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By John Wulff

In a previous paper Burwell and Wulff1 have shown by electron diffraction studies that allotropic transformations can be induced in 18-8 stainless steel by polishing to a depth of about 5 X 10-5 cm. The development of a successful etching technique, which removes accountable amounts of metal from the surface without pitting and without changing the root-mean-square profile as measured with an Abbot pro-filometer, led to the application of the whole technique and material to an investigation of various mechanical methods of surface preparation, such as grinding, lapping, superfinishing and cold-rolling. Ideally suited to such a study is 18-8 of low carbon and nitrogen content. The material can be heat-treated to produce a coarse-grained single-phase structure. On cold deformation there occurs not only a reduction in grain size but, at regions of maximum stress, a change of face-centered material to body-centered material, provided the metal is worked below about 200°C. When worked between 200"about and 415°C., diffraction studies evidence a reduction in grain size without the appearance of any new body-centered ferrite. Ferrite, which can be referred also to strains induced by carbide precipitation, is evident when the material is worked at temperatures between 4150 and 800°C. Stainless steel is advantageous because the usual surface-finishing operations do not readily oxidize it to any appreciable depth. In order to produce detectable oxide films on the surface of austenitic 18-8 in a time equivalent to that required to produce, for example, a fine ground finish on 1/2 sq. in., the sample must be held in a furnace or oxygen stream above 600°C. By using longer heating times, it is possible to achieve measurable oxide films on samples , whose surface temperatures exceed only about 250°C. Experimental Procedure The apparatus, material, and technique described in the previous paper1 were employed in this investigation. Samples of 18-8, I by I cm. by 4 mm., were carefully annealed in the austenitic range to produce a coarse-grained structure. They were then quenched and pickled to remove scale, On a lapping machine of the Graton2 type, both sides of each sample were polished to a a of 1/6 a wave length of sodium D light. Thereafter they were electrolytically etched to remove at least 1 X 10-3 cm. of the surface, a depth that is well below that of any defermations induced by surface preparation. samples of this material, carefully mounted in steel holders, were then sent to various industrial organizations known for special finishing techniques. In the instrue ment shops at the Massachusetts Institute of Technology check samples were finished by the same methods, as far as they were available. Abbot profilometer3 readings Were made on all the samples, which were then carefully degreased in double distilled benzine and alcohol, dried in a hot-filtered air blast, and kept in a desiccator. SUC-

Jan 1, 1941

By T&apos Ke, ing-sui

Accoriding to the classical theory of elasticity, the elastic portion of the stress-strain curve is represented by a straight line. such a representation implies that there is a linear relationship between strain and stress and also that strain is a single-valued function of stress and vice versa. Actually, such a one-to-one correspondence between strain and stress does not exist in real metals. A well-known example is the elastic after-effect on unloading. Another familiar example is damping or internal friction, that is, the dissipation of energy attending vibration. In an extensive review of such phenomena, zener1,2 has proposed the term "anelasticity" to denote that property of a solid in virtue of which strain is not a unique function of stress in the non-plastic region. The phenomena arising from anelasticity are called anelastic effects. The measurements on anelastic effects are important in many fields of metals technology. The, in precise instruments such as watch springs, difficulties often arise from the slight dimensional changes after fabrication. The internal friction or damping capacity of metals is often an important factor in deciding whether they are appropriate for instruments in which there are accompanying vibrations.3 However, for metal scientists, the study of anelastic effects furnishes a powerful tool for understanding many properties Of meta1s in terms of their microstructures or atomic interactions. In order to utilize the anelastic measurements to their fullest extent for acquiring such information, the experimental studies Of anelasticity must be interpreted by appropriate mathematical analysis. For a great many problems, however, the necessary information often Can be Obtained by general qualitative arguments. From the definition of anelasticity, any physical changes occurring in a specimen as a result Of the applied stress will cause anelastic effects if such physical changes are accompanied by a delayed change of elastic strain. Under these circumstances, we have the condition that strain lags behind the stress. We may mention the stress-induced transportation phenomena as examples. These include the stress-induced thermal diffusion,4-7 the stress-induced diffusion of particles,8-l2 and the stress-induced viscous slip along the microelements in metals.12-15 The differential equations describing the microscopic mechanism in these phenomena lead to relations in which stress is linear with respect to strain (and/or their derivatives). Thus if we Can demonstrate that the superposition principle is valid under the circumstances in which the anelastic effects are observed, we would expect in the macroscopic relation a linear relationship between stress and strain and their derivatives. This report is to describe a number of anelastic effects observed in alpha-iron, and an attempt is made to derive valuable information from a critical study of these

Jan 1, 1949

By T&apos Ke, ing-sui

Accoriding to the classical theory of elasticity, the elastic portion of the stress-strain curve is represented by a straight line. such a representation implies that there is a linear relationship between strain and stress and also that strain is a single-valued function of stress and vice versa. Actually, such a one-to-one correspondence between strain and stress does not exist in real metals. A well-known example is the elastic after-effect on unloading. Another familiar example is damping or internal friction, that is, the dissipation of energy attending vibration. In an extensive review of such phenomena, zener1,2 has proposed the term "anelasticity" to denote that property of a solid in virtue of which strain is not a unique function of stress in the non-plastic region. The phenomena arising from anelasticity are called anelastic effects. The measurements on anelastic effects are important in many fields of metals technology. The, in precise instruments such as watch springs, difficulties often arise from the slight dimensional changes after fabrication. The internal friction or damping capacity of metals is often an important factor in deciding whether they are appropriate for instruments in which there are accompanying vibrations.3 However, for metal scientists, the study of anelastic effects furnishes a powerful tool for understanding many properties Of meta1s in terms of their microstructures or atomic interactions. In order to utilize the anelastic measurements to their fullest extent for acquiring such information, the experimental studies Of anelasticity must be interpreted by appropriate mathematical analysis. For a great many problems, however, the necessary information often Can be Obtained by general qualitative arguments. From the definition of anelasticity, any physical changes occurring in a specimen as a result Of the applied stress will cause anelastic effects if such physical changes are accompanied by a delayed change of elastic strain. Under these circumstances, we have the condition that strain lags behind the stress. We may mention the stress-induced transportation phenomena as examples. These include the stress-induced thermal diffusion,4-7 the stress-induced diffusion of particles,8-l2 and the stress-induced viscous slip along the microelements in metals.12-15 The differential equations describing the microscopic mechanism in these phenomena lead to relations in which stress is linear with respect to strain (and/or their derivatives). Thus if we Can demonstrate that the superposition principle is valid under the circumstances in which the anelastic effects are observed, we would expect in the macroscopic relation a linear relationship between stress and strain and their derivatives. This report is to describe a number of anelastic effects observed in alpha-iron, and an attempt is made to derive valuable information from a critical study of these

Jan 1, 1949

By B. M. Larsen, L. S. Darken

Some years ago we collated all laboratory data then available to us on the distribution at equilibrium of manganese and of sulphur between metal and simple slags, and used the results in setting up an equation, which proved to be in accord with determinations of the distribution ratio of manganese and of sulphur between liquid steel and open-hearth slag, over a wide range of operating conditions. We now present an outline of our calculations and inferences on these two closely related questions, which are of especial importance because of the advisability of conserving manganese wherever possible. In general, our results show that in the open-hearth furnace equilibrium between metal and slag, with respect to both manganese and sulphur, is substantially attained during the finishing period of the heat, or in about a half hour to an hour after any additions were made. This implies that the end result will be identical whether manganese is added as alloy or metal to the liquid steel or as oxide to the slag. The proportion of total manganese retained by the steel is favored: (I) by use of the minimum amount of lime, consistent with other operating limitations, required to give a lime-silica ratio of about 2.4, which usually corresponds to a minimum practical slag volume; (2) by a high concentration in the slag of MnO relative to FeO; (3) by high operating temperature. Absorption of sulphur by the slag from the liquid metal is favored: (I) by large slag volume; (2) by a high concentration of active (or "free") lime and of manganese oxide dissolved in the slag; (3) by low concentration of silica, iron oxide, and phosphate dissolved in the slag. Distribution 02 Manganese between Slag and Metal at Equilibrium On the basis that the distribution of manganese between liquid steel and slag is controlled by the reaction FeO + Mn -& MnO + Fe [A] slag metal slag metal the distribution at equilibrium, at a given temperature, is expressed by the equilibrium constant for this reaction, which is defined as K,, _ aMnO' afe aFeO ' aMn where a is the activity of the molecular species denoted by the subscript. The activity of each of the several components, although it is not known precisely, is approximately equal to the concentration of each component expressed as its mol fraction; that is, as the ratio of the number of mols of the given component to the total number of mols of all the molecular species present in the metal or slag, as the case may be. Moreover, since the activity, or concentration, of iron in the liquid metal is in fact substantially constant, the term afe may be combined with K" to give a new constant K'. Making these changes, 7

Jan 1, 1942

By B. M. Larsen, L. S. Darken

Some years ago we collated all laboratory data then available to us on the distribution at equilibrium of manganese and of sulphur between metal and simple slags, and used the results in setting up an equation, which proved to be in accord with determinations of the distribution ratio of manganese and of sulphur between liquid steel and open-hearth slag, over a wide range of operating conditions. We now present an outline of our calculations and inferences on these two closely related questions, which are of especial importance because of the advisability of conserving manganese wherever possible. In general, our results show that in the open-hearth furnace equilibrium between metal and slag, with respect to both manganese and sulphur, is substantially attained during the finishing period of the heat, or in about a half hour to an hour after any additions were made. This implies that the end result will be identical whether manganese is added as alloy or metal to the liquid steel or as oxide to the slag. The proportion of total manganese retained by the steel is favored: (I) by use of the minimum amount of lime, consistent with other operating limitations, required to give a lime-silica ratio of about 2.4, which usually corresponds to a minimum practical slag volume; (2) by a high concentration in the slag of MnO relative to FeO; (3) by high operating temperature. Absorption of sulphur by the slag from the liquid metal is favored: (I) by large slag volume; (2) by a high concentration of active (or "free") lime and of manganese oxide dissolved in the slag; (3) by low concentration of silica, iron oxide, and phosphate dissolved in the slag. Distribution 02 Manganese between Slag and Metal at Equilibrium On the basis that the distribution of manganese between liquid steel and slag is controlled by the reaction FeO + Mn -& MnO + Fe [A] slag metal slag metal the distribution at equilibrium, at a given temperature, is expressed by the equilibrium constant for this reaction, which is defined as K,, _ aMnO' afe aFeO ' aMn where a is the activity of the molecular species denoted by the subscript. The activity of each of the several components, although it is not known precisely, is approximately equal to the concentration of each component expressed as its mol fraction; that is, as the ratio of the number of mols of the given component to the total number of mols of all the molecular species present in the metal or slag, as the case may be. Moreover, since the activity, or concentration, of iron in the liquid metal is in fact substantially constant, the term afe may be combined with K" to give a new constant K'. Making these changes, 7

Jan 1, 1942

By B. M. Larsen, L. S. Darken

SOME years ago we collated all laboratory data then available to us on the distribution at equilibrium of manganese and of sulphur between metal and simple slags, and used the results in setting up an equation, which proved to be in accord with determinations of the distribution ratio of manganese and of sulphur between liquid steel and open-hearth slag, over a wide range of operating conditions. We now present an outline of our calculations and inferences on these two closely related questions, which are of especial importance because of the advisability of conserving manganese wherever possible. In general. our results show that in the open-hearth furnace equilibrium between metal and slag, with respect to both manganese and sulphur, is substantially attained during the finishing period of the heat, or in about a half hour to an hour after any additions were made. This implies that the end result will be identical whether manganese is added as alloy or metal to the liquid steel or as oxide to the slag. The proportion of total manganese retained by the steel is favored: (I) by use of the minimum amount of lime, consistent with other operating limitations, required to give a lime-silica ratio of about 2.4, which usually corresponds to a minimum practical slag volume; (2) by a high concentration in the slag of MnO relative to FeO; (3) by high operating temperature. Absorption of sulphur by the slag from the liquid metal is favored: (I) by large slag volume; (2-by a high concentration of active (or "free") lime and of manganese oxide dis) solved in the slag; (3) by low concentration of silica, iron oxide, and phosphate dissolved in the slag. DISTRIBUTION OF MANGANESE BETWEEN SLAG AND METAL AT EQUILIBRIUM On the basis that the distribution of manganese between liquid steel and slag is controlled by the reaction [FeO + Mn ;7± MnO + Fe [A] slag metal slag metal] the distribution at equilibrium, at a given temperature, is expressed by the equilibrium constant for this reaction, which is defined as [K" aFPI OFeO ? aMn] where a is the activity of the molecular species denoted by the subscript. The activity of each of the several components, although it is not known precisely, is approximately equal to the concentration of each component expressed as its mol fraction; that is, as the ratio of the number of mols of the given component to the total number of mols of all the molecular species present in the metal or slag, as the case may be. Moreover, since the activity, or concentration, of iron in the liquid metal is in fact substantially constant, the term aFe may he combined with K" to give a new constant K'. Making these changes.

Jan 1, 1942

By R. H. Brown

EARLY workers attempted to study the structure of alloys by measurement of equilibrium electrode potentials in aqueous solutions containing ions of the metals from which the alloy was made.1 The method was subject to such limitations (e.g., the difficulty in attaining electro-chemical equilibrium at low temperatures) that it has not been widely used by metallurgists. Recently, Seltz and co-workers have introduced a greatly improved method for studying alloys by measurement of equilib-rium electrode potentials in molten salts.2-4 The mathematical treatment is the same, of course, as for equilibrium potentials of amalgams in aqueous solutions.5 This method will probably find extensive use, since it makes possible not only the deter-mination of phase fields of equilibrium diagrams but also the determination of certain thermodynamic quantities which can be used advantageously in metal-lurgical calculations. However, the method presents difficulties. With many metallic and alloy electrodes, reversibility is not readily obtainable. Also, the difficulty of obtaining suitable material from which to make the cells is increased as the temper-ature is increased. Moreover, the necessity of carrying out measurements in a vacuum requires additional apparatus and intro-duces considerable difficulty, especially at the higher temperatures.

Jan 1, 1940

By Joseph D. Weeks

FIFTY-eight years and a day, full of labor, of achievement and of honor had been completed when, at Pittsburgh, on the 5th day of May, 1892, the wheels of a life that had but just before lost its inspiration stood still, and the work here of William Powell Shinn was at an end. Born at Burlington, N. J., May 4,1834, he received such an education (and it was. the only school education he ever had) as the public

Jan 1, 1893

By John Wulff

IN a previous paper Burwell and Wulff1 have shown by electron diffraction studies that allotropic transformations can be induced in 18-8 stainless steel by polishing to a depth of about 5 X 10-5 cm. The development of a successful etching technique, which removes accountable amounts of metal from the surface without pitting and without changing the root-mean-square profile as measured with an Abbot profilometer, led to the application of the whole technique and material to an investigation of various mechanical methods of surface preparation, such as grinding, lapping, superfinishing and cold-rolling. Ideally suited to such a study is 18-8 of low carbon and nitrogen content. The material can be heat-treated to produce a coarse-grained single-phase structure. On cold deformation there occurs not only a reduction in grain size but, at regions of maximum stress, a change of face-centered material to body-centered material, provided the metal is worked below about 200°C. When worked between 200° and 415°C., diffraction studies evidence a reduction in grain size without the appearance of any new body-centered ferrite. Ferrite, which can be referred also to strains induced by carbide precipitation, is evident when the material is worked at temperatures between 415° and 800°C. Stainless steel is advantageous because the usual surface-finishing operations do not readily oxidize it to any appreciable depth. In order to produce detectable oxide films on the surface of austenitic 18-8 in a time equivalent to that required to produce, for example, a fine ground finish on ½ sq. in., the sample must be held in a furnace or oxygen stream above 600°C. By using longer heating times, it is possible to achieve measurable oxide films on samples whose surface temperatures exceed only about 250°C. EXPERIMENTAL PROCEDURE The apparatus, material, and technique described in the previous paper1 were employed in this investigation. Samples of 18-8, 1 by 1 cm. by 4 mm., were carefully annealed in the austenitic range to produce a coarse-grained structure. They were then quenched and pickled to remove scale. On a lapping machine of the Graton2 type, both sides of each sample were polished to a flatness of 1/6 a wave length of sodium D light. Thereafter they were electrolytically etched to remove at least 1 X 10-3 cm. of the surface, a depth that is well below that of any deformations induced by surface preparation. Samples of this material, carefully mounted in steel holders, were then sent to various industrial organizations known for special finishing techniques. In the instrument shops at the Massachusetts Institute of Technology check samples were finished by the same methods, as far as they were available. Abbot profilometer3 readings were made on all the samples, which were then carefully degreased in double distilled benzine and alcohol, dried in a hot-filtered air blast, and kept in a desiccator. Suc-

Jan 1, 1941

By Keith E. Robinson, Brian Stimpson

INTRODUCTION In inclined sedimentary strata slope failure may occur by sliding along bedding and along a discontinuity or weak zone, as illustrated in Fig. 1. This mode of failure may be called 'bi-linear', as the failure surface is comprised of two linear or approximately linear segments. This type of failure has been suggested for the famous Frank Slide, Alberta, Canada (Cruder and Krahn, 1973) in which an estimated 90 M 5 tons (8.97 x 10 MN) of rock separated from Turtle Mountain and buried the town of Frank. Also, with the increasing depth of open pits and the construction of highways through inclined sedimentary strata this mode of failure is of major concern to the rock slope stability engineer. A computer program for calculating factors of safety for this slope failure mode is provided and includes the ability to vary shear strengths of potential slide surfaces, ground water elevations and wedge geometry. LIMITING EQUILIBRIUM MODEL The simple limiting equilibrium model used in the analysis is shown in Fig. 2. It is assumed that jointing is orthogonal to bed- ding and that the interface between the upper and lower wedges there- fore corresponds to a joint plane or planes. No shear strength is attributed to the interface so that the resultant force, P, from the upper wedge acts normally across the interface. The normal loads

Jan 1, 1983

By R. Walker, R. J. Anslow

Today at Tampa we see the end results of a team effort: A vital link in an intermodal transportation system, the link that enables the unit-train concept to be employed with full effectiveness and the link that improves the economics of water transportation systems. Two new phosphate transfer complexes with a multi- million ton annual capacity are in operation in Tampa, Fla. Revolutionary in concept, these companion installations represent a total investment in the Tampa Bay area of $18.5 million.

Jan 1, 1970

By R. J. Block, G. H. Kehl

IN order to investigate the possibility of a spontaneous low-temperature transformation, resistivity measurements were made on a sample of eutectoid beryllium- copper. A cast specimen of 5.965 pct Be, 94.035 pct Cu was homogenized at 650°C for 22 hr, furnace cooled to 550°C, and held for 2 hr to allow the 0 - a ß-a+? reaction to proceed. In an attempt to refine the ß grain size, the specimen was then reheated to 620°C, held

Jan 1, 1960

By J. L. Meijering

Oxidation hardening of cylindrical and spherical specimens first decreases with depth below the surface, but then increases again as the center is approached. This is in agreement with the view that this change in hardness is mainly determined by the change in velocity of the oxidation boundary, which affects the dispersion of the oxide. WHEN a thick slab of silver containing 0.3 pct Mg by weight is internally oxidized, the hardness measured on a cross section is found to decrease considerably with distance from the surface.&apos; This phenomenon has been attributed to the diminution of the velocity of the oxidation boundary. The smaller this velocity is, the more slowly the free-oxygen concentration rises towards the concentration in equilibrium with the oxygen gas. And a small 0 concentration favors dissociation and thus conglomeration of the oxide. For instance, the hardness decreases more rapidly during long annealings in nitrogen than in air.&apos; Measurements by Gregory and Smith3 on sections through internally oxidized Al-silver wire showed a smaller variation in hardness, probably because the wire diameter was only 0.9 mm. Wood4 found a drop in hardness with depth in internally oxidized Al-copper strip, and also—by electron microscopy—the concomitant increase in Al2O3 particle size. Under certain circumstances internal oxidation leads to formation of rather irregular inner oxide films in the midst of dispersed oxide. This special sort of conglomeration—discussed in Ref. 5—is also favored by greater depth below the surface.3,5 In this paper hardness measurements in large diameter cylindrical and spherical specimens are described. Here the oxidation velocity* goes through ness initially decreases with depth but increases again towards the center. Normally, the diffusion coefficient D1 of oxygen is very large compared to D2, that of the dissolved metal. If, furthermore, the atomic fraction c2 of the latter is much larger than the O-solubility cl- but c2D2 << c1D1- the velocities in question are easily calculated2 to be: for the cylinder and for the sphere. Here p is the radial coordinate of the oxidation boundary and R the specimen radius, which in dilute silver alloys is constant, as no external oxidation occurs. These equations have been derived for a divalent solute; for nondivalent solutes c2 has to be multiplied by half the valency. The equations are not valid near the center. For which can be considered as a standard case,2 the Eqs [I] and [2] begin to yield U-values which are appreciably too high for p/R = 0.05 and 0.15, respectively. But at the v-minima they are still very good approximations. These minima lie at p = emlR= 0.37R in the cylinder and p = 1/2 R in the sphere. Other factors besides the velocity v will also influence the hardness. The oxide concentration cox is constant in a flat strip, apart from a narrow region in the middle,2 but in cylindrical and spherical specimens cox decreases steadily with depth. When C1 << c2 and c1D1 >> c2D2 one can calculate

Jan 1, 1961

By Kiyoshi Azuma, Hiroshi Kametani

The variation of the dissolution behavior of a ferric oxide with calcining temperature has been investigated. Samples were prepared by thermal decomposition of ferric hydroxide, nitrate, oxalate, and sulfate at low temperature, followed by the calcination in the temperature range between 600" and 1200°C. The samples of eight series and a fine crystalline sample of hematite were dissolved in 1 N hydrochloric acid at 55.2°C and the results are represented on double-log graphs for convenience. It is confirmed that all dissolution courses follouj either the accelerated process or the parabolic process except in the special case of the crystalline hematite which dissolced in accordance with the uniform dissolution of a particle. Examinations of the physical properties of the oxide powders revealed that the surface area measured by the permeability method is strikingly relevant to the dissolution behavior of the oxide. In the previous paper,&apos; detailed data were presented on the effect of the kind of acid, the solution temperature, and the concentration of acid on the dissolution of two ferric oxides. It was also shown that these sam ples dissolved in strikingly different ways. The present investigation was carried out on the dissolution of various calcined samples prepared from various ferri salts by various methods to ascertain the course of dissolution. Pryor and Evans2 pointed out a change of the dissolution rate at around 700°C for a series of calcined ferric oxides prepared from the hydroxide. Several papers374 reported also the dissolution of ferric oxide samples. It seems, however, that a systematic account of the relationship between the dissolution behavior and physical properties of the oxide has not yet been given. This paper presents the variation of the dissolution of the oxide in relation to the calcining temperature and the change of physical properties of the calcines. EXPERIMENTAL Raw materials were prepared by precalcination of ferric hydroxide, thermal decomposition of ferric nitrate, oxalate, and sulfate, and aerial oxidation of ferric chloride vapor, at as low a temperature as possible. The products were crushed, ground, if necessary, and sieved with a 100-mesh Tylor screen prior to calcination, after which the specimens were dissolved in acid solution. The following is a detailed description of the preparation of the samples. Sample H. About 500 g of ferric chloride (guaranteed reagent) were dissolved in 5 liters of deionized water and filtered. Ferric hydroxide was precipitated by addition of the minimum amount of ammonium hydroxide solution, and the precipitate was washed continuously till chloride ion was not detected by silver nitrate solution, and then filtered. The filter cake was dried at 120°C for a week and ground, and the -100 mesh portion was used. Sample S. Ferric sulfate (guaranteed reagent) was pyrolytically decomposed in a crucible at 700°C for 24 hr and the product was sieved. In this case the following calcination was carried out at temperatures over 700°C. Sample B. Commercial ferric oxide (guaranteed reagent). About 15 kg of ferric nitrate were decomposed in a furnace maintained at 800°C for 2 hr. The actual temperature of the decomposition was not measured. The product was crushed and sieved, and the -100 mesh portion was used. Sample N. About 50 g of ferric nitrate (guaranteed reagent) were decomposed in a beaker in a sand bath until a red-brown dense solid was produced. This product was crushed and sieved, and subjected to complete decomposition at 500°C. The precalcined product was again sieved and used. Sample N2.5. Since the decomposition temperature was not controlled for sample AT, a different sample was prepared in a temperature-controlled furnace. The subscript represents the decomposition at 250°C. The product was treated in the same manner as sample N. Sample Nc. Under atmospheric pressure it is prac-tically inevitable that ferric nitrate hydrate melts to form a brown liquid at about 50°C before pyrolysis. For this reason, the salt was first slowly heated under reduced pressure (about 10-3 mm Hg measured in a trap refrigerated by dry ice-alcohol) to achieve dehydration without melting. About 5 hr were required for the dehydration and the partial decomposition. Then the temperature was elevated to 500° C in air for complete decomposition. The relatively porous product was sieved and used. Sample Ov. About 200 g of ferric oxalate hydrate (extra pure) were dehydrated under reduced pressure (as described above) followed by thermal decomposition at 500°C for 6 hr in air. The decomposition of this salt was accompanied by liberation of carbon monoxide, by which the ferric salt was initially reduced to a black powder. The powder changed in turn into brown ferric oxide as the gas liberation decreased and reoxidation predominated. The product consisted of sparkling fine particles passing through a 100-mesh screen. However it was ground and sieved as for the other samples. Sample D. Commercial fine powder for magnetic tape purposes. The preparation was as follows.5 Ferric chloride vapor and preheated excess air were mixed and passed into a reaction tube where oxidation took place at 450°C. The fine powder formed was collected in a cottrell chamber. The product was vacuum-degassed at 450°C for 1 hr and sieved.

Jan 1, 1969

By C. L. Sollenbeger, R. B. Greenwalt

PERHAPS the most widely used dispersants or gangue depressants in nonmetallic flotation are sodium silicates, which vary in silica-to-soda ratio from 1 to 3.75. Typical manufactured silicates in order of decreasing solubility and increasing amounts of silica are Metso, silica-to-soda ratio of 1.00; D, 2.00; RU, 2.40; K, 2.90; N, 3.22; and S-35, 3.75.* References in flotation literature1,2 to the use of sodium silicates are often weak because they fail to mention the type of silicate used. Metso and silicate N have occasionally been mentioned, but when the type of silicate is not mentioned, it is usually assumed to be N, the cheapest of the soluble silicates and the one recommended by sodium silicate manufacturers as a flotation agent. In the All is-Chalmers Research Laboratories a systematic study was made of the effect of different alkali-silica ratios on the concentration by flotation of two scheelite ores. One of these was a high grade ore from the Sang Dong mine in Korea. The effect of such factors as pH; addition agents; and conditioning time, temperature, and pulp density on the flotation efficiency of this ore have been described previously. The other ore was a low grade ore from Getchell Mines Inc., Nevada. The mineralogy and techniques of concentrating this ore have been described by Kunze. Hereafter these ores will be referred to as the Korean and Nevada ores. Experiments were made with both to determine the effect of three factors—-type of silicate, concentration of silicate, and pH of the pulp—on recovery and grade of tungsten in a rougher concentrate. Average WO, content of the Korean ore was 1.50 pct and of the Nevada ore 0.27 pct. The predominant tungsten mineral in both ores was scheelite, which was accompanied by a small amount of powellite. The powellite and scheelite were finely disseminated through both ores and required a —200 mesh grind for liberation. Major gangue minerals in the Korean ore, in decreasing order of abundance, were amphi-boles, quartz, biotite, garnet, fluorite, and calcite. Bulk sulfides composed about 3 pct of the total weight. Gangue in the Nevada ore, in descending order of abundance, was garnet, alpha quartz, calcite, phlogopite, wollastonite, and amphiboles. Sulfide minerals were 3 to 4 pct of total weight. Batch flotation experiments were made with 500-g samples of ore, each sample wet-ground to 90 pct passing 200 mesh. The finely ground ore was floated in a Fagergren batch cell at 25 pct solids. The natural pH of the Nevada ore was 8.9 and of the Korean ore, 8.5. The D, RU, K, N, and S-35 sodium silicates were obtained in colloidal dispersions with varying amounts of water. The most alkaline, Metso, was in dry powdered form. For convenience in addition, 5 pct solutions by weight were prepared from each of the silicates, on the basis of dry sodium silicate dissolved in the correct amount of distilled water. Chemical analyses of the various silicates are given in Table I, together with the pH of the 5 pct solutions. A preliminary bulk sulfide float was made with secondary butyl xanthate as the collector and pine oil as the frother. The WO] analysis of the sulfide concentrate was nearly 1 pct for the Korean ore and about 0.1 pct for the Nevada ore. The tungsten contained in the sulfide concentrate constituted about 3 pct of the total tungsten in each ore. No effort was made to recover these tungsten values. The scheelite was floated with oleic acid. Adjustments in pH were made with sulfuric acid or sodium carbonate. A 1 pct solution of 85 pct Aerosol OT was sprayed on the froth and sides of the cell during the scheelite float to aid in dispersing the minerals and to decrease the entrapment of gangue particles. Six tests were planned for each of the six types of silicate in which concentrations of 1, 2, and 4 1b of silicate per ton of dry ore were investigated at both 6.5 and 10 pH. All tests were made at room temperature. The performance of each silicate was judged from the grade and recovery of WO, in the scheelite rougher concentrate. Tungsten recovery was calculated on the basis of the scheelite remaining in the ore after the preliminary sulfide float. Testing of each silicate at three levels of concentration and two levels of pH required 36 tests with each scheelite ore. Variance analyses were performed on the concentrate grades and recoveries to determine whether or not the type of sodium silicate, the concentration of sodium silicate, or the pH significantly affected recovery or grade. Results Concentrate Grade: A variance analysis of the concentrate grades for the Korean ore showed that concentration of the silicate and pH of the ore pulp were major factors in producing a high grade concentrate. Also, the silica- to-so da ratio was important as an interaction with pH. The concentrate grade vs silica-to-soda ratio is plotted in Fig. 1. The curves show that the concentrate grade improved with an increase in concentration of sodium silicate and also

Jan 1, 1959

By Nicholas J. Grant, Italo S. Servi

SPECIAL polishing and etching techniques were developed during an investigation of the high temperature mechanical properties of high purity aluminum (99.995 pct Al).* Electrolytic polishing was done successfully in the following electrolyte: 5 ml perchloric acid (72 pct), and 95 ml glacial acetic acid. No special precautions need be taken during the preparation of the electrolyte since no appreciable heat of mixing is evolved. Although the electrolyte is not an explosive, it is recommended that Jacquet&apos;s safety rules&apos; be followed during the polishing operation. A voltage of 25 to 60 v gives a good polish in about 2 min at room temperature after preparation on 3/0 metallographic paper. Most of the grain boundaries are visible under the microscope after polishing. Since the current is controlled essentially by the resistance of the bath, it is necessary to keep the anode-to-cathode distance as constant as possible. Accordingly, polishing of irregularly shaped pieces will be difficult. A cooling bath and a stirring system are advisable in order to keep the temperature of the bath uniform and constant. Coarse-grained samples can be macroetched in a few seconds by lowering the voltage below 10 v. This is done after electrolytic polishing, without removing the sample from the bath, Fig. 1. The specimen can be repolished in less than 1 min by raising the voltage above 25 v. The "galvanic etching" technique, which has been described elsewhere,&apos; was found to be helpful not only for macroetching, but also for microetching coarse-grained specimens. In fact, the different orientations of adjacent grains provide good contrast at the grain boundaries, when the sample is observed under polarized light. If the specimen is only partially etched, Fig. 2a, the grain boundaries can be located without completely destroying the appearance of the surface of the specimen. The unetched surface appears black under polarized light. Excellent color contrast is obtained by using a "sensitive tint" plate in the optical system of the microscope. In this case, the unetched surface has a magenta color, while the etched part of the sample assumes different colors varying from green to brown, according to the orientation of the grains. Etch pits were produced on high purity aluminum by using the technique suggested by Lacombe and Beaujard." Good results also were obtained by substituting 70 pct nitric acid for the fuming nitric acid recommended. This gave an etching reagent of the following composition: 70 ml nitric acid (70 pct), 50 ml hydrochloric acid (37.5 pct), and 3 ml hydrofluoric acid (48 pct). An example of the results is shown in Fig- 2b. The outline of the etch pits is revealed sharply if the specimen is observed under polarized light, as shown in Fig. 2c. These metallographic techniques are not suitable for the examination of commercially pure (2s) aluminum. References &apos;P. A. Jacquet: Metal Finishing (Nov. 1949) 47, p. 62. 21. S. Servi: Metal Progress (1950) 58, p. 732. 3 P. Lacombe and L. Beaujard: Journal Inst. of Metals (1947) 74, p. 1._________________________

Jan 1, 1952

By Douglas Ashmead

In his paper Mr. Braley makes no mention of the bacteriological aspects of the problem. It is now quite well established that certain bacteria play a major role in formation of acid mine waters, and it is a simple matter in the laboratory to show that under sterile conditions the rate of acid production from a pyrites suspension is only about one quarter of that obtained from a similar suspension inoculated with drainage from a mine producing an acidic pit water. Under sterile conditions the oxidation is due to direct chemical action and, from the evidence just given and from much other evidence, this increase under nonsterile conditions is due to certain bacteria. Experiments recently completed, and shortly to be published, have shown that this bacteriological oxidation can be prevented by the maintenance of pH conditions above 4. It was found that to raise this pH above 4 at the beginning of the experiments was not sufficient but that, due to the continuing chemical oxidation, alkali had to be added daily to maintain the pH conditions above 4. The amount of alkali added, however, over a fixed period, was only about one quarter of the alkaline equivalent of the acid produced when pH conditions were not controlled over an equal period. The opinion expressed by Mr. Braley that sodium hydroxide has little or no effect on the rate of oxidation of pyrites is not substantiated by the above experiments. The writer does not claim that these results show a practical solution to the problems, especially in abandoned workings, but feels that the application of an alkaline coating, such as lime wash, to exposed accessible workings might be well worth trying. S. A. Braley (author&apos;s reply)—In 1919 Powell and Parrl suggested that bacteria, or some catalytic agent, hastened the oxidation of pyritic or marcastic sulfur in coal. Carpenter and Herndon (1933)&apos; attributed the action of Thiobacillus thiooxidans. Colmer and Hinkle (1947)3 observed an organism similar to T. thiooxidans and another organism that oxidized iron. Leathen and Braley 9rst discovered this organism in 1947 in a sample of water from the overflow of the Bradenville mine (Westmoreland County, Pennsylvania). They characterized the organism in 1954" and gave it the name Ferrobacillus ferrooxidans. Although Temple and Colmer (1951)&apos; had suggested the name Thiobacillus ferrooxidans, since they claimed it oxidized both ferrous iron and thiosulfate, we have found that pure cultures of the organism do not oxidize thiosulfate, hence the name F. ferrooxidans. In 1955 Ashmead7 isolated an organism, similar to the one called Thiobacillus ferrooxidans by Temple and Hinkle, from acid mine water in Scotland. It is probable that this organism was F. ferrooxidans. In 1954 Bryner, Beck, Davis, and Wilsonh reported microorganisms in effluents from copper mine refuse. These organisms appeared to be similar but were not in pure culture. In view of this history of bacterial investigation of acid mine water and our own ten years of experience, we do not agree with Mr. Ashmead that bacteria play a major role in acid formation. We do not find that any of these bacteria will directly oxidize pyritic material. They do, however, augment the chemical formation of sulfuric acid by atmospheric oxidation. In two papers in 1953% eathen, Braley, and McIntyre discuss the role of bacteria in acid formation and postulate the mechanism through which they operate. Mr. Ashmead in his discussion of my paper has assumed that this work was carried on in the presence of acid mine water in which bacteria would be present. This was not the case. Strictly sterile conditions were not maintained, but the organisms present in mine drainages were definitely absent in these experiments. We believe that we have demonstrated that alkalis do not inhibit the chemical oxidation of pyritic material. This is also indicated by Mr. Ashmead&apos;s discussion in which he says that alkali must be added daily due to the continuing chemical oxidation. It is interesting to note that Mr. Ashmead finds that maintenance of pH above 4.00 decreases the activity of the bacteria. We have found also that a decrease in pH below 2.8 also inhibits its activity. Table XIII of published data&apos;" illustrates the decrease in activity with increased acidity, although pH values are not given. These values are in comparison with uninoculated controls and show the marked increase in acidity up to 22 weeks but a decline at 29 weeks, at which time the experiment was terminated. It is probable that after a longer period only chemical oxidation would have continued. From our studiesv we have postulated that the iron oxidizing bacterium (Ferrobacillus ferrooxidans) oxidizes the ferrous iron, resulting from chemical oxidation, to ferric iron. The ferric iron then aids the atmospheric oxidation of the sulfuritic material and is itself reduced to ferrous iron, which in turn acts as food for the autotrophic bacteria. Study of the physiologic properties of F. ferrooxidans shows that its preferred pH is about 3.00 and its activity decreases with variation in either direction. It is extremely inactive above pH 4.00 and below 2.5. This inactivity above 4.00 is indicated by Mr. Ashmead&apos;s observations. These properties of F. ferrooxidans then correlate perfectly with our hypothesis. Ferrous iron is oxidized very slowly by atmospheric oxygen in highly acid sohtion and since the bacteria become inactive, acid is formed only by atmospheric oxidation. At a pH of 4.00 or above iron is more readily oxidized by atmospheric oxygen, but the bacterial activity is decreased. However, with a pH above 4.00 the ferric iron is removed from the field of activity since its soluble sulfate hy-drolyzes and precipitates the iron as ferric hydroxide or a basic sulfate. As we have shown in the paper under discussion, the alkali does not inhibit the chemical oxidation, and thus the acid formation continues. This

Jan 1, 1957

By Y. A. Chang

Heat content values of tantalum monocarbide and tungsten monocarbide have been determined from 325" to 985°K by means of a drop-type diphenyl ether calorinzeter. Based on the values obtained in the present study and those available in the literature, best values lected and computed from 298. 15°K to temperatures close to their respectiue melting points. At temperatures higher than 1700°Kfor TaC and 27000 K for WC, values of Cp and related thermodynamic quantities were extrapolated based on the two Debye parameters: one corresponds to the metal sublattice and the other to the carbon sublattice. The contrzbutzon In the total specific heat due to lattice dilation was evaluated using the Nernst-Lindemann relalionship. The calculated values of Cp were in good agreement with the In view of their refractoriness, tantalum monocar-bide (TaC) and tungsten monocarbide (WC) are of con- experimentally determined ualues. Furthermore, the calculated values of the absolute entropies at 298.15"K were 5.03 and 4.15 in comparison to the experimental values of 5.05 and 4.15, all expressed in the unit of cal per degg-atom. Using the same Debye parameters, values of the linear coefficients of ther mal expansion for TaC and WC were calculated from absolute zero to their respective melting points using the Grüneisen equation. The calculated values are in excellent agreement with the experimental values available in the literature. Finally, the values of the bulk modulus of TaC from room tenzperature to temperature near its melting Point were also calculated using the equation recently derived by Anderson. No cot~ipari-son between the calculated and experimental values can be made due to lack of experimental data. siderable practical interest. In order to completely define these materials, it is necessary to know their thermal properties as a function of temperature. Tantalum rnonocarbide having a NaCl structure (B-1 type) melts congruently at 4250PK,1 while tungsten monoearbide with a simple hexagonal structure (Bh type) melts per itectically at 3049°K into melt and graphite.2 In the present study, the heat content values (from which

Jan 1, 1968

By J. R. Long, T. R. Graham, R. G. Feustel, R. S. Dean

THE comprehensive study of the copper-manganese-zinc alloy system in the Bureau of Mines Laboratories has so far been principally concerned with alloys that lie within the alpha solid solution field of the system. Two regions, one centering about 65 per cent copper, 10 manganese and 25 zinc, and the other centering about 70 per cent copper, 20 manganese, 10 zinc, have been carefully examined.1,2 These have indicated that when the alloys are made with electrolytic manganese considerable amounts may be readily introduced and that the strength and hardness are increased without excessive losses in ductility. In the course of the work of establishing the limits of the alpha solid solution range,3 enough of certain of the alloys was prepared to permit determination of their physical properties at a future date. The 60 per cent copper alloys concerned here are part of that series. They cross through the alpha field and into the adjacent alpha plus beta and alpha plus X fields, and are of interest because they offer some information on the effects of manganese on alloys lying in these fields. COMPOSITION AND FABRICATION OF ALLOYS The chemical composition of the alloys involved is given in Table I. They were intended to contain 60 per cent copper with manganese increasing from 5 to 25 per cent in 5 per cent steps and zinc decreasing [ ] from 35 to 15 per cent. The analyses are so close to the intended composition that the alloys will be referred to hereafter by their nominal compositions. They were finished into sheet by cold-rolling and intermediate annealing procedures calculated to produce sheet 1/16 in. thick, cold-reduced by 20, 40, 60, and 80 per cent in thickness. Physical properties were determined on standard flat tensile specimens with 4-in. gauge length, although the test gauge section used was 2 in. The properties were obtained on cold-worked material and on material annealed at temperatures ranging from l00° to 1500°F. after 60 per cent cold reduction. Since an annealing temperature of 1200°F.

Jan 1, 1946

By A. W. Jenike

A theory of gravity flow of bulk solids like ores, concentrates, coal is outlined and an example of design for unobstructed flow is given. Mass-flow and plug-flow patterns are defined and related to the geometry of the bin. The effect of these patterns on segregation, first in-first out flow, and caking is described. This paper is a report on the results from the AIME sponsored project "Flow of Bulk Solids" which was carried out under the author&apos;s direction at the Utah Engineering Experiment Station, University of Utah, during the period 1956-1962. The theory has been applied to the design of numerous industrial storage plants. A QUANTITATIVE METHOD OF DESIGN FOR FLOW There is hardly an industry which does not store and handle solid materials in bulk form. When the volume of the solids is large, gravity is invariably relied upon to cause the solids to flow out of storage, through channels and chemical reactors. Such materials as ore, coal, cement, flour, plastics, clay, soil, to which a general term of bulk solids is applied, flow by gravity or are expected to flow by gravity in thousands of installations and by billions of tons annually. The chemical and process industry depends on gravity flow of solids in process and out of storage. Mining relies on gravity flow in block-caving, in ore passes, as well as in storage and loading bins. Agriculture uses gravity flow in elevators, in feed plants, and in farm silos. In practice, satisfactory gravity flow is seldom attained. Such problems as doming, piping (rat-holing), lack of live capacity, segregation, deterioration in storage, harass industry. In spite of the universality of these problems, until recently, there has been no theory of solids flow, no method of predicting how a solid would behave, and how the channel, bin, or hopper should be designed. In the late nineteen forties and early fifties, the theory of plasticity came of age and simultaneously the computer became widely available. These two factors permitted the development of a theory of flow of bulk solids. The work was conducted during the years 1953-1961. In conjunction with the development of the theory a method to measure the flowability of solids was also developed1-7 and the theory was ap-plied to the design of ore pockets, storage plants,16 chemical reactors and adsorption columns. A comprehensive report of this work is given in a previous work." THEORY OF FLOW The most important question which a theory of flow has to answer is: what conditions need to be satisfied for a given solid to flow uniformly and without obstructions through a channel? First of all, the following observations are made:

Jan 1, 1967