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By E. O. Lilge, H. Siebert

A design of a multiple-bomb leaching unit particularly suited for the study of heterogeneous reactions, i.e. sol id-liquid-gas interfaces at high temperatures and pressures is presented. The component parts and overall design are described and illustrated in detail. The system has been tested by a limited number of experiments and found to work satisfactorily. Heterogeneous reactions at solid-liquid-gas interfaces, at high temperatures and pressures, are studied in either autoclaves1'4 or bombs5'9. Autoclaves are usually fairly large vessels which have a stirring arrangement incorporated in the design. Mechanical design limits the use of these vessels to relatively low temperatures and pressures. They are particularly well suited to rate or kinetic studies. Bombs can be designed to be operated at high temperatures and pressures, and are smaller vessels; because of this, stirring arrangements are not easily incorporated. In this paper a multiple-bomb system is described, that has been designed to incorporate the desirable features of both the autoclave and the bomb. The described unit has flexibility for an over all study of leaching. Most of the component units in this assemblage are standard equipment, designed and produced by well known manufacturers. No claim is made to the design of this equipment, and although described in some detail, this is done merely for clarity in the elucidation of the system presented. The general layout of the multiple-bomb assemblage is shown in Fig. 1A and 1B. The basic units in this system are: 1) 6 stainless steel 100 ml bombs (Fig. 4)

Jan 1, 1964

By B. Russell, J. R. Tuffley

The stability regions of the normal sulfate and the various basic sulfates of lead in 02-SO2 and PhS-SO2 gas atmospheres were calculated from available thermodynamic data over the temperature range 600o to 1200oC. Roasting experiments were carried out on samples of synthetic lead sulfide at various temperatures and for various roasting times. Compounds in the oxidized surface layers were identified by X-my techniques. The order in which the various reactions occurred was determined by considering the experimental results in conjunction with the thermodynamic calculations. The results of these investigations were applied to the sintering of lead sulfide concentrates, and the extent to which each of the various reactions occurred in a sinter bed was determined. PRODUCTS which may be formed during the roasting of PbS are PbS04, PbSO4. PbO, PbSO4 . 2PbO, PbSO4 . 4PbO, PbO, and Pb.1, 2 The formation of some sulfates has been studied by a number of investigators3-' whose experiments have mostly been confined to the temperature range between 500" and 850°C. Culver, Gray, and spooner3 were able to isolate the reactions which formed PbSO4 and PbSO4. PbO by carefully controlling the compositions of the roasting gases. The kinetics of these reactions were studied within the temperature range 673" to 807°C. Gardner4 and Merrick5 also studied the kinetics of oxidation of PbS. Gardner disregarded the existence of basic sulfates and, as a result, misinterpreted some of his experimental data. Merrick recognized that most of the products of oxidation were mixtures of basic sulfates, but was unable to identify the individual components. Hoschek6 oxidized PbS in air at temperatures up to 800°C. The products were analyzed after roasting had proceeded for some minutes, but no attempt was made to follow the reactions in the initial stages. Consequently, no roasting mechanism was derived. He also showed that PbSO4 and PbSO4 - 4PbO decomposed slowly in air at temperatures in the region of 800°C. The stability regions of sulfates in the temperature range 500" to 850°C have been only partially determined, while practically no information is available for higher temperatures. In the lead sintering process, PbS concentrates are roasted at temperatures within the range 1000o to 1200°C. In order to investigate sulfate formation, it is necessary to determine the effects of temperature and gas composition upon the various oxidation reactions and upon the regions of stability of the various lead sulfates. Kellogg and Basu2 introduced an equilibrium diagram similar to those in Figs. 1 to 3 which provides a convenient medium for represent-

Jan 1, 1964

By Fred C. Bond

THEM is acute need for a method that will measure the size distribution of finely divided materials, particularly when the particle sizes are smaller than the openings of the finest screen cloth regularly available for testing. Several methods and types of apparatus are in common use, but none are entirely satisfactory for all purposes. The commonest methods are microscopic grain counts, elutriation by liquids or air, and sedimentation. Valuable results have been secured by air elutriating devices, typified by the Haultain Infra-Sizer and the Pearson Air Analyzer. These are especially useful in obtaining sized fractions that can be examined and analyzed separately. They are particularly advantageous because the sizes of the samples produced are adequate for a considerable amount of subsequent manipulation and testing. The sedimentation methods, such as the Wagner and Klein turbidimeters, and the sedimentation balance, do not deliver sized fractions, but they do provide a means for reasonably rapid comparative determinations of fineness and surface area, which are important in many industries. The sedimentation balance consists essentially of a balance pan suspended in a liquid that contains falling particles. These are weighed as they settle onto the pan, and the time rate of settling is determined. The size distribution is computed from the settling rate. The balance appears to be inherently more accurate than any of the other methods, and it has served a useful purpose in the study of numerous problems, but there have been limitations which have restricted its scope of application. Because of the essential simplicity of the method, it was felt that intensive investigation might lead to modifications that would make it a valuable tool for the operators in industries that require precise information regarding the results secured from grinding equipment. A large number of size-distribution determinations below 200 mesh were required in connection with a particular research problem in fine grinding. The sedimentation balance was used in this investigation, and a technique was gradually developed that ultimately gave good results. A serious difficulty appeared early in the work. It was discovered that less material always settled on the sedimentation pan and more on the bottom of the containing jar than could be accounted for by calculation, and also that the material that settled to the bottom of the jar outside the edges of the pan was considerably finer than that on the pan. This segregation was so great that the distribution obtained for the finer sizes was obviously very much in error; material ground to about the degree of comminution of cement might have only 60 per cent of the calculated weight actually settling on the pan, and the error increased with the fine-

Jan 1, 1939

By Albert Sauveur

Jan 1, 1924

By Albert Sauveur

Jan 1, 1924

By F. Peter

I. GENERAL INTRODUCTION. TECHNICAL progress takes place in two directions: the improvement of methods, affecting the quality of the product; and increase in the economy of operations, affecting its cost. In the iron-industry, practice is pretty well settled, and. revolutionary changes of method are, for the present, not to be expected. Hence, in this industry, the principal endeavor is to reduce costs by the use of labor-saving inventions, such as the machines brought into use during the last decade. But it is not alone necessary to reduce the labor-cost; complete economy requires also a saving in raw material. Under this head we may rank the coal employed as metallurgical fuel; and it follows that progress includes the economic use of fuel, so managed as not to injure quality of product. In the present paper it will be shown how, by suitable utilization of the heat from the furnace, a large portion of it may be made available for other purposes. Such utilization of waste-gases is important in all industries which employ furnaces (especially heating- and smelting-furnaces); and in the first rank of these stand the iron-, glass-, and porcelain-manufactures. The following pages are devoted chiefly to the waste-gases of smelting-works, and especially to those reverberatory-furnace gases which are not combustible.'

Jan 12, 1913

By G. R. Gohn, S. M. Arnold

The results of stress-corrosion tests upon several non-ferrous sheet metals are presented in this paper. The metals include tough pitch copper, five binary brasses, two leaded brasses, one copper-silicon alloy, two tin bronzes, and two nickel-silver alloys. The tests indicate that for most of these sheet metals, externally applied bending stresses below the yield point (0.01 per cent offset) do not result in stress-corrosion cracking as determined by the A.S.T.M. Tentative Method of Mercurous Nitrate Test for Copper and Copper Alloys (B 154-41T).~ Only in the cases of low brass, high brass and medium leaded brass, all cold-worked 4 B & S numbers hard, was any corrosion cracking observed below the yield strength, and in all cases such failures occurred at stresses above the proportional limit for these materials. However, when some of the same materials which showed no evidence of stress-corrosion cracking at stresses below the yield strength, are stressed beyond the yield point, stress- corrosion cracking is quite apt to occur. Since experience has shown that some of these materials, particularly the brasses, are susceptible to stress-corrosion cracking under service conditions, these tests would indicate that, besides externally applied stress and corrosion, plastic deformation in addition to that resulting from the original cold working of the material is also required to produce conditions conducive to stress- corrosion cracking.

Jan 1, 1945

By David R. Mitchell, B. M. Bird

DENSE-MEDIA processes utilize the familiar laboratory float-and-sink procedure on a commercial scale. Just as wood chips float on water and sand sinks, so coal floats and refuse sinks when placed in a medium intermediate in specific gravity between the coal and refuse. Liquids intermediate in specific gravity between coal and refuse used in commercial plants are of four types: (1) organic liquids of high specific gravity-halogenated hydrocarbons; (2) dissolved salts in water; (3) pseudo liquids obtained by suspending solids, such as sand or magnetite, in water, and, (4) fluidizing a mass of sand or other solids by air currents. Those most widely used for cleaning coal are solutions of calcium chloride in water and a suspended sand or magnetite pseudo liquid. Laboratory float-and-sink testing is an intermittent operation during which every opportunity is given for particles lighter than the medium to float and particles heavier to sink. Commercial processes are continuous; vertical and horizontal currents of the separating medium occur as either part of the process or unavoidedly produced by the introduction of feed and withdrawal of products, 'so that the exact separation of the laboratory technique is not duplicated by commercial processes. However, separations close to the theoretical are obtained in commercial machines by careful technical control of the process. Most machines in commercial installations are crowded to get as much out of the equipment as possible, so that careful technical control is necessary is get the recoveries and grade of product desired. Sizes usually cleaned are plus ¼ in. or plus 1/8 -in. in the United States and plus 1/16-in. in Great Britain. Coal as small as 1 mm. has been cleaned in some experimental installations. The separation of coal from refuse in sizes finer than about 1/8-in. is made difficult by viscosity effects and hence at the present time cleaning is confined to the coarser sizes. Technical advances in the art of cleaning coal by dense-media processes is progressing rapidly and it is likely that equipment, media, and procedures will be developed to clean sizes down to 0.5 mm. efficiently and at low cost.

Jan 1, 1950

By Leslie F. Tedsen, John E. Dorn, Alan E. Flanigan

It is necessary occasionally to use aluminum-alloy sheet where moderately elevated temperatures are encountered. Considerable attention has been directed toward determining the influence of "artificial aging" on the room-temperature properties of the precipitation-hardenable alloys, as testified by numerous company reports and by references I to 4. Investigations on the properties at elevated temperatures are few, however, and have not always covered the range of times and temperatures of greatest interest. The present investigation was instituted to overcome this deficiency. The work was done for the Office of Production Research and Development of the War Production Board, under the supervision of the War Metallurgy Committee, as a part of the "restricted" Project NRC-548. It has been released for publication by the Office of Production Research and Development. AS is well known, the high-strength aluminum alloys achieve their remarkable properties as a result of precipitation-hardening. In production they are subjected to a solution heat-treatment followed by quenching, to retain the supersaturated solid solution. The solution treatment is followed by "aging" (precipitation-hard- ening) either at room temperature or at a suitable elevated temperature. A considerable increase in tensile and compressive yield stresses results from precipitation at room temperature ("natural aging"). Through the elevated-temperature process ("artificial aging") it is possible to obtain values of yield stress considerably higher than those attainable by natural aging. The increase in yield stress is accompanied by a smaller gain in ultimate tensile stress and by a decrease in elongation. During the first stages of artificial aging the yield stress increases steadily until it reaches a maximum value. In this condition the material is said to be "fully aged." Further exposure results in "averaging," attended by a steady decrease in yield stress. In the production of the artificially aged materials, temperatures and times are selected to achieve full aging. The following important characteristics are associated with the process: 1. The higher the temperature, the more rapidly is the fully aged condition attained. :7

Jan 1, 1946

By Leslie F. Tedsen, Alan E. Flanigan, John E. Dorn

It is necessary occasionally to use aluminum-alloy sheet where moderately elevated temperatures are encountered. Considerable attention has been directed toward determining the influence of "artificial aging" on the room-temperature properties of the precipitation-hardenable alloys, as testified by numerous company reports and by references I to 4. Investigations on the properties at elevated temperatures are few, however, and have not always covered the range of times and temperatures of greatest interest. The present investigation was instituted to overcome this deficiency. The work was done for the Office of Production Research and Development of the War Production Board, under the supervision of the War Metallurgy Committee, as a part of the "restricted" Project NRC-548. It has been released for publication by the Office of Production Research and Development. AS is well known, the high-strength aluminum alloys achieve their remarkable properties as a result of precipitation-hardening. In production they are subjected to a solution heat-treatment followed by quenching, to retain the supersaturated solid solution. The solution treatment is followed by "aging" (precipitation-hard- ening) either at room temperature or at a suitable elevated temperature. A considerable increase in tensile and compressive yield stresses results from precipitation at room temperature ("natural aging"). Through the elevated-temperature process ("artificial aging") it is possible to obtain values of yield stress considerably higher than those attainable by natural aging. The increase in yield stress is accompanied by a smaller gain in ultimate tensile stress and by a decrease in elongation. During the first stages of artificial aging the yield stress increases steadily until it reaches a maximum value. In this condition the material is said to be "fully aged." Further exposure results in "averaging," attended by a steady decrease in yield stress. In the production of the artificially aged materials, temperatures and times are selected to achieve full aging. The following important characteristics are associated with the process: 1. The higher the temperature, the more rapidly is the fully aged condition attained. :7

Jan 1, 1946

By T. Egleston

The necessity of using a refractory material capable of much greater resistance to chemical action and having a far higher melting-point than those which contain silica, which melt and sweat off in the furnace even when not exposed to bases forming with silica more or less fusible compounds, has led to a careful practical study of all those materials which contain very refractory bases. The results of these researches, extending over several years, and made on a very large scale in many of the largest works in Europe, are of the highest interest, not only considered as a step in the progress of the study of the materials themselves, but in the application of refractory materials to metallurgical uses in general. The result of the experience of the last seven years with these basic materials, as in general with all such substanccs, is that natural products cannot be used as such. They are either too uncertain in their quality, contain substances which may in certain cases be very injurious, or, when in a condition in which they might be used, are so rare as to become practically unavailable for employment on a large scale. The materials that may he used are therefore not only limited in number. but they must be prepared artificially. When the use of basic artificial material is further extended, no doubt the number of these substances will not only be greatly increased, but the methods of preparation will be both perfected and cheapened to such an extent as to permit their application in processes for which they have hitherto proved too expensive. The quantity of refractory materials required for making ingots will he from 130 to 150 Ibs. per ton, or between 6 and 8 per cent. of the metal produced. In an establishment producing 2000 to 3000 tons of steel per week, considerable space is required to handle the basic materials properly. It is proposed in this paper to briefly discuss these basic materials and their application in the only two metallurgical processes where they have as yet been applied. These are the basic Bessemer and the basic open-hearth process, known as the Thomas-Gilchrist processes.

Jan 1, 1886

By E. R. Parker, D. L. Martin

In a previous paper one of the authors observed that the rate of cooling from the anneal prior to testing greatly influenced the life of copper under sustained load at 200°C. Furnace-cooled bars of oxygen-free copper (with and without silver) had a life four to twenty-five times that of the water-quenched specimens. The addition of 0.054 per cent silver to the oxygen-free copper increased the life at a stress of 20,000 lb. per sq. in. from about 2 hr. to 50 hr. Fractures in these bars were intercrystalline. An explanation was advanced to account for the profound influence of cooling rate on the rupture properties at 200°C. The suggestion offered was that at the high annealing temperature the minor constituents are distributed at random. By water quenching, this condition is maintained at room temperature, whereas furnace cooling permits some segregation at the grain boundaries. The higher concentration of the minor constituents in the grain boundaries results in a. strengthening, so that a longer life at a given stress and .temperature results. Small amounts of cadmium or manganese have also been found to increase the life of copper at 200°C., and to a much greater extent than silver.2 The increase in the long-time strength of copper resulting from small additions of cadmium or silver appears to be related, indirectly at least, to the higher softening temperatures of such alloys. The elements, such as silver or cadmium, which greatly increase the rupture life of copper also cause large increases in the softening temperature. As little as 0.05 per cent of cadmium or silver is sufficient to raise the softening temperature more than 100°.3,4 The effects of cooling rate and of minor constituents on the rupture properties are of considerable fundamental as well as practical interest; therefore a more detailed study of their nature was conducted and is reported in this paper. Experimental Procedure Materials The materials studied in this investigation may conveniently be classified in two groups: one consisting of a wide variety of commercial coppers, and the other composed of special high-purity, laboratory-prepared coppers. The commercial materials were tested to determine whether or not the effect of cooling rate occurred with all coppers, whereas the high-purity coppers were investigated in order to establish a basis for evaluating the effect of minor constituents on the rupture properties. In Table I are given the analyses of the coppers tested. The samples I to 6 are commercial materials and were obtained for the most part from stock supplies.*

Jan 1, 1944

By D. L. Martin, E. R. Parker

In a previous paper one of the authors observed that the rate of cooling from the anneal prior to testing greatly influenced the life of copper under sustained load at 200°C. Furnace-cooled bars of oxygen-free copper (with and without silver) had a life four to twenty-five times that of the water-quenched specimens. The addition of 0.054 per cent silver to the oxygen-free copper increased the life at a stress of 20,000 lb. per sq. in. from about 2 hr. to 50 hr. Fractures in these bars were intercrystalline. An explanation was advanced to account for the profound influence of cooling rate on the rupture properties at 200°C. The suggestion offered was that at the high annealing temperature the minor constituents are distributed at random. By water quenching, this condition is maintained at room temperature, whereas furnace cooling permits some segregation at the grain boundaries. The higher concentration of the minor constituents in the grain boundaries results in a. strengthening, so that a longer life at a given stress and .temperature results. Small amounts of cadmium or manganese have also been found to increase the life of copper at 200°C., and to a much greater extent than silver.2 The increase in the long-time strength of copper resulting from small additions of cadmium or silver appears to be related, indirectly at least, to the higher softening temperatures of such alloys. The elements, such as silver or cadmium, which greatly increase the rupture life of copper also cause large increases in the softening temperature. As little as 0.05 per cent of cadmium or silver is sufficient to raise the softening temperature more than 100°.3,4 The effects of cooling rate and of minor constituents on the rupture properties are of considerable fundamental as well as practical interest; therefore a more detailed study of their nature was conducted and is reported in this paper. Experimental Procedure Materials The materials studied in this investigation may conveniently be classified in two groups: one consisting of a wide variety of commercial coppers, and the other composed of special high-purity, laboratory-prepared coppers. The commercial materials were tested to determine whether or not the effect of cooling rate occurred with all coppers, whereas the high-purity coppers were investigated in order to establish a basis for evaluating the effect of minor constituents on the rupture properties. In Table I are given the analyses of the coppers tested. The samples I to 6 are commercial materials and were obtained for the most part from stock supplies.*

Jan 1, 1944

By P. Davey Wheeler

San Francisco meeting, September, 1915) IN an article in the General Electric Review, January, 1915, reference was made to the X-ray examination of a steel casting 9/16 in. thick. Fig. 1 shows one of the radiographs thus obtained. All these radiographs showed plainly the tool marks on the surface of the casting. All but one showed peculiar markings the shape of which strongly suggested that they were indeed the pictures of holes in the interior. A circular piece, 1 in. in diameter, was punched from the casting at a point where the radiograph shown in Fig. 1 indicated that a blow-hole should be found. (Location of sample shown by circle in Fig. 1.) Fig. 2 is a photograph of the end of the punching, showing the .hole that was found. Since that article was written it has seemed desirable: (1) to obtain data from which the exposure necessary for any thickness of steel could be at once calculated; (2) to find the thickness of the smallest air inclusion which could be radiographed in a given thickness of steel; (3) to determine in what direction to hope for further progress; and (4) to develop the technique of, radiographing metals. In order to gain some preliminary data, several pieces of ½ -in(12.5mm.) boiler plate were obtained, 5 by 7 in. (12.5 by 17.5 cm.) in size. In one of these, holes were drilled in such a way that the axis of each hole was midway between the faces of the steel and parallel to those faces. The diameters of these holes were as follows: Hole number Diameter 1 1/4 in. = 6.3 mm 2 1/8 in. = 3.1 mm. 3 1/16 in. = 1.6 mm. 4 1/32 in. = 0.8 mm. 5 1/64 in. = 0.4 mm.

Jan 8, 1915

By A. Keil

TO measure the absolute conductivity of metallic specimens it is generally necessary to have exact geometrical shapes and good electrical contact with the test-piece. To overcome limitations of the standard methods, an electronic conductivity-meter* Trade name, Sigmatest; model Dr. F. Forster; Reutlingen, Ger-many. has been developed, which works on the principle of inducing high frequency eddy-currents in the specimens and measuring the reaction of these curients on a measuring coil.',' To attach the instrument to the test specimen, a flat area of about 10 mm diam is all that is necessary. The reading is taken off a scale calibrated in pet of International Annealed Copper Standard. The induced eddy-currents are propagated in a circular motion parallel to the surface. Thickness of the layer included in a measurement depends on the frequency used. With a frequency of 60 kc per sec, the penetration of the currents was 0.8 mm at the upper limit of the scale, and 2 mm at the lower limit. The method is limited to nonferrous metals and other applications have been described elsewhere." The object of the present investigation was to detect the formation and growth of surface layers of differing conductivity, and to determine the depth to which these changes could be observed. A well known phenomenon which illustrates the problem is the internal oxidation of certain silver alloys containing base metal solutes, such as copper or cadmium, when they are annealed in an oxidizing atmosphere.4, 5 Until now, the only methods available for following these phenomenon have been metallo-graphic examination and hardness tests.0, 7 Changes in mechanical properties of copper alloys by internal oxidation were recently discussed in a more general way by Martin and Smith." When measuring these conductivity changes it must be remembered that the only absolute values of conductivity are those of 1) the nontreated homogeneous specimen, and 2) the final values obtained with a surface layer of depth comparable to the penetration of the eddy-currents. All intermediate values refer to the mixed conductivities of the transformed surface layer and the untransformed alloy, and are thus readings of relative value only. Experimental Results Specimens were annealed for 1/2 hr at 800°C in hydrogen, and the internal oxidation was carried out by thermal treatment in air at 800°C. Fig. 1 shows the results of the first series of experiments. With internal oxidation of a solid solution of 8 pet Cd in silver, the conductivity rises continuously until the surface layer formed has become thick enough to be the deciding factor (about 400µ). Precipitates of CdO are mainly in the form of points, Fig. 2, and, as a result, the electric contact between the silver crystals is not distorted by them. Brine11 tests were run with a 1.25 mm ball and a 7.812 kg load. The specimen annealed in hydrogen and oxidized to a depth of 400µ had a hardness of 40 Bhn,

Jan 1, 1959

By M. E. Straumanis, J. -P. Krumme

In basic ([KOH + KCl] with a total polarity of 2) or acidic (2N H2SO4) electrolytes and at anodic current densities of more thun 2 to 4 ma per sq cnz, n-type GaAs single crystals of lozo resistivity preferentially dissol~je forming etch tunnels with triangular or civc~ilay cross sections and of a width between 0.5 arid 5 p. These etch tunnels are oriented along any one of the four possible (111) directions of GaAs. However, their growth occurs only in one direction of a given (111) whick apparently is determined by the atomic sequence Ga —As (and not the rezlerse) in respect to an individual valence bridge in the crystal. It is concluded from comparison with the cubic lattice structure of GaAs that the etch tunnels represent macroscopic evidence for the tetrahedral bonds and their polar properties. If the anodic current density is increased the tunnel fomation results in the development of a fibrous surface layer consisting of GaAs. The latter separates frorn the substrate (in an anodic s~irface disintegration process) by the growth pressure of an As,0, filnz forming in the interior of the fibrous layer, 100 to 200 µ under the surface, at more than about 50 ma per sq cni. The fibrous GaAs film has the same crystallographic orientation as the substvate and represents a skeleton of the original crystal. Since the etch-tunnel density in a separated GaAs layer is about 108 c?n-', and the etch tunnels develop only along (111) in a given polar direction, it is assurraed tlmt the dislocations have no influence on the growth of these tunnels. ElECTROLYTIC treatment of smooth surfaces of poly- and single-crystalline GaAs at high anodic current densities causes the formation of porous surface layers.' This phenomenon suggests comparison with effects being observed with magnesium,' indium,, gallium,4 and aluminum5 and known as "anodic disintegration". The purpose of the present paper is to explore and to explain the reasons for the formation of such surface layers on GaAs and, in particular, to investigate the influence of the lattice polarity of this III-V compound semiconductor in the (111) direction on the anodic dissolution behavior. GaAs SINGLE CRYSTALS For the experiments described below GaAs single crystals from the Monsanto Co., St. Louis, Mo., were used. Their impurity levels were below 1 ppm and their dopant levels between 1 and 100 ppm. They were grown in (111) using the Czochralski or the gradient-freeze technique. The crystals had n-type conductivity and electric resistivities between 1 and 5 ohm-cm. EXPERIMENTAL The GaAs single-crystal rods were cut perpendicularly to (111) into wafers of about 1 mm thickness using a wire-blade crystal slicer and an aqueous slurry of Sic or a diamond saw. The orientation of the faces of these wafers were checked by Laue back-reflection patterns. If there was a deviation from (111) the faces were abraded under a certain angle using grinding paper and distilled water. The damaged surface layer was removed from each crystal by chemical etching with a mixture of 1HF:1HNO3: 1H20 or 2HF:1HNO3:2HAc (glacial). {110) faces were obtained by mechanical cleavage, producing surfaces which did not require a further treatment. The GaAs wafers were mounted using "alligator" clamps instead of soldered electrical contacts.' Only the bare crystal surfaces were dipped into the electrolyte. The clamps were coated with insulating wax to prevent any contact with the electrolyte. The experiments were carried out in aqueous 2 N H2so4,' or in an aqueous solution of KOH and KCl1 (1 mole KOH + 1 mole KCl in 1000 cu cm solution). Anodic current densities up to several hundred ma per sq cm were applied for periods between 30 sec and 2 hr. For the purpose of investigating the initial steps of disintegration the anodic current density applied never exceeded 20 ma per sq cm. The films which partially separated from the anodic surfaces under high-field conditions were treated with KOH to further their detachment by dissolving the As2O3 formed. The washed and dried films were pasted to strips of filter paper, and Laue pictures were made. The back-reflection patterns obtained were compared with those of the original anode surface before and after anodic dissolution. Furthermore, space reciprocal lattices7 were constructed from asymmetric rotation crystal patternsa which permitted the determination of the crystallographic orientation of the detached films of the corrugated anodic surfaces. The disintegration products were identified from assymmetric powder patterns.8 The polarity of the {111) faces was determined by chemical etching with mixtures of 1HF:1H2O2(30 pct): 2H2O or 1HNO3:2H2O. Different patterns on each of two inverse (111) sides appeared.'-l8 The correlation of these patterns to the Ga{111) or the As(111) side has already been established by the use of light figures,18-20 by X-ray diffraction near the absorption edges of gallium and arsenic,'lmZ4 and by LEED measurements.25 The geometric structure of these surfaces and the interior of the anodically attacked crystals were observed and photographed with a high-power microscope using oil immersion objectives up to magnification of X1720.

Jan 1, 1968

By R. W. Ph. D. Raymond, Anton Filers, O. H. Hahn

THIS paper will treat of such works only as beneficiate ores directly in the mining districts. And when it is said that more than twenty furnaces exist in Utah, about as many in Nevada, five in Montana, and four in Cerro Gordo, Inyo County, California, it is obvious that a business so extended deserves attention. Wide apart as these different works are located, they have nevertheless to deal in nearly every case with the same or very similar circumstances and conditions, so that, with very few exceptions, virtually the same system of smelting is followed in all these establishments. This is the so-called method of reduction and precipitation in blast-furnaces. As the principal reasons for the employment of a blast-furnace process are to be considered : the low percentage of lead in the ores, the high price of the only available fuel, charcoal, and the exorbitant rates demanded for labor. The reasons why the reduction and precipitation process is preferred to a roasting, reduction, and precipitation process are the high prices of labor and materials, and the preponderance of oxidized ores over sulphurets, though in some cases the latter are quite abundant. The weight of these reasons will be better understood when the character of the ores to be treated and the object of the smelting are more minutely stated. The ores are in nearly all cases a preponderating mass of oxidized lead ores, such as cerussite, anglesite, and leadhillite, in which nests and nodules of undecomposed galena occur. Associated with these are : in Eureka, Nevada, arseniate of iron and arsenical pyrites, hydrated oxide of iron, quartz, and calcareous clay ; in Little Cottonwood Canyon and American Fork, Utah, iron oxide, and in some cases a combination of antimony, the nature of which I have not ascertained; also dolomite and quartz in widely varying proportions; in Bingham Canyon, Utah, only quartz and comparatively little oxide of iron, or iron sulphurets; in Cerro Gordo, California, oxide of iron, iron pyrites, antimonial compounds, copper ores, and, as gangue, carbonate of lime and quartz. In Argenta, Montana, occur, besides the above-named lead ores, pyromorphite, and molybdate of lead. The preponderating gangue of the Argenta ores is quartz, and there is here a larger proportion of galena than elsewhere in the West. In most of the localities named, the lead ores themselves contain sufficient silver to render its separation from the ore the main object of the smelting; but in some of the districts, and especially in Montana, the lead ores serve only to furnish the extracting agent for the silver of true quartzose silver ores, which at the same time contain a sufficient percentage of lead to make amalgamation impracticable. They are therefore beneficiated by smelting, although the lead itself has no market value.

Jan 1, 1873

By Auguste J. Rosh

The use of titaniferous ores in the blast-furnace has been the subject of much controversy for many years. Divers objections have been raised against them, and, for one cause or another, the verdict

Jan 1, 1893

By H. C. Howard

Reaction of oxygen and bituminous coal starts as soon as the coal bed is exposed to air and, with some coals, proceeds with significant velocity even at normal temperatures and at normal oxygen partial pressures of one-fifth of an atmosphere. At higher temperatures, the reaction is greatly accelerated and ultimately a condition is reached where the process is very rapid and we then speak of combustion. It is the purpose of the present paper to discuss the reactions of oxygen and coal at temperatures below those of active combustion. It is these low temperature oxidation reactions which are responsible for heating in storage and for marked changes in agglutinating proper-ties. These reactions may also be employed for the preparation of organic acids, which are of direct interest to the chemical industry. For convenience in discussion, the low temperature reactions of oxygen and bituminous coal can be roughly divided into three stages though there is, of course, overlapping. Stage I is a surface oxidation stage, characterized by the addition of oxygen, with the formation of oxygen containing groups some of which have acidic properties. Carbon dioxide, carbon monoxide and water may be formed con-comitantly and are always liberated at higher temperatures, and in cases where the oxidation is prolonged. Superficially, the coal is little affected by this primary stage of oxidation and usually only minor changes in ultimate composition result. There may be definite changes in coking and coking properties, and heat of combustion susceptibility to further oxidation. The presence of acidic groups can be demonstrated by specific reactions. These groups may show cation exchange properties like the mineral zeolites. The formation of oxalic acid has been reported. If the oxidation is continued, a large fraction of the organic material of the coal is converted ultimately into alkali soluble, acid insoluble products, which have been given the name "regenerated humic acids" and which are the characteristic products of Stage 2. These humic acids, in the solid stage, do not differ greatly in appearance from the original coal, but show large differences in chemical composition and chemical and physical properties. Along with the humic acids, carbon dioxide and some of the water soluble types of Stage 3, are also formed. If the oxidation is carried still further, the humic acids may be degraded completely to the simpler, lower molecular weight acids of Stage 3 which are characterized by solubility in acid as well as in alkaline media, and by their orange, yellow or white colors. Additional carbon dioxide is formed in the transformation from Stage 2 to Stage 3 and, for a number of American coals, a maximum yield of the water soluble types of acids is reached when about 50 pct of the carbon of the coal is converted to carbon dioxide. Primary Oxidation The initial step in the reaction of gaseous oxygen on coal, like that on carbon,

Jan 1, 1949

By J. D. Embury, R. M. Fisher, A. S. Keh

An investigation of the defect structure and properties following large strain deformation has been carried out using transmission electron microscopy and mechanical testing for a range of ferrous materials and for copper. It is shown that, for a variety of ferrous materials, a cellular substructure is developed during the initial stages of working and on further deformation the dimensions of this substructure are reduced. Quantitative measurements of the flow stress and the scale of the substructure indicate that the strength of heavily worked materials is largely determined by the spacing of cell walls. These cell walls act as dislocation barriers in a manner analogous to grain boundaries. FCC materials do not harden as extensively as bcc after cold working and the present observations on copper indicate that the dimensions of the substructure in fcc materials are not markedly reduced on deformation. The differences between the fcc and bcc structures produced by large plastic strains are ascribed to differences in the extent of dynamic recovery. It is tentatively proposed that the greater stability of substructural barriers in bcc structures results from strong interstitial Pinning effects. It is proposed that for large plastic strains the work-hardening process may be considered in terms of the reduction of substructural-barrier spacing during the working process. This pvovides a simplified hut useful analysis of the strain hardening occurring during mechanical processes. THE mechanisms of strain-hardening processes have occupied the attention of numerous investigators over the past three decades and a multitude of theories have emerged in this field. The majority of previous work has been concerned with the development of a description of the plastic behavior of single crystals in terms of dislocation theory.'" In contrast, scant attention has been given to the strengthening mechanisms operative during mechanical working processes such as rolling and drawing. The large plastic strains involved in these processes make it difficult to correlate the observations with any elementary dislocation theory. Further, as Bullen and coworkers3 have opined, for large plastic strains both hardening and recovery occur simultaneously and thus it is extremely difficult to estimate the effect of plastic strain on the ambient internal stress field. It is probable that for large plas- tic strains any theoretical estimate of the internal stress field must be made in terms of complex dislocation groups. Although some valuable theoretical work has been done toward calculating the elastic properties of dislocation groups4 any detailed self-consistent model for large plastic strain is as yet impossible. With these limitations in view it is still of value to examine the mechanical properties of highly strained materials as a function of their substructure. This relationship is explored in the present communication for a variety of materials subjected to rolling, drawing, or swaging. The primary object of this investigation has been to establish the validity and the limitations of the substructural strengthening mechanism proposed by Embury and eisher' for drawn pearlitic wire and by Meieran and Thomas for drawn tungsten wire. No attempt has been made to delineate the basic interaction mechanism which occurs between a slip dislocation and the substructure and the authors believe that a great deal more experimental evidence must be compiled before these fundamental aspects can be explored. Also, no specific attention has been given to the detailed formation of substructure during working. Experimental Details. A variety of materials were used in this investigation, the compositions and heat treatment of which are tabulated in Table I. The commercially pure iron is referred to throughout this report as Ferrovac E. The mechanical working processes were all performed at room temperature. The wire drawing was performed on a manual drawing bench. Reductions of between 10 and 20 pct in area per pass were used in both swaging and drawing. The experimental parameter used to evaluate the mechanical properties of the materials was the 0.2 pct proof stress. This was determined for wire samples using an Instron tensile machine at a crosshead speed of 0.02 in. per min. The techniques for preparation of samples for transmission electron microscopy have been described previo~sl~.~ Specimens from wire samples were prepared from longitudinal sections and in some cases from transverse sections. To evaluate the substructural characteristics of rolled materials, thin foil samples were prepared of both the face and edge sections. Results. One of the more familiar ways of expressing work hardening in mechanical working is by the flow stress as a function of reduction in cross-sectional area. Fig. 1 shows such a plot for Ferrovac E eutectoid carbon steel and for copper. The curve for Ferrovac E is characterized by an initial stage of rapid work hardening and a final stage of rapid work hardening separated by an intermediate stage with a low rate of work hardening. This behavior is typical of many ferrous materials and the drawn pearlite wire previously investigated by Embury and Fisher is a more pronounced example. Copper shows an initial

Jan 1, 1967