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By F. H. Wilson, E. W. Palmer

G. L. Bailey (British Non-Ferrous Metals Research Association, London, England)—I was glad to see this further work on the structure and properties of the Cu-Ni-Fe alloys of low nickel content in which we have been so interested in the United Kingdom since before the war." The authors' data on the variation in solubility of iron in both 5 and 10 pct Ni alloys with temperature is based on more detailed observations than we have made but is generally in line with our own work. The difficulty in these matters is in the identification of the structures obtained. The precipitation of the second phase which we presume to be the a' solid solution, richer in nickel and iron, from the a solution with which it is in equilibrium occurs in such a fine state of division that its resolution by ordinary micro-graphic methods is impossible in the early stages. We have published some electron micrographs which illustrate the effects observed more clearly but we agree with the authors when they say that dark staining characteristics when the alloys are subjected to sea-water corrosion are more sensitive in detecting the presence of the a' phase than is the microscope. After taking this point into consideration, however, I confess to some difficulty in understanding Fig. 4. I can only assume that the precipitates visible at such a low magnification as 150 diam in these relatively coarse forms are produced from iron-rich areas of the initial solid solution due to inadequate homogenization. If this is so I find it difficult to accept the authors' contention that such local variations in iron concentration as are capable of giving the heavy precipitates shown in Fig. 4 do not in fact materially affect the solvus surfaces of their equilibrium diagrams. I share the authors' enthusiasm about the resistance to corrosion of these alloys by seawater but I am not fully in agreement with them on the vexing question of the best iron content for these alloys. In Fig. 3 of ref. 8, we give many results showing that the resistance of these alloys to impingement attack in the Jet Test increases as the iron content rises to 2 pct. With higher iron contents pitting at shielded areas is likely to occur. Admittedly the addition of 0.75 pct Fe produces a large improvement in corrosion resistance compared with a pure 90/10 Cu-Ni alloy, but the further improvement on raising the iron to 2 pct is substantial. We recommend from 1.5 to 2 pct Fe as the desirable range from the point of view of corrosion resistance. While it is true that British practice generally uses a hard tube, the corrosion resistance of the 10 pct Ni alloys has in our work been little affected by the structural condition. Although the annealed alloys blacken in seawater, this effect seems to be superficial and not to be accompanied by any real decrease in

Jan 1, 1953

By Donald D. Carr, Lawrence F. Rooney

Perhaps no other mineral commodity in this volume has as many uses as limestone and dolomite. These carbonate rocks are the basic building blocks of the construction industry, the material from which aggregate, cement, lime, and building stone are made. Carbonate rocks, and their derived products, are used as fluxes, glass raw material, refractories, fillers, abrasives, soil conditioners, ingredients in a host of chemical processes, and much more. Although the use of limestone and dolomite goes back before recorded history, new uses and products are continually being found. Carbonate rocks form about 15% of the earth's sedimentary crust and are widely available for exploitation. Found extensively on all continents, they are quarried and mined from formations that range in age from Precambrian to Recent. Reserves of carbonate rock are large and will last indefinitely, although high-purity deposits may be absent or have limited availability in certain areas. Limestone and dolomite are so useful and so abundant that in 1981 about 644 million tons were produced in the United States. In fact, about 75% of all stone quarried or mined in the United States was carbonate rock. Sand and gravel was the only mineral commodity produced in greater quantity. In this chapter we have sought to provide the general reader an overview of carbonate rocks, their composition, distribution, production, and uses, with emphasis on developments since 1960. In doing so we borrowed extensively from our report on the applied geology of limestone and dolomite (Rooney and Carr, 1971). The literature on the limestone and dolomite resources of the United States and Canada is so vast and diverse that one can easily become mired down in print. We tried to list those references that are easily accessible and that provide the economic geologist with a starting point for more intensive study. The table listing selected references on limestone and dolomite resources in Canada and the United States reflects our attempt to be selective rather than exhaustive and to direct the reader to the best sources of detailed information. Geology Mineralogy The principal carbonate rocks used by industry are limestone and dolomite. Limestones are sedimentary rocks composed mostly of the mineral calcite (CaCO3) and dolomites are sedimentary rocks composed mostly of the mineral dolomite (CaCO3 • MgCO3). Aragonite (CaCO3), which has the same chemical composition as calcite but a different crystal structure, is economically important only in modern deposits, such as oyster shells and oolites. Aragonite is metastable and alters to calcite in time. Some other carbonate minerals, notably siderite (FeCO3), ankerite (Ca2MgFe (CO3)4), and magnesite (MgCO3), are commonly found associated with limestones and dolomites but generally in minor amounts. Because of their similar physical properties, the carbonate minerals are not easily distinguished one from the other. Specific gravity,

Jan 1, 1983

By Strathmore R. B. Cooke, Marcus Digre

That calcium will activate quartz for flotation with anionic collectors such as soaps has been known for a number of years,12'3 and the method has been applied to the concentration of various iron ores4 5 6 as well as to other materials. Clemmer gives the permissible pH range for the activation of quartz by calcium as between 9.5 and 12.5 with an optimum value of 11.0, and Hertzog7 has determined the calcium abstraction of iron ores and of Ottawa sand, but otherwise little quantitative data are available. The purpose of the present investigation was to determine those conditions under which dilute solutions of calcium chloride will activate quartz for anionic flotation and to determine the amount of calcium ion adsorbed by quartz. Those variables, the influence of which was primary, such as calcium, sodium, and hydrogen ion concentrations, were studied. Other factors which influenced the results are discussed in the description of the experiments. Three different experimental methods were used to determine the activation of the quartz. The first method was to treat a sample of ground, deslimed quartz with solutions of calcium chloride and sodium hydroxide, and to determine the calcium adsorbed by chemical analysis of the solution. Advantages are that a direct value for the amount of calcium adsorbed is obtained, and introduction of a collector which may affect the adsorption is avoided. The difficulty is to determine the extremely small differences in the calcium concentrations before and after the abstraction. The second method was to determine the activation of the quartz by observing the contact angle obtained on pressing an air bubble against the polished surface of a piece of quartz immersed in a solution of calcium chloride, sodium hydroxide, and sodium oleate. This is the well-known "contact angle" method. The third method was to determine those conditions under which an air bubble will pick up quartz particles immersed in a solution of the desired reagents. Disadvantages common to the sec- ond and third methods are that introduction of a collector is necessary to obtain bubble contact with the mineral; very small quantities of contaminant can give erroneous results; and no information is obtainable concerning the amount of calcium adsorbed. Advantages are that tedious analyses, which at best give approximate results, are avoided, and the conditions, especially for the third method, closely simulate those of actual flotation. Although the most consistent results were obtained with the third method, this paper describes the techniques used and the results obtained from each of the three methods. Distilled water and analytical grade reagents were used throughout except where otherwise stated. Between tests all glass articles were cleaned with a chromic-sulphuric acid mixture and sodium hydroxide. Abstraction Method The raw material for the tests was Ottawa sand sized between 14 and 28 mesh. Batches of 500 g of this sand were dry ground for 1 hr in an Abbe porcelain mill with 2700 g of quartz pebbles. The batches were split down to samples weighing approximately 30 g, and the weight of each sample was adjusted to exactly this value.

Jan 1, 1950

By John C. Branner

Within a couple of years I have received many inquiries in regard to the manganese-mines of Brazil. These inquiries were doubtless directed to mc because I had lived and traveled in Brazil for more than eight years, and was therefore supposed to be pretty well acquainted with its geology and mineral resources. Somewhat to my chagrin, I not only knew nothing of manganese-mines in that country, but I had never before heard of the mineral having been found here in quantity, and I did not even know in what State the mines were located. The present summer found me in Brazil again, trying to finish up some of my early geological investigations along the northeast coast, and I have used the occasion to find out something about the manganese-deposits. Very little is known of these mines, even in Brazil. While at Pernambuco I was told that they were in the distant interior of the State of Bahia. In August I reached Bahia, and there I found out, concerning the mines and their geology, enough to be worth telling for the benefit of those interested in the mining or using of this mineral. Thus far, all the manganese-ore shipped from this State has come from two mines, the principal one of which is known as the Pedras Pretas mine. This was the first mine opened, is the best developed, and was the original discovery; the second one is on an adjoining tract, and the general geology and natural conditions are about the same in both. The Pedras Pretas mine is on the Nazareth-Amargosa railway, twenty-six kilometers west of the town of Nazareth, which is on tide-water, at the head of navigation, and is reached from the city of Bahia by a small side-wheel steamer that runs across the bay of Bahia and up the Rio Jaguaripe

Jan 1, 1900

By W. R. Crane

The effect of mining in the red-ore mines of the Birmingham district has been observed for some time, but, except in a few localities, little difficulty has been experienced from disturbance of cover. Cave-ins near the outcrop and fracturing of the surface at greater distances are the most pronounced manifestations of disturbance, while limited areas at points distant from the outcrop and under greater depth of cover have actually subsided. were it not that the orebed is overlain by one or more water-bearing formations, the fracturing or settlement of the surface would not be serious; but because of these formations, fracturing of the top rock may in itself be of sufficient importance to warrant the adoption of protective measures. Further, the collapse of pillars over a wide area may develop squeezes that, if not controlled, may jeopardize the integrity of the mines and necessitate a change in development, from slopes to vertical shafts, at a much earlier period than is now contemplated. Drainsge in these mines has been discussed in papers on mining practice,' but the fact that water, varying from 0.16 to 3.46 and averaging 1.43 times the amount of ore mined, has to be pumped from the mines daily, indicates the importance of the problem and the advisability of making a thorough investigation of the source of mine water, its mode of entry into the mines, its effect upon mining conditions, and consideration of means of improving the conditions.

Jan 1, 1927

By AIME AIME

At the Annual Meeting of the Institute, February, 1908, the following amendments to the Constitution were proposed for action at a future business meeting (see Trans., XXXIX, xxvii) To Art. II. After the first sentence of this Article, add the following sentence « These classes may be subdivided by the Council, according to profession, length of membership, nationality, or other conditions not inconsistent with the provisions of this article." To Art. III. In the first line, substitute " fifteen " for "ten " dollars. At the Annual Meeting of February, 1909, action upon these amendments was postponed to the next business meeting (see Bulletin No. 27, March, 1909, p. xiv). Of these two amendments, the first has been withdrawn, as unnecessary-the subdivision thereby authorized being already practicable without such amendment. The second amendment will be acted upon at the next Annual Meeting, February 15, 1910, and the Secretary has been instructed to call the attention of members to the subject in such a way as to secure a general vote upon it. A special circular, now being prepared by the Secretary, will shortly be sent to all members. Year Book of the Institute. The Year Book of the Institute for 1910 is sent to all members and associates with this issue of the Bulletin. In addition to the lists of members enrolled Jan. 1, 1910, and arranged both alphabetically and geographically, this annual contains lists of officers, council, corporation, past officers, meetings, and notices concerning publications; also the constitution and by-laws of the Institute, and blank forms for proposal of mem-

Jan 1, 1910

By Grover J. Holt

In order to provide a clear picture of the development of the sink-and-float process of concentration as applied to the iron ores of Minnesota, a few pertinent facts should be brought out concerning the ores and the products of concentration. Iron ore is primarily a cheap commodity handled in immense quantities. The price of iron ore at present, based on a natural iron content of 51.5 per cent, varies from $2.55 to $2.70 per gross ton f.0.b. cars at the mine or washing plant in Minnesota. Last year 92,000,000 gross tons were shipped from the Lake Superior district (Minnesota, Michigan, and Wisconsin) to the furnaces. Concentrated iron ores have no greater value per unit of iron content than ores that can be mined and shipped direct from the shafts or open pits. For years only the higher grades of concentrating ores could be treated and sold in competition with the immense reserves of direct shipping ore available. These higher-grade "straight wash" ores required only the simplest treatment; namely, the washing out of fine sand from coarse ore particles. As the exhaustion of the " straight wash " ore is reached, rock is found replacing part of this sand, and the ore no longer responds to the former sizing treatment. Substantial tonnages of this marginal (jig ore) remained to be treated. Because of the limitations placed on concentrates by the furnaces—namely, low price of product and minimum amount of fines—iron-ore concentration oil has been and must continue to be a one-pass process. Only an increase in price or a change in structure of concentrates allowed by the ore consumer will encourage departure from this practice. Faced with the necessity of handling large tonnages, with the limitations mentioned, iron-ore research men have found their search for new and more efficient methods of treatment seriously handicapped and removed from the field of fine crushing. Sink-and-float treatment appeared to offer the best field in coarse concentration and has been proved by several plants to be well adapted to our problem. The use of ferrosilicon as a medium solid was decided upon. In our present practice, the ferrosilicon metal, carrying about 83 per cent iron, 15 per cent silicon and 2 per cent carbon and nonmagnetics, is crushed to pass 65 mesh and used without further sizing. When mixed with water the specific gravity of the medium may be controlled to within 0.02 per cent above or below the required gravity. Table I shows examples of a change in solid content of the medium for varying gravities. the I is based on clean ferrosilicon, whereas some contamination is always present in the mill circuit, tending to

Jan 1, 1947

By Grover J. Holt

In order to provide a clear picture of the development of the sink-and-float process of concentration as applied to the iron ores of Minnesota, a few pertinent facts should be brought out concerning the ores and the products of concentration. Iron ore is primarily a cheap commodity handled in immense quantities. The price of iron ore at present, based on a natural iron content of 51.5 per cent, varies from $2.55 to $2.70 per gross ton f.0.b. cars at the mine or washing plant in Minnesota. Last year 92,000,000 gross tons were shipped from the Lake Superior district (Minnesota, Michigan, and Wisconsin) to the furnaces. Concentrated iron ores have no greater value per unit of iron content than ores that can be mined and shipped direct from the shafts or open pits. For years only the higher grades of concentrating ores could be treated and sold in competition with the immense reserves of direct shipping ore available. These higher-grade "straight wash" ores required only the simplest treatment; namely, the washing out of fine sand from coarse ore particles. As the exhaustion of the " straight wash " ore is reached, rock is found replacing part of this sand, and the ore no longer responds to the former sizing treatment. Substantial tonnages of this marginal (jig ore) remained to be treated. Because of the limitations placed on concentrates by the furnaces—namely, low price of product and minimum amount of fines—iron-ore concentration oil has been and must continue to be a one-pass process. Only an increase in price or a change in structure of concentrates allowed by the ore consumer will encourage departure from this practice. Faced with the necessity of handling large tonnages, with the limitations mentioned, iron-ore research men have found their search for new and more efficient methods of treatment seriously handicapped and removed from the field of fine crushing. Sink-and-float treatment appeared to offer the best field in coarse concentration and has been proved by several plants to be well adapted to our problem. The use of ferrosilicon as a medium solid was decided upon. In our present practice, the ferrosilicon metal, carrying about 83 per cent iron, 15 per cent silicon and 2 per cent carbon and nonmagnetics, is crushed to pass 65 mesh and used without further sizing. When mixed with water the specific gravity of the medium may be controlled to within 0.02 per cent above or below the required gravity. Table I shows examples of a change in solid content of the medium for varying gravities. the I is based on clean ferrosilicon, whereas some contamination is always present in the mill circuit, tending to

Jan 1, 1947

By J. W. Wolfe

The Benedict-Webb-Rmbin equation of state was used in digital computer programs to make rapid determinations of natural gas equilibrium phase compositions. Mixture components were the nine hydrocarbons, methane through heptane. Comparative tests were made with data from field separators, plant exchangers and literature sources. For most tests made, the B-W-R equations predrcted component K-vallles, mixture enthalpies and phase aensities within tile accuracy of available correlations for rune-component mixtures: significant deviations were noted when mixtures contained components heavier than heptune. INTRODUCTION Rapid, accurate methods for calculating the properties of hydrocarbon mixtures are needed for predicting the behavior of natural gas processes. For example, because of the common use of two-phase separation methods in gas proccssing, calculations must be made for the density and composition of equilibrium vapor and liquid phases. In addition, predictions must often be made for the temperature and pressure changes associated with the flow of single- and two-phase natural gas fluids through heat exchangers, chokes and turbines. The complex nature of non-ideal mixtures makes rigorous calculations for these natural gas properties difficult and time-consuming. Natural gas properties have conventionally been determined with generalized data correlations. These correlations, such as the K-values presented in the NGAA Equilibrium Ratio Data Book, are usually based on some average property of the mixture and have proven to give satisfactory estimates for the properties of most oil and gas systems. Digital computers, however, have not only increased the utility of these correlations, but also have made practical the use of equations of state for calculating the properties of natural gases. Potentially, if basic pure component data are available, all the desired thermodynamic properties of mixtures can be derived from a single equation of state describing the mixture. Currently. the best equation of state for describing the behavior of pure, light hydrocarbons over single-and two-phase regions, both below and above critical pressure, is that of Benedict. Webb and Rubin.' The equation contains eight constants which are determined by empirically fitting the equation to pure-component PVT data. Benedict and his co-workers presented the clevelopment of their equation as early as 1940.2 The B-W-R equation is a modification of the Beattie-Bridgeman equation of state and gives better PVT predictions than the Beattie equation at densities above the critical density. Benedict et al. made the equation applicable to mixtures by relating the mixture constants to composition and the constants for pure compounds. These authors, in a serics of articles in 1951,' showed the accuracy of the B-W-R equation when applied to light hydrocarbons and their simple mixtures, and demonstrated the equation's utility for making vapor-liquid equilibria calculations. Since its inception, the B-W-R equation has been the subject of many papers. Numerous additions and modifications have been proposed,'-',"'-':' the purpose of most being to improve the equation's ability to predict PVT properties of specific mixture systems. In 1959, Opfell, Pings and Sage summarized much of the work on the B-W-R equation in their book on equations of state." Since natural gases are primarily mixtures of light hydrocarbons, the B-W-R equation is a natural choice for an equation of state to compute both phase equilibria and thermodynamic properties of natural gases. Consequent-

Jan 1, 1967

Jan 1, 1893

By P. E. Busby, C. Wells, M. E. Warga

Fundamental data on the rate of diffusion of boron in austenite and solubility of boron in the a and y phases of iron and steel have been obtained from deboronizing experiments and provide partial explanations for some of the phenomena observed in boron steels. The rate of diffusion of boron is about the same as carbon in austenite. The solubility of boron in austenite at normal heat-treating temperatures is less than 0.001 pct. A partial tentative Fe-B phase diagram in the important low boron concentration ranges and an equation representing the diffusion of boron in austenite are presented. A LTHOUGH a search of the literature revealed ALTHOUGHthat boron diffusion had not been studied quantitatively and systematically prior to 1948, a few qualitative observations which were made by following the diffusion of boron into iron packed in ferro-boron1-3 suggest that boron obeys normal diffusion laws and that the rate of diffusion increases with increasing temperature. The claim of Cornelius and Bollenrath1 that boron does not appear to influence the rate of carbon diffusion has recently been substantiated by Wells, Batz, and Mehl.4 Calculations based on data from the paper by Campbell and Fayv indicated that the diffusion coefficient (D) for boron in iron at 900°C is approximately 3x10 sq cm per sec; a value of 2x10-7 sq cm per sec at 1038°C has been reported by Digges et al in connection with decarburizing experiments on a commercial boron steel containing 0.43 pct C. During the period 1948 to 1950 several diffusivity constant (D) values for the diffusion of boron in the y phase of iron and steel and a number of solubility values for boron in both a and y phases were reported. It was concluded tentatively as a result of Metals Research Laboratory studies that D values for boron in y and a phases are about the same as for carbon in the comparable phasesa and that carbon up to 0.4 pct did not affect the rate of diffusion of boron in y iron above 1000°C within the limits of experimental error. Whether saturation of the y or a phases with carbon would significantly affect rates of diffusion of boron through them was then and still remains in doubt. The best estimate of Q (activation energy) was reported to be about 25,000 cal, somewhat lower than that for carbon in y iron. The solubility of boron in y iron at 1000°C was thought to be higher than 0.004 pct B but not as high as a more recent analysis of available data shows it to be. The solubility of boron in a iron at 700°C was reported to be 0.0004 pct B, but it would not have surprised the authors if the true solubility value is actually lower than this. Breaks in diffusion curves which were not understood when first obtained prior to 1950 have now been recognized as indicating solubility limits, and these are included in the present paper. Experimental Procedure Two methods were employed in an effort to determine diffusion coefficients (D) for boron in austenite. Early experiments involved the use of welded couples prepared in accordance with the procedure of Wells and Mehl,' but when the results of these experiments proved to be unsatisfactory for calculating D values, studies were continued by means of deboronizing experiments. In both cases, boron analyses following the diffusion anneal were carried out spectrographically and all D values were computed using the Grube solution of Fick's law. The precision of the spectrographic method used proved to be about equal to that reported by Corliss and Scribner" —average deviation from the mean about 5 pct of the amount present when the boron content is 0.003 pct. Concentration-penetration curves obtained from spectrographic analyses of welded couples generally indicated that practically no boron was transported across the weld interface during the diffusion anneal. Furthermore the concentration-penetration

Jan 1, 1954

By J. E. Ostberg, G. Phragmen, A. Hultgren, S. Wohlfahrt

Detailed study was made of a number of rimming ingots, both low and high carbon, and especially upon effects of superimposed air pressure. Requirement to suppress core bubbles is between 10 and 15 atm; at 6.5 atm freezing was in semikilled manner and at 3 atm, steel was of rising type. Probable mechanism of freezing under various conditions is discussed. AN earlier paper' reported an investigation made by a committee for studying rimming steel ingots appointed by Jernkontorets in Stockholm. The present paper is the outcome of some further work done by the same committee. Since the characteristics of ordinary rimming steel are connected closely .with the amount of gas liberated during freezing and since this amount of gas is governed by the pressure, it was considered of interest to ascertain in what manner and to what extent definite pressures applied to the top of the liquid steel in the mold would affect the solidification process and the consequent structure of a rimming steel of ordinary composition. The experiments were made at the Domnarfvets Steel Works. The steel was made according to normal practice in a 4-ton Rennerfelt electric furnace. Ferromanganese was added in the furnace; no aluminum was added, with one exception. Analyses of the four heats are given in Table I. The top-poured ingots measured about 12 in. sq x 48 in. and weighed about 1300 lb. One or two ingots of each heat were allowed to solidify under pressure, using a special device for admitting compressed air to the upper closed part of the mold, as shown in Fig. 1. A heavy plate sealed with asbestos was bolted to the top of the mold. The plate had a tapered aperture for pouring. Immediately after pouring the hole was closed by a wedged plug, and compressed air was admitted through a hole in the plug. Because of some delay in applying the plug, full pressure was not reached immediately. The pressure was adjusted to the desired value as indicated by a manometer. In order that the interior of the ingot might have the benefit of the pressure, the freezing of the top crust was delayed by a refractory lining applied to the top part of the mold, Fig. 1. Ingots were also cast from each heat without applied pressure, and with and without refractory lining at the top. Axial sections of ingots were cut either of the whole ingot or of some part of it of special interest; sections were polished and usually etched.' To facilitate description of structures the following terms may be used for different types of ingots solidified under gas evolution: 1. Box-hat or boot-leg ingot: Abundant gas evolution during casting and during rimming; no rim holes. 2. Normal rimming ingot: Lively gas evolution during rimming; usually rim holes in lowest part of

Jan 1, 1952

Jan 1, 1925

Jan 1, 1897

By R. D. Lord

The search for the best practical means of storing sulfide bearing tailings, where there is no residual excess of carbonate material is discussed in this paper• Usually the sulfide content decomposes, with the aid of bacterial action, and the resulting sulfuric acid escapes, along with any heavy-metal solutes, through embankments that are usually porous to some degree• The problem is typified in the tailings of the uranium operations of Elliot Lake, Ont., where mining started some 20 years ago• The approach to tailings disposal paralleled the practice for other hydrometallurgical plants treating gold and base-metal ores• Impoundment areas were designed to retain solids, and a clear and neutral overflow was considered satisfactory practice• Now experience has shown that these areas, some of which have been idle for over a dozen years, release acids in seepage and overflows to an unacceptable degree• To protect natural water courses, neutralizing plants are operated wherever required• Lime slurry is fed continuously into the tailings outflows in a quantity sufficient to raise the pH to 8•5 and precipitate heavy metals that may be in solution• The objection to this procedure is that the plants will require servicing indefinitely, unless a better remedy is found• The problem differs only slightly from that common to base-metal concentrators in that here the ore has been leached with sulfuric acid for the recovery of uranium• Any native content of calcareous material has been digested, and only that added for final neutralization is available to maintain a pH unfavorable to bacterial activity• Chemical oxidation slowly lowers the pH and when this reaches a level of 4•5 or less, bacteria become active and greatly accelerate the formation of acid. The bacterial process is probably at least ten times as fast as the chemical oxidation• Location and Processing The operations referred to, uranium and one copper mine, are located at approximately 46°N and 82°W longitude• This is typical Canadian Shield country, a land of lakes, deeply glaciated and rocky, with sparse soil which supports mixed forest cover• Drainage is to Lake Huron, 25 miles to the south• Average temperature is 45°F, ranging from -40° to +95°F• Annual precipitation is 38 in•, about half of which is snow• The ore is Precambrian, quartz-pebble conglomerate, with mineralization in the matrix• From 5 to 10% pyrite is present• All known means of pre-concentration have been tested, but a bulk sulfuric acid leach has proved the most efficient. Tailings have from the outset been neutralized before release• Current practice is to add ground limestone to bring the pH to 4•5, and then lime to raise the value to 10•5• Environmental regulations have recently been increased and the foregoing meets the new standards• Separate measures are taken to precipitate radium• Remedial Measures Since the outstanding environmental problem is the oxidation of pyrite by bacterial action, the solution is to contain the products, or arrest the process• Given the ambient temperature, favorable half of the time, four items are essential to the activity• 1) Pyrite• 2) Moisture pH < 4•5. 3) Oxygen• 4) Bacteria• Removing any one of these out of the range of tolerance will bring the reactions under control• A variety of proposals considered, and a number tested for the arrest of the process, are: (a) render embankments impermeable, (b) provide an impermeable cover, (c) cover with an oxygen absorbing layer, (d) provide a vegetative cover, (e) flood the site, (f) remove pyrite from current tailings, (g) add excess limestone to current tailings, (h) poison the bacteria• Bank Seal-On existing impoundment areas, where the embankments are several thousand yards in length, it is believed that any program of injecting sealants can have small chance of success• However, a moisture barrier is an indicated specification for future construction, and this can be highly expensive• Surface Seal-Depending on the configuration of the deposit, the downward travel of water should be prevented, and oxygen excluded• Burying a plastic membrane just below the surface has been considered, as has the application of a liquid sealant that would penetrate the surface. The objection to these remedies is the excessive cost of dealing with large areas and the expectation of only temporary benefit as a result• Frost penetration is over 4 ft, and frost action breaks up asphalt paving and all but heavy concrete in a few years• Organic Layer-An oxygen-absorbing layer, such as bark fines from paper mills has been proposed as a surface treatment• Cultivated into the tailings such material might be expected to arrest subsurface oxidation for some years• Estimates are 100 tons per acre of bark fines, or 35 tons per acre of sawdust, and these enormous quantities do not so far give assurance of providing a long-term remedy• Vegatative Cover-Several obvious benefits would result from a good growth of grass or other vegetation on abandoned tailings• While restoring the natural green of the tract the growth would prevent wind-blown dust and reduce erosion• Subsurface oxidation should be reduced, as well as the upward movement of ground moisture as occurs in dry weather. To this end, considerable research and field testing has been carried out to arrive at a formula - a prescription which will provide a self-sustaining growth on the tailings surface, or at least one that would survive with reasonable maintenance attention. Many test plots have been run with different combinations of surface treatment and seed mixtures. Generally, by addition and close cultivation of limestone, lime, and fertilizers, technical success has been demonstrated• Plants with a high tolerance for acid soil seem the more hardy, and a pH above 3 is indicated so that nutrients can be absorbed• Recommendations are for 12 to 15 tons of

Jan 1, 1977

Jan 1, 1881

By H. R. Ogden, E. S. Bartlett, A. G. Imgram

Unmodified disilicide coatirigs were applied to sheet-tensile specimens ofCb-Dg3 and Mo-TZM veJractovy- metal alloys. Coating thickness, degree of coating-substrate interdiffusion, and specimen geonzetry (notched and plain were included in the variables studied. Tensile tests were made to determine the ductile-lo-brittle transition temperature. The disilicide coating modestly increased the transition temperatlre of TZM, but had no effect on 043. Neither material condition (recrystallized or stress-velieved) nor specimen geometry (notched or unnotched) significantly altered the effects of coatings on the transilion temperatures of. the alloys. Cracks in the brittle coatings did not propagate into the substrate, and fracture modes appeared to be the same for both un-coated and coated specimens. MOST potential structural applications for refractory metals and alloys involve exposures to oxidizing environments at elevated temperatures. The general lack of oxidation resistance of these metals will require protective coatings to allow fulfillment of their potential. Currently preferred coatings for the oxidation protection of refractory metals are brittle intermetallic aluminides or silicides. These are typically formed on the surface of the refractory-metal substrate by a diffusion reaction between the substrate and a gaseous or liquid medium that is rich in aluminum or silicon. Because of the brittleness of these coatings, they will sustain no plastic deformation at low temperatures. They are frequently cracked by cooling from the coating temperature because of the thermal-expansion mismatch with the substrate alloy. Even if they survive cooling intact, they crack rather than sustain deformation under load at low temperatures. Thus, when a coated refractory metal is strained beyond the elastic limit of the coating at low temperatures, the mechanical environment of the substrate would include both static and dynamic cracks. These might be expected to influence the flow and fracture behavior of the substrate. This could be manifested in an altered fracture mode and/or an increase in the normal ductile-to-brittle transition temperature of the refractory-metal substrate. This paper presents the results of a research program that was conducted to determine the influence of the presence of a brittle surface coating on the low-strain-rate tensile behavior of typical refractory metals at low temperatures. EXPERIMENTAL PROCEDURES Material Preparation. Thirty-mil-thick sheets of molybdenum TZM alloy (Mo-0.5Ti-O.1Zr) and colum-bium D43 alloy (Cb-IOW-1Zr-O.1C) were obtained commercially. These alloys were selected as substrate materials representing two classes of materials important in current refractory-metal technology. The TZM was in the stress-relieved condition, and exhibited a heavily fibered grain structure. The D43 had been processed by the duPont "optimum" fabrication schedule,&apos; and exhibited slightly elongated grains typical of this process. Tensile specimens of two geometries were prepared from these materials: 1) plain specimens with 0.2-in.-wide 1.0-in.-long gage sections; 2) specimens similar to above, but with a 0.06-in.-diam hole drilled in the center of the gage section, providing a stress concentration factor, Kt, of 2.5. The "notch" geometry was selected to represent a typical condition of a rivet hole or other geometric discontinuities as might be encountered in various applications. Machined specimens were degreased, with a final rinse in acetone, prior to the application of coatings. Specimens of each substrate and configuration were pack-siliconizedin a particulate mixture of 80 pct A1203, 17 pct Si, and 3 pct NaF. Specimens were embedded in this mix (contained in graphite retorts) and coated in an electrically heated argon-atmosphere furnace under time-temperature conditions to effect nominal 1- and 3-mil-thick silicide coatings: Coating Thickness, mils Thermal Treatment 0.6 to 1.4 24 hr at 982°C 2.4 to 3.2 48 hr at 1093°C Coating kinetics were similar for both the TZM and D43 substrates. These treatments had little or no visible effect on the substrate microstructure as determined by optical metallography. The coatings on TZM were essentially single-phase unmodified disilicides, while those on D43 showed substantial evidence of modification by proportionate reaction with the respective substrate elements or phases, as shown in Fig. 1. It was recognized that these coatings might not be particularly desirable regarding protective capability. However, it was desired to circumvent possible inter -ferring chemical interaction with the substrate by pack additives such as chromium, titanium, boron, aluminum, and other elements that typify the better protective coatings for these materials.&apos; Thus, the results presented apply specifically to the simple silicide coatings investigated. They may not be rep-

Jan 1, 1967

Jan 1, 1934

By Ross W. Smith, Mine-Yun Hwang

Many studies have been made of the microflotation of quartz (de Bruyn, 1955; Fuerstenau, 1957; Somasundaran, 1964; Smith, 1973; Fuerstenau, 1976; and Smith and Akhtar, 1976) and alumina (Somasundaran, 1964; Smith and Akhtar, 1976; Fuerstenau and Palmer, 1976; Fuerstenau and Akhtar, 1976; Fuerstenau and Yamada, 1963; Modi and Fuerstenau, 1960) using various anionic and cationic heteropolar hydrocarbon surfactants as collectors. A few studies have been made on these materials using amphoteric hydrocarbon collectors (Wrobel 1969 and 1970; Smith. Haddenham, and Schroeder, 1973; Gupta and Smith, 1975) and only a few studies have been made on the use of fluorocarbon surfactants as flotation collectors Cooke and Talbot, 1955; Somasundaran and Kulkami, 1973). The present investigation compares microflotation response of the two minerals in hydrocarbon and fluorocarbon collector systems of the anionic, cationic, and amphoteric types. An attempt is made to relate flotation response of the minerals to their electrokinetic behavior and the pKa values of the collectors.

Jan 1, 1981