Search Documents

By J. W. Freeman, E. E. Reynolds, A. E. White

Fram a study of 63 systematic alloy modifications it was found that molybdenum, tungsten, and columbium, added individually or simultaneously, and increases in chromium cause major improvements in 1200°F rupture strengths of Cr-Ni-Co-Fe base alloys. Rupture strengths were a function of the effect of composition modifications on both the inherent creep resistance and the amount of deformation the alloy would tolerate before fracture. THIS paper describes the results of an investigation of a series of alloys with systematic variations of the chemical composition of the following basic alloy: C, 0.15: Mn, 1.7; Si, 0.5; Cr, 20.0; NI, 20.0: Co, 20.0: Mo, 3.0; W, 2.0; Cb, 1.0; N, 0.12; Fe, 32.0 pct. The 62 modifications of this alloy were produced under conditions which minimized all factors influencing properties at high temperatures except composition. Melting, fabrication, and heat treatment were carefully maintained constant. Stress-rupture properties at 1200°F were used as the primary criteria of evaluation of the alloy. The objective of the study was to obtain data for determining the fundamental role of the influence of alloying elements on properties of heat-resistant alloys at high temperatures. In addition the results should be useful in determining optimum chemical compositions, the sensitivity of properties to variations in composition, and the degree to which alloy content could be reduced while retaining worthwhile properties. It is difficult or impossible to develop correlations between properties at high temperatures and systematic variations in chemical composition from published data for wrought heat-resistant alloys developed for gas turbines.' ' The main reason for this is the extreme dependence of the properties on conditions of treatment of the alloys." In most cases variation in final treatments between alloys so influences the properties that the influence of chemical composition is obscured. In addition it is recognized Table I. Basic Alloy and Some Modifications Used Basic AllOy, Variations in Element Pct Composition, Pct C 0.15 0.08. 0.40. 0.60 Mn 1.1 0.03,0.25.0.50,1.0,2.5 S1 0.50 1.2, 1.6 Cr 20.0 10, 30 Ni 20.0 0, 10,30 Co 20.0 0. 10, 30 MO 3.0 0. 1.2.3, 5, 7 W 2.0 0, 1, 5, 1 Cb 1.0 0.2,4,6 N 0.12 0.004, 0.08, 0.18 Fe 32.0 that variations exist between heats of the same alloy which are related to melting practice and that there is a strong possibility that conditions of hot working influence response to final treatments. The development of heat-resistant alloys has been based on the gradual accumulation of data roughly related to composition from extensive testing programs. There is every reason to believe that in most cases the optimum compositions have been achieved by this procedure in the alloys commercially available. There are, however, very little data showing the influence of systematic variations of composition free from the influence of other factors, particularly for alloys of the type investigated. Several investigators of cast alloys have demonstrated compositional effects, notably Grant,1-6 Epremian,t Guy,8 and Harder and Gow.9 Sykes10 eviewed the work on the wrought alloy Rex 78 and the systematic variations of carbon, copper, molybdenum, and cobalt leading to the development of the stronger Rex 337A alloy. From the papers by Wilson11 and Henry12 it is possible to deduce the beneficial effect of substituting cobalt for iron in 0.45 pct C-20 pct Cr-20 pct Ni-4 pct Mo-4 pct W- 4 pct Cb alloys. Wilson mentioned but did not present the extensive compositional studies involved in developing these alloys. Binder" showed optimum properties for 3, 2, and I pct, respectively, for molybdenum, tungsten, and columbium in 20 pct Cr-20 pct Ni-20 pct Co-30 pct Fe alloys for limited systematic variations of these

Jan 1, 1953

By Calvin Bjorne, John Keeley

In the face of a highly competitive iron ore market, the Cleveland-Cliffs Iron Co. developed a process now being practiced at the company's Republic mine in Michigan's Upper Peninsula. By this process, a specular hematite crude ore is being beneficiated to produce a high iron-low silica concentrate with a suitable size structure for the production of a high quality pellet. This process involves crushing, primary grinding and primary flotation, followed by regrinding, heating and refloating the primary flotation concentrate. The ores consist predominantly of specular hematite with relatively minor amounts of magnetite and martite in a recrystallized chert gangue. A wide variety of silicates have been identified, particularly in association with intrusives of various description. The more abundant of these are sericite, talc, grunerite and chlorite with some carbonates, primarily calcite.

Jan 6, 1964

By James Norman, Oliver C. Ralston

DIATOMACEOUS earth occurs in deposits widely distributed throughout the nation. The chief producing areas are in the Western States, where many high-grade deposits are known. Eastern deposits of diatomite are unsatisfactory for many purposes either because of impurity or because of the extremely fine particle size. Eastern users of diatomite, on the whole, must pay for transportation of the material from the west coast. The freight rate is necessarily high because of the great bulk of the diatomite. A satisfactory process of purifying the diatomaceous earths of Maryland and Virginia, which are unsuited for wide use only because of impurities, should be of value to eastern users. In the past, benefication of diatomite by wet processes has been limited to classification or sedimentation for the removal of sand from diatoms. Calcination with salt is used to produce a white diatomite when iron is present in the impurities, and small amounts of clay are rendered inactive in the process. No treatment has been developed whereby a large proportion of clay can be removed from a low-grade diatomaceous earth to give a diatomite of very high purity. In August 1937 the Federal Bureau of Mines, in cooperation with Dr. R. C. Williams, of Baltimore, undertook the problem of purifying low-grade Maryland diatomite by Froth flotation. Work was done at the Eastern Experiment Station, College Park. Unless otherwise stated, the crude diatomite used was from the Patuxent River deposits near Dunkirk. This material, consisting of roughly one-third each or clay, quartz sand and diatoms, was representative of the usual low-grade marine diatomite found in the Coastal Plain Miocene beds of Maryland and Virginia and sporadically in other Atlantic coast states. As received, it contained 50 to 60 per cent moisture and probably had been wet since its formation.

Jan 1, 1942

By Oliver C. Ralston, James Norman

DIATOMACEOUS earth occurs in deposits widely distributed throughout the nation. The chief producing areas are in the Western States, where many high-grade deposits are known. Eastern deposits of diatomite are unsatisfactory for many purposes either because of impurity or because of the extremely fine particle size. Eastern users of diatomite, on the whole, must pay for transportation of the material from the west coast. The freight rate is necessarily high because of the great bulk of the diatomite. A satisfactory process of purifying the diatomaceous earths of Maryland and Virginia, which are unsuited for wide use only because of impurities, should be of value to eastern users. In the past, benefication of diatomite by wet processes has been limited to classification or sedimentation for the removal of sand from diatoms. Calcination with salt is used to produce a white diatomite when iron is present in the impurities, and small amounts of clay are rendered inactive in the process. No treatment has been developed whereby a large proportion of clay can be removed from a low-grade diatomaceous earth to give a diatomite of very high purity. In August 1937 the Federal Bureau of Mines, in cooperation with Dr. R. C. Williams, of Baltimore, undertook the problem of purifying low-grade Maryland diatomite by Froth flotation. Work was done at the Eastern Experiment Station, College Park. Unless otherwise stated, the crude diatomite used was from the Patuxent River deposits near Dunkirk. This material, consisting of roughly one-third each or clay, quartz sand and diatoms, was representative of the usual low-grade marine diatomite found in the Coastal Plain Miocene beds of Maryland and Virginia and sporadically in other Atlantic coast states. As received, it contained 50 to 60 per cent moisture and probably had been wet since its formation.

Jan 1, 1942

By James Norman

DIATOMACEOUS earth occurs in deposits widely distributed throughout the nation. The chief producing areas are in the Western States, where many high-grade deposits are known. Eastern deposits of diatomite are unsatisfactory for many purposes either because of impurity or because of the extremely fine particle size. Eastern users of diatomite, on the whole, must pay for transportation of the material from the west coast. The freight rate is necessarily high because of the great bulk of the diatomite. A satisfactory process of purifying the diatomaceous earths of Maryland and Virginia, which are unsuited for wide use only because of impurities, should be of value to eastern users. In the past, benefication of diatomite by wet processes has been limited to classification or sedimentation for the removal of sand from diatoms. Calcination with salt is used to produce a white diatomite when iron is present in the impurities, and small amounts of clay are rendered inactive in the process. No treatment has been developed whereby a large proportion of clay can be removed from a low-grade diatomaceous earth to give a diatomite of very high purity. In August 1937 the Federal Bureau of Mines, in cooperation with Dr. R. C. Williams, of Baltimore, undertook the problem of purifying low-grade Maryland diatomite by froth flotation. Work was done at the Eastern Experiment Station, College Park. Unless otherwise stated, the crude diatomite used was from the Patuxent River deposits near Dunkirk. This material, consisting of roughly one-third each of clay, quartz sand and diatoms, was representative of the usual low-grade marine diatomite found in the Coastal Plain Miocene beds of Maryland and Virginia and sporadically in other Atlantic coast states. As received, it contained 50 to 60 per cent moisture and probably had been wet since its formation.

Jan 1, 1940

By Clifford Frondel

THE aluminum oxide known as corundum has several varieties that have been used as gem materials since ancient times. These include the red variety called ruby, the blue variety sapphire, and the asteriated types of ruby and sapphire. Asteriated sapphire was known to the ancients under the name of astrios, and descriptions of this gem were given by Pliny and other early writers. The relation of these gem materials to each other as varieties of a single species, corundum, was first clearly established by Haüy in 1805 and J. M. Güthe' in 1809. Natural gem corundum is obtained principally in Ceylon, Siam, Burma, India, and Australia. Star sapphires and rubies always have been highly prized and in recent years have become particu- larly popular in the United States. Natural star rubies of large size and fine quality are extremely rare and rank with large and fine emeralds and diamonds as the most valuable of gem stones. Interest thus attaches to the recent success in commercially synthesizing star sapphires and rubies of a size and perfection unmatched by nature. Corundum was first synthesized as crystals in 1837 by A. Gaudin, who fused alum and aluminum oxide with potassium sulphate. Numerous other syntheses have been reported in more recent years. Summaries of this work are given in Doelter's Hand-buch der Mineralchemie, Mellor's Compreheizsive Treatise of Inorganic Chemistry, and other reference works. The methods employed include the reaction in the gaseous state at high temperatures of halogen compounds of aluminum with water vapor or boric oxide; the crystallization of aluminum oxide from fusion in potassium molybdate, potassium dichrom-ate or borax; and crystallization from highly aluminous silicate melts. Red, blue, or green colored varieties can be obtained by the addition of small

Jan 1, 1955

By Colin M. Sargent

THE electron diffraction pattern as seen in the electron microscope represents an approximately plane section of the reciprocal lattice. Identifying the zone axis of a diffraction pattern is often laborious for a crystal of low symmetry, especially if several crystal orientations are present. A program has been written in FORTRAN II (Version 2) for the IBM 1620 which will assist in plotting out reciprocal lattice sections. The calculation is performed by choosing a zone axis [uvw] and determining the d spacings and angle between the planes (Ow - v) and (wO - u). (This procedure is varied slightly for zone axes with Miller indices equal to zero.) Cartesian coordinates for the reciprocal lattice points are then calculated for these planes and for (ww— [u + v]). Any reciprocal lattice points within the parallelogram formed by the origin and these three points are then computed. The input and output are best described by use of an example (Monoclinic ZrO2) used in the author's work. Input consists of two cards: 1) The crystal parameters: a, b, c, a, 8, y, e.g., 5.1477, 5.2030, 5.3156, 90.000, 99.380, 90.000. 2) Three numbers, D, E, F, e.g., 5, 3, 3.0710-the first is the limit of the sum (u + v + w) considered; the second limits the absolute value of u, v, and w to (E- 1), e.g., 2, so that zones (221) would be the highest order considered in this example; the third, F, is the required constant, yL. Output is in the format shown in Table I. The reciprocal lattice sections may then be plotted on standard graph paper and compared with the unknown diffraction pattern. (Note that no attempt has been made to deal with systematically absent reflections.) A card deck for the program is available from Colin M. Sargent, ARZ, W-PAFB, Dayton, Ohio, 45433.

Jan 1, 1969

S. F. Emmons, Washington, D. C.: Mr. Malcolmson's paper on the intensely interesting deposits of the Sierra Mojada creates a strong desire to visit the region so well described. Although it is difficult to intelligently discuss a locality that one has never seen, I cannot refrain from offering some remarks in the nature of a tentative suggestion: 1. Age of Beds.—Mr. Malcolmson speaks of the enormous thickness of limestone forming the Sierra Mojada as belonging to the Carboniferous series. If this is not a typographical error, it seems that he should present some evidence for such age, for Chism,* in his previous article on the district, says the only fossils found there were said to be Cretaceous; and it is well known by the investigations of R. T. Hill and others that the great thickness of limestone in this part of Mexico is of Cretaceous age. 2. Structure of Mountains.—Mr. Malcolmson presents good reasons for thinking that the structure of the two related mountain masses (Sierra Mojada and Sierra Planchada) is not the simple anticlinal fold given by Mr. Chism's section, it being evident that there has been faulting as well as flexure. I venture to add that the facts presented by Mr. Malcolmson seem to suggest the possibility that, instead of being simply an eroded anticline, the valley between the two ranges may have been formed, in part at least, by the irregular faulting down of the intermediate block, on the surface of which the volcanic breccia had originally accumulated at a higher level. The sections of the Exploradora and the San Josh mines, in the smooth surface of the contact, with clay selvages and the occasional slickensides, certainly suggest a structural fault between the limestone and breccia. The arrangement of some of the

Jan 1, 1902

By J. F. Myers, S. D. Michaelson, F. C. Bond

THIS work was undertaken with the object of collecting plant data on rod milling, making laboratory tests on representative samples of the various ores, and arriving at a basis for comparing the relative efficiencies of different mills operating on widely different materials and under varying conditions. These efficiencies consider only power consumption and do not include the other elements of operating costs. The over-all economic efficiency may be quite different from the consumption efficiencies with which this paper is concerned. It is hoped that these collected data will be of value in indicating the most favorable conditions of rod-mill operation. Operating-plant data on 14 different installations from 11 plants throughout the United States and Canada were collected, and laboratory tests were made on samples of these ores. The plant rod mills were all operated wet, and either in open circuit or with circulating loads so small as to be negligible. Data were obtained on one roll-crushing operation at the Utah Copper Co., for comparison. The rolls were operated wet in closed circuit with 10-mesh vibrating screens, and with a high circulating load averaging about 600 pct. This particular roll operation can be considered as a model of efficiency. The collected plant data are necessarily incomplete in some instances. Each ore was assigned a code number, and the name and location corresponding to the code number are listed in Table I when permitted. [ ] The power data in every instance refer to motor input. Net power was reported by the operator for samples I-39 and I-45, and this was increased by 20 pct to compensate for motor losses and power factor. The plant rod-mill data are listed in Tables 2 and 3. In Table 2 the speeds are calculated on the basis of partly worn rod-mill liners 2 in. thick. Where D

Jan 1, 1947

The meeting of the Board of Directors, on November 22, was attended by eight directors, the Secretary of the Institute, and eight guests. The proposed James Douglas Prize and Tablet was referred to a committee of eleven. Robert H. Richards was appointed representative of this Institute to attend the meeting of the Society for the Promotion of Engineering Education. J. V. N. Dorr was made chairman of the Finance Committee in place of George D. Barron, resigned. The sum of $200 was appropriated for the 1918 expense of the American Engineering Standards Committee; the question of an appropriation for 1919 was referred to the Executive Committee for study and report. The sum of $50 was appropriated to the Treasurer's clerk. The following representatives of the Institute were elected: W. L. Saunders to succeed himself as United Engineering Society Trustee; R. M. Raymond to succeed himself as member of Engineering Foundation Board; S. J. Jennings to succeed himself as member of Engineering Council; George F. Kunz to succeed himself as member of Engineering Council; C. F. Rand to succeed himself as member of John Fritz Medal Board of Award; E. Gybbon Spilsbury to succeed himself as member of the Library Board. To members of the Canadian Mining Institute residing in Canada or Newfoundland, the privilege was extended to subscribe to the Bulletin at the price of $5. An invitation was extended to the Mining and Metallurgical Society of America to consolidate with the American Institute of Mining Engineers. The appointment of Engineering Societies' Employment Bureau was reported. Thirty-nine members and ten associates were elected. Two members were reinstated. Extension of time for the payment of clues was granted to four members. Seventeen members on active duty at the front had their dues remitted.

Jan 1, 1919

RUfUs J. Foster, Scranton, Pa. (communication to the Secretary*) :—In answer to one of the inquiries made of Mr. Conner, and as a matter of historical record, I beg to say that the idea of supporting the strata over worked-out areas in coalmines by flushing the openings full of culm originated and was put into actual practice by the late R. C. Luther, a former member of the Institute, at that time Chief Mining Engineer, and later General Manager, of the Philadelphia & Reading Coal & Iron Co. In the early 80's the Philadelphia & Reading Coal & Iron Co. purchased from Messrs. Hecksher & Co. the Eohinoor colliery, situated in the western part of the borough of Shenan-doah, Pa. On taking possession of the colliery the Philadelphia & Reading Coal & Iron Co. made a conlplete resurvey of the mine-workings, giving an absolutely correct map which showed not only the plan of the mine-workings, but also every improvement on the surface over the workings, and the marked features of the surface of the ground. Tidal elevations were shown at every eurvey-station in the mine and on the surface, so that, as is the case with all the maps of the company, contour-maps of either the surface or the bottom of any coal-seam, or geological cross-sections, could be constructed directly from the information on the mine-maps. In a cornparatively short time after the company took possession of the colliery, the workings which extended under the western portion of the borough of Shenandoah began to cause trouble and damage dwellings and other buildings in that section of the town. The lots in this section had been sold, in many cases, to individuals by the Gilbert & Shaefer Estate, owners of the coal-lands on which the colliery was located. In

Jan 1, 1912

By W. A. Backofen, D. H. Avery, G. A. Miller

An evaluation has been made of the relative importance of yield strength (?) and stacking-fault energy (y) to the rate of fatigue-crack growth in materials of fcc structure. Pure copper and its solid-solution al-loys with aluminum and nickel were chosen for the study because they provided sufficient range in both quantities of interest that either could be varied independently of the other. Experiments involved alternating tension and compression of flat specimens which were prepared with sharpened internal notches so that most, if not all, of the crack-nucleation interval could be eliminated. Growth rate (dC/dN) was concluded to be proportional to the square of the plastic-strain amplitude (€,,) over a strain range of approximately 6x 10-4 to 6 x 10-3. The factor, k, linking dC/dN and ep in dC/dN = kEp2 increased and decreased with corresponding variations in y, but it did not respond syste?>/atically to change in ay, indicating that y is the significant variable in crack growth at constant plastic-strain amplitude. In polycrystalline material, k varied by a factor of 5 over the available range of y. In a few single-crystal experiments on Cu-A1 alloys the growth rate responded less strongly to change in y. It has been suggested that single crystals behave somewhat differently than poly crystalline material because there is more extetnsive substructure near the grain boundaries in the latter, and this facilitates crack advance by separation along subgrain boundaries. A point of some controversy in current work on fatigue relates to the effects of strength and stacking-fault energy on crack growth. In recent experiments a separation was made between the cycling intervals for crack nucleation and the subsequent growth that eventually ends a specimen's fatigue life.' The study was carried out on Cu-A1 alloys primarily, fatigued in alternating four-point bending to constant deflection. A nucleation interval of about 10' cycles (at a total strain amplitude = 0.2 pct) was found to be insensitive to aluminum content in the range 0 to 7.5 wt pct, while the growth period was increased approximately forty fold over the same compositional range. The increase was not in any sense linear, however. Rather, most of the change occurred below 4 pct A1 or a stacking-fault energy, ?, of about 15 ergs per sq cm. It was argued that the plastic-strain amplitude was approximately constant, and therefore the effect of composition must have grown out of the reduction in stacking-fault energy. Several studies have shown that, with high ?, cross slip is encouraged, subgrain structure is introduced during fatigue, and cracking is aided through propagation along subgrain boundaries.1-5 Therefore, lowering ? sufficiently to interfere with substructure formation would be expected to retard growth rate. On the other hand, it is a general rule that resistance to fatigue cracking increases as strength is raised. Accordingly, there might still have been some doubt that Y was the controlling variable, since strength would be increased as y was lowered by the aluminum additions. To help in dispelling that doubt, an experiment was made on a polycrystalline Cu-Ni alloy similar in strength to the Cu-A1 alloys but of higher ?; the crack-growth interval was found to be essentially that of pure copper.' Further support for this position on stacking-fault energy as it relates to crack growth is derived from work by Boettner and McEvily,6 in which the actual crack-growth rate was measured on samples previously notched so as to minimize the nucleation period. Unfortunately, it was necessary in isolating strength level to compare different alloy systems and grain sizes. Recognizing the complication, it was still concluded that growth may be retarded by a reduction in y, per se. A related study has also been made by Roberson and Grosskreutz.7 The zinc content of a brass was systematically changed to alter strength and stack-ing-fault energy, although not below the 15 ergs per sq cm at which pronounced change in growth interval was found in the earlier work. The results were limited to more or less conventional S-N diagrams so that nucleation and growth events could not be separated. No definite conclusions were drawn, but

Jan 1, 1967

By Oliver C. Ralston, James Norman

DIATOMACEOUS earth occurs in deposits widely distributed throughout the nation. The chief producing areas are in the Western States, where many high-grade deposits are known. Eastern deposits of diatomite are unsatisfactory for many purposes either because of impurity or because of the extremely fine particle size. Eastern users of diatomite, on the whole, must pay for transportation of the material from the west coast. The freight rate is necessarily high because of the great bulk of the diatomite. A satisfactory process of purifying the diatomaceous earths of Maryland and Virginia, which are unsuited for wide use only because of impurities, should be of value to eastern users. In the past, benefication of diatomite by wet processes has been limited to classification or sedimentation for the removal of sand from diatoms. Calcination with salt is used to produce a white diatomite when iron is present in the impurities, and small amounts of clay are rendered inactive in the process. No treatment has been developed whereby a large proportion of clay can be removed from a low-grade diatomaceous earth to give a diatomite of very high purity. In August 1937 the Federal Bureau of Mines, in cooperation with Dr. R. C. Williams, of Baltimore, undertook the problem of purifying low-grade Maryland diatomite by froth flotation. Work was done at the Eastern Experiment Station, College Park. Unless otherwise stated, the crude diatomite used was from the Patuxent River deposits near Dunkirk. This material, consisting of roughly one-third each of clay, quartz sand and diatoms, was representative of the usual low-grade marine diatomite found in the Coastal Plain Miocene beds of Maryland and Virginia and sporadically in other Atlantic coast states. As received, it contained 50 to 60 per cent moisture and probably had been wet since its formation.

Jan 1, 1940

STANDING COMMITTEES Executive-SIDNEY J. JENNINGS, chairman. Membership-KARL EILERS, chairman. Finance-J. V. N. Dorr, chairman. Library-E. GIBBON SPILSBURY, chairman. Papers and Publications-BRADLEY STOUGHTON, chairman. Nominations-R. V. NORRIS, chairman.

Jan 1, 1919

By C. B. Daellenbach, T. D. Tiemann

The prevention of quartz flotation by chelation of activating ions with the tetrasodium salt of EDTA in oleic acid flotation was investigated using a small vacuum flotation cell. It was found that flotation of quartz could be entirely suppressed in the presence of activating ions during complete flotation of hematite. It was further shown that the concentration of activating ions liberated from Wisconsin Gogebic taconite is sufficient to float quartz in an oleic acid system. Large tonnages of low grade siliceous iron ores occur on the iron ranges of the Lake Superior district. Although the lower grade nonmagnetic types are currently not of economic importance, they constitute a large future potential source of iron and steel, and hence have been the subject for extensive research on their beneficiation. TACONITES Of particular interest to the Dept. of Minerals and Metals Engineering at the University of Wisconsin have been the low grade nonmagnetic taconites of the Wisconsin Gogebic Range. These occur as five members of the iron formation and have been described in detail elsewhere.' Essentially they consist of an intimate mixture of hematite, goethite and quartz, with minor amounts of siderite, magnetite, iron containing silicates, and manganese minerals. A typical mean analysis based on the Bureau of Mines analyses' is: SiO2-52.50%, Fe2O3-43.40%, (Fe-30.38%), A12O3-1.15%, P2O5-0.07%, Mn2O3-0.29%, CaO-0.07%, (S-0.03%), Loss on ignition-2.00%. The quartz in these ores is of a microcrystalline variety,2 and so intimately associated with the iron oxide minerals that extremely fine grinding, in the order of minus 325 mesh, is required for liberation. During grinding and subsequent flotation, the concentration of quartz activating ions in the pulp becomes sufficiently high to activate quartz which floats along with the iron minerals in the presence of oleic acid. cook3 and co-workers concluded that oxidized iron ores released appreciable quantities of quartz-activating ions in water pulps. This is shown to be true in the present investigation. As a matter of fact, application of this phenomenon, as well as the intentional addition of activating calcium ions, is made use of in the an ionic flotation of silica from the iron oxide minerals.4,5 In view of the above, it becomes almost impossible to effect a sharp separation of quartz in the oleic acid flotation of the iron oxide minerals from these taconites, even with satisfactory liberation. This fact led to the current investigation to find a means of linking the activating ions with a chelating agent. The aim was to establish basic data for the quartz-water-oleic acid system which might not only be applicable to iron ores, but also to the flotation of other siliceous ores as well. EXPERIMENTAL METHODS Vacuum Flotation Cell: The vacuum flotation used in this investigation is similar to that used by previous investigators.6,7,8 The cell consisted of a 100 ml graduated cylinder with the lip removed. Vacuum from a water aspirator was applied to the cell through a trap; suitable tubing, and a rubber stopper inserted in the top of the cell. Constant absolute pressure was maintained by means of a manometer connected to the trap with a tee. Flotation: The required amount of activating ion solution was pipetted into a beaker. This was then diluted to 99.0 ml with water having a pH below that desired for the test, or so adjusted with HC1. After addition of 1.0 ml of oleic acid solution (2.0 mg oleic acid per ml), the pH was readjusted to the desired value with NaOH, and the entire solution transferred to the cell containing 1.5 gm of quartz. After vigorously agitating the cell and its contents for 2 min, the vacuum was applied to the cell and the estimated degree of flotation observed for a 3-min period. Activating ions studied included Ca++, Mg++, Al+++, and Fe+ + + added as chloride solutions. In addition,

Jan 1, 1964

By William H. Emmons

Discussion of the paper of William H. Emmons, presented at the Canal Zone meeting, November, 1910, and printed in Bulletin No. 46, October, 1910, pp. 767 to S37. CHARLES R,. KEYES, Des Moines, Ia. (communication to the Secretary*) :-It is not in a spirit of criticism that I offer a supplemental suggestion or two on the subjects covered by this valuable and highly instructive memoir. There are two points which, in my opinion, should have received greater emphasis in Mr. Emmons's excellent paper. One is the fundamental role played by the chlorides under certain conditions in ore-formation. The other is the possible establishment of geographic relationships among the four phenomena of (1) excessive chloridic content of mine-waters; (2) the abundance of chloridic compounds of the precious metals ; (3) the presence of. manganese oxides; and (4) the diminishing importance, in ore-genesis, of the metallic sulphates. Although Mr. Emmons's notes refer to gold alone, it may be pertinently asked whether the same principles do not hold good for silver and copper also, since these metals form, together with gold, a distinct and well-known chemical group. That the reactions involved apply equally well to the other two metals mentioned, is shown by a number of recent observations and discussions. Chloridic ores of silver are, as I have lately endeavored to show, mainly worked in. arid or desert regions only ; and the great deposits of disseminated copper-ores are similarly characteristic of such regions, in which both classes doubtless owe their formation to the abundance of saline materials derived from desert dusts, and to the .plentiful and almost universal presence of manganese oxide. Under these climatic conditions, silver is somewhat more abundantly deposited than copper and gold, because its chloride is so much * Received Nov. 11, 1910.

Jun 1, 1911

By C. Law McCabe, R. G. Hudson

The Knudsen cell has been employed to determine the free energy of formation of Mn7Cs in the temperature range 800" to 950°C. A value of 66,440 cal was found for hH°o for a-manganese. Measurements of the pressure of manganese over a mixed carbide, (Fe,Mn),C, points to a power relationship between aun7cs and N.4,. RECENTLY Kuo and Perssonl have reported that the carbide of manganese which is in equilibrium with graphite at temperatures up to 1100° C is Mn7Ca. There are no published data on the thermo-dynamic properties of this compound. In order to determine the stability of Mn7Ca, it appeared that, by obtaining the pressure of manganese above 8-manganese and also above Mn,C, in equilibrium with graphite, the free energy of formation of Mn7Ca from 8-manganese and graphite could be obtained. In addition, the vapor pressure of manganese, reported by Kelley From data of Bauer and Brunner,' is subject to some uncertainty and further determinations of the vapor pressure of manganese seemed warranted. In this investigation of the pressure of manganese vapor above pure manganese and also above the carbide of manganese in equilibrium with graphite the apparatus used is the Knudsen orifice cell. The same apparatus, experimental procedure, and method of calculating the pressure was used in this investigation as in one previously reported.~ Care was taken to insure that the cells were at constant weight before using them in a run. The manganese charged in the cell was CP grade powder, carbon free, obtained from the Fisher Scientific Co. A spectroscopic analysis of the manganese after appreciable amounts of it had vaporized from the Knudsen cell showed that no element was present in sufficient quantities to contribute to a weighable weight loss or to decrease the vapor pressure of manganese to any appreciable extent. The spectro-graphic analysis was 0.002 pct Cu, 0.05 pct Fe, 0.002 pct Pb, and 0.002 pct Ni. 8-manganesea is the allo-tropic form of manganese which was present in the cell at temperatures used in this investigation. The manganese carbide, Mn,Ca, was made in the following way: In a closed graphite cell manganese powder was added to graphite powder, which was made from graphite rods for spectrographic use. The manganese powder was the same as that described previously; 5 pct excess graphite was added over that required for the formation of Mn7C,. The mixture was heated in a closed graphite cell for approximately 20 hr at 1350°K under vacuum. X-ray analysis revealed that there was no manganese present after this treatment, but that the lines due to Mn,C, were present. In order to prove that there was no volatile carbide of manganese which was effusing out of the cell, the following experiment was performed: A graphite effusion cell containing graphite power, in excess of that to form Mn,C, of a desired amount, was brought to constant weight on heating at 1228°K. The required amount of manganese was accurately weighed and then added to the graphite effusion cell. The cell was placed in a vacuum at 1228°K for one week, which was the time calculated for the manganese to have effused completely, assuming instantaneous formation of Mn,C8. The cell was then weighed again. This experiment was carried out on two different occasions and both times the weight loss of the cell came within 1 pct of the weight of manganese originally charged minus the weight of manganese left in the cell, as determined by chemical analysis. These data are summarized in Table I. This agreement is considered to be within experimental error and is taken as proof that no carbide of manganese is volatile in this temperature range. It was established, by X-ray analysis, that Mn,C, formed before appreciable amounts of manganese vaporized from the metal powder which was charged. The identification of the carbide of manganese which was present in the Knudsen cell in equilibrium with graphite and manganese vapor was carried out by Kehsin Kuo at the University of Uppsala. He established that the authors' sample, which was submitted to him for analysis, contained the phase

Jan 1, 1958

By D. S. Bloom

RECENTLY a report has been published on an investigation of the MO-RU system by E. Raub.' In this report it is stated that below approximately 1200°C the system consists of two terminal solid-solution phases and the intervening two-phase field; at 1200°C and above, an intermetallic compound labeled Mo,Ru, makes an appearance. Along with some other little known systems in which it was considered possible for a u phase to form, the Mo-Ru system had been under investigation in this laboratory. Since molybdenum and ruthenium have very high melting points and also since ruthenium is expensive, the investigation was confined to X-ray diffraction by sintered powder compacts. The compositions which were studied were (in atomic percentages): 75 Mo-25 Ru, 67 Mo-33 Ru, 50 Mo-50 Ru, and 25 Mo-75 Ru. All compacts were made from the pure powders, and no chemical analyses were attempted. Each compact weighed about 5 g. All annealing was done in evacuated Vycor capsules, and even though the capsules completely collapsed at 1250°C, they still admitted no air. The results of this investigation in general corroborate the work of Raub. Up to 1150°C the two terminal solutions and the intervening two-phase field were found, and at 1200°C and above an intermetallic compound was found. However, the composition limits of the compound were estimated to lie close to 70 atomic pct Mo rather than 62.5 atomic pct Mo as Raub had reported. At least the X-ray diffraction results indicated that the 75 atomic pct Mo specimen consisted of the molybdenum solid solution plus the compound, while the 67 atomic pct Mo specimen consisted of the ruthenium solid solution plus the compound and the equiatomic composition contained only very little of the compound. The most interesting observation, however, was that the diffraction pattern of the compound was similar to that of the well known u phases, except that unusually large lattice constants were indicated. The d-values, or interplanar spacings, of the diffraction lines (as produced by filtered copper KCX radiation) of the compound are given in Table I, as determined from specimens annealed at 1250°C for 9 hr and then quenched in water. Also shown are the lines of the Mn-Mo u phase as given by Decker, Waterstrat, and Kasper,' the lines of the Fe-Mo a as given by Goldschmidt," and the lines of the Mo-Ru phase multiplied by constants in order to make comparison with the Mn-Mo and Fe-Mo patterns easier. These results indicate that the compound in the Mo-Ru system is apparently isomorphous with the other o- compounds. The rather large lattice constants of the Mo-Ru a phase are acceptable in view of the comparatively large size of the constituent atoms. The data in Table I for the Mo-Ru compound check quite well with those given by Raub, not shown here, though there are some discrepancies between the two sets of data in the estimated intensities of a few lines. Although very little is known at present about this u phase, there are some things which may be pointed out, mainly in comparison with other better known u phases. Even though molybdenum and ruthenium are in the same columns in the Table of Elements as chromium and iron, respectively, the Mo-Ru u phase contains much more molybdenum than ruthenium, while the Cr-Fe u phase centers around or very nearly around the equiatomic composition; furthermore, the Mo-Ru u is stable only above approximately 1200°C, but the Cr-Fe u is stable only below about 825 °C. With respect to its being unstable below 1200°C, the Mo-Ru u is similar to the other binary molybdenum u phases in the Co-Mo and Fe-Mo systems. Similar to the latter two systems, the Mo-Ru u apparently exists over a rather narrow composition range, whereas the Cr-Fe u at lower temperatures is stable over a much wider composition range. The Mo-Ru u thus is closer to the other molybdenum u phases than to the Cr-Fe cr phase. The most striking feature of the Mo-Ru u phase, however, is the absence of any of the transition elements of the First Long Period.

Jan 1, 1956

By P. L. Allsman

Butte mining district contains extensive manganese vein deposits forming a peripheral zone. Oxidation in the veins studied usually extends to a depth of about 75 ft. Secondary minerals formed by oxidation were found to be ramsdellite—always accompanied by intermixed pyrolusite—and cryptomelane. Enrichment of the gossan is accomplished by reduction of weight upon oxidation; theoretical enrichment is 32.2 pct. Additional enrichment is caused by leaching of soluble minerals, particularly calcium and magnesium carbonates. BUTTE mining district contains extensive manganese vein deposits in the outer zone, surrounding the copper and zinc deposits and corresponding to the well known silver zone. This article describes the mineralogy of the manganese veins, the oxidation and enrichment processes, and the use of this information in prospecting. Information was derived from a study of the Emma, Star West, Tzarena, and Norwich mines, selected as representative of the district. Vein exposures at these mines were mapped, studied, and sampled on the outcrops and throughout the oxidized zone. Specimens were cut and polished for minera-graphic examination, identification, and textural studies. Knowledge of the manganese oxide minerals is scanty, previous information having been rendered obsolete by publication of the first correctly identified list of manganese oxide minerals by Fleischer and Richmond in 1943. Positive identification of the manganese oxides is possible only by X-ray analysis. Identifications for this study were made by the author with a Phillip's Diffractometer at the Montana School of Mines and confirmed by Lester Zeihen of The Anaconda Co., using a Norelco X-ray camera. It was necessiary to re-evaluate some X-ray data, as published patterns of several manganese oxides proved to be of mixtures, mostly showing pyrolusite as a contaminant. Perhaps the most useful information on oxidation and enrichment of manganese is presented in recent books by Goldschmidt1 and Rankama and Sahama.2 While their hypotheses are not conclusively proved, all laboratory and field evidence has served to substantiate them. This information was very useful in this study. Mineralogy: The primary minerals of the manganese veins are chiefly rhodochrosite and quartz. Rhodonite is abundant in the northern part of the district and in places has been found to comprise over a third of the vein matter. A variable but generally small amount of sulfides may be present, principally pyrite and silver minerals. Sphalerite is progressively more abundant near the zinc zone. Rhodochrosite is believed to form complete iso-morphous series with siderite, ankerite, and calcite. Some variation into these compositions is common, and the intermediate forms are termed manganosid-erite, manganankerite, and rnanganocalcite. Much of the rhodochrosite is remarkably pure. Other manganese minerals in the district include huebner-ite, alabandite, and helvite. Ramsdellite (MnO2, orthorhnmbic) is the principal manganese oxide mineral, comprising perhaps two-thirds of the total oxides. It is dull to iron black, and generally massive or platy in structure. A prominent platy cleavage is the only distinguishing megascopic characteristic. Pyrolusite (MnO2, tetragonal) is next most abundant to ramsdellite, with which it is usually intimately mixed. The luster is often brighter or more metallic than in ramsdellite, and needle-like crystals are diagnostic. Pyrolusite is common in small cavities formed by oxidation of pyrite grains. It is relatively abundant in zones of high limonite content. Cryptomelane (KMnO16 tetragonal ?) is rare in the outcrop, but becomes more abundant with depth. At depths of several hundred feet it is the principal oxide. Although its appearance varies, a blue-black flinty luster and blocky to conchoidal fracture are most common. A potassium flame test will identify this mineral. Hardness of all three oxides varies from 2 to 6. The three are quite commonly intermixed, and their textures can vary greatly. The commonest textures are massive or colloform, representative of colloidal deposition, or vuggy and boxwork textures, formed by partial leaching and oxidation in place. A box-work of either ramsdellite or chalcedony is formed after rhodochrosite rhombs and is indicative of ore shoots in this district. Some replacement of both quartz and the granitic wallrock by ramsdellite has been noted, but most of the oxide was deposited as a fissure filling by fine particles. No trace of manganite, hausmannite, braunite, or manganosite was found. No minerals of the psilome-lane group were detected besides cryptomelane. Amorphous MnO, was found at several spots. A specimen of oxide coated with yellow barite crystals was amorphous and not psilomelane (BaMn9O18. 2H2O). Voids formed by the leaching of sphalerite were coated with cryptomelane, not hetaerolite (ZnMn2O4) as might be expected. No manganese sulfate minerals were found in the gossans; however manganese alum (apjohnite ?) has been re-

Jan 1, 1957

COAL DIVISION Established as a Division September 20, 1929 A. Lee Barrett, Chairman Ralph E. Kirk, Chairman-elect David R. Mitchell, Secretary-Treasurer Professor of Mining The Pennsylvania State College State College, Pa.

Jan 1, 1952