1, 1953

By J. C. Bartlett

As American students of mining, philosophy, philology, music, history, or art have found it necessary or highly advantageous to supplement their course of study at home by a residence of some years at a foreign university, so, ever since mining has been practiced in this country in any other than a rude and wasteful manner, many American students of mining have sought in London or Paris, but chiefly in the Academy of Freiberg, Clausthal, or Berlin, such infor-

E. A. Peretti (University of Notre Dame, Notre Dame, Ind.)—Mr. Deitz and Professor Halpern are to be congratulated on a fine piece of work which adds to our knowledge of precious metal—cyanide-solution reactions. I should like to offer the following comments: The authors state, "the rate plots were always linear, indicating a zero order reaction rate." This appears to conflict with the data of Fig. 6 which clearly show the rate to vary with the NaCN concentration. It seems to me that the rate curves are linear because of the experimental setup. The volume of solution is so large that over a three-hour period the change in NaCN concentration is very small. A rough calculation for the experiments of Table I where the initial NaCN strength was 0.0096 mol per liter show a change of NaCN concentration of about 0.0009 mol per liter at the end of three hours. In short, over the period of time that the experiment was in progress, the NaCN strength was practically constant; hence the rate of dissolution remained practically constant. Eq. 10, as written, specifies that 1 mol of H202 and 2 mol of hydroxyl ion are formed when 2 mol of silver react. Is this true? The effect of H,O2 on the rate was made in solutions having an oxygen pressure of 4.8 atm. Were any tests made in solutions containing hydrogen peroxide, but no oxygen? G. M. Willis (University of Melbourne, Melbourne, Australia)—The authors have shown that, under their experimental conditions of high O2 concentrations, the rate of solution of silver in aqueous cyanide solutions is controlled by diffusion of O2 or CN- to the metal surface. With diffusion control, it is generally not possible to obtain further information about the mechanism of a process.

Jan 1, 1955

By Louis L. Stott

It is well known that the oxide of beryllium was identified as a new "earth" in 17971 and the metal first isolated in 18272. The history of the many difficulties encountered by early investigators, the laboratory achievements of Lebeau3, Fichter4 and Oesterheld5, and the eventual development of methods for commercial production are well covered in the literature, particularly in the authoritative published work of Siemens and Halskes reviewing their comprehensive investigation of the element. Accordingly it has seemed desirable to restrict this paper to the properties and uses of beryllium and its alloys. PRopeRties of Beryllium A comprehensive summary of the available data on the properties of beryllium is given in " Gmelius Handbuch der Anorganischen Chemie7." The metal is steel gray in color. A fractured surface exhibits a bright luster, which does not appear to change with long exposure to air, probably because of a thin, transparent protective oxide coating. The specific gravity is approximately 1.8. Although there is no recorded actual determination of Young's modulus of elasticity, it has been estimateds, according to Fessenden's law, to be 30,000 kg. per sq. mm., or about 30 per cent higher than steel. Beryllium appears to have an electrical conductivity approximately 1/12 that of copper. The physical constants as available in the literature are given in Table 1. One of the outstanding properties of beryllium is its great affinity for oxygen, nitrogen, sulfur and carbon. One gram of beryllium takes up 1.774 grams of oxygen and will liberate approximately 15.23 kilogram-calories in the combination. The metal apparently reacts with all known oxides at high temperatures; in fact, beryllium will alloy with thorium and zirconium if melted in crucibles of their oxides. The true physical properties of beryllium are still somewhat in doubt, since very small amounts of impurities appear to cause a large variation

Jan 1, 1936

By K. F. G. Hosking

I read Professor Gaudin&apos;s paper with great interest and pleasure because for some time I have held that the chemical aspect of comminution is a subject of considerable importance to the mineral dresser and deserves to be thoroughly investigated. It does seem appropriate, however, to emphasize the fact that "fresh" edges and corners produced by the grinding of solids display enhanced reactivity has been recognized and utilized in the development of certain mineral identification techniques. Some of these techniques are worth noting, not only because they might facilitate research in the aspect of mineral dressing under discussion, but also because they emphasize the fact that many mineral species commonly regarded as being very inert can display a surprising reactivity when in the freshly ground state. In 1951 Isakov6 published a number of tests for the components of certain mineral species which depend essentially on grinding in a mortar a mixture of the material under investigation with a solid reagent. Thus when stibnite, 4(Sb2S3), is ground with sodium or potassium hydroxide. the antimony is revealed by a momentary development of a yellow color which changes in air to orange-red. Other antimony minerals need a preliminary treatment before the test can be carried out. This consists of grinding with aluminium sulfate, ferric sulfate or potassium bisulfate, and breathing upon the resultant mixture. I have employed a similar technique to determine the approximate magnesia content of certain limestones.&apos; The method depends essentially on the fact that when a sample of limestone is ground under controlled conditions with solutions of sodium hydroxide and Titan yellow the color of the final product is, within limits, a function of the amount of magnesia present. I have also shown that the components of a wide range of minerals can be identified by applying chemicals to their streaks on portions of vitrified, unglazed floor tiles, etc. Under such circumstances the diversity of the reactions which take place in the cold (because of the reactivity of fresh corners and edges) is surprising. Thus, for example, if a garnierite, (Ni,Mg)3Si2O5(OH)1, streak is treated first with a drop of 0.880 ammonia and then with a drop of a 1 pct alcoholic dimethyl-glyoxime it immediately becomes red, indicating the presence of nickel.&apos; Stevens and Carron9 have evolved a simple field test for distinguishing minerals by "abrasion pH." A soft nonabsorbent mineral is scratched in a drop of water on a streak plate until a milky suspension is formed. A piece of pH indicator paper is dipped into the suspension, after which it is removed and the maximum deviation from neutrality noted. When a hard mineral or one which absorbs water is being tested, fragments are first ground for 1 min with a few drops of water in a mortar to make a heavy suspension. The importance of the findings of such tests to mineral dressing may be judged by the abrasion pH values, Table 11, recorded by Stevens and Carron for certain species usually regarded as comparatively inert. The combined results Of the above researches clearly indicate that comminution is capable of altering the pH of a pulp and of causing the chemical nature of the surfaces of some of the components to be profoundly changed&apos; Depending On circumstances such surface alterations may have a beneficial or an adverse effect if these products are subsequently subjected to flotation. The tests also suggest that by grinding "inert" minerals with appropriate solid or liquid reagents "reactive" surfaces may be developed which might facilitate separations by flotation. It is an interesting and instructive problem to determine the reactions that are likely to take place when dry solid substances are subjected to comminution and to the unavoidable heat liberated during the process. To do this it is theoretically necessary to know the free energy values of the reactants and possible resultants, but unfortunately there is a dearth of such data! However, the heats of formation of many substances are known, and generally speaking, if in a reaction of the type AB + CD = AD + CB the sum of the heats of formation of AB and CD is less than that of AD and CB the reaction will probably proceed to the right. Thus, according to a note I have (the author of which I cannot name) if PbS (black) is warmed with CdSO, (white), PbSO., (white) and CdS (yellow) are formed, and that the reaction does, in fact, take place is indicated by the change in color of the mixture. The reaction is expected, as the sum of the heats of formation of PbS and CdSO, is less than that of PbSO, and CdS (as shown below). PbS + CdSO4 = PbSO4 + CdS 22.2 + 218.0 < 216.2 + 33.9 Finally, certain other aspects of the chemistry of comminution, which are neither mentioned by Professor Gaudin nor referred to by me are to be found in a paper by Welsh" and in the printed discussion thereof. A. M. Gaudin (author&apos;s reply)—The observations contributed by Dr. Hosking are indeed welcome, as they add to our experimental knowledge of a topic which is believed to be of the first importance. In connection with the experiments cited it should be kept in mind that oxidation, hydration, and carbonation at various rates should always be deemed to be possibilities when grinding is done in water or in air, even in "industrially dry" air. Special precautions might lead to sufficient minimizing of these reactions and to the assertion, instead, of deliberately-created reactions. The author wishes to thank Dr. Hosking for his contribution.

Jan 1, 1957

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Jan 1, 1938

By Earl G. Alexander, W. R. Runyan

The nature of silicon growths which form on amorphous silicon dioxide during epitaxial deposition in unmasked areas was investigated. Octahedral silicon crystals nucleate and grow on the oxide at pinholes, adjacent to foreign matter, and probably at oxygen-deficient sites. Generation of these oxygen-deficient sites on the oxide surface is shown to be thermody-namically favorable under usual deposition conditions. The conditions which affect saturation (SiCl4 concentration, flow rate, temperature) determine the number of sites on which silicon will nucleate and grow. Reaction product HCl is likely responsible for suppressing silicon growths on the oxide near exposed areas of silicon. Evidence is given that the oxide-silicon interaction occurs in hydrogen only and involves water as a transport agent. SINCE shortly after the first epitaxial layers of silicon and germanium were grown over large areas, efforts have been underway to grow selectively on specified portions of the surface. Such selective growth should be particularly applicable to monolithic integrated circuits. Usually the approach has been to use a mask to delineate the desired area,&apos;-7 but the VLS methoda can also be used, and direct programmed atomic beam deposition has been suggested.9 The masking techniques may embody two forms: in one the mask is a material which can later be removed along with any growths attached to it; in the other, attempts are made to prevent growth on the mask, so that over a whole slice the only deposition that will occur is in the unmasked regions. The present work is concerned with only the latter case, and specifically with silicon. Joyce and Baldrey1 suggested the use of thermally grown silicon dioxide as a mask material and showed that for the proper choice of operating conditions (total flow, SiCl4 concentration, total deposition time, and temperature) spurious growth could be minimized and that if the deposition times were not too large, and the criteria not too stringent, a usable process occurred. Later Schnable et al 4 observed that after extended deposition times, during which most of the silicon dioxide became covered with growth, there was always a band of oxide around the exposed silicon area that was quite free of spurious silicon crystallites. This latter observation is particularly intriguing since it extends the hope that with proper precautions masking can be much more versatile than it presently is. EXPERIMENTAL PROCEDURE Silicon substrates oriented to within 1.5 deg of a (111) plane were prepared by etch polishing lapped

Jan 1, 1967

By K. M. Busen, J. Lindmayer

A heterojunction model is suggested for descrihzng the electronic conditions at oxide -semiconductor interfaces. Detailed study of the silicon oxide-silicon interface shows that the heterojunction model explains many experimental facts; however, it is necessary to assume that a transition layer exists at the interface. It will he demonstrated that ionic contrbution way also he present. Extended low-temperature heating stabilizes the oxide to a charge carrier density in the order of 10&apos; cln-: determined by the heterojuncton model. OXIDIZED semiconductor surfaces are widely used, since they offer technological advantages and "passivate" the surfaces of semiconductor devices. However, it has been recognized that there are always n-type inversion layers formed in the silicon oxide-silicon system, which must be regarded as a definite disadvantage. An added complication is the "instability" of these inversion layers;&apos; the inversion layer appears to vary with the processing and they change at temperatures as low as 100" to 200°C This paper will point out that the inversion layer is a result of the dissimilarity of the contacting materials and therefore must always be present. The dissimilarity is the essence of the heterojunction or electronic model and involves directly the structure of the materials involved. In addition, one finds the contribution from ions; this disturbance, however. can be eliminated for the case of silicon oxide-silicon interface. The strength of the inversion layer or channel will be expressed in terms of the density of elementary charges per square centimeter, N*, maintaining the channel. The next section contains the formulation of the heterojunction model by assuming a contact between two homogeneous materials. This calculation should not imply that silicon oxide is homogeneous; it serves only to point out the general properties of the electronic model. Following the electronic model, the practical case of the silicon oxide-silicon interface will be discussed. I) THE HETEROJUNCTION MODEL Contacting an oxide with a semiconductor, a work-function difference must be accommodated. Fig. 1 represents the oxide and the semiconductor before and after contact. When the contact has been made, one finds that qVi + qV, = A@; i.e., the work-function difference is distributed between the oxide and the semiconductor. Normally, the work-function difference appears on the wide-bandgap material, but in the present case the oxide is thin and far from being a single crystal. Accordingly, a significant fraction of the work-function difference must appear on the semiconductor. The work function of silicon2 is about 4.8 ev, but we shall not assign any particular work function for the oxide as it may vary. However, oxides usually have lower work functions and therefore the potentials must build up in the manner shown in Fig. 1. Such an argument predicts that the inversion layer must be n type, as opposed to the clean surface which is p type. Another important factor to be considered is that the oxide is disorderly and therefore contains many trapping levels. As a result, the charges in the oxide arise primarily from the change in trap occupation, while on the semiconductor side the space charge is composed of mobile free electrons. The consequence of this fact is that a change to another thermal equilibrium will require some time, dictated by the traps in the oxide. The conditions can easily be calculated on the semiconductor side. Assuming an intrinsic semiconductor, Poisson&apos;s equation is

Jan 1, 1965

By Richard V. Hughes, Rudolf J. Pfister

The necessity for getting more water into sands of low permeability in any secondary-recovery water-flood operation in order to recover all the available oil always has been a major problem. In the early days of water-flooding the addition of soda ash and caustic soda to fresh input waters was recommended and tried without success in the Bradford field. The most frequent difficulty was sand plugging. The use of natural and artificial brines often has been suggested for water-flooding, in the belief that laboratory observations of decreasing fresh-water throughput rates in measuring water permeabilities of consolidated sand cores might be partially explained by swelling of clays. A review of available literature bearing on the subject and related laboratory experiments are presented herein, offering an explanation for failure in use of soda ash and caustic soda waters and supporting the recent concept that every water used for input purposes in the secondary recovery of oil should possess such physical and chemical characteristics as to keep the clay content of the producing sands in a permanently flocculated condition. Produced brines meet this requirement. Their use is recommended as a means of increasing intake rates of tight sands and oil recoveries, as a solution to brine-disposal problems, and as a means of conserving a natural resource. Introduction There is a general belief among those engaged in the secondary recovery of oil by water-flooding that one of the most important requirements for the success of any such project is an adequate supply of good, fresh water. Fresh waters have the advantages of being more easily stabilized than salt waters and of being usable about the lease for all purposes. The use of brines for water-flooding never has been given much consideration in the Pennsylvania Grade area. The use of brines in Mid-Continent operations has been considered largely as a substitute for fresh waters, which were economically unobtainable for many operations. Estimated recoveries for some water-drive fields indicate that less of the original oil in place will be left upon abandonment than with the above-average practices used in Pennsylvania Grade water-flood operations. Lower residual oil saturations than 25 pct of the pore space following the water-flooding of Third Bradford sand cores in the laboratory are unusual. In comparison, water-flushed sands surrounding any virgin oil pool are found to be practically devoid of oil. Such lower natural residual oil saturations may be the result of a time factor much longer than economic under artificial water-flood operations, but neither the producer of primary oil nor the producer of oil by secondary recovery can obtain maximum recoveries unless full advantage is taken of all natural forces and

Jan 1, 1947

By Richard V. Hughes, Rudolf J. Pfister

The necessity for getting more water into sands of low permeability in any secondary-recovery water-flood operation in order to recover all the available oil always has been a major problem. In the early days of water-flooding the addition of soda ash and caustic soda to fresh input waters was recommended and tried without success in the Bradford field. The most frequent difficulty was sand plugging. The use of natural and artificial brines often has been suggested for water-flooding, in the belief that laboratory observations of decreasing fresh-water throughput rates in measuring water permeabilities of consolidated sand cores might be partially explained by swelling of clays. A review of available literature bearing on the subject and related laboratory experiments are presented herein, offering an explanation for failure in use of soda ash and caustic soda waters and supporting the recent concept that every water used for input purposes in the secondary recovery of oil should possess such physical and chemical characteristics as to keep the clay content of the producing sands in a permanently flocculated condition. Produced brines meet this requirement. Their use is recommended as a means of increasing intake rates of tight sands and oil recoveries, as a solution to brine-disposal problems, and as a means of conserving a natural resource. Introduction There is a general belief among those engaged in the secondary recovery of oil by water-flooding that one of the most important requirements for the success of any such project is an adequate supply of good, fresh water. Fresh waters have the advantages of being more easily stabilized than salt waters and of being usable about the lease for all purposes. The use of brines for water-flooding never has been given much consideration in the Pennsylvania Grade area. The use of brines in Mid-Continent operations has been considered largely as a substitute for fresh waters, which were economically unobtainable for many operations. Estimated recoveries for some water-drive fields indicate that less of the original oil in place will be left upon abandonment than with the above-average practices used in Pennsylvania Grade water-flood operations. Lower residual oil saturations than 25 pct of the pore space following the water-flooding of Third Bradford sand cores in the laboratory are unusual. In comparison, water-flushed sands surrounding any virgin oil pool are found to be practically devoid of oil. Such lower natural residual oil saturations may be the result of a time factor much longer than economic under artificial water-flood operations, but neither the producer of primary oil nor the producer of oil by secondary recovery can obtain maximum recoveries unless full advantage is taken of all natural forces and

Jan 1, 1947

By R. Schuhmann

Available thermodynamic data applicable to copper smelting systems are collected and tabulated, and the important gaps are pointed out. A few examples are given of estimations which can be made from the available data. An experimental research program is proposed to supply the thermodynamic data that appear most essential to better quantitative understanding of the chemistry of copper smelting. The proposed program is designed also to shed specific light on the practical problems of slag losses and magnetite behavior. OPPER smelting, from flotation concentrates to V-/ blister copper, is conspicuous among the large scale chemical processes which are conducted with only relatively incomplete knowledge of the physical chemistry involved. For example, no common metallurgy text explains adequately why copper enters the matte phase while iron enters only to the extent that sulphur is left over after satisfying the copper. Explaining this important phenomenon as a manifestation of the greater affinity of sulphur for copper than for iron is unsound because the affinities of copper and iron for sulphur are about the same at smelting temperatures. As will be shown, other affinities are really decisive in the relatively clear-cut separation of copper in the matte. In contrast, thermodynamic studies have contributed much to our understanding of copper refining, zinc oxide reduction, magnesium production, steelmaking, etc. For each of these processes, the important reactions are clearly recognized, and fair to good quantitative values of the free-energy changes and equilibrium constants are available. Such data have proved to be of constantly increasing practical value in process development and improvement. Work in other fields has furnished much thermodynamic data applicable to copper smelting systems. In fact, several promising starts have been made in applying such data to specific smelting problems. Kelleyl made an appraisal of the possibilities of recovering elementary sulphur from low grade matte. His calculations and compilations of thermodynamic data have represented the starting point for much of the work in this field, including the present survey. Huang and Hayward2 nd Aksoy3 used thermodynamic methods in the study of copper losses in reverberatory slags. Peretti4 used thermodynamic data in explaining the chemistry of converting. The recent publications of Darken and Gurry"." and of Darken,&apos; dealing with the iron-oxygen and iron-silicon-oxygen systems, respectively, present equilibrium data that are applicable to copper smelting systems. Also additional data were reported recently on the affinity of sulphur for copper, manganese, and iron8 and on the sulphur pressures of iron-sulphur melts." The survey presented in this paper was made as the basis for planning an experimental program on the thermodynamics of copper smelting. Few researches on the chemistry of copper smelting have been reported in recent years, so that a reappraisal and coordination of old and new data are essential if further work is to take the directions of maximum value. The experimental program is now in progress, and the plan of attack is outlined at the end of this paper. Progressive Oxidation and Desulphurization of Copper-bearing Liquid Phases: The chemical activities of sulphur and oxygen are two of the most important thermodynamic yardsticks to be applied to copper smelting processes. Virtually the entire smelting and refining sequence involves a series of systems characterized by decreasing sulphur activity and increasing oxygen activity. In this section, therefore, an attempt is made to define and explain these activities in terms of equilibrium partial pressures of SO2, s2, and O,. Also, estimates of these quantities are presented, the estimates being based largely on calculations presented in a later section of this paper. The sequence of steps from raw flotation concentrate to fully oxidized copper ready for poling involves progressive and controlled oxidation. Iron is oxidized and enters the slag. Sulphur is oxidized and leaves in the gas. Table I summarizes several important features of this oxidation and desulphurization sequence, starting at the beginning of the matte blow in the converter. The top line gives in order the principal smelting and refining stages up to fully oxidized copper, plus the additional step, not used commercially, of oxidizing all the way to Cu,O. In the second line are shown the principal copper-bearing liquid phases which characterize the process. Through most of the sequence the copper

Jan 1, 1951

By M. W. Bartley, Hugh M. Roberts

SUBSTANTIAL deposits of Bessemer hematite have been found recently by drilling beneath Steep Rock Lake, Ontario, which is situated in the northern part of the Lake Superior Region. It will be practicable to divert the waters flowing into this lake and develop open pits on the upper part of two large ore bodies by damming off and pumping out the water in the part of the lake in which they occur. Ultimately, the bulk of the ore will be mined by underground methods. Owing to the generally massive nature of the rocks in the area, no underground flows of major consequence are anticipated after diversion of the lake. The Steep Rock deposits are attributed in origin to hydrothermal replacement. They were formed, for the most part, along an unconformable, brecciated contact between the Steep Rock limestone and an overlying younger volcanic series. The replacing solutions came in as igneous after-effects, following upon the intrusion of basic igneous rocks that invaded the hanging-wall volcanics. It is believed that this took place in a geological period roughly equivalent to late Middle Huronian, which was the period when the most extensive iron-bearing rocks of the Lake Superior Region were formed. Comparison is made with other deep-seated iron-ore bodies in the Lake Superior Region, the origins of which are ascribed in the discussion to hydrothermal replacement.

Jan 1, 1943

By Charles C. Fatino, Joel S. Hirschhorn

Loose compacts of strained and annealed stainless-steel powders were sintered at various temperatures and times to determine the effect of residual strains on the sintering behavior. The atomized powders were prepared by annealing, ball milling, and rean-nealing. The residual strains and domain size were determined by a Fourier analysis of X-ray diffvaction dala. The specimens were prepared by siwzultaneously sintering cylinders of both strained and unstrained powder. The evaluation of the sintered compacts included density measurements, metallographic examinations, and analyses of X- ray diffraction data. The results of these studies reveal a definite increase in sintered density and sintering rate for the strained powders. THE pressure compacting of metal powders causes deformation of the particles, mechanical interlocking, and increased contact area. After the deformation, severe residual strains remain in these particles. The subsequent contributions of these strains to the sintering process have been considered to be negligible, since the recovery and recrystallization temperatures usually occur prior to the temperature required for the sintering process. Sintering is con-sidered to be the process by which the powders are transformed into solid compacts at temperatures below their melting points. The sintering operation for stainless steel usually takes place in the range of 2050" to 2400°F (0.84 to 0.95 T,, where T, is the absolute melting point or liquidus temperature) while the temperature required for recovery is approximately 1800°F (0.75 T,). However, it has been shown for several metal powders that densification becomes significant in the range of 0.35 to 0.45 T,.&apos; It is the purpose of this study to determine what effect residual strains have upon the sintering behavior of stainless-steel compacts. Loose compacts were selected for study in order to isolate the strain contributions and eliminate the variables inherent in sintering of pressure-formed compacts. Additional variables were minimized by using only one mesh size, one composition, one particle shape, and also by simultaneously sintering both types of powder. Very little work has been carried out previous to the present study to delineate the effect of strains on sintering behavior. Lenel et 01.2 observed that residual stresses in copper compacts caused shrinkage at comparatively low temperatures. Delisle3 loose-sintered ball-milled electrolytic iron and observed that bonding among particles began at a lower temperature as compared to the behavior of annealed powder. Increased densification of ball-milled oxide powders has also been noted.4&apos;5 EXPERIMENTAL PROCEDURES Powder Preparation. The powder used for this study was a commercial-type 316L stainless steel made by the atomization process. A typical chemical analysis is: C- 0.025 pct Mo- 2.2 pct Cr-18.6 pct Ni-12.5 pct Fe—Balance The atomizing process is essentially the rapid freezing of liquid droplets. This nonequilibrium cooling causes coring to occur and two distinct phases are present within the solid particle, the austenitic phase and the ferritic phase. Due to the presence of this ferritic phase, the particles tended to fracture as well as become cold-worked during the subsequent ball-milling operation. (It was also found that this type of cooling produced a broadened and shifted

Jan 1, 1968

By C. H. Mahoney, A. L. Tarr, P. E. Le Grand

Magnesium, it is now generally realized, differs in some important aspects from most other structural metals, not excepting even its close neighbors, the aluminum-base alloys. This is particularly true with respect to the effects of elevated temperatures on the two light metals when in the molten state. Aluminum, 0&apos; the one hand, should not be raised above its melting point any higher than is absolutely necessary if one is to avoid danger of gas absorption and a tendency toward grain growth in the resultant casting.&apos; Magnesium alloys, in sharp contrast, actually benefit by being heated to temperatures considerably above their melting point, It is a commonly accepted practice to establish the desired fine grain in the industrial magnesium alloys of the aluminum-hearing group by raising the temperature of the melt after the refining treatment to some 250°C (482°F.) above the melting range. To recall briefly the typical practice for magnesium alloys, the molten metal is refined by fluxing at about 730°C. (I350°F.), and after the melt has been covered with a suitable flux, the temperature is raised to between 870°C. (I600°F.) and 930°C. (1700°F.). It is then cooled as quickly as possible to the casting temperature. This superheating, as it is called, results in a fine-grained cast metal structure which has superior mechanical properties, enhanced amenability to &apos;solution heat-treatment, and better machinability than cast metal that has not been superheated. The minimum temperature of superheating varies to some extent with the composition of the alloys to be treated and usually increases with the percentage of magnesium in alloys containing the same constituent metals.&apos; It should be noted that the grain-refining effect of superheating is markedly apparent only in connection with the alloys containing aluminum as an alloying Constituent—the binary alloy containing 1.5 per cent manganese, for example, is not refined in grain to any noticeable extent by a superheating effort. While the phenomenon of superheating is well known in the magnesium industry, the mechanism of the process has remained a mystery During the superheating cycle something occurs that forces a fine grain upon the solidifying metal. The process has been controlled in an empirical manner, and occasionally, especially on large-scale melts, and for no apparent cause, no grain refinement is obtained from a superheating treatment. Only a few papers of importance have been published on the subject. Of these, one of the most helpful is the paper by Achenbach, Nipper and Piwowarski,3 which gives considerable data concerning the effect of superheating on various properties such as fluidity, shrinkage and hot crack

Jan 1, 1945