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By W. D. Ludemann, J. E. Dor, L. A. Shepard

Recovery of the creep resistance of 99.99 pct pure Al was studied at temperatures 540°, 573°, 600°, and 611°K. Poly-crystalline specimens crept under a stress of 950 psi to a strain of 5.5 pct were allowed to recover for periods of from 1 min to 16 days under a residual stress of 4.4 psi. Increased creep rates upon reapplication of the 950 psi stress evidenced softening of the material. The activation energy for the recovery process was found to be 64,000 cal-per mol. THREE major observations have clearly revealed that the creep of polycrystalline aluminum above about 510°K is controlled by the rate of climb of jogged edge components of dislocations past the barriers impeding their motion: 1) Extensive polygonization, characteristic of climb, takes place during creep.'9' 2) The activation energy for creep equals the estimated activation for self-diffusion. 3) The stress law for creep coincides with theoretical predictions based on the climb mechanism.4,5 The decreasing rate during the primary stage of creep must be ascribed to the introduction of additional barriers to the glide of dislocations. During secondary creep the density of barriers must remain constant, the rate at which new barriers are formed being equal to the rate at which they recover. For this reason the nature of the barriers, and their rates of formation and recovery, are significant to a complete understanding of creep. It is proposed here to study the kinetics of the recovery of barriers to creep of high-purity polycrystalline aluminum in the climb range. The technique will consist of creeping a series of tensile specimens under a prescribed stress to given state following which the specimens will be recovered for various times and temperatures under approximately zero stress. The amount of recovery will be determined by comparing creep curves following the recovery. EXPERIMENTAL PROCEDURE The material used for this investigation was a 99.99 pct pure Al supplied by the Aluminum Co. of America in sheets of 0.001-in. thickness having an H-18 temper. The spectroscopic analysis of impurities gave Cu-0.004 wt pct, Fe-0.002 pct, Si-0.001 pct, others-0.000 pct. Creep specimens were machined with their tensile axes in the rolling direction of the sheets. Annealing in a molten potassium nitrate-potassium nitrite bath for 1 hr at 686K, followed by air-cooling, resulted in a grain diameter of from 0.22 to 0.27 mm. Creep machines were equipped with constant stress lever arms of the type suggested by Fullman, Carreker, and Fishher,' which maintained the applied stress to within 0.04 pct of the reported value of 950 psi. Creep strains were calculated from extensions over a 6-in. gage section to the nearest 3 X 10"5. The temperatures of testing, 540°, 573", 600°, and 611°K, were obtained by immersing the specimen and extensometer assembly in a molten KNO2-KNO3 bath. Temperatures during the periods of creeping could be maintained constant to within better than ± 1°K. Correlation of creep data at different temperatures of testing demanded the use of an appropriate temperature-compensated time 8. Previous investigations have shown that the creep of pure metals at temperatures above about 0.55 of their melting temperatures can be correlated by the functional relationship3" e=f(0), s= const. [1] where e = total plastic strain during creep f = a function that depends on stress a = stress 6 = te-Q/RT = a temperature-compensated time t = time under test Q = 35,500 cal per mol = activation energy for creep R = gas constant, and T = absolute temperature In the present series of tests all of the creep was conducted under the same stress of 950 psi. To provide identical initial conditions for the recovery all specimens were first crept to a temperature-compensated time of = 47 X 10-14 min which resulted in a creep strain of 0.055 + 0.005 regardless of the creep temperature. During recovery, a small stress (4.4 psi) was permitted to remain upon the specimens to maintain tautness in the pulling assembly and to prevent mechanical damage to the soft specimen. After each recovery period, the full stress was reapplied and

Jan 1, 1961

By Gregoire Gutzeit

THE development reported in this paper was begun by the author a number of years ago, while he was a lecturer on complex chemistry and metallurgy at the University of Geneva, Switzerland, and in charge of that institution's research laboratory. Completion of the development and reduction to practice did not occur until last year at the Westport mill, laboratories and testing plant of the Dorr Company, where this method is now in general use for identifying and localizing the mineral constituents of both metallic and nonmetallic ores. It has proved to be a practical tool of the metallurgical staff at the Westport mill, devising unusual milling flowsheets for complex and refractory ore bodies. In a number of instances the findings have been successfully used as fundamental factors in the design and specification of complete metallurgical plants. Seven examples of the use of this method in solving practical milling problems are included in this paper. GENERAL OUTLINE The microscopic study of an ore, at first only of scientific interest, has proved extremely useful both in practical geology and in ore dressing. The binocular magnifying lenses for rough observation of the products of an ore-dressing plant have been in use for a long time; but only within the last few years has a systematic microscopical examination of ore samples become a normal tool of any research laboratory dealing with ore-dressing problems. Such an investigation avoids considerable loss of time as well as empirical trials and useless experimentation. It will generally indicate the correct grinding and often will suggest the proper method of treatment. The petrographic determination of transparent minerals in thin sections, or even in grains, has been perfected, and very accurate methods have been devised to meet any requirement, such as Feodorof's rotating stage on the petrographic microscope. Almost all transparent minerals can be positively identified by their optical properties; i.e., isotropism, anisotropism, color, pleochroism, refractory index, cleavage, crystal form, birefringence, and others. The identification of opaque minerals is a much more difficult problem and can be done only by using polished specimens. Unfortunately, most of the valuable metallic ores, and even some of the nonmetallic ones, are not transparent; therefore it has been necessary to develop a special technique for the determination of these minerals. Some optical properties-for instance, isotropism, anisotropism, color, cleavage, reflecting power-are often adequate in roughly classifying the mineral. Only "reflecting power" is a measurable value, provided special photometric equipment (ocular photometer or Orcel's photoelectric cell) is available. The other optical properties mentioned are more or less relative,

Jan 1, 1942

By T. A. Rickard

Flaubert, as we know, laid stress on the selection of the right word, le mot juste, the precise epithet, the word that belongs to the thing. A sentence, or even a paragraph, may be spoiled by the use of a word that is not proper, that does not fit or is foreign to the meaning intended. An Australian mining expert is reported to have said: You have a property of considerable value, and what I saw warrants a good development of very rich cubicular galena, with gossan intermixed. 'Cubicular' means `belonging to a small bedroom', a `cubicle' being a sleeping compartment. He meant `cubic', of course. This is a malapropism, and reminds me of the lady from Chicago that, on her return from Europe, said how much she had enjoyed the rural parts of France, because, among other things, it was "so delightful to hear the French pheasants singing the mayonnaise to the tune of the Los Angelus". It is impossible to amalgamate coal-tar thoroughly with the pulp in the agitating-tank. In metallurgy, `amalgamate' refers to the combination of mercury with one or both of the precious metals, forming an amalgam, which is an alloy of mercury with another metal. It differs from other alloys, such as brass or bronze, in being made without the aid of heat, inasmuch as mercury is molten at the ordinary temperature. The word comes to us from the Greek. through Old French and means `something soft'. It is a mistake to use technical terms, having a specific meaning, for purposes that are foreign to that meaning. The writer of the quotation is not discussing any combination of metals; he is dealing with the physical process of mixing and is using 'amal-

Jan 1, 1931

By H. B. Pulsifier

THE following report on the structure of copper is the result of work done in the laboratory of the Rome Wire Co. early in 1925. Previous work had indicated to the author that excellent results might be expected if a suitable technique in surfacing and etching could be developed. The resources of the Rome Wire Co. enabled this metal to be studied more intensively than previously, although none of the materials were investigated exhaustively. The material presented is hardly more than a preliminary summary of the most obvious character of the metal; a much longer research would have been necessary to solve many of the pressing problems connected with the casting and working of copper. The Rome Wire Co. has generously released the paper; to Dr. E. H. Darby, technical supervisor of the company, are due particular thanks for his appreciation of the importance of metallographic study of copper and for his effective support in the prosecution of the work and in making its publication possible.

Jan 1, 1926

By A. R. Troiano, E. A. Steigerwald, F. W. Schaller

The initiation of localized cracking in hydrogenated high strength steel was dependent on the developmeni of a critical hydrogen conceniration and relatively insensitive to the magnitude of the applied stress. The stress was believed to influence the deluyed failure process by providing the means for grouping the hydrogen. On the basis of an assumed distribution law the observed changes in the lower critical stress as a function of notch acuity, yield strength, and temperature were predictable over a significant range of these variables. THE phenomenological characteristics of delayed failure in high-strength steel have been comprehensively investigated and the behavior has been attributed to the strong embrittling action of hydrogen.1-3 Delayed failure or, as it is also termed, static fatigue, is the most sensitive means of detecting hydrogen embrittlement since it allows the maximum time for hydrogen diffusion during a test.3 The nature of delayed failure cail be aptly described by four parameters which are schematically depicted in Fig. 1. The upper critical stress corresponds to the rupture stress in a conventional notch tensile test. The lower critical stress or static fatigue limit is the stress below which no delayed failure will occur. The incubation period is the time required for the formation of the first crack and the fourth parameter is the failure time. An increase in hydrogen content, notch acuity, or strength level of the material increases the susceptibility for delayed failure by decreasing the lower critical stress, the incubation period, and the time to failure.lY3 A decrease in test temperature prolongs the incubation period in accordance with the lower diffusion rate of hydrogen, and also de-

Jan 1, 1961

By J. Walter Snavely

PRESENT-DAY processing in many industries, calcining, sintering, briquetting, beneficiation and nodulizing, increasingly calls for the handling of large volumes of hot bulk materials. Various types of conveyors have been employed. This discussion will cover the factors governing their selection. For temperature ranges up to 400°F, or approximately 200 °C, a wide range of conveyors is available. Special constructions of rubber conveyor belts, steel conveyor belts, vibrating and shaker conveyors, apron conveyors, and drag chain conveyors, all are used successfully. As temperatures go well above 400 2F, however, choice of conveyors is narrowly limited. This paper will consider the problem of handling bulk materials only where the temperatures exceed 400°F. The arbitrary selection of 400 °F as a dividing point undoubtedly can be challenged, as special conveyor belting constructions are available which are suitable for temperatures in excess of 400°F. However, when the relatively short life of such belts and the cost of their replacement, with the attendant down time, are balanced against the reliability and long service life of the properly designed steel constructed units to be discussed, there is little question in any operator's mind that the special belts are more expensive to use. Because the conveyors under study are for the handling of bulk materials, inevitably including a high proportion of fines, obviously wire mesh belts cannot be included for consideration. Even though this type of conveyor is widely used at high temperatures, i.e., for carrying glassware through a lehr, it is unsuited for the conveying of bulk materials, and therefore will be excluded from further discussion in this paper. Preliminary to the study of the conveyor itself is the determination as to whether the material is to be cooled while it is being handled, or whether the processing requires retention of all heat and the maintenance of a given temperature range. In the majority of cases cooling is incidental to or part of the handling process, when the handling, for example, follows completion of sintering, roasting, calcining, refining, or some other process. To meet such operating conditions successfully, the conveying medium used must have: 1—a construction capable of withstanding maximum initial temperatures of the material being handled. 2—a construction providing efficient heat transfer for cooling. 3—a construction providing dependable operation and long life with minimum service requirements, and 4—a construction providing controlled and efficient conveying. Under the usual conditions of cooling during the handling, the construction selected to withstand the initial maximum temperatures does not necessarily involve using alloys, as excellent results can be achieved with normal carbon steels and cast irons, when they are properly applied and proportioned. The earliest and simplest type of conveyor for handling very hot materials is the cast steel drag chain conveyor, still widely used for handling hot cement clinker, as illustrated by Figs. I and 2. Because of the rugged and generous proportions of the chain link design, low carbon steels are entirely suitable for the links. The pins, however, must be alloy steel. The simple, rugged construction of this type of conveyor makes it readily capable of withstanding high initial temperatures, even though the chain is operating buried in the material. The drag-chain type of conveyor has advantages and limitations. Although the efficiency of the heat transfer is relatively poor, the life of the conveyor is reasonably long, and because of its crude simplicity it does not require much servicing. However, as a conveyor, it is limited in capacity, and largely limited to horizontal runs. Furthermore, because of the crude design, heavy weight, and the chain operating at the temperature of the material, greatly reducing permissible operating chain pulls, this type of conveyor is limited to relatively short centers. Another type of conveyor that has been used for very hot materials is the cast pan conveyor. Because of its very generous proportions the cast pan, which is made of either cast iron or malleable iron, can withstand initial maximum temperatures. It also provides efficient heat transfer for cooling. Further, it is on efficient conveyor construction, which can be used for inclines. Because the chain employs rolling friction instead of sliding friction, and is not in the maximum temperature zone, much longer centers are possible. It is this type of conveyor that is frequently used in the casting of various metal pigs, pig iron, and aluminum; it is obvious, therefore, that very high initial temperatures are being handled. With this kind of conveyor the return run is frequently sprayed with water to accelerate heat transfer. The build-up of residual heat in the very heavy cast pans is thus overcome. The outboard roller steel pan conveyor is an improved pan conveyor' which provides high rates of heat transfer and substitutes formed steel pans for the heavy cast pans. It is a very efficient conveying medium. The details of this particular construction are clearly shown in Fig. 3. An early application of this type of conveyor is shown in Fig. 4. In this case the conveyor units are handling roasted phosphate rock at average temperatures of 1000" to 1500°F, and frequent maximum temperatures as high as 1900°F. Several widths are used. The capacity of the unit at a speed of 50 fpm is approximately 30 tph per inch of width at peak loadings, average capacity being about 1/3 of peak loading. The assembled conveyor is shown in Fig. 5, with views of both the top and the underside to show all the construction details. In particular, the following general design principles were carried out in this construction:

Jan 1, 1954

By D. L. Passmore, J. D. Bennett

The degree of injury and days lost from work due to an injury are examined for selected electrical sources, occurring in conjunction with falls of the injured miner or with selected machinery, that could have been eliminated by use of diesel equipment. Although the number of preventable electrical source injuries is small relative to the total number of injuries during the period examined, many lost-time injuries could have been precluded and thousands of days lost from work could have been avoided.

Jan 1, 1986

By G. D. Cremer, J. J. Cordiano

ALUMINUM powder is a well-known article of commerce and in various forms has been marketed widely for use in paint, for pyrotechnic purposes and for exothermic mixtures. For a number of reasons, how- ever, aluminum powder has not been employed extensively in powder metallurgy, although a great many proposals along this line have been offered. Aluminum and aluminum-alloy powders oxidize readily upon exposure to air and the thin film of oxide (or hydroxide) thus formed is highly refractory, in that ordinary gaseous reducing agents such as hydrogen or carbon monoxide do not reduce the oxide to metal at temperatures below the melting point of aluminum. It has been thought that the presence of these films of oxide on aluminum particles would interfere markedly in powder metallurgical work and a number of suggestions have been made, either for preventing the formation of the film through the production of the powders in inert or reducing atmospheres, or for the removal of the oxide by means of powerful reducing agents, including "nascent" or atomic hydrogen released from metal hydrides. 4 second and more serious difficulty in the use of aluminum and aluminum-alloy powders in powder metallurgy resides in the fact that during compression such powders tend to adhere or cold-weld to the die walls, thus interfering with the formation and ejection of a compact. A third difficulty, which has been encountered only with aluminum-alloy powders, is their hardness when compared with elemental aluminum. Certain of these powders are susceptible to age- hardening, which further hinders the formation of strong green compacts. These conditions are particularly true of atomized aluminum-alloy powders. Even in the annealed condition, plastic deformation of alloy powders under pressure is low when compared with unalloyed powders. This fact, coupled with the lower corrosion resistance of the alloy powders, is probably the significant factor in our failure to obtain strong sintered pieces. METHODS OF PRODUCING THE POWER Many methods have been proposed for manufacture of aluminum powder, only a few of which are used commercially. Several of the more important processes include: (I) atomization of the molten metal; (2) mechanical pulverization and other types of comminution; and (3) graining, in which molten aluminum is stirred during freezing. For pigment and certain pyrotechnic uses aluminum flake powder is desirable, because of its greater proportion of surface to volume; and large quantities of such material are made by a procedure that involves stamping or ball milling. In making flake intended for use as pigment,

Jan 1, 1943

By Richard T. Newcomb

Federal and utility industry research has largely ignored coal beneficiation techniques in the implementation of SOx control. This paper accepts the hypothesis that beneficiation cum scrubbing is the cheapest way for the vast majority of seams in the eastern coal provinces to comply with standards. Comparisons are based on point estimates of average beneficiation costs from a model of coal preparation (COBET) designed to simulate four levels of cleaning. The paper describes how economic theory can be applied to derive econometric supply functions from actual data on the geology of minable seams, washability and technical constraints. West Virginia is taken as an example of a producing region. Spatial supply functions are derived empirically from the engineering model simulations.

Jan 1, 1977

By Edwin M. Chance

During the last decade many conditions have been encountered that have materially increased the cost of the production of coal. As in most cases it has not been practicable to increase the selling price of such coal sufficiently to insure the necessary margin of profit, the mine management has been forced to avail itself of what might be termed unusual means that costs might be held at as low a figure as possible. The so-called efficiency engineer has been called upon, costly power plants have been built and machinery has been installed to replace manual labor wherever possible. Another aid used recently to secure economies through the more intelligent production of coal, is the chemist. As the coal industry, barring the production of byproduct coke, does not at once give evidence of its need of the services of the chemist, the writer will endeavor to point out a few of the services that this branch of the staff has been able to render. The preparation of coal in the past has been carried on entirely upon an empirical basis, that is, the criterion adopted has been an ocular inspection. Unfortunately, the appearance of a coal and especially of an anthracite, has but little relation to its fuel value, and as long as coal is purchased for the heat that can be obtained from it by its combustion, the quantity of such heat that is purchased must be one of the principal desiderata in selecting or preparing a coal. Were coals purchased for use as bric-a-brac or for exhibition in museums it might be both wise and just to purchase them upon their appearance. After 4 or 5 years of investigation the fact has been established that coals of very inferior appearance, and I now have special reference to anthracite, might and often did possess heating and burning properties superior to those possessed by bright coals which in the past had commanded considerable and uniform premiums in the market. This being the case the question arose as to whether the trade could be convinced of this fact. While at first some difficulty was experienced in establishing the quality of such dull coals, still it was found that the real obstacle to the sale of these materials in the past had been the fact that the coal producers' own sales departments felt convinced of the inferiority of this type of fuel and when complaints were registered they were given ready credence. Upon convincing the sales department of the quality of this type of fuel, but

Jan 1, 1917

By George M. Fowler, F. E. Gregory, William M. Agar, Joseph P. Lyden

The fact that most of the zinc-lead ores of the Tri-State district are associated with abundant chert in the Boone formation has led us to give much consideration to the manner of occurrence of the chert throughout the formation and to its relationship to the structural and other geologic features having bearing upon the sulfide mineralization. Necessarily the question of the source and the manner of deposition of the chert has come up in the course of these studies. We do not pretend to have arrived at the answer to all the questions regarding the chert. However, we have made a very large number of field observations, which present certain facts about the chert in this district that may be worth elaboration. Whatever theories may be drawn upon to explain the presence and distribution of the chert must necessarily be capable of reconciliation to these facts. The more important theories that have been presented are briefly summarized, and some of them discussed, in this paper. This paper is in three distinct parts, each complete in itself, wherein is recorded the evidence gained from three separate methods of attack. In an earlier paper,(3)‡ we briefly described the chert and its relation-ship to the ore deposits. Chertification, as used in this paper, means the replacement of limestone by introduced silicic acid. It is a common phenomenon in many widely distributed limestones. The products of chertification may be chert, cotton rock, or tripoli, depending upon the extent to which the replacement has been carried. Chertification is used instead of silicifica-tion in order to reserve the latter for the siliceous emanations so common in connection with the sulfide ore deposits of this and many other districts. Broadly, it is meant to include all silicification in this district prior to the introduction of the jasperoid, the latter being contemporaneous with the ore-bearing solutions.

Jan 1, 1935

By William M. Agar, F. E. Gregory, Joseph P. Lyden, George M. Fowler

The fact that most of the zinc-lead ores of the Tri-State district are associated with abundant chert in the Boone formation has led us to give much consideration to the manner of occurrence of the chert throughout the formation and to its relationship to the structural and other geologic features having bearing upon the sulfide mineralization. Necessarily the question of the source and the manner of deposition of the chert has come up in the course of these studies. We do not pretend to have arrived at the answer to all the questions regarding the chert. However, we have made a very large number of field observations, which present certain facts about the chert in this district that may be worth elaboration. Whatever theories may be drawn upon to explain the presence and distribution of the chert must necessarily be capable of reconciliation to these facts. The more important theories that have been presented are briefly summarized, and some of them discussed, in this paper. This paper is in three distinct parts, each complete in itself, wherein is recorded the evidence gained from three separate methods of attack. In an earlier paper,(3)‡ we briefly described the chert and its relation-ship to the ore deposits. Chertification, as used in this paper, means the replacement of limestone by introduced silicic acid. It is a common phenomenon in many widely distributed limestones. The products of chertification may be chert, cotton rock, or tripoli, depending upon the extent to which the replacement has been carried. Chertification is used instead of silicifica-tion in order to reserve the latter for the siliceous emanations so common in connection with the sulfide ore deposits of this and many other districts. Broadly, it is meant to include all silicification in this district prior to the introduction of the jasperoid, the latter being contemporaneous with the ore-bearing solutions.

Jan 1, 1935

The fact that most of the zinc-lead ores of the Tri-State district are associated with abundant chert in the Boone formation has led us to give much consideration to the manner of occurrence of the chert throughout the formation and to its relationship to the structural and other geologic features having bearing upon the sulfide mineralization. Necessarily the question of the source and the manner of deposition of the chert has come up in the course of these studies. We do not pretend to have arrived at the answer to all the questions regarding the chert. However, we have made a very large number of field observations, which present certain facts about the chert in this district that may be worth elaboration. Whatever theories may be drawn upon to explain the presence and distribution of the chert must necessarily be capable of reconciliation to these facts. The more important theories that have been presented are briefly summarized, and some of them discussed, in this paper. This paper is in three distinct parts, each complete in itself, wherein is recorded the evidence gained from three separate methods of attack. In an earlier paper,(3)‡ we briefly described the chert and its relation-ship to the ore deposits. Chertification, as used in this paper, means the replacement of limestone by introduced silicic acid. It is a common phenomenon in many widely distributed limestones. The products of chertification may be chert, cotton rock, or tripoli, depending upon the extent to which the replacement has been carried. Chertification is used instead of silicifica-tion in order to reserve the latter for the siliceous emanations so common in connection with the sulfide ore deposits of this and many other districts. Broadly, it is meant to include all silicification in this district prior to the introduction of the jasperoid, the latter being contemporaneous with the ore-bearing solutions.

Jan 1, 1935

By F. E. Gregory, George M. Fowler, William M. Agar, Joseph P. Lyden

The fact that most of the zinc-lead ores of the Tri-State district are associated with abundant chert in the Boone formation has led us to give much consideration to the manner of occurrence of the chert throughout the formation and to its relationship to the structural and other geologic features having bearing upon the sulfide mineralization. Necessarily the question of the source and the manner of deposition of the chert has come up in the course of these studies. We do not pretend to have arrived at the answer to all the questions regarding the chert. However, we have made a very large number of field observations, which present certain facts about the chert in this district that may be worth elaboration. Whatever theories may be drawn upon to explain the presence and distribution of the chert must necessarily be capable of reconciliation to these facts. The more important theories that have been presented are briefly summarized, and some of them discussed, in this paper. This paper is in three distinct parts, each complete in itself, wherein is recorded the evidence gained from three separate methods of attack. In an earlier paper,(3)‡ we briefly described the chert and its relation-ship to the ore deposits. Chertification, as used in this paper, means the replacement of limestone by introduced silicic acid. It is a common phenomenon in many widely distributed limestones. The products of chertification may be chert, cotton rock, or tripoli, depending upon the extent to which the replacement has been carried. Chertification is used instead of silicifica-tion in order to reserve the latter for the siliceous emanations so common in connection with the sulfide ore deposits of this and many other districts. Broadly, it is meant to include all silicification in this district prior to the introduction of the jasperoid, the latter being contemporaneous with the ore-bearing solutions.

Jan 1, 1935

By Robert Glass Cleland

[NEW YORK OFFICE James Douglas President Chairman of Board Walter Douglas Vice-president President Louis S. Cates President Cleveland H. Dodge Vice-President Chairman of Board]

Jan 1, 1952

By P. Duwez, C. B. Jordan

The phenomenon of the change of volume of pressed powder compacts upon sintering is well known in the field of powder metallurgy. Depending upon the metal or metals involved and the pressure used in forming, a compact may, in the course of time of sintering at a given temperature, expand mono-tonically, contract monotonically, or first show a volume change of one sign followed by a change of the opposite sign. It is clearly desirable to have accurate knowledge of the magnitude and sign of the change in dimensions to be expected in any given case, both from the point of view of direct usefulness in the fabrication of parts by powder metallurgy, and from the longer range viewpoint of elucidating the fundamental mechanism of metallic sintering. The present study was therefore undertaken as a first step in acquiring systematic and reasonably quantitative knowledge of the change in density of metal powder compacts during sintering. For practical reasons, copper was selected as the material to be studied first, and its densification followed as a function of temperature and time of sintering in hydrogen and in vacuum. Experimental Procedure The copper powder used was that designated by the manufacturer (Metals Disintegrating Co., Elizabeth, N. J.) as MD-151. This powder was sifted through Tyler standard screens to separate the fraction having particle size range between 200 mesh and 325 mesh, and this fraction was used in all the subsequent work. Compacts weighing about 10 g were then pressed in a 1 in. diam round die, using a pressure of 20,000 psi throughout. Sintering was carried out in commercially built electric furnaces in which the resistance windings are so disposed as to produce a nearly uniform temperature along the axis of the furnace for a length of about 18 in. centrally located. In order to be able to sinter in a controlled atmosphere, a 2 in. stainless steel tubing was inserted in the furnace. Each end of the tube was cooled by a water jacket about 7 in. long, and closed with a rubber stopper. The hydrogen used for one series of specimens was purified as described in Ref. 1. For the other set, a pressure of about 0.5 mm Hg was maintained during sintering by a Welch Duo-Seal Pump. The specimens were heated on square trays made of stainless steel. In placing specimens in the trays, a thin even layer of powdered aluminum oxide was first sprinkled on the bottom of the tray. A copper guard disk about half the thickness of the specimen was then placed in the tray and covered with a second layer of alumina. The actual specimen was then set on the guard disk, and a final coat of alumina sprinkled over the specimen. This technique was evolved for sintering the specimens in such a way as to reduce the influence of unknown extraneous factors to a minimum. If the specimen is placed directly on the tray and sintered, it is found that the resulting shape is that of a frustum of a cone, rather than a section of a right circular cylinder, since friction with the tray prevents the bottom of the specimen from contracting at the same rate as the top. In the arrangement used in these experiments, the guard disk provided a support which shrank at the same rate as the specimen, and the alumina powder reduced to a minimum friction between guard disk and tray, and between specimen and guard disk. The procedure followed in sintering consisted of bringing the furnace to the required temperature, and then inserting the specimen into the central heated portion of the furnace tube in one of the two atmospheres used. At the end of the heating period, the specimen was cooled by bringing it into a portion of the furnace surrounded by a water jacket. These manipulations were carried out without opening the furnace, by means of rods which were attached to the trays and operated through a sliding seal in the rubber stopper. The progress of densification of the copper compacts was studied at 1300, 1400, 1500, 1600, 1700, and 1800°F. At each of these temperatures, a specimen was allowed to sinter for each of the following time intervals: M, 1, 2, 4, 8, 16, 32, and 64 hr. The thickness and diameter of each specimen were measured with micrometers before and after sintering, and each was weighed on an analytical balance after sintering. Results The techniques described in the preceding section were found to give satisfactory results. The specimens were not detectibly warped after sintering, and were usually of uniform diameter (that is, truly round) to within 0.001 in., a very few showing a variation in diameter of ±0.002 in. All specimens were found to have the same diameter

Jan 1, 1950

By K. K. Clark, W. H. Somerton

The feasibility of reducing pressures needed to fracture formations by heating the borehole intensively has been investigated on a laboratory scale. Reductions in fracture pressures of heated Bandera, Berea and Boise sandstone cores were observed at various confining pressures, simulating reservoir stress conditions to a depth of 5,000 ft. Both permeable and impermeable borehole boundary conditions were tested. Three heating conditions were used in the tests. One group of samples was heated in a furnace to a temperature of 600C, cooled to room temperature., and then tested for fracture pressures. Two other groups of samples were heated with a borehole heater to maximum borehole wall temperatures of 625 and 792C, then cooled and tested. In all cases, heated samples showed substantial reductions in fracture pressures compared to unheated samples. The higher temperature borehole heated samples showed the greatest reduction, amounting to 70 per cent in the extreme case. In actual application to wells, it was concluded that fracture pressures may be reduced by 20 to 50 per cent by intensive borehole heating before fracturing. INTRODUCTION Hydraulic fracturing of oil and gas wells is an accepted and effective technique for increasing well productivity in many areas, but is notoriously unsuccessful in other areas. The technique becomes less interesting for production stimulation purposes when excessive fracture pressures are necessary. Formations which do fracture but require high pressures, probably form horizontal fractures. There is good evidence to indicate that some formations do not fracture at all, but yield plastically under high pressure. Thus, any technique which will make formations easier to fracture or will reduce fracture pressures is potentially interesting to petroleum producers. Horizontal fractures generally occur in planes of weakness, such as bedding planes, and at pressures equaling or exceeding the effective overburden stress. In the unusual case where planes of weakness do not exist, a slightly higher pressure must be applied to overcome the tensile strength of the rock. In general, high fluid-loss fracturing fluids are conducive to the formation of horizontal fractures.1 Vertical fractures, when they do occur, are initiated at pressures generally lower than overburden pressure and are favored by low fluid-loss fracturing fluids or impermeable boreholes. The pressure necessary to create a vertical fracture in an impermeable, elastic medium can be predicted from the so-called "thick-walled cylinder" equation: Pf = 2 or+ st.............(1) where pf = fracture pressure or = radial stress st = tensile strength of medium. This equation indicates that to fracture it is necessary to overcome a tangential compressive stress, induced by and equal to two times the radial confining stress, plus the tensile strength of the medium. If the above equation held strictly true for rocks, very little could be done to reduce fracture pressure. The tensile strength of the rock might be reduced somewhat, but any change in st would be small compared to the magnitude of the tangential stress at reasonable subsurface depths. Laboratory tests have shown that actual fracture pressures exceed values predicted from Eq. 1 by factors of 1.4 to 28.6.1,2 Eq. 1 thus does not properly describe the

Jan 1, 1966

By J. W. Powell, F. H. Spedding

A complete review of the use of chelating agents in the sepa ration of rare earths by ion-exchange is given as well as a concise description of the recent pilot-plant operations of the Ames Laboratory. The two chelating agents which show the greatest promise are ethylenediamine-N,N,N',N'-tetraacetic acid and N'-(2-hydroxyethyl)ethylenediarnine-N,N,N '-triacetic acid. The first successful separations of rare earths by ion exchange were reported in a collection of papers which appeared in the November, 1947, issue of the Journal of the American Chemical Society.1'9 Some of this work was performed at the Ames Laboratory of the A.E.C., the remainder at the Oak Ridge National Laboratory. The processes developed at Oak Ridge, as well as some of the early Arnes methods, employed 5 pct citric acid-ammonium citrate eluant at low pH and were carried out on either H+-state or NH:-state resin beds. These techniques were successful for the separation of small quantities of either naturally occurring or radioactive rare earths and are still used for the isolation of rare-earth activities from fission products. Concentrated citrate is not economical, however, for use in moderate or large-scale rare-earth separations. For this reason, the Ames Laboratory turned its attention to lower concentrations and higher pH's in order to make more effective use of the eluting agent.10-14 Although elutions have been performed successfully over a wide range of conditions, 0.1 pct citrate at a pH of 8.0 is highly recommended for use on H+-state resin beds.15,16 Elu-tion with 0.1 pct citrate in the pH range from 5 to 9 brings about the separation of the constituent rare earths into a series of flat-topped elution bands which progress down the resin bed, head to tail, without actually pulling apart as do the rare-earth peaks which develop when trace quantities are eluted with 0.25M (5 pct) citrate at low pH's. Because of this, elution with 0.1 pct citrate at pH 8.0 do not produce pure rare earths unless sufficient quantities are present to provide developed bands which are at least several inches long on the columns. Although other eluting agents have proved more effective than citrate solutions, articles concerning the use of citric acid for separating rare earths still appear in the literature occasionally. For example, Ketelle and Boyd17 reported some further studies on the separation of rare earths with 5 pct citrate in 1951. They used 270 to 325 mesh Dowex-50 columns at 100°C and a pH of 3.28. vickery18 compared the effectiveness of a number of eluants for the separation of rare earths on NH+4 state Dowex-50 in 1952. He found that citric acid was more efficient than acetic, malic, tartaric, and aminoacetic acids. In 1953, Mayer and Freiling18 reported that citrate was inferior to malate, glycolate, lactate, and EDTA for the resolution of Sm-Eu and Y-Tb mixtures on 250 to 500 mesh, NH+4-state, Dowex-50 at 87°C. pinta20 used 5 pct citrate in the pH range 2.8 to 3.4 to obtain some rare earths for analytical work the same year. Trombe and Loriers21 reported the use of citric acid in their laboratory to separate rare earths in kilogram quantities. Lariers and Quesney22 reported some separations with citrate in 1954. They used 5 pct citrate at pH 2.8 to separate yttrium and the yttrium-group rare earths from the cerium-group rare earths. briers23 used 5 pct citrate at pH 3.2 and 90°C as late as 1956 to isolate thulium in fair purity. For the separation of tracer quantities of rare earths, Mayer and Freiling19 have recommended pH 5.00, 0.24M lactate at 87 °C on 250 to 500 mesh, NH+4-form Dowex-50. Freiling and Bunney24 have also employed lactic acid for the separation of fission-product rare earths. Cunninghame, Size-land, Willis, Eakins, and Mercer25 have reported a 4-hr separation of Y, Eu, Sm, Pm, Nd, and Pr with 1M lactic acid at pH 3.25 on Zeokarb-225 at 87°C. Stewart, et al.,26 reported separation factors for rare earths distributing between Dowex-50 and 0.25M glycolic acid. stewart27 also reported a 30-61 separation of Y, Tm, Er, Tb, and Lu tracers with buffered, 0.25M glycolic acid containing 0.05 pct Aerosol OT. The resin bed was 400-mesh Dowex-50 (X12). The pH of the ammonia-buffered eluant was 3.5. Various aminopolyacetic acids have also been used to obtain varying degrees of separation of the rare earths. In 1951, Fitch and Russell28 investigated iminodiacetic acid (IDA) and nitrilotriacetic

Jan 1, 1960

By J. W. Pugh, J. D. Nisbet

F. B. Foley—The use of data published by Wever and Jellinghaus in 1931 to fix boundaries of the sigma phase in the Fe-Cr system, in the face of the author's own references to the suggestions of Bradley and Goldschmidt, Aborn and Bain, and Hougardy that the phase is much more extensive, and the very much more accurate work, which weighs heavily in favor of these suggestions, of Cook and Jones, published in 1943 and evidently disregarded by the authors, makes their derived ternary diagram, especially fig. 15 for 400°C, quite inaccurate on the Fe-Cr side and affects the extent of phase boundaries in the most controversial and important part of this ternary system. In commercial Fe-Ni-Cr alloys the occurrence of sigma has been observed time and time again at lower chromium contents than that of the 24 pct Cr, 16 pct Ni, 60 pct Fe alloy which is the lowest permitted by fig. 15 of practically carbonless metal. Newel1 reports sigma in 27 pct Cr-Fe even with some carbon present to be one of the greatest detriments to its extensive application, whereas Pugh and Nisbet set a low limit of 36 pct Cr for sigma in the binary Fe-Cr system. J. J. Heger—The diagrams presented by the authors do not agree with observations made on commercial Fe-Cr and Fe-Cr-Ni alloys, nor do they agree with two recent investigations made on the Fe-Cr and the Fe-Cr-Fe systems. I refer first to the investigation made by Cook and Jones1' on the sigma region of the Fe-Cr system. On the basis of their results which were published in 1943, Cook and Jones established new boundary limits for the sigma and the alpha plus sigma regions. These new limits have been accepted and are incorporated in the Fe-Cr diagram that appears in the 1948 edition of the Metals Handbook. This diagram is shown here as fig. 34. As will be noted, the boundary limits of the alpha plus sigma region in this diagram extend to much lower chromium contents than do those in the diagram presented by the authors in fig. 2. These new limits indicate that sigma phase should form in an Fe-Cr alloy containing 26 pct Cr, and experience with commercial alloys confirms this finding. Indeed, recent studies on a commercial Fe-Cr alloy containing 17 pct Cr have shown sigma phase to be stable in this alloy at 550°C. I recognize that the authors' work did not include studies on the sigma region; however, I believe this is a serious omission because sigma phase may profoundly affect the physical properties of these alloys and should be evaluated in any investigation which attempts to relate physical properties to the equilibrium diagram. The second investigation to which I refer is that made on the Fe-Cr-Ni system by Rees, Burns, and Cook,'' who used pure alloys and employed heating 17 W. P. Rees, B. D. Burns, and A. 3. Cook: Journal Iron and Steel Institute. (July 1949) 162, Part 3. p. 325. times that extend to 200 days. These investigators published their results in July 1949 and from these results constructed isothermal sections at 800" and 650°C. The isothermal section at 650°C is shown here as fig. 35. This diagram indicates sigma phase should form in a pure 18 pct Cr-8 pct Ni alloy. Although sigma phase has not been observed after 10,000 hr at 1200°F in commercial 18-8 alloys containing carbon and nitrogen, it has been observed under the same conditions in 18-8 alloys modified with titanium and columbium, both of which serve to reduce the effect of carbon and nitrogen. This section and the one at 800°C suggest that the constant iron sections which are presented by the authors, should be considerably altered, if they are to represent an accurate picture of the system. A few of the suggested alterations are as follows: In fig. 9, the section at 50 pct Fe, the gamma plus sigma region should be widened, not narrowed at 800" and 650°C. In fig. 10, the section at 60 pct Fe, the gamma plus sigma region should be widened at 800° and 650°C. In fig. 11, the section at 70 pct Fe, an alpha plus sigma, an alpha plus gamma plus sigma, and a gamma plus sigma region should be added. In fig. 12, the section at 80 pct Fe, the alpha plus gamma region should be widened at 800°C. In fig. 13, the section at 90 pct Fe, the alpha plus gamma region should be widened at 650° and 800°C. Undoubtedly, the chief reason for the discrepancies between the authors' data and those of Rees, Burns, and Cook is that the authors did not employ long enough heating times to allow for transformation. In this connection, I wish to warn that transformations in these alloys, particularly transformations at temperatures below 800°C, are extremely sluggish and may require a year or more to approach completion. Therefore, unless extremely long heating times are employed or steps are taken to accelerate these transformations by such means as mechanical working, the results will not yield an accurate picture of the alloy system. Certainly, an accurate picture is needed for the development of better high-temperature materials. E. J. Dulis-The purpose of this work is not clear. If an improvement of the ternary equilibrium diagram of the Fe-Cr-Ni system was wanted, it seems logical that testing techniques superior to those previously used would be a prime requirement. To approach equilibrium in this system, long holding times are needed; a fact established long ago but apparently ignored by the present authors, who used the continuous heating and cooling tests in equilibrium studies. A publication on the same system by Bradley and Goldschmidt6 was criticized by Monypenny in a

Jan 1, 1951

By F. B. Plummer, R. B. Newcome

The practice of introducing acid into oil wells to increase production of oil and gas has been in use since 1894, when it was first used in the Pennsylvania oil fields30.‡ It is only since 1928 that it has been used to any extent in the Mid-Continent18. The process has proved successful in increasing production, at least temporarily, in depleted oil fields where the producing formation is highly calcareous and where water drive is not too pronounced. In the Zwolle field in Louisiana, where the producing horizon is a chalk, increases of 100 per cent have been recorded25. In north-central Texas, where the oil is produced from the Marble Falls limestone, equally pronounced increases have resulted3. The production also in some fields yielding oil from quartz sand cemented with calcitc has been benefited. The evidence of actual increase in total recovery of oil, however, has been questioned by some engineers18. It has been pointed out that the results of the treatment of a well in a now district, where the process has never been tried out, can never be predicted with certainty, since other factors besides percentage of calcareous content of the oil sand play a large part in determining the success of the method. Numerous articles have been published on acid treatment and on the effects of acid on limestone1-35, yet very little has been written concerning experimental work on the actual effect of acid on capillary pores and larger oil-coated voids of oil sands. This is due partly to difficulties in duplicating field conditions in a laboratory and partly to the fact that the process has been carried out largely by contracting companies that have been unwilling to publish details of their results for fear of loss of business to competitors. The authors, using equipment developed to measure the radial permeability of oil-sand cores2', have developed a method of investigating the results of acid treatment which has enabled them to test numerous cores and to study in some detail the action of acid on the different types of rocks, particularly fine-grained rocks.

Jan 1, 1936