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By Carl Zapffe

The object of the Bradley process is to free manganese oxide from its associated gangue and separate the contained iron oxide by dissolving the manganese and precipitating it from the solution. This results in producing two oxides as concentrates, the one to be converted into a manganese sinter and the other into an iron sinter. The manganese sinter may be made to contain as high as 70 per cent. inanganese and as low as 1 per cent. silica, with phos'phorus not to exceed 0.02 per cent, and from that figure downward to about 0.005 per cent., and with sulfur at 0.007 per cent. The iron sinter contains about 2.50 per cent. manganese, making the total recovery of the manganese 98 per cent. The method involves selective roasting, which converts the manganese into a form in which it is soluble in an aqueous solution of ammonium sulfate, then precipitating the manganese as a hydrate by using ammonia gas, then stabilizing and washing the hydrate, followed by sintering; concurrently most of the iron oxide is converted by roasting into an insoluble form and becomes a residue with magnetic qualities, which makes possible the recovery of much of the iron in the ore. Leaching manganese by using sulfur dioxide gas was shown possiblc Inany years ago. Mr. Bradley tried it for a year, working in conjunction with the original experimenters of that method, and found that while relatively pure inanganese oxide could be produced, the likelihood of developing a commercial process along this line was not very encouraging. He also attempted leaching with nitric and sulfur acids, but the cost of recovery mounted and the quality of the product was not as good Mr. Bradley tried nearly every leaching method proposed, and the expen-ments were made on a large scale in the spacious laboratories of John C. Wiarda & Co., in Brooklyn, N. Y. Insufficient encouragement was discernible in the results obtained. Upon the suggestion of N. Arthur Laury, of John C. Wiarda & Co., Bradley undertook using arnrnoniurn sulfate. Because a high rate of recovery appeared feasible, Bradley planned the erection of a 4-ton pilot plant at the State of Minnesota Mines Experiment Station, at Minneapolis. The results of that work are described in this treatise.

Jan 1, 1929

By Charles E. Wait

HAVING had some experience in the use of gasoline-gas in a laboratory, I have been induced by frequent inquiry to present a few hints concerning it, which I hope may be of some value to those who are out of the reach of coal-gas, and who contemplate using this gas. While I will not delay to describe the method by which this gas is made, it may not be out of place to note that, unless frequent charges are put into the carburetter, the gas is variable in richness. This may be partially avoided, it is said, by repeatedly pumping from one cell in the carburetter to another. If a machine is in constant use for many months without re charging, the gas becomes rather poor for illuminating purposes ; but in this condition it may be burned in a Bunsen burner with advan tage. Could the gas be used always in this condition, no difficulty would be experienced, and it would be quite satisfactory for general laboratory purposes. Considerable annoyance, however, is experi enced whenever the machine is filled with gasoline. The Bunsen and other burners then produce a flame too smoky to be used with com fort, and, in fact, with most of them, a full supply of air; turned on at the base of the burner, will not suffice to completely burn off all the carbon. Finding it necessary to adopt some method by which I could get a flame free from unconsumed carbon, I adopted a plan which has in every way proved satisfactory. In addition to the pipe conveying the gas to the table, and ar ranged with a stopcock, there is brought to the table, within a fern inches of the gas-pipe, another pipe, conveying air direct from the pump. This pipe is also arranged with a stop-cock. The air- and gas-pipes are now connected with one pipe by a T joint; and to this last pipe is attached, by rubber tubing, the Bunsen or other burner. I have successfully used this simple system in connection with both small and large Bunsen burners, a burner with three tubes, arid a Fletcher burner; and recently I have added a new still to our equipment, and have been tising with it a Fletcher special high power burner No. 6, to which this system has been applied. With

Jan 1, 1886

By R. J. Woody

Design of the most economic continuous counter-current decantation (CCD) circuit is based on selection of the number of stages and the wash volume that will give the minimum summation of the following items: 1) Capital and operating costs of the CCD circuit. 2) Capital and operating costs of the precipitation circuit. 3) Value of the dissolved product lost.

Jan 1, 1959

By AIME AIME

ON Thursday a most interesting symposium on "Gases in Metals" was held, with both morning and afternoon sessions. The morning was devoted principally to the considerations of the steel maker, the nonferrous field being taken up in the afternoon period. Dr. John Johnston, as chairman, introduced the subject with "A Short Analysis of the Gas-metal Problem and Its Practical Importance." He then introduced P. H. Brace who explained in considerable detail the various vacuum fusion and other methods in use at present, both here and abroad, in the study of "gases" in metals. He was fol¬lowed immediately by H. W. Graham on "The Effect of Oxygen in Steel." The papers elicited considerable discussion, the point being particularly noted by both Dr. Rawdon and Dr. Sauveur that a knowledge of "total oxygen" alone is not sufficient information for the metallurgist, distribution of oxygen being probably the more important. Dr. Johnston, in commenting on the lack of agreement among many of the methods now in use, such as the Ledebur and vacuum fusion, spoke of the contemplated plan of the Iron and Steel Division to have a number of standard samples analyzed by many laboratories by the various methods, the Bureau of Standards acting as a clearing house, so that more definite information may be obtained on the comparative accuracy of the method.

Jan 1, 1933

By Harrison R. Cooper

With problems of diminishing ore grades and increasing cost of facilities, the mineral industry is acutely aware of the needs for improving beneficiation processes. Industry and universities are directing intensive technical effort to develop- ment of techniques with potential for using digital computers in automation and process analysis. The main problem of early attempts at on-line computer process control methods was that of economics. Now, with new advances in analysis and modeling making practical application economically important, it appears that minerals beneficiation is on the threshold of a significant jump in operating technology. In reviewing this work, particular note was taken of research and development applied to fundamental processes and the significant areas of effort where operations research techniques are used for process applications leading to the current state-of-the-art. Development of data automation and on-line control methods for process industries is deferred to the next section of this volume. This section deals with computer-facilitated mathematical-modeling development and reviews this work in conjunction with associated prior fundamental research leading to development of the methods. Flotation The 1960 state-of -the -art in flotation modeling was com- piled by Arbiter and Harris in the volume, 50th Anniversary of Froth Flotation, edited by Fuerstenau1. Many workers in the field of flotation initiated their research through flotation models, and this effort has led to use of simulation and operations re search methods employing computer techniques to facilitate advance of this work. The flotation model of Imaizumi and Inoue, published with supporting data in 1962, was expanded in 1968 with the objective of developing a basis for process automation.2,3 The fundamental work of Woodburn and Loveday in 1965 has led to techniques applicable to flotation circuit design optimization.4 This analysis is described in this volume by Woodburn in conjunction with King, Buchalter, and Piper. Niemi5,6 derived models for dynamics of a flotation circuit which were employed in developing a model describing

Jan 1, 1969

By Luther W. Bahney

(San Francisco Meeting, October, 1911.) LIME is the alkali that is almost universally added to the solutions in the cyanide process of gold- and silver-extraction for maintaining the so-called, protective" alkalinity. It is produced by the burning of limestone. The value of lime for this purpose depends upon the percentage of calcium oxide contained, which is determined by three factors : 1, purity of the limestone used; 2, degree of the burning-temperature and the period of burning; and 3, length of time of storage of burned material and the condition stored, and whether it has been damp or wet during the storage. These three factors render uncertain the quality of lime bought in the open market. In the United States, lime bought from reliable manufacturers, who thoroughly burn a pure limestone and deliver at once to the consumer from the kilns, may be of a fairly-high and uniform composition ; but in Mexico and Central America, where it is purchased from many small producers, who often start with a poor grade of limestone and burn it in small crude kilns with as little fuel as possible, the quality of the product is quite variable. In consideration of the foregoing, it is apparent at once that there is a great need for a rapid technical method for the valuation of the lime to be used in a cyanide-plant. The determination of calcium by the gravimetric method, with the necessity of determining also the proportion of carbon dioxide, silica, and iron, requires too much time, and is usually out of the question for an isolated plant unequipped with a skilled chemist and, the necessary apparatus. The calculating of all the calcium so found to calcium oxide, although sometimes done, is manifestly very inaccurate.

Nov 1, 1911

By E. E. AGGER, Arthur Notman

THE proposal has been made in a bill introduced into Congress at the last session by Representative Jones of Michigan that an import duty of 6 c. per lb. shall be placed on copper. This action is urged after eighty years of prosperity for the industry in this country; during most of which copper has been on the free list, and during all of which a tariff would have been without real effect. To comprehend the general situation upon which this action would be imposed, we must refer to the past history of the industry and its trends at the present time. The following table supplies us with a picture of the physical growth of the industry in this country and its relation to that of the world as a whole down to Jan. 1, 1921:

Jan 1, 1925

Percolation infers the passage of a liquid through, the interstices of any material or materials permitting it. Leaching is the process of extracting soluble matter by percolation. Lixiviation is analogous to leaching. Percolation and leaching may occur simultaneously. A filter may be used either to strain suspended or finely divided matter from a liquid, when it is known as a clarifier, or to separate a liquid from a solid. Clarification usually infers the addition d: some settling or flocculating agent which permits the decantation of the clear supernatant liquor. The simple separation of solid from liquid, such as occurs when a thickened flotation concentrate is filtered, is usually termed dewatering. The word filtration is used more to cover the complex process of separating, as far as possible, solid from liquid by vacuum or pressure, removing the residual solution by wash, and at the same time leaching any recrystallized, absorbed, or undissolved matter, by percolation with the solvent. The final product of metallurgical treatment should be reported as a recovery when the yield is refined metal. When the metallurgical operations are incomplete and a concentrated but not refined-product is obtained, the metal content should be reported as an extraction.

Jan 1, 1919

By David C. Russell

The Department of the Interior used to be a quiet, noncontroversial, almost boring agency. It, after all is the fifth oldest of the Departments, and as an old line Federal agency it has studiously performed its preservation and resource management functions in a caretaker mode--though some would say more "undertaker" than "caretaker"--locking up the body and soul of America piece-by-piece. Yes, quiet, serene. That is until Jim Watt showed up. And we have all seen that version of Mt. Vesuvius which resulted--only it was the environmentalists who blew their tops. Ronald Reagan chose Jim Watt as Secretary of this fine old agency to prove that one-third of our Nation's land and over a billion acres on the Outer Continental Shelf can work for this Nation. At the foundation of President Reagan's charge to Secretary Watt is a belief in the tenets of the free enterprise system, and in the individual freedoms upon which this country was founded. There are those who don't share this belief in democracy and free enterprise, and those who believe this 205 year experiment called the United States of America will fail. Nikita Krushchev said "we will bury you"--obviously he didn't agree with our system. An Italian sociologist, Franco Ferrorotti, said bureaucratic stagnation will kill capitalism. Certainly we have all felt the ravages of bloated bureaucracies. Perhaps one indicator in the United States is the Federal Register, that daily compilation of Government's largesse. In 1970, 20,000 pages of the Federal Register were published. A decade later, in 1980, that volume had quadrupled to 80,000 pages. The Federal bureaucracy can stagnate from excessive budgets as well. The Interior Department spent $60 million on administering Federal coal leasing in 1981. That's nearly two bits a ton for every ton of coal leased in 1981. You wouldn't stay in business very long if your administrative overhead on inventory was that outrageous. But the pessimism of our critics is apparent from more than red tape and bloated budgets. For decades America has been fasting--consuming too little of America's wealth of minerals, subsisting instead on a diet heavily reliant upon mid-east oil, with little emphasis or concern for inventorying and developing domestic energy and mineral resources. Economics--yes. But short-term, short-sighted economics. Excessively dependent upon foreign imports, of oil, cobalt, chrome and other strategic minerals, the U.S. measures its time before another embargo--or fallen Shah, or Soviet manipulation, or Saudi shift, or, as we witnessed in Egypt, assassination--an untimely loss to mankind and efforts to bring peace to the troubled mid-east. These disruptions, in addition to their tragic human tolls, impair the free world's security. Huge chunks of the United States have been locked away in dozens of single land use categories in the name of conservation, with only the foggiest idea of what resources might be denied the American people-and this at a time of unacceptable levels of energy and strategic mineral imports. More than half and perhaps two-thirds of all Government-owned lands are totally withdrawn from or severely restricted to development under the mining and leasing laws. We must continue to rid Government of the overly zealous restraints which have been keeping us from drawing upon that which can help restore our economy and national security. When we assumed responsibility, the United States was dependent on foreign sources for about 40 percent of its oil. In 1981, our oil import bill was approximately $83 billion--nearly 17 times what it was in 1972. Our reliance on foreign sources for essential minerals is even more disturbing. We must look to other countries--some unfriendly, some unstable--for 22 of 36 strategically critical minerals. Yet the energy resources on federal lands which are owned by the American people could meet our needs for centuries if properly managed. Eighty-five percent of the crude oil yet to be discovered in America is likely to come from public lands, as will 40 percent of the natural gas, 35 percent of the coal, 80 percent of the oil shale, nearly all of the tar sands, and substantial portions of uranium and geothermal energy. Our vast hardrock-mineral wealth includes untapped deposits of essential elements we now import, such as chromium, copper, platinum, and cobalt. The obvious question is, if these abundant resources can help to revitalize our economic strength and to preserve our national security, why aren't we using them to better advantage? To a large extent, the answer can be found in past decisions to restrict public access to the federal estate, thus deferring to us or our successors the tough decisions that flow from Congress' mandate to provide for environmentally responsible development of America's energy and mineral treasures. Here is the legacy this Administration inherited: In January 1981, 7 years after the onset of the Mideast oil embargo: ---Less than 15 percent of federal onshore lands were under lease for oil and gas development; ---No oil and gas leases had been issued in Alaska for 15 years;

Jan 1, 1982

By A. Eilers

ALTHOUGH the process to which I refer in this paper has been in successful operation for nearly five years, during which time it has been introduced, superseding all other processes having in view the same end, in almost every lead refinery in the country, no description of it, giving economical data, has ever appeared in print, nor has the process been known in its details to any considerable number of engineers beside those conducting it at their works. A discussion of this subject at the present time becomes especially interesting in view of a late publication in the Prussian ministerial organ for Mining and Metallurgy, by Dr. Wedding, in which the method of treating the zinc-silver-lead alloy by distillation, as finally settled upon at Tarnowitz, is very minutely and fully described. It is the more interesting, because in that article reference is made to the American method in an unfavorable light, while, at the same time, it is clear from the article itself, that the most important details of the process, besides the one that it is conducted in black-lead retorts, were not at all understood. In publishing herewith the details of our American method, one of my objects is to invite comparisons between our simple and direct process and the elaborate one at Tarnowitz. In extracting the silver from work-lead by means of zinc, it is always the intention, in this country, to obtain a zinc-crust so rich in silver that the rich lead resulting from subsequent distillation

Jan 1, 1875

By A. Eilers

Although the process to which I refer in this paper has been in successful operation for nearly five years, during which time it has been introduced, superseding all other processes having in view the same end, in almost every lead refinery in the country, no description of it, giving economical data, has ever appeared in print, nor has the process been known in its details to any considerable number of engineers beside those conducting it at their works. A discussion of this subject at the present time becomes especially interesting in view of a late publication in the Prussian ministerial organ for Mining and Metallurgy, by Dr. Wedding, in which the method of treating the zinc-silver-lead alloy by distillation, as finally settled upon at Tarnowitz, is very minutely and fully described. It is the more interesting, because in that article reference is made to the American method in an unfavorable light, while, at the same time, it is clear from the article itself, that the most important details of the process, besides the one that it is conducted in black-lead retorts, mere not at all understood. In publishing herewith the details of our American method, one of my objects is to invite comparisons between our simple and direct process and the elaborate one at Tarnowitz. In extracting the silver from work-lead by means of zinc, it is always the intention, in this country, to obtain a zinc-crust so rich in silver that the rich lead resulting from subsequent distillation

By Owen Thornton

Recently equations have been presented by Rose and Bruce' and by Rose², showing how the relative permeability of a reservoir rock may be determined from the capillary character of the rock. In particular, equations were developed to show the relationship between capillary pressure and the effective permeability to the wetting phase in a poly-phase flow system. The equations are as follows (nomenclature the same as in the Rose and Bruce paper) Rose and Bruce assume that the average length of path (L,), which the wetting fluid follows in flowing through a porous media is independent of the saturation to the wetting phase, so that 1 is a constant dependent only on the k rock, and the permeability to the wetting phase is a function of the saturation and of the capillnry pressure: In measuring the flow of ekctric current through partially saturated core samples, it has been observed that the electrical resistance usually is not a simple linear function of saturation. This fact indicates that the average length of path in the flow of electric current is not independent of saturation, but rather that the tortuosity of the path depends upon the average saturation to the conducting fluid as well as upon the characteristics of the rock. itself. Inasmuch as the flow of fluid and the flow of electric current in many respects are analogous, it may be indicated further that the length of path for fluid also may not be independent of saturation. The following relationship can be derived to express the resistance to flow of electric current through a core sample partially saturated with conductive wetting phase, the non-wetting phase being non-conductive: where L is the average length of path followed by the current in flowing through a length L of partially saturated core, where L is the length of current path when the core is fully saturated, and where Rs and R, are the specific resistivities of the partially saturated and saturated core sample, respectively. It will be noted that R., the specific resistivity of the core sample when S, = 1.0, is equal to the "formation resistivity factor"' multiplied by the specific resistivity of the saturating fluid. If it be assumed that the average lengths of path for fluid flow and for the flow of electric current are the same, then equation (5) may be combined with equations (l), (2) and (3) to give the following relationship: The above equation suggests including a correction for tortuosity when calculating the relative permeability of a reservoir rock to a wetting phase. The correction factor may be obtained from the resistivity-saturation relationship. For instance, the following calcu- lations are obtained for the unconsoli-dated sands described by Leverett Kw Kw Sw R°/Rs Pt/Pc¹ (Calc.) (Obs.) 0.30 0.08 0.88 0.02 0.0 0.40 0.16 0.94 0.06 0.04 0.50 0.27 0.97 0.14 0.11 0.60 0.40 0.98 0.26 0.21 0.70 0.53 0.98 0.39 0.35 0.80 0.68 0.99 0.57 0.54 0.90 0.84 0.99 0.77 0.76 1.00 1.00 1.00 1.00 1.00 It will be noted that the agreement between the calculated points and the observed data is rather good. Further investigation of the above method for obtaining relative permeabilities may be merited. For many sands within specified ranges of saturations the following relationship has been found to hold approximately': — =SW"......(7) Rs The exponent n in the above equation has been found to equal two for many sands so that equation (6) reduces to the following: The writer acknowledges the permission of The Texas Co. to submit this note for publication. 1. Walter Rose and W. A. Bruce—Jnl. of Pet. Tech., Vol. 1, No. 5, p. 127 (1949). 2. Walter Rose—Jnl. of Petr. Tech., Vol. 1, No. 5, p. 111 (1949). 3. G. E. Archie— -Trans. AIME, 146, 54 (1942). 4. M. C. Leverett— Trans. AIME, 142, 152 (1941). 5. M. C. Leverett—Trans. AIME, 132, 149 (1939).

Jan 1, 1949

By Owen Thornton

Recently equations have been presented by Rose and Bruce' and by Rose², showing how the relative permeability of a reservoir rock may be determined from the capillary character of the rock. In particular, equations were developed to show the relationship between capillary pressure and the effective permeability to the wetting phase in a poly-phase flow system. The equations are as follows (nomenclature the same as in the Rose and Bruce paper) Rose and Bruce assume that the average length of path (L,), which the wetting fluid follows in flowing through a porous media is independent of the saturation to the wetting phase, so that 1 is a constant dependent only on the k rock, and the permeability to the wetting phase is a function of the saturation and of the capillnry pressure: In measuring the flow of ekctric current through partially saturated core samples, it has been observed that the electrical resistance usually is not a simple linear function of saturation. This fact indicates that the average length of path in the flow of electric current is not independent of saturation, but rather that the tortuosity of the path depends upon the average saturation to the conducting fluid as well as upon the characteristics of the rock. itself. Inasmuch as the flow of fluid and the flow of electric current in many respects are analogous, it may be indicated further that the length of path for fluid also may not be independent of saturation. The following relationship can be derived to express the resistance to flow of electric current through a core sample partially saturated with conductive wetting phase, the non-wetting phase being non-conductive: where L is the average length of path followed by the current in flowing through a length L of partially saturated core, where L is the length of current path when the core is fully saturated, and where Rs and R, are the specific resistivities of the partially saturated and saturated core sample, respectively. It will be noted that R., the specific resistivity of the core sample when S, = 1.0, is equal to the "formation resistivity factor"' multiplied by the specific resistivity of the saturating fluid. If it be assumed that the average lengths of path for fluid flow and for the flow of electric current are the same, then equation (5) may be combined with equations (l), (2) and (3) to give the following relationship: The above equation suggests including a correction for tortuosity when calculating the relative permeability of a reservoir rock to a wetting phase. The correction factor may be obtained from the resistivity-saturation relationship. For instance, the following calcu- lations are obtained for the unconsoli-dated sands described by Leverett Kw Kw Sw R°/Rs Pt/Pc¹ (Calc.) (Obs.) 0.30 0.08 0.88 0.02 0.0 0.40 0.16 0.94 0.06 0.04 0.50 0.27 0.97 0.14 0.11 0.60 0.40 0.98 0.26 0.21 0.70 0.53 0.98 0.39 0.35 0.80 0.68 0.99 0.57 0.54 0.90 0.84 0.99 0.77 0.76 1.00 1.00 1.00 1.00 1.00 It will be noted that the agreement between the calculated points and the observed data is rather good. Further investigation of the above method for obtaining relative permeabilities may be merited. For many sands within specified ranges of saturations the following relationship has been found to hold approximately': — =SW"......(7) Rs The exponent n in the above equation has been found to equal two for many sands so that equation (6) reduces to the following: The writer acknowledges the permission of The Texas Co. to submit this note for publication. 1. Walter Rose and W. A. Bruce—Jnl. of Pet. Tech., Vol. 1, No. 5, p. 127 (1949). 2. Walter Rose—Jnl. of Petr. Tech., Vol. 1, No. 5, p. 111 (1949). 3. G. E. Archie— -Trans. AIME, 146, 54 (1942). 4. M. C. Leverett— Trans. AIME, 142, 152 (1941). 5. M. C. Leverett—Trans. AIME, 132, 149 (1939).

Jan 1, 1949

By W. J. Sharwood

In the cyanide process, gold and silver are dissolved from crushed ore as double alkali-metal cyanides, from which they may be precipitated by such positive metals as sodium (amalgam), aluminum, or zinc, or by electrolysis. Two extreme conditions may be noted. Some works, especially slime plants practising decantation, use a relatively large volume of solution—possibly 4 or 5 tons per ton of ore—nearly all of which may require precipitation, so that the solutions handled are of much lower value per ton than the ore. On the other hand, in some leaching plants it is possible to extract with very little solution, and to percolate some of this more than once through the charge before precipitation, so that the solution to be precipitated may be much less than half the weight of ore, and proportionally richer. Solution intended for further use need not have all its precious metal removed, but any that has to be thrown away should be impoverished as far as is economically possible. In spite of certain advantages possessed by other precipitants, zinc in some form has been almost universally used.. In some of the first attempts to utilize cyanides as gold solvents, a "piece or plate of zinc" was suggested as a precipitant, but extension of surface was early recognized as a desideratum. . Macarthur and the Forrests adopted a "metallurgical filter" of zinc shaving, turned from disks or rolled sheets. They had previously experimented on other forms of zinc, ax! Mscarthur records having tried zinc dust, which had of course been long known as a general reducing agent. It had also been known and used as a precipitant of precious metal from plating and photographic solutions, and comminuted zinc had been patented for recovering copper, etc., from ore leaches. Other inventors proposed the virtual making of zinc powder by the attrition of balls of zinc, and by similar means, during the passage of a stream of gold-bearing solution. Sulman claimed the use of zinc dust, or fume, in a special apparatus, effecting a more or less regular feed of dust and solution by means of intermittent siphons; the mixture or "emulsion" (as it is still called) rising with diminishing velocity through an inverted cone in which it

Jan 1, 1918

By F. G. Miller, E. B. Wilson

In 1972, coal mine productivity was in steady decline and labor and maintenance costs were spiralling upward. Yet, despite this sad state of affairs, nowhere in the US at that time was there a comprehensive and coordinated coal research and development plan in the offing. The Bureau of Mines had not yet been charged with such a responsibility, and industry was content to rely on machinery manufacturers for innovations. It was during this period that Bethlehem Steel Corp. determined that a new approach to coal mining research was needed for the industry as well as for the company itself. After studying Bethlehem's own mining practices, the state-of-the-art of mining research elsewhere, and development work by manufacturers, a comprehensive research package was presented to company management in late 1972. The ideas and experience of many operating and management personnel in the company contributed to the formulation of the final plan as approved.

Jan 10, 1976

By Lyall, Zickrick

As a result of the studies on recrystallization and crystal growth made in this laboratory, certain theories have been developed. These are expressed briefly in a paper by Dean and Hudson.' One of the principal points brought out in that paper is that in the deformation of a crystal, the energy supplied is distributed to the atoms of the lattice, probably by the forced formation of molecules. It is found that a Maxwellian distribution of the energy among these atoms will account for the grain growth at various temperatures. According to such a distribution the number of atoms with energy above a certain critical value, E, necessary for recrystallization at the absolute temperature T is given by n = Ne-E/kT where N is the total number of atoms. It is apparent that if this line of reasoning is correct, a metal which has been cold-worked and reheated to a temperature below that of complete annealing will have the atoms with the higher energy recrystallized, that is, reduced to normal energy and there will remain only atoms below a certain energy. If this metal is again cold-worked the peak in the number-energy distribution curve will, as compaied with its position after the first cold-working, be displaced toward the regions of lower energies, that is, the temperature of recrystallization will be higher. By a repetition of this process the position of this maximum and hence the recrystallization temperature of the metal could be raised considerably. In order to check this theory, experiments have been made on copper wire. The wire was drawn from 1/4-in. rod to 22 B & S gage and then sample lots were annealed at 400 and 220° C., respectively. The wire annealed at 400° C. gave an elongation of 34 per cent., whereas that annealed at 220° C. gave only 23 per cent. These wires were then drawn by identical practice to 34 B & S gage and the elongation determined after an anneal of 3 min. in an oil bath held at various temperatures. The figures obtained have been plotted in Fig. 1. It will be seen that the

Jan 1, 1927

By J. A. Morgan

IN the art of roasting sulfides it is well known that the lower the temperature and the higher the pressure of SO, the larger will be the amount of sulfate present in the product. However, the mechanism of sulfate formation is not generally understood. The following experiment" demonstrates in a direct way that, in the roasting of Cu2S, the sulfate forms from the reaction of Cu2O, formed by the oxidation of Cu2s, with gaseous SO, (or SO3) and 0,. Thus, the sulfate does not form at the sulfide surface. The reaction at the sulfide surface is the same whether or not sulfate is formed. Using an indirect method, Ong, Fassell, and Wadsworth' infer that sulfate forms after oxidation, during the roasting of sphalerite, agreeing with the observations of this paper. The method presented here of demonstrating that sulfate forms after formation of Cu2O is to roast a sample of Cu2S and then to locate and identify the phases formed.' A solid cube of cuprous sulfide, made by melting Fisher reagent grade Cu2S powder and measuring about 1.5 cm on edge, was placed on a Nichrome wire grid suspended over the top of an Alundum combustion boat. The assembly was placed in a tube furnace at 600°C and oxygen gas, flowing at 0.60 liters per min, was passed around the specimen for 24 hr. The furnace tube diameter was 1.5 in. The partially roasted sample was removed from the furnace and impregnated with resin No. BR 0014, obtained from the Palmer Products Co., and the impregnated sample was then mounted in Lucite. A cross section was obtained by grinding and the surface was prepared by the following steps: 1) grinding—60 grit, 3M disk, dry; 2) preliminary polishing —60 through 600 grit, 3M disk, dry; 3) polishing— 8 µ diamond putty, silk cloth; and 4) final polishing —1evigated magnesia in isopropyl alcohol, Selvyt cloth. The color micrograph of the polished surface is shown in Fig. 1. The layers present in the micrograph are given along the side. The comwositions of the various layers were established by Debye-Scherrer patterns. From this evidence the following sequence of reactions which occur in the roasting of Cu2S is inferred: 1) The oxidation of Cu2S occurs with oxygen which has been transported through the oxide-sulfate layer by either gaseous or solid state diffu- sion. The products of this reaction at the Cu2S surface are Cu2O and SO,. 2) The SO, diffuses out through the pores in the Cu2O and finally reaches a position in the Cu2O where the oxygen pressure and the SO, pressure have values such that the thermodynamic conditions for the formation of CuSO4 are fulfilled. Then, the mixture of SO2, SO3, and oxygen reacts with the Cu2O to form CuSO1. 3) The CuSO, decomposes by the evolution of SO,, or SO, and O2, to form the basic sulfate. This is reasonable, since the SO, gradient will decrease toward the oxygen gas phase from the CuSO4 layer. 4) For this same reason the basic sulfate will decompose to form CuO. The above sequence of events is based on the assumption that diffusion through the oxide and sulfate layers, rather than the reaction at the sulfide-oxide interface, is rate-determining. This assumption is supported by the observation that these oxide and sulfate layers combined are almost nonperme-able to the flow of gases through them. Acknowledgments This research was supported by the U. S. Air Force, through the Office of Scientific Research of the Air Research and Development Command. The authors wish to acknowledge the helpful suggestions of Ralph Wells of the Applied Research and Developmeit Laboratory, U. S. Steel Corp. References E. A. Peretti: A New Method for Studying the Mechanism of Roasting Reactions. Discussions Faraday Soc. (1948) 4, p. 174. - J. N. Ong, Jr., M. E. Wadsworth, and W. M. Fassell. Jr.: Kinetic Study of the Oxidation of Sphalerite. Trans. AIME (1956) '206, pp. 257-263; Journal OF Metals (February 1956).

Jan 1, 1957

By C. S. Yust, Lida K. Barrett

The change in shape of the void in a sirzterir~g copper mass has been investigated as a juntction of' density. A serial sectioning' technique was used to eoaltrate the irregular shape of the void at two levels qf density. A measure of the void size and configuration, the proximity number, is defined and used to describe the progress of void removal. The process of. void removal deduced front the observations of this study contrasts with current sintering models in that it takes into account the irregularity of structure of a sintering mass and demonstrates that isolated Porosity does not occur first as spherical pores, but as large, definitely nonspherical sections of the void void volume. The process of sintering, about which there is much practical and theoretical knowledge, has evaded a direct and thorough analysis despite the intensity with which it has been studied for 60 years or so. This is due, of course, to the complex structure of a sintering mass and the inability to observe directly the development of a fully dense solid from the initial particulate arrangement. Extensive theoretical analyses have been based on the adoption of one or another of several model systems, that is, by visualization and analysis of some sort of regular assembly or arrangement of geometric "particles" approximating the conditions of a sintering mass. It seems appropriate at this time to try to examine experimentally in some detail the extent to which a sintering mass of irregular particles dlffers from these models. Many models deal with neck growth and the initial stage of sintering and follow the direction established by ~ucz~nski' in 1949 for the sintering of spheres to flat plates. Recently Johnson and cutler2 have adapted these models to sintering of powder masses. coble3 has presented a mathematical model for sintering that applies to the middle and final stages of the process. These papers, without exception, assume a regular geometry, generally spheres in contact in a regular array. Rhines~ and coworkers, however, are studying the sintering process by applying a model based on the topological concept of genus which permits them to consider an irregular structure. whites has described the various models with the exception of that of Rhines et al., and the assumptions on which they are based and their shortcomings. The present paper examines the geometric changes that occur in the powder mass during sintering by examination of the void. The method is to analyze a series of partially sintered structures and to propose from this analysis the sequence of events which occur in the removal of the void space as a sintering mass progresses from a collection of individual particles to a solid body. The irregular nature of the stacking of particles and of the particles themselves will be taken into account. The significant points derived from this study are: first, accurate reconstructions of the irregular void shapes are presented; second, it is clearly established that closed porosity occurs first as widespread volumes of interconnected porosity, definitely nonspherical in shape; and third, a new factor, the proximity number, is defined, which serves in this paper as a tool for describing the void shape changes observed, and which will be used in a later paper as part of the basis of a mathematical model for sintering. While the specific material studied is copper, the observations are thought to be relatively general as indicated by comparison of the results with partially sintered structures in other materials presented in the literature, both metallic and nonmetallic. EXPERIMENTAL PROCEDURE Four series of specimens representing progressive stages of the sintering process were prepared by sintering high-purity copper powder for various time periods. A relatively large particle size was used so that the void-solid interface could be readily distinguished at low magnification. In three series of specimens a loose stacking of particles was obtained by pouring powder into an alumina mold and lightly tapping the mold. The green density of such compacts was approximately 40 pct of theoretical density. Two of these three series utilized irregularly shaped particles in the size range -230 +325 mesh, one series sintered in vacuum and one in hydrogen at 950°C. The third series of loosely stacked particles consisted of spherical particles in the size range -270 +325 mesh, sintered in hydrogen at 950°C. A fourth series was prepared from compacted irregular particles sintered in hydrogen at 950°C. The specimens for this series were formed by lightly pressing the irregularly shaped particles in a steel die; the green density of the pressed pellets was approximately 60 pct. The irregularly shaped particles used in this study are shown in Fig. 1. The density of these particles, measured by a toluene picnometer technique, is 98.2 pct of theoretical density. Each particle is highly convoluted, and in some instances appears in cross section to contain internal porosity. The density measurement, however, indicates that completely enclosed porosity is very small so that the individual particles have a highly irregular surface but are essentially fully dense copper. Therefore, most of the void space that appears in two dimensions to be isolated within the particle is actually at the particle surface and connected to the external void in the dimension not included in the plane of the cross section. The void space that appears as void surrounded by the par -ticle or within folds in the particle w~ll be r~fc\r?

Jan 1, 1968

By David Reger

Introduction THE exhaustion of oil and gas in the United States is proceeding at a rapid pace. This is especially true in fields where the light oils that furnish the most fuel for internal-combustion engines are found, leading to a late estimate by Arnold that the petroleum resources are 36 per cent. exhausted.1 The further remark by Dr. David T. Day at the New York meeting of the Institute, in February, 1916, that the operators of the country are now scarcely able to supply the ever-increasing demand for gasoline, leads the writer to believe that a determined effort will soon be made to secure deeper producing horizons in those regions that now furnish high-grade oil, and in which pump stations and pipe lines offer convenient means for the economical handling of new production. A study of Arnold's table shows further that the States that produce paraffin oil exclusively are 45 per cent. exhausted, this figure being much higher than the average of paraffin and asphalt States altogether. The most extensive of all the paraffin-oil-producing areas is the Appalachian Field, extending with the Appalachian Geo-Syncline from western New York southwestward through western Pennsylvania, western West Virginia, Ohio, Kentucky, and Tennessee, where oil of high gravity is always secured. Of these States, Pennsylvania and West Virginia rank highest in. the quality of their product. In West Virginia, the oil sands dip to a lower level than in any other locality in the Appalachian Geo-Syncline, the Pittsburgh Coal of the Pennsylvanian being only 50 ft. above sea level along the Nineveh Syncline at Wileyville, Wetzel County.2 The very significant fact that the sands of the Mississippian and Upper Devonian Measures furnished the richest oil pools of the State along this

Jan 9, 1916

By F. Keller, E. H. Dix, L. A. Willey

The consideration of alloying elements for aluminum has led to a series of investigations of the equilibrium relations between aluminum and those alloying elements. Therefore, the aluminum end of the aluminum-antimony diagram has been studied. The general form of the aluminum-antimony equilibrium diagram has been worked out by Campbell and Mathewsi and by Tammann.2 Canlpbell and mathews described principally the beginning of solidification. They found the curve of beginning of solidification rising gradually from the melting point of pure alunlinum to a maximum at about 67 per cent. aluminum. After a slight lowering of the curve at a little greater antimony concentration the curve again rises to a maximum at 18.4 per cent. aluminum, which corresponds to the compound AISb. The curve then drops to the melting point of pure antimony. Tamrriarln explained the maximum occurring at about 67 per cent. aluminum as the result of the slow formation of the single compound AISb. The space lattice of the compound AISb, according to Owen and Preaton,³ is face-centered cubic, the antimony atoms being intermeshed with an identical aluminum lattice. Very little, if any, work has been done on aluminum alloys containing small amounts of antimony. The Present Investigation It has been the purpose of this investigation to determine the solid solubility of antimony in aluminum and also to investigate the eutectic temperature and concentration. The experimental work has been carried out in a manner similar to that described in a previous paper4 from this laboratory.

Jan 1, 1931