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By R. R. Jones, R. W. Kraft

Zn-Mg2Znn eutectic alloys nzay freeze willr either rodlike or lanzellar rnorphology. Alloys with slighlly more than /he eutectic arrzount of rnagnesillrn usually contain three-cnned dendrjles of MgzZnll in a eutec-lic ttlulris. All three morphologies haue the same cryslallographic orientution relationship: (0UOl) zn - 11 (111) Mg2Znll and (2310)Zn 11(101) Mg2Znll, but u3ith different prej-erred groulth direclions. The lurnellae lo rods transifion in con/rolled ingols qf euleclic cotnposition occurs because lhe large kinelic undercooling due to MgzZnll minirrzizes /he ejj-ecl of the solid-solid inlerface energy. The eutectic morphology is influenced by the presence of lhree-nned dendrites 0-f MgzZn11 which may conlrol /he rricroslrccture by acting as nuclealion sites. In recent years there has been much interest in eutectic solidification and several theories have been proposed. One of the confusing factors is the existence of various morphologies in which the solidified phases may form. The lamellar microstructure seems to be most common in metal eutectics, and it has been claimed' that all regular eutectics should be lamellar if sufficiently pure. However, there still remain eutectic alloys which are not lamellar or which change their morphology as a function of growth conditions. The eutectic between zinc and the intermetallic phase Mg2Znll was chosen for this investigation because it has been found to solidify in more than one morphology. The diagram in anssen' locates the eutectic point at 3.0 wt pct Mg and 367°C. lliott gives 364°C as the eutectic temperature, leaving the phase compositions unaltered. Since the growth conditions determine the micro-structure of the solidified alloy, the factors controlling the transition from one morphology to another could be studied. The lamellae to rods transition is of particular interest. PROCEDURE Alloys were prepared from carefully weighed portions of 99.999 pct Zn and 99.97 pct Mg by melting in Pyrex containers under argon and casting into graphite boats. The resulting ingots were remelted under argon and solidified unidirectionally in a horizontal tube furnace at growth rates ranging from 2.0 to more than 50 cm per hr under a temperature gradient, measured over a 5-cm length, of 9" to 14°C per cm. The solid-liquid interface appeared to be planar at all growth rates although no attempt was made to confirm this by decantation or quenching. A few ingots were allowed to freeze uncontrolled. Most alloys were of the nominal eutectic composition, 3.0 wt pct Mg according to Hansen2 and lliott, but some contained as much as 3.35 wt pct Mg. Chemical analyses were not run since metallographic examination confirmed that the desired composition was achieved. Specimens were cut from the middle portion of the ingot normal to the growth axis, polished mechanically, and etched with 2 pct Nital. Suitable areas were selected for the determination of crystallographic orientation relationships by a tiontechniqueof described previously by one of the authors.4 The (2310) planes of zinc and the (8701, {944}? (1032) planes of Mg2Znll were found suitable for orientation determination; experimental error was on the order of 2 or 3 deg. RESULTS Three different morphologies were found in the unidirectionally solidified alloys: lamellar eutectic, rod-like eutectic, and a structure whose most predominant characteristic was the presence of three-vaned (cellular) dendrites of Mg2Znll. These dendrites were only found in alloys with more than the eutectic amount of magnesium. In some ingots fine hexagonal needles of Mg2Znll surrounding a core of MgZn2 were observed. They were probably due to incomplete alloying and seemed to have no effect on the eutectic morphology. In addition hexagonal spirals like those discussed by Fullman and wood5 and Hunt and acksonh ere observed in some ingots frozen without directional control. Both MgZZn,, and MgZnz were detected by X-ray diffraction in these alloys. Since the morphology could not be grown unidirectionally and no characteristic orientation relationship between the phases was found, further study was limited to the lamellar: rodlike, and three-vaned dendrite morphologies. Alloys of Eutectic Composition, No Dendrites. The mcrostructures of allovs with no three-vaned dendrites were either lamellar or rodlike depending on the growth rate. At rates below 10 cm per hr the morphology was lamellar, consisting of two sets of parallel plates intersecting at about 54 deg like the Mg-MgzSn eutectic described by raft.7 At growth rates faster than 14 cm per hr the microstructure showed rods of zinc in a matrix of MgnZnll, while intermediate rates yielded mixtures of rods and lamellae in small groups. The lamellar "grains" were often several millimeters in cross section, but contained small irregular areas which divided each grain into perfect islands 100 or 200 p in diam. Lamellae were parallel to each other throughout the grain in spite of these defects in the structure, Fig. 1. Rods, on the other hand, could only be produced in small groups arranged like fish scales and separated by irregular areas of appreciable thickness, Fig. 2. Alloys Not of Eutectic Composition, With Dendrites. In alloys with 3.1 to 3.35 wt pct ME,-. three-vaned dendrites bf MgzZnll were usually found surrounded by eutectic. At growth rates slower than about 10 cm per hr the dendrites were separated from each other by small areas of both lamellar and rod eutectic, Fig. 3.

Jan 1, 1969

By Linn Bradley

Introduction MARKED differences of opinion have been expressed by engineers interested in cleaning iron blast-furnace gases for use in hot-blast stoves and under boilers, in reference to the advantages of a hot-dry method over a cold-wet method. One point at issue involves the sensible heat energy in the moisture contained in the gas. Some advocates of the cold-wet methods claim that the condensation and resultant removal of the greater portion of this contained moisture by wet scrubbing, spraying or similar methods, results in a saving of some of this sensible heat energy, by reason of the fact that water vapor has a high capacity for sensible heat energy and may carry from the exit of a hot-blast stove, for example, more heat units than are sacrificed or lost when the gas is cleaned by this cold-wet method. Other advantages claimed for the latter method are: That gas burns more readily when it is free from moisture in any form; that because gas is made denser by cooling and removing the moisture it has a higher calorific value than hot gas carrying moisture; and that higher flame temperatures are obtained when the gas is cleaned by the cold-wet method. A search through the available literature fails to disclose any extensive calculations or records of conditions obtained in practice, bearing upon these phases of gas cleaning. This paper deals with these problems from the standpoint of the economy of using a gas of higher flame temperatures, of improved stove design, and of economy in the gas-cleaning department. Calculations have been made which show that by cleaning the gases by a cold-wet method the sensible heat energy of the blast-furnace gases is greatly reduced; and, in general, this loss of heat energy is far greater than that lost from the stoves or boilers due to the sensible heat capacity of the water vapor if carried away by the exit gases. By making use of the

Jan 2, 1917

By E. P. Pfleider

Important economic planning by industries, companies, financial firms and governments is predicated on estimates of future growth potential. Prior to the passage of the Taconite Amendment by the people of the State in November 1964, various admittedly conservative forecasts were made of the future of Minnesota's iron ore industry. Since that date, 3 new taconite plants are under construction, 2 are being expanded, one has just gone "on stream," and a seventh is in the design stage. These plants have a total capacity of about 35 million tons of pellets annually. The pessimism of 1964 today is being replaced by unbounded optimism. In the light of such recent developments, it becomes essential to update forecasts related to production, employment and capital investments. New projections show 50 to 58 million tons of pellet production from Minnesota by 1975. This tonnage, together with some 6 to 8 million of natural ores, should provide an annual full-time employment of 15,000 by the mining companies, plus 700 in related railroad and power producing activities and 1000 in plant construction. Total capital investment in new plants should reach $1.5 billion by 1975 and $2 billion by 1990. These current estimates indicate that the conservative goals as set in 1964 for the year 1990 should actually be achieved by 1975 or 1980. BACKGROUND Various forecasts1,2,3 have been made of the future consumption and production of iron ores within the United States. The most recent of these is by Harrison,1 delivered at the American Mining Congress meeting in Las Vegas in October. His estimates reflect the latest iron ore developments on a world wide front as well as the accelerating trend toward pellets. Minnesota's Natural Resources council prepared a detailed report in 1964 outlining the various factors that affect the future of Minnesota's iron ore industry. It presented estimates predicated on the

Jan 1, 1967

By E. E. White

(Cleveland Meeting, October, 1912.) IN, August, 1911, I read a paper before the Lake Superior Mining Institute' on surveying and sampling diamond-drill holes. The present paper gives a more thorough description of these methods, together with a few changes and notes suggested by further experience. Since August, 1911, the methods, used constantly by the Cleveland-Cliffs Iron Co., have been developed to a higher degree of efficiency, and have given great satisfaction. Until a few years ago but little attention was paid to the determination of the actual course of drill-holes, to the accurate sampling and analysis of the material, or to the scientific location of the drill-holes. It has now been common practice for several years in many districts to test the inclination of drill-holes by etching glass tubes with hydrofluoric acid, but the direction of deviation from the vertical has not often been determined. Methods of determining the direction by means of a compass were first developed in connection with drilling in Victoria. The latest method used on the Rand in South Africa has been recently described by John I. Hoffman.2 In the same paper Mr. Hoffman describes an ingenious method of wedging-off a drill-bole so as to start new holes at several successive points. By this means a hole can be deflected in any desired direction, and the curvature can be controlled to a considerable extent, provided the rock is soft enough to permit the hole to be wedged off. Unfortunately, in the Lake Superior district, the jasper iron-formation is so hard that it is very difficult, if not impossible, to do this. I tried to deflect one hole so as to avoid drill-rods stuck in the hole, by using a 1 Proceedings of the Lake Superior Mining Institute, vol. xvi., pp. 100 to 120 (1911). 2 Recent Practice in Diamond-Drilling and Borehole Surveying, Bulletin No. 91, Institution of Mining and Metallurgy (Apr.. 11, 1912).

Nov 1, 1912

By Albert F. J. Bordeaux

Discussion of the paper of Albert F. J. Bordeaux (Bi-Monthly Bulletin, No. 23, September, 190S, pp. 629 to 640). A. H. BROMLY, Zihuatanejo, Guerrero, Mexico (communication to the Secretary*) :-The following criticism of what "is offered as a summary which may be found useful by mining engineers," is not dictated by any captious spirit, but in the interest of historical and scientific accuracy. The States of Queretaro and Oaxaca have produced sufficient silver to warrant more extended notice. Referring to Pachuca, State of Hidalgo, the somewhat loose and. inexact statement is made that "the ore-deposit is an andesite, intermixed with quartz-veins, rich from the surface." A better description would be,-the ore-deposits consist of quartz-veins in andesite. It is notable that many of the rich shoots worked in recent days did not come to surface. In consequence, Pachuca, is often quoted by the ill-informed as a camp in which values improve with depth, the truth being that the veins carry shoots, or clavos, some of which were exposed at surface and some not. The name of " electric plow," applied to the mechanical stirrer of recent use, is certainly not to be recommended. The stirrer, or agitator, consists essentially of a traversing gang-plow, operated by power through shafting, drums, and wire-rope. The fact that in certain plants the motive-power used is electricity does not make it an electric plow. Such a name suggests a machine of which the motor is an essential and integral part; which is not so in this case. A lathe in a factory driven by water-power is not called a hydraulic lathe. My experience agrees with Dr. Raymond's note as to azulaque, which in sortie districts is also applied to blue copper carbonate. The El Oro, Esperanza, and Mexico mines should be allocated to the State of Mexico; the Dos Estrellas being in Michoacan, as stated. The El Oro quartz certainly does not appeal to me

May 1, 1909

By Augustus Locke

San Francisco Meeting, October, 1911.) Two Opposed Interpretations of the Tonopah Structure.-The important geological publications concerning the Tonopah mining-district are those of Spurr 1 and of Burgess.2 In these publications are presented fundamental differences of interpretation, which are the more interesting because both authorities have had ample opportunity for observation, and because both are geologists of proved ability. I was vastly puzzled to know which had the better of it, and in order that I might reach a conclusion in my own mind, I recently spent some time in the district going over the physical evidence. Surprising as it may seem, this evidence looks agreeably conclusive. A review of it will, I believe, be of interest to those who are familiar with the previous publications. The general geological features of Tonopah are shown in Fig. 1, and the differences of interpretation referred to are outlined in the accompanying notes. Briefly, Burgess regards the various rocks as flows, lying in the order of their deposition. Spurr regards them in part as flows, and in part as flat-lying intrusives. The disagreement, then, concerns the rocks regarded on the one hand as intrusives, and, on the other hand, as flows. These rocks are chiefly the so-called calcitic andesite, the upper rhyolite, and the lower rhyolite. Economic Importance of the Question of Interpretation.-The economic importance of the question of interpretation is, of course, limited to its bearing on the probable distribution of 1 Geology of the Tonopah Mining District, Nevada, Professional Paper No. 42, U. S. Geological Survey (1905). Report on the Geology of the Property of the Montana-Tonopah Mining Co. (1910). An abstract of this report is given in the Mining and Scientific Press, vol. cii., No. 16,p. 560 (Apr. 22, 1911). 2 The Geology of the Producing Part of the Tonopah Mining District, Economic Geology, vol. iv., No. 8, pp. 681 to 712 (Dec., 1909).

Feb 1, 1912

By C. A. LINDBERG

Several new methods have been developed on the Iron Range to remove the material adhering to truck bodies in freezing weather. A machine known as a Gradall, incorporating the features of digging both above and below the horizontal, digging angle of blade control, full revolving, travel almost anywhere, and operated by one man, has proven successful in trials at body cleaning. Several of these units are in use with great saving in box-cleaning costs and improvements in efficiency of the truck operation with full capacity boxes. In addition to their winter use, the same machines have been used for ditching and excavating in the summer with great saving. The latest method of combating this freezing problem is to carry the exhaust from the engine through the body, making use of the tremendous heat that is now being wasted. To do this, the present wood sandwich which is used between the bottom of the box and the wear plate is removed and replaced with angles or channels run lengthwise of the box and spaced to permit gases to flow between or through them and also provide a good sup- port for the wear plate. The channels or angles are cut a little short on each end to form a cross passage that permits the gases to flow through the area. In the front end, openings are made in the wear plate and connect to a manifold created by welding a plate across the whole front of the box, spaced from the original end by the original vertical reinforcing angles at that point. The body being described is for a Euclid truck which is the only truck that has been adapted to this body-heating idea to date. At the rear of the truck, the holes from the cross passage are made in the bottom plate of the body and lead into a triangular-shaped body cross member under the scoop end of the truck.

Jan 1, 1949

By F. M. Lewis, R. B. Bhappu

In 1977 a paper was presented which reviewed the cost trends in producing copper by conventional processes for five years, 1972 through 1976. In this paper these costs have been updated to include the years 1977 and 1978.

Jan 1, 1982

By H. N. Eavenson

In a discussion in the Transactions of the Institute (vol. Xl, page 835 et seq.) the writer gave some data about the explosions of gas and dust in the coal mines of the United States, Canada, and Mexico…

Jan 1, 1915

By AIME AIME

On Nov. 11, 1909, M. Alexandre Pourcel, of Paris, France, upon the proposal of a large number of distinguished members, and the unanimous recommendation of the Council, was elected by the Board of Directors an Honorary Member of the Institute. M. Pourcel has devoted forty-three years to the metallurgy of iron and steel ; and the work which he did between thirty and forty years ago constitutes an important part of the founda¬tion of the practice of to-day. Among his striking contribu¬tions are : (1) his perfection, in 1869, of the manufacture of high-grade ferro-manganese in a carbon-lined open-hearth furnace, instead of the costly crucibles previously used; (2) his discovery, in 1874, of the method of making solid steel cast¬ings; (3) his manufacture, in 1875, of ferro-manganese and silico-spiegel in the blast-furnace; and (4) his anticipation, in 1875, of modern American blast-furnace practice, by the pro¬duction, in a very small furnace, of Bessemer pig containing 2.5 per cent. of silicon, from a burden yielding only 46 per cent. of iron, and with a consumption, per ton of pig, of only 1,8401b. of coke, containing 15 per cent. of ash. These brilliant pioneer achievements, together with his contributions to cur¬rent technical literature, won for him the Bessemer gold medal of the Iron and Steel Institute ; the great" medal of honor," which is the highest award of the French Society of Mineral Industry, and other gold medals, as well as the distinction of honorary membership of the Comité des Forges de France, which was conferred upon him in 1891. In recent years, M. Pourcel has been instrumental, as consulting engineer of the Société de Commentry-Fourchambault, at Decazeville, France, in an extraordinary development of the manufacture of special steels. The Invar plant, of this company, is said to make a greater variety of such steels (includ-

Dec 1, 1909

"In the mines producing over 500 tons per day, skips have replaced the old method of hoisting ore by cars run onto cages. In the car and cage method, two men (station tenders) trammed the loaded cars onto the one-deck cage, and as the production increased the one-deck cage was increased to two decks and later to four decks. Landing chairs at the underground stations were necessary in this method and were the cause of many serious accidents by being carelessly left in the shaft by the station-tenders when leaving one station for anotherabove. The labor and time occupied in loading the leaving cages were con¬siderable, and, at times of rapid hoisting, four men were necessary in taking off empty and caging loaded cars. This also required at the surface landing, as many as ten men on a shift to remove the loaded cars and replacing them with empties, and tram the loaded ones to the surface ore bins, where the railway cars were loaded.The skips used in Butte are generally of 100 cubic feet capacity and hold five tons of ore, and weigh 7,500 lbs. The cage above, to which the skip is attached, weighs 2,300 lbs. The skips dump automatically into a pocket of 50 tons capacity. Two men are with the skips underground and load them from 125 ton capacity ore-pockets, under each station, the bottoms of the pockets having an inclination of 50 degrees from the horizontal. At the bottom of these pockets a gate is operated by compressed air. The labor of loading the skips amounts only to the opening and closing of a valve in the air-line, the ore running by gravity into the skips.Besides the saving in labor, the use of the skips has removed the necessity of underground landing chairs in the shaft and the accidents which are inevitable where such chairs are used."

Jan 1, 1913

By G. L. Schroeder

Investigations were conducted at two underground locations, foreman's room and 5702 area, of the Kermac Nuclear Fuels Corp. uranium mining installation, Ambrosia Lake, New Mexico. The rock environment is stratified sandstone. Pressures were varied from minus 0.4 an Hg to plus 3.8 cm Hg with respect to barometric pressure, and were maintained for periods ranging from several hours to 21 days. One cm Hg overpressure (-1.5% of normal barometric pressure) produced a 20-fold decrease in Rn flux into the foreman's room as compared to the Rn flux observed during dilution ventilation. The 5702 area experienced a 5-fold decrease in Rn flux for a similar overpressure. During 21 days of continuous 1 cm Hg overpressure in the 5702 area this reduced Rn flux was maintained. The smaller reduction in flux for the 5702 area results in part from the proximity of the foreman's room to a non-pressured area and the presence of an impermeable shale lens overlying the ceiling of the 5702 area. A 0.4 cm Hg underpressure of the 5702 area increased the Rn flux into the area by 3-fold over the non-pressured value. A barometric pressure influence on Rn flux into the mine and on air Rn concentrations in non-pressurd areas of the mine was measured. A falling barometric pressure causes an increase in the flux of interstitial gas into the mine; a rising barometric pressure decreases this flux. These effects are not seen in overpressured mine areas. Radon concentrations in rock interstices show, during overpressure, decreases of all locations monitored except in the immediate vicinity of the shale lens above the 5702 area ceiling. These reductions are the result of air flowing from the mine into the rock interstices under the influence of the pressure gradient induced by the overpressure. The relative humidity of the 5702 area was reduced after 2 days of 1 cm Hg overpressure from a pre-overpressure value of 96% to 81%. The control of harmful or noisesome gases which emanate into underground mining areas from surrounding rocks is often a costly necessity. In uranium (U) mines this problem is presented by the high interstitial concentrations of radon-222 (Rn), a radioactive noble gas of 3.82-day half-period, formed in the decay scheme of U238, and the relative ease with which this noble gas diffuses from its parent rock into the interstices of the rock and then to a working area. Long-term exposure to moderate concentrations of Rn (3000 µµc per 1) and its short-lived alpha-ray emitting daughter products, RaA (Po218) and RaC (po214), has been found to result in an increased incidence of bronchial carcinomaa2 The acceptable limit of Rn daughter products in a mine atmosphere is presently set at a concentration of short-lived radon daughters which would be in equilibrium with 100 ppc of Rn per 1 of air. Ventilation of mines is conventionally accomplished by continuously diluting the mine air with fresh air brought in by fan or natural convection from above ground surface. The diluted air is allowed to vent freely to the atmosphere. This process does nothing to retard the rate at which gases (including Rn) diffuse into the mine from surrounding rock. It merely reduces the concentrations of these gases within the mine. It is suggested that in a sufficiently permeable rock environment a slight pressurization of the mine air may induce air flow from the mine into the interstices of rock surrounding the mine. The convective flow of comparatively fresh air will reduce the concentration and the concentration gradient of undesirable gases in the rock interstices adjacent to the mine. Radon will diffuse counter-current to this convective flow at a rate proportional to its concentration gradient. In time, a steady state of convection and counter diffusion will be established. The Rn flux into the mine will never be reduced to zero, and will only asymptotically approach zero as the overpressure (and hence the convective velocity of purging air) approaches infinity. During 1963 and 1964, an investigation into the effect which such applied pressures have upon the Rn characteristics of a mine atmosphere was conducted at the Kermac Nuclear Fuels Corp. uranium mines, Ambrosia Lake (near Grants), New Mexico.

Jan 1, 1967

By R. R. Angel

Drilling rate is a parameter that should be considered in determining the volume requirements for air and gas drilling. The use of past methods which ignore the effects of the solids content upon the pressure and velocity of the annulus flow stream can result in undercalculation of the required volurne by as much as 50 per cent. A vertical-flow equation is presented for determining volume requirements. This equation includes the effect of the solids that are transported up the annulus in the flow stream by incorporating the drilling rate as one of the parameters. The effect of down-hole temperature on required circulation rates is also ana-lvzed. A simple approximate method of determining volume requirements is presented. This method is more accurate than the methods used in the past. Hole cleaning difficulties are analyzed for a recent air drilling job where past methods indicated that - excess air was being used. Sample curves of calculated boitom-hole pressures are presented for air and gas drilling in several hole sizes. INTRODUCTION In certain areas the use of air or natural gas as a circulating medium for drilling oil and gas wells is becoming a common practice. Large increases in penetration rate and bit life are achieved through the use of these media in preference to mud or water. Drilling rates as high as 90 ft/hr have been obtained in shales. The importance of maintaining adequate circulation rate is generally recognized; however, much disagreement exists among drilling operators as to what constitutes "adequate" circulation rate. In quarry drilling, where annular velocities can be accurately determined, an annular velocity of 3,000 ft/min of standard air is required for best results in rocks having approximately the same density as those commonly penetrated in drilling oil or gas wells'. Although this standard air velocity has proven satisfactory for quarry drilling, some oil and gas well drilling operators believe that an equivalent annular velocity of more than 4,000 ft/min is required; others believe that as little as 2,000 ft/min . is sufficient. Much of this disagreement results from determining the required circulation rates with methods which fail to incorporate the drilled solids in an equation which is applicable to vertical flow. Hughes Tool Co. Bulletins No. 23' and 23-A3 present data for determining circulation rates based on the Weymouth formula. These data do not include the drilling rate as a parameter and, therefore, neglect the effect of the solids being transported up the annulus. In spite of this apparent defect and the fact that the Weymouth formula is not applicable to vertical flow, the Hughes data have well served the drilling industry in many areas and are important and timely contributions to the science of air and gas drilling. The Hughes data purposely omit a correction for increasing down-hole temperature. At slow drilling rates this effectively compensates for the use of a formula which is not valid for vertical flow; however, volumes determined by the Hughes method are not sufficient to support rapid drilling rates at moderate and great depths. For example, Phillips Petroleum Co.'s Cauthorn "D" No. l in the Vinegarone field for Val Verde County, Tex., was air drilled from 1,500 to 9,300 ft using a compressor delivering 1,400 cu ft/min. The 8 3/4-in hole was drilled with 5-in. drill pipe, and drilling rates as high as 90 ft/hr were obtained between 7,000 and 9,300 ft. No water or caving hole was encountered. At 7,728 ft it was necessary to wash-out 60 ft of cuttings to reach bottom after a trip to change bits. At 8,130 ft a twist-off occurred and the drill col-lars were stuck in drill cuttings. These difficulties indicate that the 1,400 cu ft/min of air was not sufficient to keep the hole clean. Hughes data indicates that 1,180 cu ft/min is sufficient to produce an annular ve-

Jan 1, 1958

By J. J. Frawley, W. J. Childs

Experiments were carried out to induce grain refinement during solidification by applying vibrational energy (freq 20 kc) to small specimens of bismuth, tin, and bismuth-tin alloys. The results show that if the intensity of the applied sound -field is not great enough to fragment the growing dendrites of a pure metal, no grain refinement is observed and the pain size of the dynamically nucleated specimens is the same as the grain size of a specimen statically supercooled the same amount. Bismuth specimens did not show any grain refinement; whereas, the tin specimens did show grain refinement. This phenomenon is the result of the difference in growth habit between the bismuth and tin dendrites. The bismuth-tin alloys showed grain refinement and, in addition, the segregation pattern was changed. THE solidification process is a change in phase requiring the nucleation of the solid phase from the liquid and the growth of this solid phase at the expense of the liquid phase. Since many physical properties and also the integrity of a casting are dependent on the solidification process, understanding and controlling this process are very important.' A good example in the controlling of a cast structure using heterogeneous nucleation theory is the reduction of grain size in aluminum castings by nucleation catalysis.2 This mechanism of nucleation catalysis has been explained by Turnbull.3 Another technique for grain refinement, which has received much attention but the mechanism has not been fully understood, is to vibrate the solidifying melt. Vibrations can be applied to the melt either by vibrating the mold directly or by introducing a vibrating rod into the melt.4-13 Three mechanisms have been proposed to explain this phenomenon: 1) The mechanical fragmentation of the original dendrites that grew into the melt. These crystals or fragmented dendrites act as new growth sites. 2) The nucleation of new grains in the liquid by the generation of very high pressure pulses caused by cavitation in the liquid. 3) The remelting of the dendrite arms during the solidification process. This mechanism is operative only in alloy systems and would be enhanced by stirring or mechanical vibration. The purpose of this investigation was to determine the mechanism that will increase the number of grains when mechanical energy is introduced into a solidifying melt. APPARATUS The unit used to generate the ultrasonic vibrations was manufactured by the Redford Co., and is similar to the one used in ultrasonic soldering. Fig. 1 is a sketch of the major components used for generating ultrasonic vibrations. The crystal transducer assembly consisted of four lead zirconate ti-tanate piezoelectric crystals in an aluminum holder. An acoustical horn, which was fabricated from stainless steel, was attached to the holder by a set screw. The resonant frequency of this unit was 20,000 cycles per sec. A Pyrex crucible, 4 in. in diam and 4 in. high, was contained in a hole in the top of the horn. The piezoelectric crystals changed volume when excited by an electric signal, thereby generating a sound signal which passed through the horn. The crucible was coupled to the horn by a liquid silicone oil. The purpose of the couplant was to transmit the soundwaves from the horn to the crucible. Without the couplant, much of the sound energy would be lost. The energy transmitted was sufficient at the resonant frequency used, so that acoustical cavitation always occurred in the molten metal. The presence of acoustical cavitation was detected by the characteristic hissing sound emitted from the liquid. EXPERIMENTAL PROCEDURE The influence of ultrasonic vibration on the grain refinement of bismuth, tin, and bismuth-tin alloys was studied. These metals were chosen because of their low melting temperature and the relative ease with which they can be thermally supercooled. The following procedure was used for obtaining large amounts of supercooling. Pure bismuth (99.999+), which was received in bar form, was mechanically broken into pieces small enough to be accommodated in a 50 ml beaker. About 200 to 300 g of bismuth and a few grams of SnCl2 as a flux were placed in the 50 ml beaker and melted by induction heating. The melt was held for 20 min at

Jan 1, 1970

By Adrian C. Dorenfeld, Theodore Balberyszski, Strathmore R. B. Cooke

This paper reports results of studies of sulfidiza-tion of base-metal oxides and silicates with gaseous sulfur, hydrogen sulfide gas and pyrite and of their subsequent flotation with xanthate collectors. It has been established that a 100% conversion of the oxides of lead, zinc, copper and manganese into their respective sulfides is possible and is a function of reaction time and temperature. Sulfidization of chrysocolla (with malachite and azurite inclusions) resulted in a product containing covellite, chalcocite and digenite in proportions depending on conditions of sulfidization. Reacting cassiterite with gaseous sulfur, H2S or pyrite at various reaction temperatures resulted in its partial conversion to a tin sulfide. Flotation of the products of sulfidization indicated that their behavior is similar to that of natural sulfide minerals, the recovery being a function of the con-version of the oxides to their respective sulfides. The gradual depletion of high-grade sulfide mineral deposits has turned the attention of the mineral industry to the recovery of metals from the oxides and silicates. Anionic (fatty acid) and cationic collectors have in some cases made flotation of nonsulfides possible, although, in general, flotation of oxide ores is not as yet an economic process. Consequently, many attempts have been made to sulfidize the surface of the relevant oxide mineral and thus make it amenable to to In recent years, Bautista and sollenberger4 have investigated the conversion of a number of oxides to sulfides by reacting them with molten sulfur. This paper presents the results of .investigations carried out at the School of Mineral and Metallurgical Engineering at the University of Minnesota to study the flotation characteristics of some sulfidized minerals. It is divided into two parts: The first describes the sulfidization of a number of oxides and a silicate, and the second presents the flotation behavior of the products of sulfidization. SULFIDIZATION OF METAL OXIDES AND SILICATES Experimental Procedure: SULFIDIZATION WITH HYDROGEN SULFIDE GAS — Sulfidization with H2S gas was carried out in a horizontal tube furnace (Fig. 1). The temperature of the furnace was regulated by means of a Variac and determined with a chromel-alumel thermocouple. The constant temperature zone in the furnace was about 6 in. in length, and it was within this zone that the experiments were carried out. The gases employed were supplied from standard compressed gas cylinders, and passed through a glass-wool filtering tower before entering the Pyrex reaction tube. Gaseous products were bubbled through a water tower (used as a flow indicator) and excess H2S was burned off at the end of the outlet tube. Samples of reagents or minerals were placed in a 3-in. Alundum boat and inserted within the constant temperature zone of the furnace. Nitrogen gas (6 ppm O2 content) was passed through the tubes at room temperature to remove air in the tube, and continued to pass while the furnace was heating up. When the required temperature was reached, H2S was allowed to enter the tube and the supply of nitrogen was shut off. At the end of the reaction period, the reverse procedure was carried out, the samples being cooled to room temperature in a nitrogen atmosphere. The flow rate of H2S gas was maintained fairly constant in all experiments, although the rate was not determined. SULFIDIZATION WITH SULFUR POWDER - To study the sulfidization of minerals with sulfur (liquid or gaseous), samples of the mineral, together with a measured quantity of sulfur powder, were placed in a stainless steel (SS316) reaction vessel (Fig. 2). The reaction vessel was heated in a vertical resistance coil furnace, the temperature being regulated through a Variac. At the end of the experiment the vessel was cooled to room temperature before the sample was removed. Cooled products were leached with CS2 to remove any free sulfur. SULFIDIZATION OF TIN CONCENTRATES - Fifty gram samples of sulfidized tin ore were prepared by mixing -48 mesh Bolivian tin concentrate with -48 mesh Ottawa sand in various proportions and sulfi-dizing these samples with H2S in the horizontal tube

Jan 1, 1969

By K. H. Kilgren

At high formation pressures the distillate produced from a gas-condensate reservoir may be black in color. In this event the dense gas phase existing above the dew point is correspondingly dark. Volumetric phase data and an analysis of a reservoir fluid exhibiting these characteristics, together with a description of the visual equilibrium cell in which these observations were made, are presented in this paper. INTRODUCTION Previously the author, like many others in the oil and gas industry perhaps, tacitly assumed that the expressions black or dark oil system, crude oil system and bubble-point system were synonymous. Crude oil reservoir fluids are bubble-point systems and yield a black or dark stock-tank oil of relatively low API gravity. Conversely, a clear or amber colored trap distillate of high API gravity is assumed indicative of a dew point system or a gas-condensate reservoir fluid. This broad classification appears satisfactory for shallow reservoirs, but as the following study demonstrates, may be misleading when applied to deep reservoirs. Theoretically, there is no reason to exclude the possibility of producing a dark, low-gravity distillate from a gas-condensate reservoir. At sufficiently high values of pressure and temperature, heavy, dark-colored hydrocarbons may exist in the vapor state of a multi-component system. If enough dark-colored components are present in the reservoir vapor phase, the resulting condensate will be dark. The reservoir fluid investigated in the present study supports this contention. Stock-tank production was black in color and measured 29" APT gravity. From outward appearances, the liquid closely resembled a medium gravity crude oil. Experimental measurements proved the reservoir fluid was in reality a gas-condensate system. Volumetric phase data for this high-pressure system and a description of the visual cell in which the study was conducted successfully are presented in this paper. THEORY Phase behavior of a reservoir fluid can be predicted accurately with reference to a pressure-temperature phase diagram. If the reservoir temperature is lower than the critical temperature of the hydrocarbon fluid in place, bubble-point behavior will be observed. If the reservoir temperature lies between the critical and cricondentherm temperature, dew point behavior and retrograde condensation will occur. For reservoir temperatures above the cri- condentherm, only a single gas phase can exist in the reservoir regardless of pressure. Providing the composition of the reservoir fluid were known, it would be possible to predict the critical temperature and estimate the phase behavior from equilibrium relationships. However, the usual practice is to obtain a sample of reservoir fluid, subject it to varying pressures at the reservoir temperature and observe the phase behavior experimentally. The latter method was used to obtain the data reported here. WELL AND TRAPPING INFORMATION A summary of pertinent data for the well from which the reservoir fluid was sampled is presented in Table 1. This well is located offshore Louisiana. Except for the pressure which substantially exceeds hydrostatic pressure, the information does not appear unusual. Prior to the sampling program, the well was produced for 22 hours at a stock tank oil rate of 139 B/D. Average trapping conditions and gauging data for the six-hour test period that followed are summarized in Table 2. Samples of the first-stage trap gas and liquid were obtained during the latter portion of the test period. Ambient temperature remained 5 to 10F below trap temperature and presented no problem for sampling. Surface wind and moderate foaming of stock-tank oil presented some difficulty in obtaining accurate stock-tank gauges. SAMPLE ANALYSIS Compositions of the gas and liquid samples are shown in Table 3. The trap gas was analyzed by isothermal chromatography which revealed only a trace of heptane in the stream. The trap liquid was initially analyzed by low-temperature fractional distillation, yielding a bottom product of heptane and heavier components. Specific gravity of this fraction was measured and the mol weight was determined by freezing point depression. The hexane and lighter overhead gas collected during distillation was

Jan 1, 1967

By Jonas Svensson

A new method is described for the production of cold-bonded pellets using a hydraulic binder, such as portland cement. Large-scale pilot-plant tests have proved that self-fluxing pellets of high reducibility and good handling strength can be made by the method. Blast-furnace trials have shown that the pellets are an acceptable burden material, comparable with self-fluxing sinter or heat-hardened pellets. Economic factors of commercial-scale production are discussed. The Grangcold Pellet Process—for which patents have been applied or already granted in a number of coun-tries—uses a hydraulic adhesive such as portland cement, slag cements, pozzolanic cements, etc., for the production of cold-bonded pellets. The idea of using a hydraulic binder for the agglomeration of iron-ore fines is not new. Portland cement was proposed as an adhesive for cold-bonded iron-ore briquettes in patents granted more than 50 years ago.' In a report on the briquetting of iron-ore fines, published in Stahl und Eisen in 1959; it is stated that briquettes bonded with portland cement are used on a small scale at an ironwork in Germany. According to the report, the briquettes showed excellent strength in the blast furnace although their general use was made impossible because they required a long hardening time, during which they are sticky, soft, and difficult to store and handle. The Grangcold Pellet Process has overcome this particular disadvantage by mixing the balls with a suitable amount of the balling concentrate before storing them. The pellets are embedded in the concentrated during storing in such a way that they are isolated from each other and thus prevented from sticking together to form clusters. Thanks to the embedding concentrate, the pellets are subjected to a more or less uniform pressure from all sides which does not deform them. Thus, the mixture can be stored in a stockpile or in a bin until the pellets have hardened sufficiently. The concentrate is separated from the pellets by means of screening. The concentrate is returned to the balling operation and the pellets are either shipped to the blast furnace or stored for final hardening. The binder preferred for the Grangcold Pellett Process is portland-cement clinker, ground without the admixture of gypsum in order to avoid sulfur in the pellets as far as possible. Usually a 10% binder content is used. Two-thirds of the portland-cement clinker consist of lime and the rest is silica, alumina, and ferric oxide. Thus, self-fluxing or overbasic pellets are produced with this binder if the amount of silica in the concentrate used does not exceed 4%. The Grangcold Pellet Process was developed by the mineral Processing Laboratory of the Granges Co. Work started in 1963 with batch-scale tests. In 1966, a small pilot plant was put into operation in which 1800 tons of pellets were produced using 10% of rapid-hardening portland cement as a binder. Favorable results from a blast-furnace test with this batch led to the decision to erect a larger pilot plant which went into production in the summer of 1967. Since then, approximately 100,000 tons of cold-bonded pellets have been produced, mostly with 10% gypsum-free portland cement as a binder. Several full-scale blast-furnace trials have been performed with the pellets. The results of the trials indicate that the Grangcold pellets constitute a satisfactory blast-furnace feed. An industrial plant for the production of Grangcold pellets with a rated capacity of 1.5 million tpy is now under construction at the Granges Co.'s mine at Grangesberg. The plant will come into operation in the summer of 1970. Results from Laboratory Work Pellets made from iron-ore concentrate bonded with portland cement harden slowly and their handling is very critical until they have hardened enough to loose their stickiness. It is therefore especially important to study the progress of the hardening action and the factors influencing it. This is best achieved by investigating the relationship between the compressive strength of the cement-bonded pellets and the curing time under varied conditions. The general course of this relation-

Jan 1, 1971

By J. Chipman, N. J. Grant, H. L. Bishop, H. N. Lander

Data of several studies on the equilibrium between molten iron and open hearth-type slags have been combined to determine some of the chemical reactions involved in steel-making. Effects of slag composition and temperature on the iron oxide activity, distribution of sulfur between slag and metal, and the carbon content of the metal are discussed. Also, an overall reaction for the equilibrium between sulfur and oxygen is presented. DURING the past 15 years, a number of significant equilibrium studies have been carried out between liquid iron and simple basic and acid slags in an effort to throw light on the chemical reactions involved in steelmaking. This paper is a summary of the experimental reports on investigations which have been conducted at the Massachusetts Institute of Technology, and of related work in other laboratories. The investigations summarized in this paper include the works of Fetters and Chipman1 and Taylor and Chipman,' which dealt with simple slags that are similar to those found in the open hearth. The sulfur determinations of the slag-metal tests of Fetters and Chipman as reported by Grant and Chip-man" are included. Also, the investigations by Win-kler and Chipman' and Grant and ChipmanQ f more complex slag systems are included in this summary. The experimental procedure is described in detail in each of these papers and will not be discussed. Since the previous reports have been somewhat independent, it is desirable to review and combine the data of the various investigations to determine, as accurately as possible, the reactions in the slag-metal systems of the open hearth. It is the object of this report to present the combined data in such a way as to enhance their utility and applicability. Oxidizing Power of Slags of the System (CaO+MgO)-Si0,-FeO in Equilibrium with Carbon-Free lron The slags selected to determine the iron oxide activity in equilibrium with pure liquid iron were those containing less than 2 pct each of P,O,, MnO, or A1,0, on a weight percentage basis. The method used to calculate activities of iron oxide in liquid slags was that developed by Taylor and Chipman.' The solubility of oxygen in molten carbon-free iron under pure iron oxide slags can be expressed by the following eauation —6320 log (pctO)-------------— + 2.734 [1] where T is the absolute temperature. The oxygen solubility values as determined from Eq. 1 were used throughout this study to calculate the iron oxide activity. The iron oxide activities of slags of various iron oxide contents are plotted in Fig. 1 as a function of the basicity, which is defined as the ratio (pct CaO + pct MgO)/pct SiO,, and are based on molecular percentage values of the components. The percent (FeO), is the total iron content in the slag calculated to FeO. Fig. 1 shows that as the basicity increases at constant mol pct (FeO),, the iron oxide activity increases rapidly and reaches a plateau which extends on the basicity scale from about 1.3 to 2.3; the iron oxide activity then decreases rapidly until a basicity of about 3.0 is reached, where it tends to level off. The solid portions of the curves represent the experimental data of Fetters and Chipman and Win-kler and Chipman. Their experimental heats were made in magnesia crucibles, and hence the slags were saturated with magnesia. The broken lines on the left represent the experimental data of Taylor and Chipman, who used a rotating crucible. In general, these slags contained less than 3 pct MgO. The absence of data for slags containing less than about 40 mol pct (FeO), and basicity ratios greater than about 2.5 made it necessary to calculate curves using ionic concepts of slags. The broken lines on the right, which disregard the solubility limits of di and tricalcium silicate and lime, were obtained by following the treatment of Flood and Grjotheim,"

Jan 1, 1957

By J. E. Steiner, J. M. Hodge, M. A. Orehoski

Ingots of four steels (1045, 1080, Ni-Mo-V, and Ni-Cr-Mo-V) were cast at pressures varying from about 1 to 760 mm of mercury, so as to obtain a range of hydrogen contents in each steel. The susceptibility of these steels to flaking was evaluated by cooling hot-rolled blooms at a range of cooling rates, varying from water quenching to slag cooling, and studying the occurrence of flaking as a function of cooling rate. The steels exhibited differences in susceptibility to flaking, and a tlzreshold value for hydrogen content for each steel was found, below which the susceptibility was very low and above which the susceptibility increased markedly with increasing hydrogen content. Mechanical property evaluations, metallogvaplzic exantinations, and X-my diffraction determinations o,t retained austenite were made on samples from the blooms. A mechanism of flaking which is consistent with the observed behaviors, the effects of hvdrogen content, and the differences in susceptibility among the steels investigated is postulated, based on the results of mechanical property evaluations and metallographic and X-ray diffraction studies. ThE important role of hydrogen as a factor in the occurrence of "flakes" or "hair-line cracks" in steel has now been established by many investigations. These have included investigations by steel producers and forging manufacturers, to whom the prevention of flaking is a very real and serious problem, and many research studies aimed primarily at establishing the mechanism of this behavior Several investigators3 have reported that steels cast at reduced pressures (absolute pressures of about 1 mm) not only are low in hydrogen content but are essentially insensitive to the formation of flakes. These investigations have shown that a general relationship exists between hydrogen content and susceptibility to flaking. The difficulty of obtaining suitable samples of steels of a given composition with the desired range of hydrogen contents, particularly in the relatively large sections in which flaking most commonly occurs, has been the principal obstacle to quantitative evaluations of these relationships. Steels with intermediate hydrogen contents between 1 ppm, and the 4ppm or higher of air-cast steels are generally not available in commercially produced steels. Laboratory procedures, in which the hydrogen is introduced into solid steel samples by heating in a hydrogen atmosphere under pressure, generally involve a limitation in the size of the sample which can be treated, and thus are not representative of the behaviors in large sections. The availability of a facility at the South Chicago Works of U.S. Steel, in which several ingots could be cast from a single heat of steel at total air pressures ranging from 0.25 to 760 mm of Hg, has made it possible to overcome this obstacle and to obtain ingots of a given steel covering the intermediate range of hydrogen contents desired. These ingots, furthermore, are of a size suitable for the production of product with section sizes large enough to be representative of the products in which flaking most commonly occurs in commercial production. In these experiments, this facility was used to study the relationships between hydrogen content and the susceptibility to flaking of four steels, two plain carbon steels at 0.45 and 0.80 pct C and two low-carbon alloy steels representing a medium and a rather high hardenability level. These flaking studies were supplemented by evaluations of mechanical properties and by metallographic studies on samples from the blooms, in order to obtain pertinent information on the factors other than hydrogen content which influence the susceptibilities of these steels to flaking. Based on the results of these tests, a mechanism for the initiation and propagation of the flaking cracks, which is consistent with the observed behaviors, is postulated. MATERIALS AND EXPERIMENTAL WORK Steelmaking and Conversion. To provide material for the investigation, five 29- by 35-in., hot-topped, big-end-up ingots were cast from each of four 80-ton, basic electric-furnace heats of four different steels (a 1045 steel, a 1080 steel, a Ni-Mo-V steel, and a Ni-Cr-Mo-V steel). A double-slag practice was used on all steels and the two plain carbon steels were Si-A1 deoxidized with an addition of 2 lb of A1 per ton, while the Ni-Mo-V and Ni-Cr-Mo-V steels were deoxidized only with silicon and

Jan 1, 1964

By A. T. Aldred

HIS note reports the existence of several new scandium intermetallic compounds of the A2B and AB stoichiometries where the A element is scandium and the B element is from group VIII or IB of the periodic table. Alloys were arc melted from high-purity materials using 2-g charges. Typical lot analyses for the materials used are given in Table I. Chemical analyses were not made on the alloys as there was little or no weight loss on melting. After annealing the specimens for 14 days at 600°C and water quenching, metallographic and X-ray techniques were used to determine the occurrence of the various phases. Table II lists the relevant data for the A2B phases. The Ti2Ni structure,2 has ninety-six atoms in a face-centered cubic cell, whilst the Al2Cu structure is body-centered tetragonal.3 The occurrence and stability of the various A2B type phases in transition metal alloy systems has recently been considered by Nevitt.4 The Ti2 Ni-type phases occur over a relatively narrow range of radius ratios from 1.14-1.26 with A partners mainly from the titanium group and B partners predominantly from the cobalt group. This suggests that both a favorable relative size of the atoms and a favorable electron concentration are necessary conditions for the existence of this structure type. A12Cu-type phases involving Ti group elements as A partners are formed with B partners from the cobalt and nickel groups, predominantly the latter, and have a higher radius ratio (1.27-1.29) than the Ti2Ni-type phases. The occurrence of both Sc2Pd and Sc2Co can be rationalized in terms of these considerations but SczNi is anomalous because of its high radius ratio. The radius ratios are calculated from the Goldschmidt CN12 radii and it might be postulated that the scandium atom is reduced in size in the compound. Unfortunately the apparent atomic size of scandium in the compound cannot be calculated from a knowledge of the structure and lattice dimensions. The crystal structure of the Sc2Au compound could not be identified from the powder diffraction pattern, but it is interesting to note that it is isostructural with a series of A2Au phases where A is a rare earth element.5 Pertinent information concerning the AB phases found in this investigation is given in Table 111. All the phases have the ordered bcc CsCl structure. The occurrence and stability of CsC1-type phases have recently been discussed by Dwight,7 who concludes that the relative sizes of the atoms do not appear to be a controlling factor (the radius ratios of all the known phases vary between 0.985 and 1.439) but that the occurrence of the phase is predominantly dependent on the relative positions of the A and B partners in the periodic table. As a measure of the stability of a given CsCl phase it has been customary to define a lattice contraction on alloying, DAB — dAB, where DAB is the AB interatomic spacing as calculated from the Goldschmidt CN8 radii and dAB is the AB interatomic distance in the compound (= v3/2 ao). Values of the parameter DscB -dScB for the compounds found in this investigation are given in column 5 of Table III and are plotted in Fig. 1. If the lattice contraction does in fact reflect the stability of a phase then Fig. 1 shows two very interesting trends when the position of the B partner in the periodic table is considered. Firstly, within any given group the stability increases in order on going from the first to third long period. Secondly, within any given period the stability increases in order as the B partner is taken from the copper, nickel, and cobalt groups. In the case of the second long period, the lattice contraction reaches a maximum at ScRh and then decreases to ScRu. The same trend could

Jan 1, 1962