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By S. R. Titley

The recent emphasis placed upon the use of molybdenum as a geochemical indicator has stimulated considerable inquiry into the behavior of molybdenum in the zone of oxidation. This paper represents a summary of recent and continuing experimental work and calculations in an investigation of a portion of the system Mo-Fe-S-H20 and treats the stability of various iron and molybdenum compounds with respect to oxidation potential and pH. Using experimentally determined free energy values for ferrimolybdite, diagrams of the stability fields of this mineral have been calculated with respect to ilsemannite (?), molybdenite, pyrite and limonite. This theoretical approach is the one utilized by Garrels3'4 in studies of the relationships of various minerals in the zone of oxidation. Use of this approach is particularly suited to the study of geochemistry in the zone of supergene processes because of the low temperatures, low pressures and other relatively easily determined and duplicated factors that exist in the near surface environment. Such a study of molybdenum, however, is complicated by several factors. One of these is the fact that the strong amphoteric behavior of molybdenum makes possible a wide variety of substances and complexes whose exact chemical natures are unknown. The second factor is the dearth of thermodynamic data for many of the simplest of the possible compounds and ions important to the study. For the purpose of this study, the problem of complexes has been approached through considering only the simpler possibilities realizing that the complexes and systems so treated may be gross oversimplifications. All the complexes considered, however, have been suggested in the chemical 2,7,9,12 or geologi-cal literature. EXPERIMENTAL WORK Studies of the behavior of molybdenum ions and ferrimolybdite have been carried out in aqueous sys- tems, and reactions have been followed by simultaneous measurement and recording of pH and oxidation potential. A major problem involved in this study was the long periods of time necessary for equilibrium to be established in some of the systems considered; in a few instances, these periods exceeded four weeks, that is, four weeks during which measured conditions changed continuously. Another problem, in some instances, was the indeterminate nature of the reactions that have taken place. Because of the tendency of molybdenum to complex, reactions which take place under some of the more extreme imposed conditions of oxidation and acidity or alkalinity are unknown. However, useful data for the present work were obtained from studies of the molybdate ion and ferrimolybdite between pH 2 and 8 and under only moderately oxidizing to nonoxidizing conditions. Instruments used in the experiments were a Hewlitt-Packard Model 412A VTVM, a modified Beckman Zeromatic pH Meter and two Varian model 11 recorders. pH was measured between glass and calomel electrodes and Eh was measured between calomel and platinum electrodes. Conditions of pH were varied with 1N H2SO4 and 1N NH4OH and 1N NaOH. Eh was varied with gaseous nitrogen, oxygen or aqueous H202. Ambient temperature was essentially uniform at 24ºC and was increased in the reaction vessel by the positioning of a magnetic stirrer whose temperature was sufficient to bring the temperature to 2S°C in the reaction. The temperatures of reaction did not vary more than 1/2ºfrom 25°C. Two reactions were investigated, the ferrimolybdite-limonite-water reaction and the reduction of molybdate ion. Studies of both reactions yielded useful data that were used in preparation of the Eh-pH diagrams. The traces of the reactions are shown on Fig. 1. Ferrimolybdite-Limonite- Water: Studies of this reaction involved analysis of the solution of ferrimolybdite and simultaneous formation of ferric hydroxide. The data are summarized on Fig. 1. In this reaction, equilibrium was attained at various pH's when coexistence of the two solid phases (ferrimolybdite and ferric hydroxide) was attained. At the proper pH, controlled by the amount of ferrimolybdite and thus the dissolved content of molybdate species, both phases were observed and reaction times to complete the transition were on the order of weeks. The reac-

Jan 1, 1963

By Richard Downs, Stephen P. Burke

The oxidation of pyritic sulphur associated with coal is important for the following reasons: 1. It is the predominant cause for the formation of acid mine drainage issuing from bituminous coal seams. This drainage pollutes the streams in coal regions, making the water unfit for industrial purposes and causing the disappearance of fish and wild life. As a consequence the movement of industry and especially recreational industry, so important to the population of these areas as an alternative means of livelihood, is impeded. 2. It is instrumental in effecting a series of reactions, which bring about the degradation and ultimately result in the spontaneous combustion of bituminous coal in storage. 3. It contributes to the breaking and shattering of the coal structure and is one of the causes of roof falls and floor lifts in mines. 4. It is the primary cause of the many nuisances associated with gob piles and the refuse of cleaning plants. 5. Its proper control and application might possibly be employed in the preparation of coal to reduce the inorganic sulphur content. The research that has been conducted on the oxidation of the various forms of iron sulphides is extensive and the literature voluminous. Nevertheless, few efforts have been made to determine experimentally and with some precision the mechanism of the reaction under the conditions of its occurrence in bituminous coal mines. It has generally been accepted that the oxidation of pyritic sulphur proceeds according to the reaction 2FeS2 + 2H2O + 7O2 ? 2FeSO4 + 2H2SO4 [1] The ferrous sulphate in the drainage streams is further oxidized by air to produce ferric hydroxide and more acid. Yet the literature fails to disclose any pertinent investigation on the mechanism of this reaction. The present contribution is concerned primarily with this aspect of the problem and while the work to be reported is not yet complete, it has yielded results from which interesting and significant conclusions may be drawn.

Jan 1, 1938

By Richard Downs, Stephen P. Burke

The oxidation of pyritic sulphur associated with coal is important for the following reasons: 1. It is the predominant cause for the formation of acid mine drainage issuing from bituminous coal seams. This drainage pollutes the streams in coal regions, making the water unfit for industrial purposes and causing the disappearance of fish and wild life. As a consequence the movement of industry and especially recreational industry, so important to the population of these areas as an alternative means of livelihood, is impeded. 2. It is instrumental in effecting a series of reactions, which bring about the degradation and ultimately result in the spontaneous combustion of bituminous coal in storage. 3. It contributes to the breaking and shattering of the coal structure and is one of the causes of roof falls and floor lifts in mines. 4. It is the primary cause of the many nuisances associated with gob piles and the refuse of cleaning plants. 5. Its proper control and application might possibly be employed in the preparation of coal to reduce the inorganic sulphur content. The research that has been conducted on the oxidation of the various forms of iron sulphides is extensive and the literature voluminous. Nevertheless, few efforts have been made to determine experimentally and with some precision the mechanism of the reaction under the conditions of its occurrence in bituminous coal mines. It has generally been accepted that the oxidation of pyritic sulphur proceeds according to the reaction 2FeS2 + 2H2O + 7O2 ? 2FeSO4 + 2H2SO4 [1] The ferrous sulphate in the drainage streams is further oxidized by air to produce ferric hydroxide and more acid. Yet the literature fails to disclose any pertinent investigation on the mechanism of this reaction. The present contribution is concerned primarily with this aspect of the problem and while the work to be reported is not yet complete, it has yielded results from which interesting and significant conclusions may be drawn.

Jan 1, 1938

By W. C. Phalen

INTRODUCTION NOBODY will dispute the fact that the conservation in every legitimate manner of our valuable high-grade phosphate-rock deposits is a present-day problem of importance. The table and curve, given herewith, show. that during the past 10 years the exportation of high-grade rock has averaged very close to half the total output of the entire country. The bulk of this exportation is from Florida, for obvious reasons. It is plain that the deposits in this State, more particularly, are being wastefully depleted under a system of selecting the cream of the product for exportation to Europe, leaving the comparatively low-grade rock, running from 65 to 70 per cent., and under, in bone phosphate of lime, for our own n fertilizer manufacturers to work up when all the best rock is gone. In this paper the writer has endeavored to make a point of describing in some detail the important methods of production and conservation in Tennessee. These ought to prove of educational value to our American agriculturists and fertilizer manufacturers, and should result in a demand for the highest-grade rock, both for direct application to the soil and for use in making acid phosphate. It is certainly evident that the European

Jan 10, 1916

The Tooele plant is situated at the mouth of Pine Canyon, five miles northeast of Tooele City. The site forms one terminus of the Tooele Valley railway, which runs southwest through Tooele City to Warner, a station on the Los Angeles and Salt Lake Railroad, thirty-five miles southwest of Salt Lake City. An aerial tramway, four miles in length, crosses the Oquirrh mountains and connects the plant with the Bingham district. The plant consists of a lead-zinc flotation concentrator, lead smelter and copper smelter.

Jan 1, 1925

By F. O. Shuck, F. E. Butler

A diaphragm diffusion cell suitable for use with liquid metals was designed and tested by measuring the diffusion coefficients for a Hg-10 pct In alloy at 25°C. The binary diffusion coefficient and the coefficients for In and Hg tracers were measured at this composition. The measured coefficients for both tracers were less than the binary diffusion coefficient. When these coefficients were combined with the activity correction term of Darken, the predicted binary coefficient was somewhat higher than the experimental value. In recent years a number of investigators have been studying diffusion of liquid metals in order to gain a better understanding of the liquid state and to examine possible applications to liquid metal processing. The bulk of this work has involved either self-diffusion or diffusion of low concentrations of solute metals in an essentially pure solvent metal. The most common experimental technique employed has been the capillary-reservoir method of Anderson and saddington1 since it is well-suited to measurements involving low concentrations of solutes. As an expansion of previous studies, an investigation of the variation of diffusion coefficient over large composition ranges has been undertaken in this laboratory. Although it is possible to modify the capillary-reservoir method for such measurements, the technique loses its principal advantage of requiring only small quantities of solutes. Therefore, it was felt desirable to investigate other possible experimental techniques applicable to measurements over large composition ranges. A technique which has been used widely in measurements of other liquid systems and seemed potentially applicable to studies of liquid metals was the diaphragm cell. This method has been found to combine relative simplicity of operation with accurate and reproducible results. In use with normal liquids, the tyiical diaphragm cell utilizes a porous glass disk. However, because of the high surface tension, it is not possible to use a diaphragm of such fine pore structure with liquid metals. Furthermore. projected use at high temperatures makes the use of glass undesirable. Consequently, the first problem was the search for an appropriate cell design. EXPERLMENTAL Diaphragm Cell. A number of possible cell designs were examined. Prototypes of several were constructed and tested. The final design is shown in an exploded view in Fig. 1. The cell consists of two identical chambers, one on either side of a 0.20-in.-thick partition. The chambers are 0.15 in. deep and have a volume of 3.45 cu cm. Each chamber is provided with two small threaded holes for filling and emptying. The filling holes may be sealed with stainless-steel screws. Drilled lengthwise through the center partition is a 0.250-in.-diam hole. Inserted into this hole is a rod having seven 0.059-in.-diam holes drilled radially through it. The total "hole" volume is 0.078 cu cm. When the rod is properly aligned, the holes in it constitute the "diaphragm" through which diffusion occurs. The center section was of Teflon and the rod and face plates were of Plexiglas. Four such cells were constructed and used in this study. Subsequent to this investigation, a similar cell constructed entirely of iron was fabricated and tested at higher temperatures. Several considerations led to this final design. It is desirable to minimize the volume of the cell chambers to decrease the time required for a measurement. However, the total volume of metal in the diaphragm must be small in comparison with that in the chambers. To facilitate filling and emptying it is desirable to have a diaphragm which may be closed.

Jan 1, 1970

By P. W. Bridgman

IT is characteristic of most scientific investigators that they are not satisfied with the discovery of new facts, no matter how curious or unexpected, but that along with the factual discovery there is a constant effort to understand It appears that. one's interest in, and satisfaction with, the discovery of an array of news experimental facts is enormously increased if one has at the same time a theory or hypothesis guiding one's expectation of what sort of new experimental discovery may lie around the corner Conversely, as a theoretical physicist one's satisfaction with his theory is greatly enhanced if along with the development of the theory can go the discovery of new experimental facts, confirming or perhaps modifying the theory as it grows Of course, there have been long and stretches in the history of physics in which new data of unquestioned ultimate importance ham e piled up, without much inspiration or illumination in the way of understanding For 50 years spectroscopy had such an and history, but how irksome this was felt to be is plainly shown by the almost audible relief that greeted the first success by Bohr in injecting understanding into the situation, and by the fresh rush of experimenters into this field when the prospect of understanding had once been offered The investigations in the field of high pressure, which have occupied me for a long time,1 until the last few years have been in very much the Same sort of situation as spectroscopy before the advent of Bohr A great many kids, of data were collected for a great many solid and liquid substances, and there could be no question of the importance of these data, because the uniform change of dimensions produced by hydrostatic pressure is perhaps the simplest conceivable type of alteration to which a body can be subjected But except for a few isolated flashes, there was no theoretical illumination, so that it had to be to a large extent the enthusiasm of the collector that kept me going However, within the last few years the wave-mechanics theory of solids has progressed so rapidly that

Jan 1, 1938

"The reduction works of the Boston & Montana Reduction department, near the north end of this dam is one of the reduction plants belonging to the Anaconda Copper Mining Company, the other being at Anaconda. These works employ about 1,100 men and have a capacity of about 3,800 tons of crude ore per day. This plant is now being remodeled to embody results of experiments and investigations which have been made with a view to more economic.al treatment of ores. A brief description of the plant as it will be after the remodelling is as follows:Concentrator Department: Consists of six units or sections, each section treating from 550 to 600 tons of crude ore per day. This department is not being. remodelled at the present time. A concentrating process, however, has been developed and partially installed in the old mill, and an experimental section embodying this concentration process has also been installed at the concentrator at Anaconda."

Jan 1, 1913

By C. C. Wright, T. S. Spicer, R. G. Bowman

In recent years considerable publicity has been given to the problem of atmospheric pollution by fuel-burning equipment. Legislation has been stimulated and smoke ordinances have been enacted, the provisions of which show a definite trend toward stricter control of the emissions not only from the stacks of industrial fuel users but also from the chimneys of domestic consumers. As a result of war conditions, some slackening in the enforcement of these ordinances may be noted, but this is only a temporary expediency caused by the changes necessary in the distribution of the nation's fuel supplies and difficulties in securing the necessary equipment. Previous trends may be expected to continue in the postwar period. Largely because of the consumer demand for automatic heat, but partly because of the legislation against smoke emission, there has been a marked increase in the use of domestic underfeed stokers with the past decade. When correctly adjusted and operated, these units reduce the smoke emission materially, so that even the high-volatile bituminous coals may be burned with little or no emission of objectionable smoke. Unfortunately, however, the use of the domestic underfeed stoker introduces another problem; namely, fly-ash. Production of Fly-ash The term "fly-ash" is a misnomer, since the fly material is generally a mixture of small carbonaceous particles varying from green coal to coke, and inorganic particles ranging from fluffy ash to small particles of fused clinker. For want of a more comprehensive name, however, the term fly-ash is used throughout this paper to include all the fly material. Even with hand-fired furnaces a certain amount of fly-ash is produced, which necessitates periodic cleaning of the boiler flues or furnace radiator, the smoke pipe, and occasionally the chimney itself. With stoker operations the amount of fly-ash is increased many fold, because of the higher velocity of air travel through the fuel bed. Frequently the amount of this fly-ash attains such proportions as to constitute a definite nuisance to the householder and his neighbors and distracts very materially from the otherwise automatic or semi-automatic performance of the stoker. Virtually all the boilers and hot-air

Jan 1, 1944

By T. S. Spicer, C. C. Wright, R. G. Bowman

In recent years considerable publicity has been given to the problem of atmospheric pollution by fuel-burning equipment. Legislation has been stimulated and smoke ordinances have been enacted, the provisions of which show a definite trend toward stricter control of the emissions not only from the stacks of industrial fuel users but also from the chimneys of domestic consumers. As a result of war conditions, some slackening in the enforcement of these ordinances may be noted, but this is only a temporary expediency caused by the changes necessary in the distribution of the nation's fuel supplies and difficulties in securing the necessary equipment. Previous trends may be expected to continue in the postwar period. Largely because of the consumer demand for automatic heat, but partly because of the legislation against smoke emission, there has been a marked increase in the use of domestic underfeed stokers with the past decade. When correctly adjusted and operated, these units reduce the smoke emission materially, so that even the high-volatile bituminous coals may be burned with little or no emission of objectionable smoke. Unfortunately, however, the use of the domestic underfeed stoker introduces another problem; namely, fly-ash. Production of Fly-ash The term "fly-ash" is a misnomer, since the fly material is generally a mixture of small carbonaceous particles varying from green coal to coke, and inorganic particles ranging from fluffy ash to small particles of fused clinker. For want of a more comprehensive name, however, the term fly-ash is used throughout this paper to include all the fly material. Even with hand-fired furnaces a certain amount of fly-ash is produced, which necessitates periodic cleaning of the boiler flues or furnace radiator, the smoke pipe, and occasionally the chimney itself. With stoker operations the amount of fly-ash is increased many fold, because of the higher velocity of air travel through the fuel bed. Frequently the amount of this fly-ash attains such proportions as to constitute a definite nuisance to the householder and his neighbors and distracts very materially from the otherwise automatic or semi-automatic performance of the stoker. Virtually all the boilers and hot-air

Jan 1, 1944

By C. W. Lawr

The ores mined by the Santa Gertrudis Co. at Pachuca, Mexico, arc mainly silver-bearing; they also yield some gold and carry a little copper. Strong cyanide solutions are used to dissolve the silver and gold, and the mechanical loss of cyanide at the tailings filter has been considerable. Prior to the year 1923, the pulp, after agitation, was given a 35 to 37-min. wash with barren solution in a Butters-type leaf filter; the discharged slime cake was repulped and pumped into eight Merrill self-sluicing slime presses in which the slime was given a further wash with barren solution for 25 to 35 min., followed by a 10-min. water wash. At that time the barren solution titrated around 0.350 per cent. free KCN and 0.500 per cent. total KCN. (Aero brand cyanide is used.) It can readily be seen that a 10-min. water wash would leave considerable cyanide in the filter cake, which of course was a total loss. This averaged 0.522 kg. (1.15 Ib.) KCN per ton of solution. As the daily discharge to the dam was 1600 tons' of slime of a 2:1 ratio of liquid to solid, the value of this mechanical loss of cyanide was an important item and it's recovery held alluring possibilities. Principle of Cyanide-recovery Process As it had acquired the patent rights to theLayng (H. R.) and Halvor-sen (A. L.) processes, also those of Mills (L. D.) and Crowe (T. B.) after considerable experimental work in its own laboratory and at Tonopah, Nev., The Merrill Company of San Francisco early in 1923 notified the Mexican Corporation and compania de Santa Gertrudis of its process for the recovery of cyanide from weak wash solutions, or for the transference of cyanide from a foul mill solution to a clean alkaline solution. This method is known as the Mills-Crowe process, the principle of which is as follows: The solution from which the cyanidc is to be removed is made acid by bringing it into contact with sulfur dioxide (SO2). The acidified solution is the; transferred to a closed tank in which air and solution are brought into intimate contact. The air leaving the tank charged with HCN is then passed to another tank in which it is mixed with an alkaline solution,

Jan 1, 1930

By Erwin L. Zodrow

A geological model of the modes of formation of magnetite and its distribution in the Smallwood iron-ore mine, Labrador, Newfoundland, is given, based on observation and geological mapping. This is called the conceptual model. If mathematical expressions plus probabilistic uncertainty are used to represent the conceptual model, then this is termed a mathematical model. The purpose of this paper is to test if there exists a correspondence between the conceptual model and two related mathematical models (called factor analysis). Details of the statistical technique are given. The results of factor analyses in relation to the magnetite formations in the Smallwood mine are discussed. Several practical mine applications are presented. The difficulty of maintaining quality control over ore mined from any deposit naturally depends on geological conditions; these are usually imperfectly known to concerned mining geologists. One geological condition that would greatly facilitate ore predictions is if a relationship between the observed ore particle distribution* and its mode of origin could be demonstrated. Such a casual interrelationship is normally sought through the application of well-defined geochemical principles of primary mineralization in given geological environments. However, the application of conventional tools of geological research, including geochemistry, to areas that have undergone repeated periods of geological deformation and metamorphism subsequent to primary mineralization becomes rather difficult. More important, the interpretation of such research results are nearly impossible on an objective basis. Mineral assemblages may have been reworked and changed due to tectonic influences to the extent that the present-day observable mineralogy and ore-particle distribution can effectively obscure the mode of origin of the ore. Quantitative measurements, based on petrological investigation of mineral assemblages, reflect the sum-total of all geological influences. Which of several influences had the most effect on existing ore particle distribution is difficult to assess, for these influences can neither be measured directly nor quantified by petro-logical logical or geochemical means. The present study is concerned with the magnetite distribution and its modes of origin within the Small- wood mine,' located in the southern extension of the Labrador geosyncline; see Fig. 1. This geosyncline is thought to have undergone at least two periods of geo-tonic tectonic deformation, separated in time, since the fer-rugenous rugenous sediments were deposited." Detailed geological observations and mappings (1 in. to 40 ft) have highlighted subtle, distinctive features of the magnetite distribution in the Smallwood mine: (1) The magnetite is generally concentrated in bands or layers within this ore body; these bands alternate with specularite-rich bands and quartz bands. The banded or layered nature is common in Precambrian iron-ore deposits, and this has been interpreted as a result of changes in depositional environments. (2) The grain size of the magnetite varies; near the contacts between the iron and quartz-carbonate formations, the magnetite occurs as well-crystallized octa-hedra. In areas of intense folding, magnetite is extremely fine grained and concentrated in bands and occurs in association with earthy manganese minerals. (3) Magnetite tends to be more highly concentrated near the geological contacts of the iron and quartz-carbonate formation in the northeast part of this mine, Figs. 2, 3, and 4. (4) Magnetite is also fine grained and tends to higher concentration near and parallel to fold axes; however, in this case, the ore is much softer than given in item 2. (5) Magnetite mineralization decreases along strike and away from the areas of intense folding, i.e., towards the approximate center of the mine, Fig. 3. How can these variations of magnetite be explained on a geological basis? We can postulate a conceptual model that the distribution of magnetite appears to be related to three basic geological influences: (1) geo-tectonics, i.e., concentrations of magnetite near geological contacts of the iron and quartz-carbonate formations, the fine-grained nature of magnetite and its higher concentrations near fold axes, and decrease of magnetite towards the approximate center of the mine; (2) secondary alterations, i.e., variation of grain size of magnetite near the iron and quartz-carbonate contacts, and in areas of intense folding where magnetite occurs together with earthy manganese minerals: (3) original

Jan 1, 1971

By Robert J. Anderson

DURing the past 5 years no subject has aroused more interest or received more attention among mill operators than flotation. One reason for this is, undoubtedly, the remarkable success of the process in Australia where that country has risen to the position of furnishing one-fifth of the world's supply of zinc. The plant of the Butte & Superior Copper Co., designed by James M. Hyde in 1912, was the first important large flotation plant in this country; other installations have been made since then with considerable frequency, particularly so in the last 2 years. Without going into complete detail, it may be safely said that although flotation is a highly successful commercial process, it is more or less on an empirical basis. Upon scanning the literature, it is found that the flotation investigations have, in the main, dealt with a solution of the problems which accrue to practise; until recently no attempt was made to remove the difficulties in the way of the formulation of a consistent and harmonious theory. Of late this phase of the work has been receiving considerable attention, particularly by the United States Bureau of Mines at its Salt Lake City station, by the Mellon Institute at Pittsburgh, by the General Engineering Co. at Salt Lake City, by many of the mining schools, and private individuals almost ad infinitum. There is, at present, an enormous amount of laboratory work being carried on in flotation research, and probably the time is not far away when a generally acceptable explanation of flotation phenomena can be set forth. However, at this time, it seems as though the current technology is befogged with a superabundance of contradictory evidence; this confusion can only be dispelled as time proceeds and the knowledge of the subject becomes more complete. Many phenomena are supposed to contribute to the flotation of minerals, whether in whole or in part is a mooted question. I shall only sketch roughly the present tendency of ideas and make no reference to the first early and crude notions which have little value other than histori-

Jan 1, 1917

By Tran K. Van, Francois E. Heuzé, Richard E. Goodman

Sound design of structures founded in or upon rock requires that the deformability of each rock member involved be characterized. This can be done by means of loading tests (plate bearing, flat jacks, borehole jacks, pressure chambers, etc.) or through convergence measurements (tunnel convergence, roof sag, etc.) in exploratory works. Analysis of data will be qualitative (degree of nonlinearity, creep behavior, scattering of results over a number of sites, etc.) and quantitative (modulus of elasticity or deformation). Some of these tests involve a very bulky apparatus and are expensive to perform. On the other hand, for the purpose of mapping and describing the various rock members which occur within a given site, many feet of diamond drill holes are frequently completed. Even with the optimum equipment and expert drillers, however, quantitative characterization of the rock units on the basis of tests on returned samples is apt to be misleading; the softer and weaker components of the rock tend to be lost and the fabric of the rock block- fracture system in situ is not sampled. Laboratory moduli of elasticity have proved to be consistently higher than in-situ values selected for engineering purposes. This led to the design of instruments which would operate in boreholes, combining the advantages of a reduced size and a deeper investigation, from the surface to several tens of feet. BOREHOLE DEFORMABILITY MEASURING INSTRUMENTS In the last 10 to 15 years, a number of testing devices have been con- structed which can be inserted into a borehole to apply a load and mea-

Jan 1, 1972

By Zay Jeffries

This paper will include a brief discussion of Prof. Howe's paper on The Supposed Reversal of Inheritance of Ferrite Grain Size from that of Austenite.l The general subject of grain refining in steel and iron will also be treated. The conclusions reached are stated in the following hypotheses which are discussed more in detail below. 1. The ferrite grain size in pure iron, the ferrite and pearlite grain size in hypoeutectoid steel, the pearlite grain size in eutectoid steel and the cementite and pearlite grain size of hypereutectoid steel are not inherited from the grain size of the mother austenite. 2. The only structural feature that is generally inherited from the austenite of hypo- and hypereutectoid steels on cooling through their transformation ranges is the position of the excess ferrite or cementite at the austenite grain boundaries, sometimes causing complete and sometimes incomplete networks which outline the old austenite grain boundaries. Rapid cooling through the transformation range will cause the non-inheritance of this structural (network) feature. 3. The austenite grain boundaries themselves are nearly always effaced in all steels and also in pure iron during the At transformations. 4. The grain-size refining of steel and iron is brought about by the combined effect of non-inheritance of the transformation products on either heating or cooling, i.e., the austenite transformation products do cst inherit their grain size from the austenite on cooling through the transformation range nor does austenite inherit its grain size from the products which form austenite on heating. 5. In general, in both iron and carbon steel the larger the austenite grain size, the larger will be the grain size of the transformation products on cooling. This, of course, assumes all other conditions constant except the austenite grain size. An exception is found to this general rule in very pure iron such as electrolytic iron. In this instance small austenite grains may form very large ferrite grains on cooling through Arg.

Jan 1, 1918

By John R. Low

A number of cases of low-temperature, intergranu2ar brittle fracture of metals containing small amounts of certain impurities, have now been identified. Some degree of understanding of this phenomenon exists for the simpler binary systems of a metal and a single impurity, but the profound effects of other impurities and alloying elements in modifying this type of behavior remain unexplained. Current research in this area is reviewed and some of the newer techniques of investigation which should make possible a more quantitative study of the structure and composition of grain boundaries in impure metals are described. To indicate the subject matter of this lecture, we may begin by reviewing the experimental observations concerning low-temperature intergranular brittleness in impure metals, particularly those examples in which the embrittlement appears to result from what has been called "equilibrium grain boundary segregation."' These are the systems in which it has been impossible, at least up to now, to detect the presence of any second phase film at the brittle interfaces. When second phase films are present they are usually readily detectable by fractographic methods, often appearing as epitaxial films in geometric or dendritic patterns. An example is shown in Fig. 1 for the case grain boundary carbides in a sensitized stainless steel which failed by intergranular brittle fracture at 78?k2 In contrast to this type of embrittlement there are numerous examples of low-temperature intergranular embrittlement in which the fractographs are essentially featureless, for example, that of an oxygen-embrittled iron shown in Fig. 2. The only second phase particles visible are the small, widely separated, round oxide particles typical of the bulk material. The fracture surface is extremely smooth and the fracture path appears to follow the intergranular interface without deviation. This type of fractograph also implies that crack propagation has occurred without plastic deformation at the crack tip, since localized slip or twinning ahead of the crack would be expected to distort the interface and be readily visible in the fractograph. Such indications are occasionally seen in these fractographs, but are not characteristic. A second example of this type of fractograph is shown in Fig. 3, which is from a temper-embrittled, carbon-free, Fe-Cr-Ni alloy containing Sb, broken at 1OO?C.3 The similarity to the oxygen embrittled iron case will be apparent. In the case of the temper embrittled Cr-Ni ferrite containing antimony, it is possible to remove the embrittlement by suitable thermal treatment. The grain boundaries may then be examined by thin film transmission in the electron microscope for the material in both the nonembrittled condition and in the embrittled condition. Two boundaries are shown in dark-field transmission in Fig. 4, one in the nonembrittled

Jan 1, 1970

By H. Hansen, A. U. Seybolt, P. Yurcisin, B. W. Roberts

The Bi-Mn phase diagram in the region near BiMn was investigated, using principally thermal analysis and changes in magnetization with temperature. Of chief interest are the findings related to the magnetic transformation in Bi-Mn. THE Bi-Mn system is of both theoretical and practical interest because of the occurrence of the compound BiMn which exhibits unusual ferromagnetic properties. Because the Bi-Mn phase diagram reviewed by Hansen' (see Fig. 1) in 1936 is based on work done by BekierY in 1914 and by Siebe" in 1919, which left considerable doubt about the nature of the diagram. it appeared desirable as an aid in understanding the alloying characteristics and magnetic behavior to examine the pertinent regions of the phase diagram. The most interesting reaction is the peritectic at 445°C which forms BiMn by the reaction: Liquid + Mn(sulfield) ? BiMn(sol field) There is also a eutectic at 262° C between pure bismuth and BiMn. Hansen draws in BiMn dotted, since in 1936 evidence for its existence was uncertain. Experimental Materials—Preparation of Alloys Electrolytic manganese of about 99.97 pet purity and bismuth of 99.99 + pet purity were used as starting materials.

Jan 1, 1957

By R. Wachtell

IN order to study better the phenomena at work in various phases of diffusion of the Fe/Si system when compounded and alloyed by powder metallurgy methods, several attacks have been planned. Electrical, hardness and other measurements have been discussed e1sewhere.l,2 The metallographic phenomena will be considered here. Concerning the metallography of the ferrosilicon alloys, some initial discussion is in order. As this laboratory discovered to its chagrin, there are many traps that lie in wait for even the experienced metal-lographer when he deals with alloys of high silicon content. Chief of these is probably the anomalous behavior of these materials under conventional etching techniques. We have before us, for instance, Corson's paper" of 1928, wherein is mentioned and illustrated (probably for the first time) the peculiar "barley shell" structure sometimes found in these alloys. Again in 19412 he same author reports the structure in 5-14 pct silicon irons. Houghton and Becker mention its presence' but make only tentative effort to explain it. In 1943, Hurst and Riley6 discussed the "barley shell" and declared it to be a false structure, resulting from the peculiar and characteristic film-forming propensities of the alloy. At about the same time, Wrazej7 proved correct the contentions of Hurst and Riley, establishing pretty well the mechanisms of formation and identifying the constituents involved. Hurst and Riley6 a1so describe in their paper (1943) a "cracked film" structure, also a pseudo-morph, the precise nature of which they do not suggest. Careful examination of such a film reveals that it not only cracks but begins to curl away from the surface of the metal and peel, much in the manner of flaking paint. The careful microscopist will be able to focus on the topmost edge of the flake, and, by optical sectioning, follow it down to the metal surface. We have been able, by oblique illumination of such specimens, to observe the raised segment of the film, the shadow that it casts, and the mating segment on the metal into which it fits. As late as 1946, Hurst and Riley8 found occasion to correct misinterpretation of this "cracked film" structure in a work by others on a 12 pct Si/Fe alloy. The "barley shell" and "cracked film" pseudo-morphs are not the only ones encountered in studies of these materials. A third pseudomorph, which may, however, have some structural significance is a fine striation of the surface. Closely spaced and parallel striae extend entirely across single grains. Each grain shows a different direction for the striae, and different closeness of the spacing. The regularity of this structure, and the fact that the striae do not cross from one grain to another, suggest that the structure is a film cracking controlled in some way by the crystal plane orientation of the surface being etched. In general it is wise for the metallographer dealing with these alloys to cultivate a feeling of uncertainty not only of the more complex questions of interpretation, but also of the basic question of whether that which he sees is indeed a true representation of the structure. We have taken, as a first test of the validity of a structure, its reproducibility "in situ" after repolishing and re-etching of the samples. Thus we knew the "barley shell" to be false (fig. 1) even before encountering the definitive works on the subject. The Metallography of Silicon Diffusion in Laminate Bars: As a first step in the study of the metallography of the diffusion process, we have pressed a series of laminate bars. These bars, or "sandwiches" as we have termed them, were pressed with covering layers of iron powder, and a "filler" of the Fe/Si master alloy under study. Bar dimensions were approximately %, x 3 x 1/4 in. The total

Jan 1, 1951

By G. R. Fitterer

NONMETALLIC inclusions in steel have received much attention by metallurgists during the past few years. Many investigators have been emphatic in stating their belief that these impurities are the chief causes of steel failures, while others think that their effects are negligible. One of the main reasons that definite information on the effects of these impurities is lacking is that no reliable method has been developed for the exact determination of the amounts of these different impurities in steel. Some valuable new information has been brought out by a reliable method for nonmetallic inclusions which has been developed at the Pittsburgh Experiment Station of the U. S. Bureau of Mines, in cooperation with the Carnegie Institute of Technology and the Metallurgical Advisory Board. This procedure satisfactorily extracts some of the more common inclusions from steels, thus enabling the investigator to correlate steel failures with inclusion content. Although the data given herein are the first to be published on the subject of the electrolytic extraction method, the interest in the subject is evidenced by the fact that it is already being used by some 20 to 30 steel companies for their various purposes. Some of the comments received from these laboratories indicate that the method is highly satisfactory: the unfavorable comments, when traced to their sources, have been found to be based on some small mistake made in either installation or operation. The chief discrepancy seems to have occurred in attempts to apply the method to the extraction of inclusions from alloy steels. The procedure can be used only for the plain carbon steels and for such low alloy steels as those containing the usual amount of copper (0.2 to 0.3 per cent). Steels containing the carbide-forming alloys such as chromium, tungsten, etc., present far too many difficulties for the accurate determination of inclusions. Luckily, the iron and manganese carbides do not offer any difficulties and no contamination of the oxide-sulfide residue results. It is highly probable that some modification of the following

Jan 1, 1931

By H. M. Faust

THERE are a number of different types of power plants. Some use coal to generate steam, others use oil or gas either in the form of steam or internal combustion equipment, while still others avail themselves of water power as a source of energy. A general comparison of the relative power production with different sources of energy in the United States, for several different years is set up in Table 1. This table shows that coal was used to generate 85.6 per cent of the total heat power requirements of 1909, and only 59.2 per cent of the 1930 requirements. The increasing proportion of modern heat energy generated by the use of fuel other than coal is apparent. If coal is to maintain its importance as a source of heat energy, the necessity for its improved perform-ance, in which preparation plays an -important part, cannot be stressed too strongly.

Jan 1, 1933