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By W. E. Ruder

IT has been pointed out by Stead 1 that grains of considerable coarseness may be developed in steels containing from 3 to 5 per cent. of silicon, and in a previous paper 2 the present author has shown that under the proper conditions of annealing single grains having an area of 50 sq. cm. may be obtained. It is the purpose of this paper to discuss in more detail the conditions, promoting the growth of these grains, in the hope that the experiments described may throw some additional light upon the general problem of grain growth in metals. These silicon steels lend themselves particularly well to such experiments because of the ease with which the change in structure may be followed and because of the fact that the effect of the carbon present is largely obliterated by the high percentage of silicon. This forms a solid solution with the iron, which acts very much like a pure metal. This alloy has been found to have but one critical point, viz., Are. This point, determined by Roberts-Austen for Hadfield's 4 per cent. Si alloy, was found to lie at 703° C. Vigouroux3, in working with pure Fe-Si alloys, finds this point to rise from 750° C. for 0.5 per cent. Si to 860° for 6 per cent alloy, with a flat region in the curve from 3 to 4 per cent. Si. No accurate determination of this point has been undertaken by the present author, but it has been roughly determined to lie between 730° and 750°.

Jan 12, 1913

By Louis J. Demer, Paul A. Beck

As reported in a previous publication,1 isothermal grain growth in high purity aluminum and in an aluminum alloy with 2 pct magnesium can be adequately described by means of the empirical relation: [ ] or in some cases, by the simpler relation, [ ] Here, D is the average grain size after an annealing period t. The annealing period includes the time for complete recrystallization R, and the time for grain growth [to]. DA is the grain size as recrystallized, n is a parameter depending on the temperature and on the material. The effect of 2 pct magnesium in solid solution was to decrease D, and to increase R, A and n at a given temperature. The present work was undertaken in order to investigate the above listed effects of magnesium in solid solution, as functions of the magnesium content. The work also includes the study of certain anomalous effects observed in the recrystallization and grain growth of the 2 pct magnesium alloy at 350°C. EXPERIMENTAL PROCEDURE The method of producing the ingots used in this work was described in detail1 and need not be reproduced here. The materials used were high purity aluminum, furnished by the Aluminum Co. of America, of lot analysis shown in Table I and magnesium from a high purity distilled stock of magnesium crystals. [ ] Ingots were prepared for a series of binary aluminum-magnesium alloys of increasing alloy content. The numbers used to designate these ingots and their magnesium contents by chemical analysis are given in Table 2. [ ] The analyses showed no difference in composition between the top and the bottom of the ingots. Spectrographic analysis of the ingots for elements other than magnesium showed, within the limits of accuracy of the method, no increase in impurities over the amounts given in the lot analysis for the high purity aluminum in Table I. Careful microscopic study of ingot 21 in the as-cast condition, at magnifications up t0 1500X, revealed a cer-

Jan 1, 1948

By N. A. Stockett

SOUTHEAST Missouri is the largest and oldest lead-producing district in the United States. For the year 1941, the statistical picture of pig-lead production, stated in short tons (partly estimated by the Engineering and Mining Journal) is as follows. [Tons World production 2,000,000 United States production 460.000 Southeast Missouri production 242,000] The consumption of primary lead in the United States in 1941 was approximately 900,000 tons, or almost double the country's production. The largest previous year's consumption in the United States was 718,000 tons, in 1926. The largest quantities of lead are used for cable sheathing, storage batteries and white lead. During 1941 tetraethyl lead for auto and aviation gasoline consumed 50,000 tons of lead. The entire lead production of Southeast Missouri is now mined by the St. Joseph Lead Co., whose dominant position as the largest producer in the United States of lead directly from ores is best shown by the fact that in 1941 it produced approximately 31 per cent of the lead production of the United States from its mines in southeast Missouri, where 22,000 tons of ore, averag¬ing over 3.00 per cent lead, is mined per working day. It is known that lead was mined at Mine La Motte, Madison County, Missouri, by Renault in 1723. Other white men and Indians probably did some mining prior to that time. Since 1865, the recorded production to Jan. 1, 1942, shows that the St. Joseph Lead Co. and the various other companies that have operated in St. Francois County mined lead ore, which, after milling and smelting losses produced 5,00,000 short tons of pig lead. About 95 per cent of the present lead production of Southeast Missouri is mined in St. Francois County. The northern part of this area is 60 miles south of St. Louis. The remainder of the lead is obtained at Mine La Motte, about 25 miles southeast from the center of the producing area in St. Francois County. PROSPECTING In this district, most of the ore is discovered by surface and underground diamond drills and by prospect drilling underground with rock drills. Each 2-ft. length of the cuttings from these Jackhamer prospect holes is assayed for lead. These holes are marked and the records are entered on maps. It has been found that close drilling--100-ft. centers of holes, and sometimes less-is necessary in order to locate most of the smaller commercial ore bodies, many of which previously had been missed by drilling the areas with holes spaced 200-ft. centers or more.

Jan 1, 1943

By I. R. Kramer

The apparent activation energy, U, JOY plastic deformation of aluminium, copper, and gold single crystals and polycrystalline aluminum was found to he dependent upon surface condition. At low strains, the value for U for aluminum single crystals was 4200 cal per mole ; however, this value decreased to 920 cal per mole when the specimens were polished during the test at a rate of 50 X 10-5 win-1 The activated volume also was found to increase with the rate of metal removal. That the surface plays an important role in plastic-deformation processes has been adequately demonstrated.1-4 Of particular interest at this time are the observations4 that the creep rate of single crystals of fee metals is increased markedly when specimens are polished during the deformation process. These observations were interpreted in terms of a dislocation debris layer at the surface regions of the crystal. This layer, which appears to be a region containing a high concentration of dislocations or segments of dislocations, not only will impede the egress of dislocations on the primary slip system, but will also provide a barrier against which dislocations may pile up. By this means, a stress which opposes the motion of dislocations will be generated. It is considered that this stress must be taken into account in any theory which describes the plastic-deformation process. Although a detailed dislocation model cannot be given at this time, it may be stated that the stresses opposing the motion of dislocations arise from the dislocations in the debris layer, Ts, and ti due to the resistance to motion imposed by internal obstacles such as Lomer-Cottrell barriers, subgrain and grain boundaries, forest dislocations, and so forth, as well as the resistance due to the presence of jogs on dislocations and the interaction of the stress fields of dislocations, and so forth. In essence, we have added an additional term, ts, to the usual form of the equation T = Ta- Tb, where Tb is the back stress due to the various types of obstacles which impede the motion of dislocation. Accordingly, the net stress, t, acting on a dislocation may be written as where Ta is the applied shear stress. For deformation which occurs by a thermally activated process5,8 ?=Ae-u/kT = A e(u,-VT)/kT [2] and U = Uo- Vt PI where U = activation energy for plastic flow, y = shear strain rate, Uo = activated energy for plastic deformation in the absence of stress and depends upon the particular deformation process, V = activated volume, k = Boltzmann constant, T = temperature, OK, and A = frequency factor. From Eqs. [I] and [3], U = Uo- V(Ta - Ti - TS) [4] and it is seen that if Ts decreases, the activation energy, U, must decrease if V remains constant. However, as will be shown, V is a function of the surface conditions. In their work on aluminum, Lytton and coworkers7 reported that at low strains the activation energy was 3400 cal per mole and at high strains it was 28,000 cal per mole. The lower value was interpreted in terms of the energy necessary to overcome the Peierls force, while the higher value was associated with the energy necessary for dislocations to move by a cross-slip process. It will be shown that the lower activation energy is associated with the surface debris layer rather than with the Peierls force. EXPERIMENTAL PROCEDURE Single crystals having a nominal cross section of 1/8 in. and a 3-in. gage length were prepared by a modified Bridgman technique using a multiple-cavity graphite mold. The initial purity of the metals was 99.997, 99.999, and 99.999 pet for aluminum, copper, and gold, respectively. The orientation of the specimens is given in Fig. 1. The measurement of the activation energy as a

Jan 1, 1964

By Robert Adams

Secondary or scrap materials appear at all stages in the industrial process and in a bewildering variety of forms, grades, and values. It is useful to begin analyzing them by dividing the broad concept of "Secondary Supply" into three parts First, the concept must encompass the stock, or pool, of secondary materials. In the process of satisfying his wants, man produces desired products from the materials and natural resources found around him. As long as the rate of production is greater than the rate of obsolescence of a given product, the total stock or pool of materials embodied in that product will increase in size This stock concept relating to secondary materials is directly analogous to the "resource" concept used for primary raw materials in the preceding chapter, and includes all materials embodied in existing products (Obviously, this excludes those materials which are destroyed in the consumption process, viz , fuel oil burned to provide heat.) Consumption of a primary material in a productive process tends to reduce the resource base of that primary material In direct contrast, however, the production or use of products increases the resource base of the secondary material. Thus, we find that a country which has no resource of a primary material can, by importing products that contain the material, build up a large enough stock to provide a basis for secondary recovery. The estimated growth of the pool of copper in use in the United States through 1967 is shown in Table 5.B.1.a The estimate of 39 3 million tons at the end of 1967 includes only technologically recoverable copper and is, therefore, somewhat less than the stock concept described previously, which does not distinguish between recoverable and unrecoverable material. Nevertheless, Table 5 B.1 does give an idea of how a nation's secondary resource of a material can grow over the years. A second aspect of the concept of secondary supply is the generation of secondary materials. This includes materials generated as scrap in production as well as the movement of a material out of the stock of existing products via wear, damage, or obsolescence The quantity of materials generated is usually either nearly or completely independent of the technologic capabilities and economic forces which prevail in the secondary recovery market.b The justifications for and the qualifications to this statement are considered later. The final aspect of the concept of secondary supply consists in the secondary recovery process It is at this point that the technologic and economic forces of the secondary recovery market become the controlling fac-

Jan 1, 1976

J. M. Wadsworth,' Okmulgee, Okla. (written discussion).—It seems to me that thc young man must first be absolutely sure that the work he has taken up is to his liking and then I would advise that he get into the practical end of it and learn as much about it as he can as fast as he can. For instance, in the refinery business the college man, graduated in chemical engineering, should ground himself by going through the various departments in a refinery and working in them until he is thoroughly familiar with the operating problems. In a short time he would be able to apply many things which appear in the abstract form in his college work and this would opcn up an opportunity for him to capitalize on them, promoting his own interest. I do not criticize the present-day college men as a class, but I have found that many of them come into your plant with the idea that mere possession of a diploma should insure rapid promotion; in a short time they are impatient and usually leave. We have found in employing men that the single attribute most difficult to find in them is a lot of energy and whole-hearted interest in the work at hand, and it seems to me that if a man combines these with a careful technical training he should be fairly well equipped to gamble on his future. They must learn that the biggest satisfaction to be gained in life is in their work. Procedure for Attaining Objective of Young Petroleum Engineer H. B. Fell,+ Ardmore, Okla. (written discussion).—Of course, the first thing to be ronsidered in any proposition is the ultimate objective that is desired to be attained. 1 presume that the desired objective of most of the young men graduating in petroleum engineering will be that of chief executive of one of the companies in the petroleum industry, or one of the allied industries, or to become an independent oil producer, or oil refiner, or possibly an oil distributor. The next phase then to be considered is the procedure which should most logically be followed to attain the objeckive of the indivitlual, since in these cases these young men will have been trained in a course in petroleum engineering and it would logically be presumed that the attainment of their objective should be through the operating end of the branch of the business with which they are connected. The operating end is, of course, the department of each branch of the business that develops the resources, or refines the products, or distributes the products, from which the profits are derived, and is a part of any business which is filled with enough interesting work to appease the desires of the most ambitious young men. In order to get the best possible training it would appear to me that the place for a young man to start after graduation would be at the bottom of that branch of the industry which he expects to follow. For example, if he is going in the producing end he can gct no better training than is secured by starting as a roustabout in the ficltl, where he romes in constant rontact with the character of work that is necessary

Jan 1, 1928

By A. K. Mukherjee, J. E. Dorn

A modified Peierls model is Presented for the rationalization of the asymmetric plastic behavior of single crystals of bcc metals. The model assumes that the asymmetry of slip arises from a tendency toward asymnetric splitting of the a/2[111] screw dislocation. The approach differs from former theories however insofar as it assumes that the splitting is so minor ttut only the core energy is modified and that no real partial dislocations exist. As a consequence, the concepts of a line energy of a partial dislocation, interaction between partial dislocations, constriction energies, and stacking fault energies are not invoked. Instead the present analysis is based on a specialization of the Peierls mechanism which assumes an asymmetric dislocation core which is modified by the effective stress and permits cross slip. The theoretical predictions on the stress-temperature -strain rate and orientation relationship agree qualitatively with the limited experimental data that are currently available. Additional experimental work over wider ranges of conditions is suggested to provide more complete evaluation of the possible validity of this theory. RECENT experimental investigations on the low-temperature thermally activated deformation of bcc metals have confirmed the existence of several unique orientation effects. These will be described with the aid of the standard stereographic projection shown in Fig. 1. If slip were determined exclusively by crystal symmetry, the deformation characteristics would be symmetrical about X; = 0 and independent of whether the specimen were subjected to a tension or a compression stress, regardless of what combinations of slip planes might be operative. Experiments, however, reveal that neither of these symmetry based predictions are valid. A schematic representation of the commonly observed asymmetry of both the yield stress and the plane of slip is shown in Fig. 2. A reversal of the direction of stressing results in an inversion of the asvmmetric behavior. 1) Asymmetry bf Yielding. A detailed investigation on the asymmetric yielding in an Fe-2.7 pct Si alloy was repoEted by Tabka, Tikeuchi, and Furubayashi,1 Similar trends have been observed by Keh and Nakada on iron,' Stein on molybdenum,3 Bowen, Christian, and Taylor4 on columbium, Sherwood, Guiu, Kim, and pratt5 on Ta, Cb, and Mo. The degree of asymmetry not only depends on the atomic number and alloying but, in all cases that have been examined, it also increases with a decrease in the test temperature. 2) Asymmetry of the Slip Plane. Asymmetric $I-~: curves of the type shown in Fig. 2 have been found for several Fe-Si alloys6-8,1 and columbium.4 There is general agre_ement that near X: = 30 deg slip occurs by the [111](211) mode so that ?1 = 30 deg. As X; decreases it appears that [111](211) to [111](101) cross slip takes place leading to slip band traces on intermediate planes. And as xi approaches 0 deg, sharp

Jan 1, 1970

By A. U. Seybolt, J. L. Walter

The effects of the addition of 0.5 pct ThO2 (by volume) on the grain structure and texture of heavily rolled tungsten sheet were studied. Powder metallurgy ingots were rolled to sheet, 0.001 in. thick, and samples were annealed at temperatures from 1200" to 2500°C. The heating rate to the anneal temperature was varied from 3°C per min to 6500°C per min. The orientations of the largest grains were determined by X-ray diffraction. The disposition and loss of the ThO2 particles were determined by electron transmission microscopy and the activation energy for remozlal of the thorium was measured by mass spec-troscopy. Heating rates below about 800 C per min produced large, highly elongated grains. Higher heating rates produced much smaller, less elongated grains. The grain structure and texture of the slowly heated samples were identical to the structures and textures of heavily rolled tungsten foil conventionally doped with aluminum, silicon, and potassium but the recrystallization temperature was about 200°C lower. There was stringer-like dispersion of larger ThO2, particles superimposed on a uniform dispersion of fine particles. The particles increased in size and decreased in number with time at temperature. The loss of particles was accompanied by formation of grain boundary voids and surface pits. The activation energy for removal of the ThO2 was about 40 kcal per mole. THE addition of small amounts of aluminum, silicon, and potassium to tungsten has a profound effect on the grain structure of heavily rolled sheet1 or drawn wire."4 Thus, "doped" tungsten sheet, rolled to 0.001 in. and recrystallized, develops a structure consisting of large, highly elongated grains of a specific preferred orientation.' It has been shown that the elongated grain structure was caused by a dispersion of particles, identified as mullite (Al6si2O13),1,4 in strings parallel to the rolling direction in sheet or to the wire axis. Identical results were obtained for iron which was doped with glass and rolled to 99 pct reduction of thickness and recrystallized.5 Again, the glass particles were disposed in strings parallel to the rolling direction. The strings retarded boundary migration in the lateral direction but grain growth was able to proceed relatively unhindered along the direction parallel to the strings.1,5 In both the doped tungsten and the glass-doped iron, the particles were highly plastic during the high-temperature deformation. Since mullite melts at about 1800°C and the glass employed melts at about 810ºC, the particles were probably molten during the recrystallization anneals (above 1800°C for the doped tungsten and 850°C for the glass-doped iron). There are indications in the literature that particles not plastic at hot-working temperatures (up to about 1550°C for tungsten) may also impart elongated grain structures by primary recrystallization of worked alloys. Examples are dispersions of tantalum carbide in chromium,6 and ThO2 in nickel where elongation ratios of recrystallization grains of up to 20:l were obtained.7 Strings of ThO2 particles in W-ThO2 wire have been seen by Rieck.8 In view of the available evidence, it was of interest to extend the previous studies of doped tungsten and glass-doped iron to include W-ThO2 sheet materials. Of specific interest was the grain structure, preferred orientation, recrystallization temperature, and disposition of the thoria particles. EXPERIMENTAL PROCEDURE A) Material Preparation. About 380 g of blue tungsten oxide (approximate composition WO3) was wet with a sufficient amount of aqueous solution of Th(N03)4 to provide 0.5 vol pct ThO2. The wet mixture was stirred to distribute the doping material uniformly throughout the powder. Stirring was continued while the mixture was heated until it was completely dry. The dried, doped mixture was then reduced to tungsten powder by heating at 850°C for 2 hr in a stream of dry hydrogen. The doped tungsten powder was hydropressed in a rubber sack at pressures of 50,000 psi to produce an ingot approximately 2 cm diam by about 5 cm long. Next, the pressed cylinder was heated in hydrogen for 2 hr at 1350°C to render it strong enough for machining. The cylinder was machined to a square cross section of 1.6 by 1.6 cm with rounded corners. Finally, the bar was heated for 2 hr at 2150°C in hydrogen to provide a sufficiently dense mate rial to withstand the hot-rolling operation. Prior to rolling, the ingot was reduced in thickness by about 20 pct by forging at 1550°C. This served to increase the density of the material and to widen it slightly for better rolling characteristics. The forged ingot was then rolled at 1550°C to a reduction of 45 pct of thickness, following which the rolling temperature was reduced to 1300°C and the slab rolled, with several reheats, to 0.050 in. Further reduction was accomplished at 800°C in tungsten sheet packs to a total reduction of about 99.85 pct. B) Annealing Treatment and Observation of Structure. Small samples of the rolled foil were annealed in one of two ways. Some of the samples were suspended in a covered tungsten can and annealed at temperatures from 1200" to 2200°C for various times in vacuum of l0-7 to 10-6 mm Hg. The can was heated by induction and temperatures were determined by optical pyrometry

Jan 1, 1970

By A. G. McGregor

IN THE Southwest a number of large steel chimneys discharge the gases from the copper smelting furnaces. Some of these chimneys show no deterioration after twenty years, others show serious deterioration after tour years service. A steel stack 20 ft. 7 ½ in. (6.3 m.) in diameter by 279 ft. (85 m.) high, Fig. 1, used for roaster gases only at the Calumet & Arizona Mining Co.'s plant at Douglas, Ariz., was lined to the top of the bell, 40 ft. (12 m.) from the base, with common brick placed on end, lime and cement mortar being used. Above the bell, the stack was lined with 4 by 4 by 8 in. (10 by 10 by 20 cm.) building tile, placed on end, making a lining 4 in. thick. The tiles were supported on angle-iron rings, riveted to the inside of the chimney shell about 15 ft. apart. The chimney was put into use in the latter part of 1913. Four years later, considerable of the tile lining had fallen out of place and mixed with the flue dust at the bottom of the chimney. About a year later, several . flattened and distorted sheets were noticed about 70 ft. below the top. An investigation showed that the thickness of these distorted sheets, which was originally ¼ in., had been reduced one half. One year later, or six years after the chimney went into use, several holes, a square foot and smaller in area, appeared near the flat spots mentioned. Soon afterwards, when the chimney was shut down for repairs, it was found that most of the tile lining for 125 ft. from the top had fallen out and that the steel shell was badly corroded; but where the lining remained in place the shell was undamaged. Many of the tile which had fallen out of place had become soft or flaky and crumbling, others were as hard as when placed. An analysis of the hard and soft tile is shown on p. 2. These tile were of a fireclay mixture, and were used instead of common brick on account of lower cost. The steel forming the upper 125 ft. (38 m.) was replaced, and a 4 ¼ -in. (11-cm.) lining of firebrick was laid from the bell to the top of the chimney. The brick were placed on end, wedges and keys being used. After each 8-in. course was set, keyed, and wedged tight, thin mortar -water, sodium silicate, and finely ground silica-was worked into the joints. The brick are supported on angle-iron rings, every 15 ft., in the same way as the tile.

Jan 1, 1921

By G. R. M. Del Giudice, A. M. Sadler, Arthur F. Taggart, M. Hassialis

FLOTATION of sulphide minerals and native metals is no longer a practical difficulty. The underlying scientific principles of the method, although not explored in anything like complete detail, have been formulated with sufficient breadth so that the direction of attack on any specific case is clearly indicated. It has been known since the earliest days of flotation that certain of the nonsulphide nonmetal minerals-e.g., sulphur and graphite-would respond to flotation by oils as sulphides do; therefore they have been grouped with sulphides in many patents. But since the development of the chemical theory of collection, 1,2,3 this similarity in action has been one of the facts cited in disproof of the theory by opponents of the hypothesis. 4 5-1 Air levitationt of certain oxidized minerals, both metalliferoust and nonmetalliferous, and separation thereby from other oxidized minerals, is a recent development in practice, although the discovery of the method dates back 17 years .7 This paper presents evidence that the principles underlying the air levitation of the nonsulphide nonmetal minerals are the same as those utilized in the flotation of the sulphides and native metals. It will be apparent immediately to anyone with knowledge of mineral concentration that separation of air-levitated minerals in water from minerals not so levitated is a simple matter of water-gravity concentration, the separating device employed depending solely upon the size of the particles treated and the buoyancy differences effected by the levitation. The usual separating means employed are: (1) a flotation machine for fine, slimy and for well aerated granular material; (2) shaking tables for granular less aerated material. By using large quantities of oil, it is possible to form substantially air-free oil-bound masses or granules of nonsiliceous minerals and to

Jan 1, 1937

By John Norton

THE tremendous increase in the use of metals that have been prepared by the various cold-working processes during recent years has greatly stimulated the investigation of problems concerned with the fundamental nature of these processes. It has been observed in practice that different methods of bringing about the same dimension changes in a sample result in a rather wide range of properties. Cold working reduces the ductility of a metal, or what is perhaps more nearly correct, its "working capacity," and naturally the manufacturer wishes to produce an article that has as large a working capacity as possible, and to produce it with the smallest number of operations, It has also been known for some time that cold deformation produces a parallel alignment of the crystal grains of a metal, and that the type of this preferred orientation depends to some extent at least upon particular processes employed in the deformation. The present investigation has for its purpose the study of the relations between the various factors of a cold-working process and the preferred orientation of the metal crystals resulting from this deformation. The work is chiefly confined to a study of cold-drawn seamless tubing.

Jan 1, 1932

By J. F. Lewis

Much has been written on this great engineering work, principally from the civil engineer's stand-point. In presenting the subject to the Institute, it seems necessary to include something of geology as well as engineering. In this case, it is particularly the glacial and post-glacial periods with which we are concerned; for it has been clearly proved that the canal recently excavated has not for the first time opened the Des Plaines valley for drainage away from Lake Michigan, and that this valley, as well as the site of this city, is very closely connected with the processes and effects of the ice period. We have simply renewed a channel and a drainage direction which formerly existed. As the days of deep water-ways for commercial purposes are fast approaching, engineers may find the consideration of ancient topography and geologic changes highly useful. For what I may say on this subject I am greatly indebted to Mr. Ossian Guthrie, who has made an earnest study of glacial geology and labored especially to decipher the records of its history in this region. * Chicago is situated in the track of one of four great glacial ice-streams that swept down from the North: one moving due South from Marquette and entering the Illinois valley at Ottawa; one through the Lake Michigan valley, entering the Illinois valley near Lemont; one from Saginaw Bay diagonally across the States of Michigan and Iadiana, entering through

Jan 1, 1898

By Daniel R. Hull

In 1926 Gendersl reviewed the existing theories of this subject and stated his views in support of the gas-pressure theory. Again, in 1937, the subject was thoroughly reviewed by N. B. Vaughan3 and by Phillips and Brick,2 so that no résumé is called for here. The purpose of this paper is to describe certain observations made in the course of mill work, and to point out that they mostly tend to confirm the gas theory of Genders. Vapor Segregation There is, however, one type of inverse segregation that can be accounted for by considering the volatility of one of the constituents of an alloy. The most familiar case is ordinary brass, which is subject to a zinc enrichment of a few tenths of a per cent at the surface of a chill casting. This has been noted in 70-30 brass by Genders, and a typical example of it is given in Table 1, which represents a cylindrical billet 7 in. in diameter by 55 in. long. After lathe-turning 1/32 in. from the surface, the remaining distance to the center was sampled at six equally spaced intervals. the lead, which is essentially the same throughout, will be mentioned later. Consider a brass-mill mold, either round or rectangular in cross section, standing several feet high. It may require a minute or two for pouring. Before it is full, the metal in the lower end has partly solidified and contracted somewhat away from the mold. The initial shell of solidification follows not far behind the top of the column, even if the central portion is liquid for a long way down. There is, then, a space between metal and mold that is filled with zinc vapor. The vapor has no exit, because the liquid at the top of the rising column is not only in contact with the mold but keeps UP a fresh supply of zinc vapor, which has, perhaps, already begun to condense in the lower portion. The cycle is short. Within a minute or two after the mold is full the bar has cooled enough to condense all the zinc. Some of it may condense on the mold; it might be expected that most of it would condense there, but the mold at that time is well coated with a velvety carbon residue from the oil dressing, overlain by fluffy zinc oxide that commenced covering the inside of the mold as soon as pouring began. The clean skin of the freshly cast brass offers a preferred surface for condensation. Reabsorption is quick and inevitable. A simple experiment indicates that a surprisingly large quantity of zinc vapor is trapped in the space between mold and

Jan 1, 1941

By Daniel R. Hull

In 1926 Gendersl reviewed the existing theories of this subject and stated his views in support of the gas-pressure theory. Again, in 1937, the subject was thoroughly reviewed by N. B. Vaughan3 and by Phillips and Brick,2 so that no résumé is called for here. The purpose of this paper is to describe certain observations made in the course of mill work, and to point out that they mostly tend to confirm the gas theory of Genders. Vapor Segregation There is, however, one type of inverse segregation that can be accounted for by considering the volatility of one of the constituents of an alloy. The most familiar case is ordinary brass, which is subject to a zinc enrichment of a few tenths of a per cent at the surface of a chill casting. This has been noted in 70-30 brass by Genders, and a typical example of it is given in Table 1, which represents a cylindrical billet 7 in. in diameter by 55 in. long. After lathe-turning 1/32 in. from the surface, the remaining distance to the center was sampled at six equally spaced intervals. the lead, which is essentially the same throughout, will be mentioned later. Consider a brass-mill mold, either round or rectangular in cross section, standing several feet high. It may require a minute or two for pouring. Before it is full, the metal in the lower end has partly solidified and contracted somewhat away from the mold. The initial shell of solidification follows not far behind the top of the column, even if the central portion is liquid for a long way down. There is, then, a space between metal and mold that is filled with zinc vapor. The vapor has no exit, because the liquid at the top of the rising column is not only in contact with the mold but keeps UP a fresh supply of zinc vapor, which has, perhaps, already begun to condense in the lower portion. The cycle is short. Within a minute or two after the mold is full the bar has cooled enough to condense all the zinc. Some of it may condense on the mold; it might be expected that most of it would condense there, but the mold at that time is well coated with a velvety carbon residue from the oil dressing, overlain by fluffy zinc oxide that commenced covering the inside of the mold as soon as pouring began. The clean skin of the freshly cast brass offers a preferred surface for condensation. Reabsorption is quick and inevitable. A simple experiment indicates that a surprisingly large quantity of zinc vapor is trapped in the space between mold and

Jan 1, 1941

By W. C. Roberts-Austin

The subject with which the Council of the American Institute of Mining Engineers has entrusted me is one of much interest. It has been so admirably treated in America by Prof. Carl Barus* that I should have hesitated to deal with it had not the adoption of pyrometric methods in England recently occupied much attention, especially in relation to metallurgical industries and research. I shall endeavor to show what is the present state of our knowledge of practical pyrometry by briefly tracing the history of the efforts which have been made to measure high temperatures. This paper will, therefore, be limited to the consideration of those forms of appliance which have either marked distinct stages of advance, or have remained in use with more or less modification through a considerable range of time. The earliest pyrometers were essentially thermoscopes, and although their graduation presented great difficulties, their importance as affording a means for the measurement of high temperatures has been recognized for centuries. It would be difficult to illustrate this better than by a brief record of the testimony which has from time to time been offered by those who have had to apply the heat of furnaces in research or in industry, and it is mainly for the sake of the light incidentally thrown on the progress of both that the following historical notes are offered. In the eighth century, Geber, the chemist, wrote a treatise on furnaces, and showed that he was familiar with many and varied means of applying heat; but he points to the difficulties that are met with in conducting operations at high temperatures, which he attributed to inability to measure heat, his actual words being: " sed quoniam non est res ignis, quae mensuari possit." t

Jan 1, 1894

By Hugh M. Roberts

In the spring of 1915, then a 30-year old geologist in the employ of the E. J. Longyear Co., of Minneapolis, Minn., I accompanied prospectors to ex- amine outcrops of supposed nickel ore situated a mile or two in from the shore of a lake in the Kenora district of northwestern Ontario. The deposit proved to be bog iron ore containing traces of nickel. We were stormbound there for three days, a circumstance which gave rise to a tale that was told at our fire one night. It seems that Sandy and Jock, two prospectors, were crossing the bay of a large lake in a canoe. They were bucking headwinds; the waves grew higher. Jock called out from the stern, "Sandy, can ye na pray a little." Sandy pressed his knees a little closer into the bow and, between strokes of his paddle, sought for words, which came haltingly, "Save us this time . . . Oh Lord . . . and we promise . . ." when Jock, peering through the spray sang out, "I would na commit yourself, Sandy, I think I see lond ahead."

Jan 1, 1965

By Milton E. Wadsworth, John N. Ong, W. Martin Fassell

The temperature and oxygen concentration dependence on the reaction of sphalerite in oxygen at pressures from 6 to 640 mm Hg have been investigated in the temperature range 700° to 870°C. Sphalerite has been found to oxidize linearly over this entire temperature and pressure range. At higher rates, considerable self-heating was observed. The dependence of the oxidation rate on the oxygen concentration may be expressed by: Rate = k' where k' is the specific rate constant and 0 = K1[O2]/(1 + KI[O2]), where K1 is the equilibrium rate constant for the adsorption of oxygen on sphalerite. Values of the activation energy and the enthalpy of adsorption were found to be 60.3 and —59.6 kcal per mol, respectively. Data have been presented that indicate conditions under which either a sulphatizing or an oxidizing roast may be obtained. ROASTING processes have been employed in the metallurgy of a great number of basic metals in use today. Until recently, however, little attempt has been made to deduce the fundamental mechanism by which oxidation takes place. Structural changes upon oxidation have been investigated1 = and thorough work has been performed with regard to the reaction products and the thermodynamics of the oxidation reactions. The objective of this investigation was to determine the rate of oxidation of sphalerite and to apply the absolute reaction rate theory in the theoretilcal interpretation of the experimental results." "O Description of Apparatus The apparatus contains the following features: 1—a furnace with gas system, 2—an autographic weighing system, and 3—a temperature control system. Furnace With Gas System—The furnace was mounted by a yoke on each end and was free to travel up and down on steel guide rods, permitting the introduction and removal of samples from the apparatus with minimum difficulty. The furnace was heated by three sections of Kanthal wire wound externally on a zirconia tube and insulated with Fiber-frax. Pure gases or mixtures of gases were introduced into the lower end of the furnace through two flowmeters, a mixing chamber, and a gas-tight sparger, Fig. 1. The gaseous products of the reaction and the unused gases were prevented from escaping to the atmosphere by maintaining a small negative pressure on the system. This procedure permitted air from the outside to enter through the small an-nulus around the quartz suspension fiber and prevented the escape of the internal gases. Autographic Weighing System—The autographic weighing system consisted of an adapted gold balance, a photoelectric circuit, and a weight recorder, Fig. 2. The sample was suspended from one end of the balance beam by means of a platinum chain outside the furnace and a long thin quartz fiber on the inside of the furnace. On the other end of the balance beam, the necessary weights were added to counterbalance the sample. In addition, a calibrated chain was added to the balance which was linked directly to the weight recording unit. Control was effected by means of a photoelectric circuit." A parallel beam of light from a strong source was directed onto a small front-surfaced aluminum mirror mounted in the middle of the balance beam and then to a front-surfaced mirror mounted on the ceiling of the room. The beam was then reflected onto a front-surfaced right prism at a distance of 9 ft from the balance

Jan 1, 1957

By F. A. Schaufelberger

Early work on chemical precipitation of metals from metal salt solutions is reviewed. The chemistry and thermodynamics of precipitating copper, nickel, cobalt, and cadmium metals by reaction with hydrogen are discussed. Mechanisms of metal precipitation, nu-cleation, growth, and agglomeration are reviewed, as well as some solubility phenomena of cleation,gases and solids at elevated temperatures. Experimental data presented deal mainly with the reaction of copper sulfate solution with Hz. METAL can be recovered from a leach solution either indirectly by precipitation as a compound that is later reduced or directly by electrolysis, cementation, or chemical reduction, for example, with hydrogen. The widely used electrowinning processes suffer from the inefficiency of converting fuel to low voltage dc and from low current efficiency when complete recovery is attempted. With the batch hydrogen reduction methods outlined here, a unit of fuel converted to hydrogen in modern gas reform plants will make two to three times as much metal as can be obtained with electrolysis. With continuous hydrogen reduction, four to six times as much metal is obtained. Precipitation by reducing a metal salt solution with H, has been known for almost 100 years.' Commercial use of the process, however, awaited the research and development program initiated by Chemical Construction Corp. Within the last few years this program has brought about construction of commercial plants, listed on p. 701. Ideal hydrogen reduction will precipitate a pure metal from a solution obtained by commercial leaching methods at a rapid rate without excessive temperatures and pressures. The metal precipitate will be of desired size and density, less than a percent left in the vessel being deposited on the wetted parts. The present discussion will outline Chemical Construction Corp.'s early development program and will discuss the chemistry and mechanics of reducing copper, nickel, cobalt, and cadmium from solution by H2. Work on selective reduction of nickel from cobalt has been described earlier.2 The article is not concerned with precipitation of copper by disproportionation of cuprous solutions where yield is limited" to 50 pet.* It does not discuss use of gaseous reducing agents other than hydrogen, such as SCV which may lead to contamination with sulfur, or CO," which is considerably more expensive than hydrogen and produces a gaseous reaction product, CO2.† The article does not include use of other nongaseous reducing agents: which are far more expensive than CO. Also, notes on the history, engineering design, and performance of commercial plants have been given elsewhere." It will be shown that a pure metal can be precipitated by reduction with hydrogen from solutions obtained by commercial leaching methods when the solution cohposition is controlled and proper acidity, proper metal ion concentration through controlled complex formation and hydrolysis, and adequate agitation for suspension of metal and for transfer of reducing gas are maintained. Reasonable temperatures and pressures are used which are less excessive than those used by previous workers, although they are maintained at above equilibrium values because of process kinetics.' It has also been found necessary to induce nuclea-tion and to control growth and agglomeration in order to get a powder product of suitable physical properties. Review of the Literature Muller, Schlecht, and Schubardt of I. G. Farbenm claimed a successive reduction of silver, copper, nickel, cobalt, and zinc from ammoniacal solution by applying progressively higher temperatures and hydrogen pressures. Metals produced by this technique were not pure, since no attempt was made to adjust the solution composition between the different reductions. It is doubtful that the zinc product contained any metallic zinc. The major contribution to the literature" was made by the Ipatiews,12 who prepared platinum, iridium, copper, nickel, cobalt, lead, tin, arsenic. antimony, and bismuth at often extreme conditions, up to the critical temperature of water (373"C), at 1500 to 7500 psi, for as long as several days. Even cadmium and zinc were claimed to have been observed in trace quantities precipitated together with basic salts. In the early experiments solutions were not stirred. Extensive formation of oxides and basic salts occurred. probably long before sufficient hydrogen could be supplied in the unstirred liquid to decrease the metal concentration in solution by reduction. The importance of hydrogen pressure was

Jan 1, 1957

By C. Scala, F. Bernstein

General expressions are derived relating the streaming potential to the electrochemical potential of a permeable junction separating two electrolytic solutions. By the methods of irreversible thermodynamics, these potentials are related to the flux of mobile species arising from differences in pressure and chemical composition. The flux is conveniently expressed as a transference number, the equivalents of a mobile species transferred through the junction per faraday of electricity. At constant pressure, the flux equation gives the electrochemical potential across the permeable junction. The streaming potential across the junction is obtained by imposing the condition of constant chemical composition. The familiar expression for the borehole SP is shown to be a particular solution of the general flux equation. The derived exprersions were verified in experiments with seven shale samples. Both the theory and experimental data provide additional proof of the presence and magniturle of the streaming potential in shales. INTRODUCTION In the interpretation of electric logs, there has been much concern over the correction to be made to the recorded SP for an electrokinetic or streaming potential originating from the difference in pressure between the mud column and the formation. It was long recognized by M. R. J. Wyllie that such an electrokinetic potential source mas in the mud cake opposite permeable sands.' More recently, M. Gondouin and C. Scala2 showed an additional but opposing electrokinetic source of potential to be in shale beds. Their work was supported by the very extensive and excellent work of Hill and Anderson.3 n the present contribution, the general relationships between the electrochemical potential and the corresponding streaming or electrokinetic potential are examined and clarified. A notable advance towards understanding the relation between the various sources of electrical potential in a borehole has been the application of the now common methods of irreversible thermodynamics to describe the passage of ions and water through charged electrolyte junctions such as in shales.' The advantages of these methods are twofold. Unlike classical thermodynamics, they can be applied to non-equilibrium sys- tems, i.e., systems in which flow takes place, provided the flow processes have reached a steady state. They also permit conventional thermodynamic properties to be related to the steady-state dynamic properties. These methods arc used here specifically to derive expressions relating the potential behavior of shales in terms of ion and water transport. Experimental verification of the expression for the shale streaming potential is given which in turn offers theoretical support to the existence of a streaming potential in shales.' Importantly, the relative contribution of transport parameters to the SP is clarified. The theoretical treatment is essentially that of Lori-mer, Boterenbrood and Hermans3 ut has been extended to derive the general expression for the SP.

By J. L. Bruce, N. B. Braly, F. A. Linforth, Wm. B. Daly, Paul A. Gow, C. L. Berrien, R. H. Sales, P. F. Beaudin, John Gillie, G. W. Roddewig

Butte mining district is situated in Silver Bow County, in the southwestern part of Montana. Butte originated as a placer mining camp, gold having been discovered in 1864, on Silver Bow Creek, near the southerly end of what is now Main Street. The Butte placer gold was heavily alloyed with silver, and only commanded $13 an ounce. Placer mining was vigorously prosecuted along Silver Bow Creek and its tributary gulches for about 5 years, at the end of which time, in 1870, the Butte camp was practically deserted. In the meantime, the quartz veins prominently traceable over the hillsides were located, the first location, July 12, 1864, being made by the Missoula Mining Co. and called the Missoula Lode Claim, and later relocated by G. 0. Humphreys. Reasoning from the presence of the gold placers, free milling gold and silver ores were eagerly looked for by the early prospectors. Claims covering the great Rainbow and other silver lodes were located in the 60's. The presence of valuable silver ores in these veins caused the staking of many claims, believed to be valuable only for silver, but which later, at depth, proved to be enormous copper producers.

Jan 1, 1925