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By H. L. Miaw, A. M. Gaudin, D. W. Fuerstenau

A quantitative method for evaluating density of slime coatings has been developed and applied to formation of iron oxide slime coatings on quartz and on corundum. Slime coating density is related to flotation recovery and to properties of the electrical double layer at mineral surfaces. IN spite of considerable study, the nature of slime coatings in flotation is still not completely understood. However, phenomena that control floc-culation and dispersion of colloidal systems are now interpreted in terms of electrical double layers.",' Colloids will flocculate even though the particles carry the same charge, but when two dispersed colloids of opposite charge are mixed. flocculation ensues even more rapidly. Analogous phenomena seem responsible for slime coating on minerals in flotation systems. To shed new light on the issue it was considered desirable to devise a tool that would measure slime coatings. The usual method has been to examine photographs of presumably representative surfaces, after. an intervening washing in running water. But such an examination is non-quantitative, and the changes in chemical environment represented by the washing may have removed the slime coatings that existed during flotation. To provide the possibility for a correlation with electrical double layer phenomena, the experiments were made with quartz, corundum, and iron oxide, for which elec-trokinetic data are available.'-" Since the properties of the electrical double layers of these oxides depend on the pH of the solution, pH will be the most important variable. Furthermore, because the zero point of charge for silica, iron oxide, and alumina occurs at pH 3.7, 8, and 9.5, respectively, the relative charge on the slime and mineral can be changed over wide ranges. Because of its practical importance in quartz flotation, iron oxide powder was chosen as the slime. Also, its uniform composition, contrasting color, and ease of analysis make experimentation simple. In this investigation, correlation was sought between the effect on flotation recovery of slime addition and slime coating density. Materials and Methods Details are available in a thesis by Miaw." The quartz was selected from pure Brazilian crystalline quartz, crushed, sized (65/150 mesh) acid-cleaned, washed, and stored in conductivity water. The corundum (synthetic alumina of high purity prepared by Linde Co., Chicago) was crushed, sized (65/100 mesh) deslimed, boiled in nitric acid, washed, and stored in conductivity water. The iron oxide slime, reagent-grade ferric oxide (—400 mesh) from Allied Chemical & Dye Corp., was heated to 160°C, cooled, and stored in a vacuum desiccator. In the electron microscope the slime particles appeared to be about 0.3µ in size, but their large specific surface (87,900 cm per g, by gas-adsorption method, using krypton) suggests that the actual particles are smaller than 0.3r. Had they been perfect nonporous spheres, they would have had a diameter of 0.13µ.

Jan 1, 1959

By R. H. Widmyer, G. M. Wood

This investigation was prompted by the absence of a simple, accurate method to predict optimum second stage separation pressure in three stage separation operations. Three stage separation as used here includes two separators plus the stock tank. The first stage pressure is usually fixed by gas sales conditions and the third stage is at atmospheric pressure. Thus, the second stage pressure is the only one that may be varied in-discriminantly during production operations. No variations in temperature were considered in this study, even though it will vary among systems, for a change in temperature has little effect on the optimum pressure. Optimum pressures may be determined from flash calculations, but these are tedious unless a computer is available. An early attempt to develop a simpler method&apos; yielded an equation which gave the optimum pressure only as a function of initial and final pressure. Experience, however, confirms theoretical relationships which show that composition as well as pressure and temperature must be a factor. This indicates that the basic relationship should be an equation of the form, where P, is second stage pressure, P, is first stage pressure, A is a function of P. (stock-tank pressure) and the system composition, and n is a function of the number of stages and the system composition. Fig. 1 shows the basic variation of P2 with P for a fixed system composition. A series of such figures clearly showed the effect of composition. The peak of each curve reflects that second stage pressure at which the stock-tank recovery (gal/MMcf) residue gas is a maximum value. DEVELOPMENT OF NEW CORRELATION Wellstreams having 17 different analyses, ranging from low gravity crude to condensate, were used to determine the effect of composition. Each wellstream was flashed through three stages to determine the optimum second stage pressure for each first stage pressure. Equilibrium vaporization ratios proposed by Latham and Campbell were used throughout. The heptane plus fraction, for simplicity, was assumed to have the properties of octane. The results were subjected to an empirical analysis in an attempt to develop a correlation- that would be (1) simple, (2) accurate, and (3) eliminate the need for any flash vaporization calculations. This analysis yielded two equations, one for wellstreams having a specific gravity greater than one (air = 1.0) and one for those less than one. For crude streams (specific gravFor condensate (specific gravity < 1.0),

By C. A. Stiles, J. W. Nyhus

Erie Mining Co. is a 10.3-million-tpy pellet producer on the east end of the Mesabi Range 60 miles north of Duluth. Its complex includes facilities for mining, crushing, grinding and beneficiation in addition to a pellet plant and power plant. A 74-mile railroad links the mine and plant to Taconite Harbor on the shore of Lake Superior. The concentrate recovery ratio at Erie is about 1: 3, and this, along with stripping activity, makes it necessary for the company to mine nearly a million tons of material a week. At the outset, all crude ore mined at Erie was hauled entirely by rail, but with expansion into additional mining areas, the company made a gradual transition towards truck-to-rail haulage. Today, in Erie&apos;s 11th year of operation, over 50% of all crude taconite mined is transported by truck to loading pockets where it is transferred to rail cars. Future years will see more taconite moved in this manner. Thus, the company has an increasing interest in tire performance.

Jan 6, 1969

By H. Kazemi, G. W. Thomas, M. S. Seth

The double-porosity model of Warren and Root7 for examining pressure drawdown and buildup phenomena in naturally fractured reservoirs has been extended to intetpret interference test results. Both analytical and numerical solutions are presented. The practicality of some of the assumptions in the Warren-Root model was also investigated. The standard procedure for interpreting interference tests in naturally fractured reservoirs beretofore employed an equivalent homogeneous reservoir model. A comparison of our results with the equivalent homogeneous model indicates the latter is inadequate for early time responses. For late time responses, however, the simpler equivalent homogeneous model yields favorable results. Finally, the effects of well spacing and the magnitude of the interporosity flow parameter are briefly cited. INTRODUCTION Interference tests can be used to provide reservoir information not obtainable from conventional pressure drawdown and buildup tests. The technique involves measuring the response in one or more wells arising from a pressure perturbation introduced into another well. It has been. successfully applied to single-layer, homogeneous, unfractured, isotropic and anisotropic formations to arrive at values of well storage capacity and a measure of directional permeability.l The techniques of interference testing usually can be extended to heterogeneous systems, provided the permeability contrast between any existing rock layers is not excessive.9 In such cases, the practical interference effects in an observation well of an interconnecting heterogeneous reservoir can be predicted using an equivalent homogeneous model. The calculated properties are then average values. Russell and Prats2 have demonstrated the utility of this approach for a single-phase, two-layer system. For naturally fractured reservoirs, some different approaches usually are necessary. The major departure from homogeneous or nearly homogeneous reservoir treatment is to characterize the fractured system as an entity having "double-porosity"; namely, we suppose the existence of both primary and secondary porosity, where the former is contained within a systematic array of identical rectangular matrix blocks and the latter is contained within an orthogonal system of continuous, uniform fractures (see Fig. 1). It is sufficient to assume that the permeability of the rock matrix is so small that movement of reservoir fluids to the producing wells is entirely through the fracture network. This assumption has been validated by Barenblatt3 and .employed by others?-7 Warren and Root7 used the double-porosity model to develop an interpretation of pressure drawdown and pressure buildup tests in naturally fractured

Jan 1, 1970

By M. R. Tek, L. K. Thomas, D. L. Katz

Threshold displacement pressures are needed to determine how much overpressure can be used in storing natural gas. An experimental technique for determining threshold pressures by displacing water with gas from samples saturated with water is presented. Threshold pressures for eight low permeability samples were measured. Threshold pressure data obtained in this work, plus data on higher permeability samples reported in the literature, are correlated with porosity, permeability, surface tension and formation resistivity factor. Mercury injection pressures also were measured and correlated with air-water threshold pressures. Threshold pressures were found to be independent of time. An aerial photograph of gas emerging from the top of a core shortly alter its threshold pressure has been exceeded shows that the gas bubbles are uniformly distributed across the face of the core. Channeling will occur, however, when an increased gas phase permeability is reached, A porous medium can be re resealed alter its threshold pressure has been reached, provided it has not been desaturated below a fixed saturation. Its new threshold pressure will be lower than when the sample is 100 percent saturated with water. INTRODUCTION The degree of overpressure in excess of the discovery pressure that a gas storage reservoir can withstand is determined by the ability of its caprock to contain gas, providing the pressure does not exceed the structural limit of the reservoir. The retention of gas in a reservoir by a caprock saturated with water is a result of the capillary forces acting at the gas water interface. Without the presence of water in a caprock, gas would leak out of the reservoir at a rate determined by the permeability of the caprock to gas. The ability of a caprock to contain gas is expressed in terms of its threshold displacement pressure, which is defined as the minimum pressure needed to initiate the displacement of a wetting phase by a nonwetting phase from a porous medium 100 percent saturated with the wetting phase. The gas industry must be able to predict how much "overpressure" a gas reservoir can withstand before leakage occurs by gas displacing water from caprock overlying the reservoir. This is of economic importance since the storage capacity of a gas reservoir is proportional to its pressure. The discovery pressure for most reservoirs is found between the upper and lower limits1 shown in Fig. 1. Discovery pressures in excess of their hydraulic pressure gradient are attributed to the compaction of an isolated shale formation by the overburden.2.3 The lower limit of 0.433 psi/ft corresponds to the weight of the overburden, the gradient of the rock itself. Somewhere between

Jan 1, 1969

By I. Cadoff, E. Miller, K. Komarek

Jan 1, 1960

By F. W. Bowdish

Analysis of data on the equilibrium exchange of sodium ions from salt solutions for calcium ions, from various fractions of an oxidized calcareous iron ore from Lorraine, France, strongly suggests that the calcium may be attached to the solid by only one of its bonds. Nearly equal values were found for the equilibrium expression from data covering concentration ranges of 1000 fold for the salt and 235 fold for the ion-exchangeable calcium. Differences indicated between the exchangeable calcium contents of the slime and the sandy portions of the ore, as well as the equilibrium relationship itself, are of importance in the flotation of the ore. During an experimental program on the flotation of oxidized calcareous iron ores from Lorraine, France, ion-exchangeable calcium was found in the ore. Because this source of calcium ions, if not controlled, could thwart all efforts at flotation, an extensive study was made of the phenomenon. The part of that study reported here was to obtain data on the equilibrium established between ore solids and solutions of sodium chloride, and to analyze the data to try to understand better the physical chemistry of the exchange. The ore contains oolites of goethite and quartz grains embedded in a matrix consisting of calcite and a brown cement believed to be the residue from oxidation of the silicate minerals found in fresh unoxidized ore. When ground, a substantial fraction of the ore becomes a fine slime in which is concentrated more than half of the alumina content of the ore. It is believed that the alumina occurs as unidentified clay minerals with which most of the ion-exchange capacity of the ore is associated. A preliminary experiment on the exchange of ions from the ore for sodium ions from solutions of NaCl showed that calcium was about ten times as abundant as magnesium in the exchange solutions. Thus calcium was the predominant ion in causing difficulties with flotation, and it was the only one for which data was obtained in this study. It is believed that the omission of magnesium ion exchange from consideration does not invalidate the results. It is possible, however, that inclusion of magnesium in the analyses and calculations or its prior elimination from the samples would have improved the consistency of the results. EXPERIMENTAL Data about the equilibrium exchange of sodium from solutions for calcium from the solids were obtained using two different samples of material. The solids

Jan 1, 1963

By R. B. Booth, W. F. Linke

The continuous interest of the American Cyanamid Company in producing superior polymeric flocculants and dispersants for the mining industry has resulted in a broad, general study of the physical chemistry of mineral-polymer systems. The aim of this program has been to establish a sound theoretical basis on which practical problems could be analyzed, and which would lead to the development of new and improved flocculating and dispersing agents. This study has required the cooperative effort of physical, analytical, and polymer chemists, as well as engineers familiar with mining problems. This report summarizes the results of some of our investigations over the past two years. Further studies along these and other lines are in progress and will be reported in the near future. MEASURING FLOCCULATION IN THE LABORATORY The foremost problem in studying flocculation in the laboratory has been to establish reproducible methods of comparing and evaluating the effectiveness of various reagents. Previous workers have measured settling -rates 1,8 filtration rates2 , and sediment volumes3 . Direct observations of the floc size, or the clarity of the supernatant liquid, can also be used. AIthough these parameters are all interrelated, they do not always measure the same physical properties of the suspensions, and hence are not equally useful or reliable. Whatever the method of comparison selected. the testing procedure must be carefully defined and standardized. The results must be satisfactorily reproducible, and for practical purposes must accurately reflect the results obtained in mill use. In order to compare the data obtained in these various types of test, the physical nature of the flocculated system must be examined in some detail. In an unflocculated system, only the larger or denser particles (the "sands") settle at a useful rate. The sediment can be observed to build up from the bottom of the cylinder, while the fines remain in suspension for a long period of time. If the system is not disturbed, even the microscopic fines can be seen to classify themselves as they fall over a period of days. When a high molecular weight polymer is added to the system, the colloidal particles are tied together randomly in flocs, and the sands and fines settle together. The line of demarkation between solid and liquid phases moves downward from the top of the cylinder. The settling rate of the flocs depends on their size and on their effective density. For a given mineral sample, the larger the flocs, the faster the settling. Since the large flocs cannot pack as closely as small ones, they produce a sediment with more pore spaces, and hence of larger volume, which is easier to pump and to agitate. Although it is nearly impossible to measure individual floc sizes, it is relatively easy to determine settling rates and sediment volumes. Of these two, the settling rate is simpIer to measure, and hence generally more practical. Reproducible sediment volumes can only be obtained by allowing the solids to pack for a rather long period of time (e.g., hours to days), and although the volumes thus observed are directly related to the degree of flocculation (average floc size), it is often impractical to wait so long for the results.

Jan 1, 1961

By E. Martinez

The effect of ultrasonic energy transmitted through a liquid on chrysotile asbestos was investigated. Ultrasonic energy was effective in fiberization of chrysotile crudes as well as standard grades of milled asbestos fibers. Treated samples of several grades of milled fibers had increased wet bulk volumes and decreased settling and filtration rates compared to untreated fibers. Ultrasonics may be a method for fiberization of chrysotile without decreasing length or use of chemical additives that alter surface properties. Cavitation of the liquid on the surface of fiber bundles is believed to be the cause of the fiberization. It was found that ultrasonic energy greatly increased the rate of precipitation of latex on asbestos. When chrysotile asbestos fibers require additional opening or fiberization, the usual method employed is some type of high speed impact or grinding to open the fibers and produce a larger surface area. These methods always cause some degradation in length due to breaking of fibers. In addition, the efficiency of mechanical methods decreases as the diameter of fiber bundles decreases. Chemical methods have been proposed and it is claimed that fiberization down to individual fibers of 200-300 A diam is possible with some wetting agents. However, large amounts of reagent are required, approximately EDWARD MARTINEZ is with Central Research Laboratories, American Smelting and Refining Co., South Plain-field, N.J. TP 63H226. Manuscript, Aug. 12, 1963. Discussion of this paper, submitted in duplicate prior to Mar. 15, 1964, will appear in SME Transactions, September 1964, and AIME Transactions, 1964, vol. 229. 50 pct of the weight of fiber treated, and some of the wetting agent remains on the surface of the chrysotile and cannot be removed by any solvent which does not destroy the asbestos.&apos; This investigation was directed at determining whether ultrasonic energy transmitted through a liquid would be effective in fiberizing chrysotile asbestos. Samples of asbestos crudes and commercially milled fibers were treated; settling and filtration rates of treated and untreated milled fibers were obtained. EQUIPMENT A Westinghouse Corp. ultrasonic cleaning system WEHH was used in this investigation. See Table I for a breakdown of this ultrasonic unit. RESULTS AND DISCUSSION Fiberization of Chrysotile Crudes: Samples of chrysotile crudes were pulled apart with tweezers so that coarse bundles of fiber approximately 1/16 in. in diam were obtained. The bundles were put into a bottle with 200 ml of methanol and the mixture placed into the ultrasonic tank for 30 min at a power output of 1200 w. The test was repeated using water instead of methanol. During the irradiation it was noted that the surfaces of the bundles were being fiberized. The liquid eventually became cloudy with dispersed solids. Fig. 1 is an electron micrograph of the fibers, some reduced to unit dimensions, and a fine material released by the ultrasonic energy. The platy particles in Fig. 1 were identified by electron diffraction and differential thermal analysis as brucite, Mg(OH)2, which must have been intergrown in the chrysotile crudes. Electron micrographs of bulk specimens of chrysotile have shown a fine material filling the interstices between tubular fibers.2,3 Electron diffraction patterns of the fine material collected after ultrasonic treatment indicate that it is amorphous. After decanting the solution, bundles of chrysotile remained somewhat decreased in diameter. Continuing the ultrasonic irradiation of the remaining material resulted in additional fiberization. The opening of the fibers occurred in both methanol and water. Cavitation of the liquid by the ultrasonic energy is undoubtedly responsible for the fiberization. When sound waves are transmitted through a liquid at a

Jan 1, 1963

By R. W. Bartlett

DISILICIDE coatings, MeSi2, on refractory metals are usually grown by a solid-state diffusion reaction similar to the parabolic oxidation of metals. Two or more silicide compounds occur in each of the binary silicon-refractory metal systems. When an adequate source of silicon is available during the coating process, the lower silicide compounds are usually not formed.1 However, during service application of the coated refractory metal, continued heating causes further diffusion and growth of the lower silicides. A study of the growth kinetics of the lower silicides in the molybdenum and tungsten binary systems with silicon was previously reported.2 The present study is concerned with the growth kinetics of Ta5Si3 and Cb5Si3, formed as conjugate layers between TaSi2/Ta and CbSi2/Cb diffusion couples, respectively. Diffusion couples consisting of disilicide-coated tantalum and columbium sheet coupons were subjected to diffusion heat treatments, cross-sectioned, and scanned by an electron-microprobe analyzer to determine the relative X-ray intensity profiles. These profiles correspond closely to concentration profiles for the constituents, and were used to identify phases and locate phase boundaries. The analysis of a single specimen after a diffusion-anneal provides only one value for the Me5Si3 phase thickness, corresponding to the time and temperature of the diffusion treatment. Consequently, each isothermal curve showing the rate of accumulation or depletion of silicide phases required several samples with identical diffusion temperatures but different diffusion times. The disilicide coatings were prepared by pyrolizing commercially pure silane in a hydrogen carrier gas. The hydrogen was purified by passage through a palladium membrane. Commercially pure tantalum and columbium sheet metal coupons, 0.005 by $ by 2 in., were used. All of the coated specimens for each system were prepared together in a single group in order to minimize coating variations among individual specimens. During pyrolysis, the brightness temperature was maintained at 1200°C. With suitable flow rates at this temperature, only the disilicides of tantalum and columbium were formed in detectable amounts. Coated specimens were subjected to diffusion an-neals in a tube furnace with automatic proportional control within ±10°C. A H2-Ar mixture, deoxidized and dried over anhydrous magnesium perchlorate, was used to prevent oxidation during the diffusion anneal. Diffusion couples were cross-sectioned, polished and examined with an A.R.L. electron-microprobe X-ray analyzer. Both metal constituents in each specimen were simultaneously scanned using a 1-p beam spot size and either 1- or 2-µ steps. Analyses were performed using the Ka radiation of columbium and silicon, and the La, radiation of tantalum. For all specimens, an acceleration voltage of 30 kv was used, and integration was made against the specimen current. LiF and A DP monochrometers were used to isolate characteristic radiations. Three or more traverses were made on each specimen. The intensity scales were adjusted using the constituent metals and standard samples of the silicide compounds which had been verified by X-ray diffraction. The relative intensity profiles were used directly, in conjunction with the standard samples, to identify compounds and phase boundaries. The stoichiometries differ considerably between the silicide compounds in both systems, and the homogeneity range for these silicide compounds is narrow. These characteristics result in marked differences in relative intensities of the fluorescing elements—differences which permit ready identification of phases and phase boundaries. Projections of both electron back-scattered images and characteristic

Jan 1, 1967

By W. H. Bassett

In considering the effects of reducing gases on hot solid copper the following conclusions have been reached. (1) Depth of deoxidation of copper heated in reducing gas is greater the smaller the amount of cuprous oxide originally present in the copper, the range studied being from 0.015 to 0.136 per cent. oxygen. It is suggested that the reason for this difference in depth of deoxidation is that, when the copper is low in cuprous oxide, the reducing gas is diluted less by the gas that is formed in the reaction than when the copper is high in cuprous oxide; and the greater the concentration of the reducing gas the deeper the deoxidation. (2) The rate of deoxidation is much mire rapid at the beginning of exposure than at the end, a condition especially noticeable at temperatures around 900° C.; that is, deoxidation is retarded as the depth penetrated by the reducing gas increases. (3) Within the accuracy of the experiments arsenic in copper up to 0.5 per cent. has no tendency to increase or decrease the action of a reducing gas on the cuprous oxide present in the copper. IN 1912 pieces of 0.365-in. hard copper rod 1/2 in. long were heated in a porcelain tube in an electric furnace, while illuminating gas was passed through. An approximate analysis of this gas is: FIG. 1.-EFFECT OF TIME AND TEMPERATURE ON DEOXIDATION RATE OF 0.365-IN. COPPER BY ILLUMINATING GAS; COPPER PLUS SILVER, 99.983 PER CENT. Hydrogen 38 per cent., carbon monoxide 30 per cent., illuminants 13 per cent., methane 10 per cent., ethane 3 per cent., carbon dioxide 3 per cent., nitrogen 2 per cent., oxygen 0.4 per cent. After heating for various lengths of time at various temperatures, samples were quenched

Jan 1, 1926

By Gorr W. W., Wyche E. H, R. Smith

The combination of high strength and corrosion resistance of cold-worked 18 Cr, 8 Ni steel has been advantageously utilized for some time, particularly in aircraft and rail car structures. There are, however, certain limitations on the use of such materials because the high strengths can be obtained only by cold-working, limiting the available products to sheets, strip, wire and tubes. The authors sought to overcome these limitations by resorting to precipitation-hardening, which has been used so successfully in nonferrous metallurgy but only to a limited extent in iron-base alloys. Accomplishment of this objective not only overcame the limitations, but also effected certain improvements in mechanical and other properties. This paper is an account of the development by Carnegie-Illinois Steel Corporation of a precipitation-hardening 18-8 stainless steel (called Stainless W‡ and tentatively identified as type 322). A description is given of its composition and metallurgical characteristics, heat-treatment, physical and mechanical properties and corrosion resistance. Development of the New Steel For a considerable length of time the authors were unable to determine the mechanism of the precipitation-hardening process that had been noted by Ffield18,19 in 18-8 Ti or 18-8 Cb after cold-working and reheating to moderately elevated temperatures. All known variables were exhaustively studied, but with little success. However, results began to indicate that chemical composition was the most important variable, particularly the ratio of austenite-forming to ferrite-forming elements. The investigators then focused their attention upon the composition, and, in particular, upon the element titanium and its mode of alloying in the presence of other elements. A heat was obtained that could not be brought to the softness level of annealed 18-8. The response to cold-straining and aging* was very marked by previous standards, and, more important, cold-straining was found to be entirely unnecessary to produce the precipitation-hardening effect. The chemical composition of this heat was: C, 0.06 per cent; Mn, 0.54; P, 0.016; S, 0.016; Si, 0.58; Ni, 7.28; Cr, 17.60; Ti, 0.90; Al, 0.17. For some time the development work, particularly on composition, was carried

Jan 1, 1947

By Gorr W. W., R. Smith, Wyche E. H

The combination of high strength and corrosion resistance of cold-worked 18 Cr, 8 Ni steel has been advantageously utilized for some time, particularly in aircraft and rail car structures. There are, however, certain limitations on the use of such materials because the high strengths can be obtained only by cold-working, limiting the available products to sheets, strip, wire and tubes. The authors sought to overcome these limitations by resorting to precipitation-hardening, which has been used so successfully in nonferrous metallurgy but only to a limited extent in iron-base alloys. Accomplishment of this objective not only overcame the limitations, but also effected certain improvements in mechanical and other properties. This paper is an account of the development by Carnegie-Illinois Steel Corporation of a precipitation-hardening 18-8 stainless steel (called Stainless W‡ and tentatively identified as type 322). A description is given of its composition and metallurgical characteristics, heat-treatment, physical and mechanical properties and corrosion resistance. Development of the New Steel For a considerable length of time the authors were unable to determine the mechanism of the precipitation-hardening process that had been noted by Ffield18,19 in 18-8 Ti or 18-8 Cb after cold-working and reheating to moderately elevated temperatures. All known variables were exhaustively studied, but with little success. However, results began to indicate that chemical composition was the most important variable, particularly the ratio of austenite-forming to ferrite-forming elements. The investigators then focused their attention upon the composition, and, in particular, upon the element titanium and its mode of alloying in the presence of other elements. A heat was obtained that could not be brought to the softness level of annealed 18-8. The response to cold-straining and aging* was very marked by previous standards, and, more important, cold-straining was found to be entirely unnecessary to produce the precipitation-hardening effect. The chemical composition of this heat was: C, 0.06 per cent; Mn, 0.54; P, 0.016; S, 0.016; Si, 0.58; Ni, 7.28; Cr, 17.60; Ti, 0.90; Al, 0.17. For some time the development work, particularly on composition, was carried

Jan 1, 1947

By A. Moskowitz, L. S. Redmerski

The corrosion resistance of stainless steels can be strongly affected by surface treatments. Changes in corrosion resistance can relate to surface composition, integrity and stability of the passive film, and to surface profile (roughness). Operations producing oxidation at the surface, such as annealing, heat treating, and welding, can result in a chromium-rich scale and a chromium-depleted metal surface. In order to restore full corrosion resistance, chemical or mechanical clean-up techniques must remove not only the oxide, but also a very thin layer of metal. Laboratory and field test studies show that these factors are particularly significant in less highly alloyed steels. Annealing stainless in a reducing atmosphere (bright annealing) avoids chromium depletion, but as-bright-annealed material does not display optimum corrosion resistance in certain environments. Electro passiva-tion can be applied to improve pitting resistance without significantly changing bright surface appearance. Potentiometric studies show that electropassivated material also displays significantly greater resistance to breakdown of passivity in acid solutions. The application of special surface finishes for appearance purposes can affect corrosion resistance. Roughness is a key factor. Samples of related appearance but with different surface profiles can show significant differences in corrosion resistance. Thus nonreflec-tive stainless with a relatively smooth surface produced by a special rolling process is much superior to material chemically etched to a similar low reflectivity. THE corrosion resistance of a stainless steel is affected by other factors in addition to its bulk composition and metallurgical structure. These other factors include those relating to the specific chemical and physical condition of the steel&apos;s surface. This paper will consider certain aspects of surface condition in relation to corrosion resistance. In particular, studies will be described on the effects of oxidation encountered in heat treating or welding operations, of passivation after bright annealing, and of different surface finishes. EFFECTS DUE TO OXIDATION When stainless steels are exposed to high temperature in an oxidizing environment, as in annealing or welding, the oxides formed are relatively rich in chromium. As a consequence of oxidation, the metallic layer directly beneath the scale may be low in chromium to some very thin but finite depth.1"8 Such a change in chromium content could lower the corrosion resistance at the surface, whether or not the oxide layer is removed. Studies were performed relating to the effect of oxidation and chromium depletion produced during annealing and welding on the corrosion resistance of stainless steels. The nominal compositions of steels used in this study and others are given in Table I. A) Annealing Studies on 17 pet Cr Steels. 1) Effects of Pickling Treatments. Studies were performed to investigate the corrosion resistance of air annealed type 430 stainless as a function of the amount of electrolytic pickling after annealing. The material used in this study had been air annealed and electrolytically pickled in the mill. All scale had been removed, and yet the material showed unusually poor corrosion resistance. Laboratory electrolytic pickling studies were performed to determine whether additional metal removal from the surface would improve corrosion resistance. Electrolytic pickling was performed in a sulfuric acid bath using various conditions of bath acidity, temperature, time, and current density. The samples were then rated for corrosion resistance in a ferric chloride spot test. For this spot test, a solution was prepared by dissolving 10 g of FeCl3 . 6H2O, 5 g of NaCl, and 2.5 ml of concentrated HC1 in 200 ml of water. An area on a specimen was cleaned and a drop of test solution was placed on the prepared area. After 5 min, the drop was rinsed off and the area wiped dry. The spot was then rated between 1 and 5 by visual comparison with standard spots. The numerical rating of the standard spots can be described as follows: 1—No clouding of surface; 2—very slight clouding of surface; 3—slight clouding of surface; 4—moderate clouding of surface; 5—strong clouding of surface. A rating of 1 or 2 was considered to have passed the test, a rating of 4 or 5 represented failure, and a rating of 3 was considered borderline. The severity of etching in this test has been related to the actual chromium content at the surface.4 Etching (clouding) occurs on type 430 stainless (rating of 4 to 5) when the surface chromium content is 14 pct or less. The effects of current density and retention time when electrolytically repickling this material in 6 pct sulfuric acid are shown in Fig. 1. Increasing the cur-rent density or retention time improved corrosion resistance as measured by the spot test. Similarly, increasing acid concentration of the bath or bath tem-perature was found to improve corrosion resistance. The conditions making for improved spot ratings resulted in increased metal removal, regardless of specific pickling conditions used, Fig. 2.

Jan 1, 1970

Jan 1, 1961

By Don K. Smith

The Reclamation Program for the Northern Zone of the Indus Plains in West Pakistan involves the construction of 30,000 irrigation wells to serve 20 million acres with an annual pumpage of nearly 40 million acre-ft. Detailed hydrologic studies indicated that mild steel would be satisfactory for casing; however, within two years after construction, about 10% of the wells began to fail due to encrustation and corrosion of the casing. A search to find a noncor-rosive substitute for the steel casing disclosed that only fiberglass-reinforced plastic pipe satisfied all requirements. The results of initial use of fiberglass have been highly satisfactory and have resulted in a lower over-all well cost. Advances in technology pomise further reduction in prices and improvement in performance. The northern zone of the Indus Basin comprises a vast area of essentially level land in West Pakistan which is irrigated by means of a complex system of canals that distribute more water to more land than any other irrigation system in the world. In spite of the development of this extensive irrigation system, production of food and fiber has not met the requirements of the country. The major reasons that crop production has not reached anticipated levels are the lack of adequate irrigation supplies and effective subsurface drainage. As a result, yields per acre are among the lowest in the world for areas where irrigation is practiced, and many thousands of acres of valuable crop land have been removed from production or seriously affected by salinity and waterlogging. To rectify the problems of irrigation supply and drainage the Government of Pakistan has undertaken a program of Salinity Control and Reclamation which is being administered by the Water and Power Development Authority. The Authority retained Tipton and Kalmbach, Inc., of Denver, Colo., as engineers for the program in the northern zone of the Indus Basin. This program consists of the construction of about 30,000 irrigation wells to provide drainage for waterlogged lands and full irrigation supplies, including leaching requirements, for all cultivated lands. The program will ultimately ensure the productivity of 20 million acres and involve an annual pumpage from groundwater storage of nearly 40 million acre-ft of

Jan 1, 1970

By W. C. McClain

The amount of vertical subsidence occurring over a longwall operation is a function of the thickness of material removed, the quantity and quality of any fill material, the width of the extraction, and the depth. The relationship between these variables is empirically determined, and subsidence can be predicted using only a few easily established constants which are subject to local conditions, such as the angle of draw. Associated with the vertical subsidence are both tensional and compressional horizontal strains. The component of strain in the direction of face advance is temporary, while the component perpendicular to the direction of working is permanently retained by the ground. It is these horizontal strains and the vertical strain (tilt) which result in damage to surface structures. It is possible to ameliorate the consequences of mining subsidence by utilizing the well-proved techniques described in this paper in the underground operations and on the surface. INTRODUCTION In the past, American mining practice in stratified deposits has been mostly restricted to production by the room-and-pillar system where a sizable percentage of the salable product is left in place as pillars. These pillars are usually regularly spaced and provide a permanent support for the roof of the mine and the surface above. The longwall system employs an advancing face which may be as much as several hundred yards long and some sort of breaking and loading machine which moves back and forth along the length of the face. The roof is supported behind the face only to a distance required to provide working space for the production machine. The supports are then withdrawn and the roof is allowed to cave. The longwall system therefore possesses the various advantages of complete extraction, thus effectively increasing reserves, while at the same time eliminating the necessity and cost of installing artificial supports such as roof bolts and heavy steel girders over large areas. Longwall mining has long been practiced in Europe, where it has undergone an involved development, culminating in the recent perfection of powered-loading machines and automatic self-propelled supports, offering high productivity. With ever-in creasing

Jan 1, 1967

By Cyril Wells, Paul E. Busby, Donald P. Hart

EARLY workers in the field have established that the diffusion of nitrogen follows normal diffusion laws. Concentration-penetration data from layer analyses of reasonably pure iron specimens nitrided in an atmosphere of CO-NH, are given in the literature,&apos; and were utilized to calculate diffusion constants for nitrogen. The diffusion of nitrogen in y-iron may be represented approximately by the equation D - 1.07x10-&apos; e-:".&apos;m&apos;"&apos;r The diflusion coefficients, D, given by this relation represent mean values, since carburization occurred simultaneously with nitriding. The rate of diffusion in a-iron has been determined from calculations based on data obtained by measuring the internal friction of samples at each of several frequencies and temperatures.&apos; The expression for the diffusion of nitrogen in a-iron derived from these experiments is D= 1.4x10-1 e-it tudent Increasing carbon content decreases the diffusion of nitrogen in a-iron.3 Oxygen, either dissolved or combined, has been shown&apos; to exert a marked influence on the diffusion of nitrogen from a nitriding atmosphere. D values increase rapidly with increasing amount of dissolved oxide in the metal, but diffusion is completely inhibited if preliminary oxidation has produced the slightest trace of iron oxide on the surface. Diffusion coefficients have also been calculated from permeability and solubility data,&apos; but these values are of questionable accuracy since the boundary conditions assumed may not actually exist. Experimental Method The method selected for determining the diffusion coefficient of nitrogen in a-iron in the present investigation was the so-called fractional saturation method. This method consists of heating the specimen in an atmosphere of H2-NH8 mixtures of known composition for a predetermined time. Following this treatment, the specimen is analyzed for nitrogen; and the diffusion coefficient is calculated from a known relationship of the fractional saturation, time of diffusion, and dimensions of the specimen. This relation is based on a solution of Fick&apos;s second law and assumes that the surface of the specimen immediately reaches a given concentration which remains constant during the diffusion anneal. Tabular solutions are available4-5 and provide the relationship between fractional saturation and the quantity \/Dt /a, where D is the diffusion coefficient in cm2 per sec, t is the time of the diffusion anneal in seconds, and a, in the present experiments, is the half-thickness of the slab specimen in cm. The method is adequately discussed elsewhere.9-10 Material The material for this study consisted of 3/32 in. thick (0.24 cm) carbonyl iron plate. The major impurities in this iron are oxygen and carbon, which are readily removed by long time high temperature treatment in an atmosphere of purified hydrogen. In order to reduce the diffusion anneal time for saturation runs, some of this material was rolled to a thickness of 0.015 in. (0.038 cm) prior to the hydrogen treatment. Hydrogen treatments were carried out in a hydrogen-purified Armco iron tube heated in a global

Jan 1, 1957

By R. S. Montgomery

Laboratory experiments simulating rock drilling were conducted on a number of commercial grades of tungsten carbide in order to determine their wear rates when they are used as inserts in percussive rock drill bits. The test rock was Barre granite and tests were made at conditions similar to those of the carbide buttons near the periphery of a large, down-hole, button bit. In addition, some wear rate measurements were made at a low blow energy. Wear rates of these carbide buttons were an extremely sensitive function of their cobalt contents and hardnesses and were proportional to e-°.57Hup to a hardness of about 91 RA. The point of minimum wear rate, which occurs at about 92 RA, corresponds to the point of maximum compressive strength. Modern percussive rock drill bits have inserts of cemented tungsten carbide on their wear faces. These inserts have drastically reduced bit wear in comparison to that of earlier all steel bits. The most common cemented carbide grade used in percussive rock drill bits contains about ten weight percent cobalt, although grades containing more or less cobalt are also used. Contrary to the case with carbide in metal-cutting tools, alloying materials are rarely used in mining grades. There are a number of designs of rock bits in current use. The most common form is an X bit which has four chisel-form radial wings. The button bit is another important design and one which has been recently developed. This design uses a flat steel face studded with relatively small hemispherically tipped carbide buttons. These types are illustrated in Fig. 1. Studies have been made of the sliding wear of cemented tungsten carbide on rock 1-4 and multiple-impact fracture&apos;, 5-6, b~t there has been comparatively little published on the percussive wear of this material although the wear of the impact face is the most important. There is some available data on the rate of dulling of rock bit inserts in actual drilling 7 but no laboratory studies. Sliding wear studies are useful for understanding the wear of coal and mineral cutting tools and gauge wear of percussive drill bits. but the

Jan 1, 1970

By Y. C. Liu

Both the habit plane of martensite and the orientation relationship between the matrix and martensite platelets of different habit planes have been investigated in binary titanium alloys with molybdenum, chromium, and iron. The effect of the mode of deformation on the martensite habit plane was studied. A micrograph of an exposed mar-tensite platelet is presented. IN the study of martensitic transformation in Ti-Mn alloys,&apos; two martensite habit planes—{334), and {344)8—were reported. The {334), habit was also observed in unalloyed titanium upon transformation,&apos; although there is disagreement with respect to the exact indices. The other habit plane, {344),, has not been reported in martensitic transformation in any other alloys. The present investigation was made to determine whether other binary titanium alloys with P-stabil-izing elements would exhibit a crystallography of transformation similar to that of Ti-Mn alloys. Furthermore, since martensite platelets can be induced by deformation under certain conditions, it was of interest to investigate whether the mode of deformation, compressive or tensile, would influence the formation of martensite platelets on a specific plane in an alloy system which possesses two martensite habit planes. Experimental Procedure The material used for the preparation of the binary alloys of iodide titanium with molybdenum, chromium, and iron had the following purities: 99.99 pct iodide titanium, 99.9 pct molybdenum, 99.423 pct chromium, and 99.9 pct iron. The compositions of alloys listed in this paper are in nominal weight percentage. All specimens used were prepared and treated according to the procedure described in reference 1, unless stated. For the subzero temperature treat,ment the following experimental schedule was followed. After specimens had undergone the grain-growth treatment, they were quenched into an ice-water bath and were then metallographically examined. In specimens of higher alloy content, no martensitic transformation was observed. In those in which mar-tensitic transformation did occur, only specimens in which the martensite platelets existed as fine needles in localized regions were used. All specimens were reannealed 17 hr at 1200°C, quenched into ice water. and the capsule was broken. They were held in the ice water for from 5 to 10 sec, then transferred to a liquid-argon bath. This stepped quenching procedure was found to be more efficient than direct quenching into liquid argon. In the latter case, as soon as the hot specimen was immersed in the liquid argon, a protective, insulating layer of argon gas formed, and the specimen continued to glow vividly in the bath for some time. In the study of the habit behavior of martensite produced by deformation, specimens were deformed at room temperature either by compression, tension, or rolling. Martensite habit planes were determined by the two-surface analysis procedure described in reference 1. A stereographic net of 153/4 in. diam was used throughout the investigation. The method for determining the orlentation relationship between martensite and the matrix follows that used by Greninger and Troiano.&apos; A diamond-polishing table with its auxiliaries was used in order

Jan 1, 1957