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By M. L. Fuller

During the last several years many papers have appeared dealing with the structure of highly polished metal surfaces. The awakening of interest in this subject is due to the applicability of the electron diffraction technique to the study of surfaces. The original theory of Beilbyl considered the surface of polished metals as of the nature of a supercooled liquid or a vitreous, amorphous solid. The electron diffraction effects from polished metals have been interpreted by rnany to be a direct experimental proof of the correctness of the Beilby theory. This interpretation has been strongly opposed by others, so that at the present time the subject is in an uncertain and controversial state. In the present paper new, and hitherto unpublished, electron diffraction effects from polished zinc are desrribed. These observations indicate that the polished surface of zinc is crystalline. Published Work Many papers2""10 have interpreted the electron diffraction evidence as proof of the Beilby amorphous theory. All investigators agree that highly polished metals give rise to two diffuse diffraction haloes, similar to those obtained by the diffraction of X-rays in liquids and vitreous solids. It is this similarity that leads to the amorphous-layer interpretation of polished metals. Strangely, the interatomic distances calculated from these haloes are very similar for the various metals investigated, in spite of a rather wide range of such distances in the crystalline and liquid states. The calculated atomic sizes are, furthermore, smaller than are experienced in the normal states of the metals. In spite of these anomalies, the amorphous-layer interpretation has been adhered to by many. One investigator, S. Dobinski," differs from the others in his experimental results. By polishing under benzene in order to avoid the possibility of oxidation, Dobinski obtains diffuse haloes of radii different from those previously obtained. He thus obtains a more rational quantitative correlation of the diffuse haloes with the amorphous-layer theory.

Jan 1, 1939

By M. L. Fuller

During the last several years many papers have appeared dealing with the structure of highly polished metal surfaces. The awakening of interest in this subject is due to the applicability of the electron diffraction technique to the study of surfaces. The original theory of Beilbyl considered the surface of polished metals as of the nature of a supercooled liquid or a vitreous, amorphous solid. The electron diffraction effects from polished metals have been interpreted by rnany to be a direct experimental proof of the correctness of the Beilby theory. This interpretation has been strongly opposed by others, so that at the present time the subject is in an uncertain and controversial state. In the present paper new, and hitherto unpublished, electron diffraction effects from polished zinc are desrribed. These observations indicate that the polished surface of zinc is crystalline. Published Work Many papers2""10 have interpreted the electron diffraction evidence as proof of the Beilby amorphous theory. All investigators agree that highly polished metals give rise to two diffuse diffraction haloes, similar to those obtained by the diffraction of X-rays in liquids and vitreous solids. It is this similarity that leads to the amorphous-layer interpretation of polished metals. Strangely, the interatomic distances calculated from these haloes are very similar for the various metals investigated, in spite of a rather wide range of such distances in the crystalline and liquid states. The calculated atomic sizes are, furthermore, smaller than are experienced in the normal states of the metals. In spite of these anomalies, the amorphous-layer interpretation has been adhered to by many. One investigator, S. Dobinski," differs from the others in his experimental results. By polishing under benzene in order to avoid the possibility of oxidation, Dobinski obtains diffuse haloes of radii different from those previously obtained. He thus obtains a more rational quantitative correlation of the diffuse haloes with the amorphous-layer theory.

Jan 1, 1939

By Hiroshi Oikawa, R. G. Blake, A. G. Guy

An equatzon has been derivedfor conveniently calculatzng the couvse of homogenzzation in a three-corviDonent solid solutiorz. The necessary assumptions are that the initial distributions of concentration are sinusoidal and that the four interdiffusion coefficients are constant. Employed in the deriuation were the Laplace transform and the fouter Fourier sine transfovwz. The final equation is shown to be in good agveetnent with the experimental results of Kirkaldyet al. on Cu-Sn-Zn alloys. COMMON boundary conditions for representing physical problems are those of the finite solid and of the infinite solid. Many metallurgical phenomena, however, have the geometrical form of a finite pattern reproduced throughout an infinite solid. Precipitation within a uniform matrix and segregation during solidification are examples. The purpose of this treatment is to show that a convenient and useful mathematical analysis is possible in those cases in which the finite pattern can be approximated by a sine function. The particular topic to be considered here is the elimination of segregation by diffusion, but the mathematical model has applicability in many other areas. It should be recalled that the mathematical solution of a typical problem involving a finite solid, such as diffusion into a thin layer, is quite involved.' Various types of solutions are used depending on the degree of advancement of the diffusion process and on the initial conditions. A step function is the simplest initial condition, but even in this case the general solution has the form of an infinite series. Kirkaldy et a1.2 have

Jan 1, 1968

By Henry E. Colton

NeaR the town of Christiansburg, Va., occurs a singular feature in topographical as well as geological structure, which may be said to have an important bearing on a large area to the southwest. The great water-shed ridge, which divides the waters flowing into the St. Lawrence from those flowing into the Atlantic ocean, coming southwestward, forms all of what was the boundary of Maine as agreed upon by the treaty of 1783, and a part of the present boundary, all of the northern New Hampshire boundary, and entering Vermont, continues south of Lake George. Passing irregularly through New York, it enters Pennsylvania, and there bifurcating, sends one prong to the west as a divide between the waters of the lakes and the Ohio, while the other becomes the steady, regular ridge which gave it the name of Alleghany, and thus passes on southwestward through Virginia. At no point has it ever been the geological divide. Its course, commencing in the Archean rocks, has passed through nearly every series of formation, and comes into Virginia in the Carboniferous strata. The geological divide—the line between the fossiliferous and the non-fossiliferous rocks—lies, in Canada, to the west of it, but from New York south into Virginia is far to the east. Reference to Dr. Hitchcock'k map will show this. But at the locality noted these positions are changed; the water-divide becomes the eastern chain, and the geological divide is the western, returning, it may be said, to the positions occupied in the region where they originated. These relations are shown on the large map accompanying the present paper. For several miles, the track of the Norfolk and Western Railroad

Jan 1, 1888

By R. L. Stone

None of the currently used methods of testing bentonites as binders for strengthening iron ore pellets is entirely adequate by itself. Since more knowledge was needed about 1) which properties of bentonite most affect pellet strength, and 2) the precise mechanism by which strengthening is produced, attention was paid to possible new techniques for rating bentonites. With the structural nature of bentonites — in particular, the montmorillonite component — the possibility of rating bentonites on the basis of zeta potential was investigated. These bentonites were also rated by conventional tests and measurements, including colloid content, barrel yield, pH, chemical analysis and physical tests on green and dry pellets. A mechanism for pellet bonding based on electro-kinetic forces between the bentonite and the iron ore concentrate appears to be feasible. In pelletizing, from 6 to 18 lbs of bentonite is added per ton of concentrate to give strength to the green and dry pellets. In some operations even more bentonite than is required for strengthening purposes must be added for moisture adsorption to pennit balling of the concentrate. Since bentonite is thus a major item in pelletizing, more knowledge about the way in which bentonites act as binders and better ways of rating this ability would help in the difficult job of selecting the right bentonite for a given concentrate. The fact of the matter is that although several methods are in current use for testing bentonites, none of these methods are consistently foolproof. For example, a given bentonite may rate high by several standard tests yet turn out to be a poor binder, and of course the reverse also occurs. Actually, more knowledge is needed about 1) which properties of bentonite most affect pellet strength, and 2) the precise mechanism by which strengthening is produced. In this study attention is therefore paid to possible new techniques for rating bentonites. With the structural nature of bentonites as a starting point, we investigated the possibility of rating bentonites on the basis of the zeta potential, i.e., the electrokinetic ootential on the montmorillonite colloids — the main component of bentonite binders. The zeta potential technique was applied to a range of commercial bentonites from several areas in the U.S. and abroad. These bentonites were also rated by conventional tests and measurements, including:

Jan 1, 1968

By E. H. Crabtree, J. D. Vincent

Probably no metallurgical process in the history of the mining industry has been responsible for such increased mineral production as has flotation. It has made possible the economic treatment of low grade and complex ores which, with the old methods of gravity concentration, would have been classed as worthless. Starting with the sulfide ores of copper, lead, and zinc, the process has been applied to almost all metallic and nonmetallic minerals. Today, the sulfides of the common metals not only can be readily recovered, but can be separated from each other. Thus, three or four mineral recoveries from the same ore, such as galena, chalcopyrite, sphalerite, and pyrite, are possible. Molybdenite is recovered initially with copper sulfides and the two are subsequently separated. Flotation of metallic gold and of native copper and graphite is being commercially practiced. The carbonates of some of the base metals, principally those of lead, can also be concentrated. Flotation of the oxides, silicates, phosphates, and other so-called non- metallic minerals represents the greatest advance in the art in the last few years. Today, commercial plants are successfully treating such minerals as feldspar, garnet, ilmenite, muscovite, cassiterite, cement rock, fluorspar, phosphate rock, sylvite, and a host of others. Flotation of the various types of iron ores along with other concentration methods is today the subject of a tremendous amount of investigation on the iron ranges. EARLY PATENT HISTORY OF FROTH FLOTATION Although what we call the froth flotation process as distinguished from bulk oil processes was not used commercially until 1905, many investigators had recognized its possibilities long before the twentieth century. The principal patents issued throughout the years give us a method of recording early flotation history. BULK OIL PROCESSES: In 1860, William Haynes patented (British Patent 488) a process for separating oil-wetted sulfide minerals from water-wetted gangue minerals by agitating the dry ground ore with oil and then the mixture with water. In 1877, the Bessel brothers patented (German Patent 42, Class 22) a process where a mixture of graphite ore was mixed with 1 to 10% oil; after adding water, the

Jan 1, 1962

By W. N. Best

Crude oil attracted attention because of its excellence as a fuel for openhearth furnaoes; for making crucible steel and brass; for melting copper, lead, tin, zinc, nickel, silver, malleable iron, gray iron; and for the production of steam in all sizes and types of boilers. For heating furnaces, mold-drying ovens, core ovens, ore roasters, calciners, hotair furnaces, sand drying, asphalt road work, etc., its superiority over other fuels is due to the fact that the heat is at all times under perfect control, so that a constant temperature may be attained and maintained at the will of the operator. This mcans a maximum amount and uniform quality of work. Crude oil is of two kinds, paraffine base and asphaltum base, and varies from 11 to 46 gravity BaumB. The light-gravity oil does not require heating before use; but oil of less than 20 gravity Baumé should be heated to just below its vaporizing point, in order to reduce its viscosity and to obtain the highest efficiency of combustion. Heavy California oil vaporizes at 230". F., Mexican crude oil at from 175" to 210" F., and Beaumont, Texas, oil at 142" F. Fuel oil vaporizes at 130" F. Scientific Installation Essential The burning of oil is an art based on science, and the "rule of thumb" should never be employed, especially in heating heavy crude oil. Thermometers should be used on both suction and supply pipes so that the fireman or smith will at all times know the temperature of the fuel. The indicators on such thermometers should be large enough to be readily seen by the operator, night or day. It is necessary to have an unvarying pressure of steam or air through the burner, to atomize the fuel. Also, the air used to support combustion should be delivered through a nozzle under the burner at a constant pressure. The oil pressure must not fluctuate; under no eircumstances should it vary more than 1 1b. The oil pump, which should be brass-lined, with the aid of the pulsometer and superheater, will insure a constant

Jan 1, 1916

By D. H. Davis

HAND picking was the earliest form of coal preparation, first practiced to improve the outward appearance of the coal being loaded and to remove any pieces that might appear objectionable to the buyer. It is still extensively practiced on the plus 1-in. sizes and particularly on the plus 4-in. and larger sizes. The percentage of ash reduction that can be obtained by hand picking depends entirely upon the amount of free impurity occurring in the coal. In a particularly dirty seam, where a considerable quantity of rock occurs with the coal as mined, hand picking produces sizable reductions in ash. If the coal is prepared clean at the working face hand picking is a final check; in some cases, on the smaller sizes, it is practiced only to show that an effort is being made to prepare a clean product. Because of the variety and different methods of handling coal, the early plants were not always adapted for e5cient hand picking. At most mines an attempt is made to - remove the visual impurities at one or more of the following places in the surface plant: (1) in the tipple during screening; (2) on picking band, belt, or shaking conveyors; (3) during the loading of the coal as it goes into the railroad car. Whatever the physical arrangements of the plant may be, the usual practice is to run the coal over the screen, picking table or boom at such a rate that each piece of impurity is exposed to the view of the picker. Coal should be uniformly sized and spread out on the table so as not to exceed one particle in depth. The flow should be even in tonnage and the speed of travel should be from 30 to 60 ft. per minute and not exceed 80 ft. per minute. The dirtier the coal, the slower the speed required for a fixed number of pickers. Actually, picking capacity depends on the number of particles per minute that can be picked out and rejected. The percentage of impurity removed is determined by this and the average weight of piece rejected. Handling a mixture of sizes from nut to the largest lump over the same picking table or conveyor is not conducive to efficient separation by hand picking because the lump hides the smaller impurities. Picking tables should not exceed 5 ft. in width, so that a picker on either side will be able to remove impurities from the center of the table. Guards usually are placed at the side of the screen, boom or table, to allow the pickers to stand close enough to remove the impurities without too long a reach.

Jan 1, 1950

By William B. Phillips

The concentration of natural magnetites has been carried on in this country for several years, and more or less information has been collected on the subject. Various inventors, availing themselves of the magnetism which is inherent in such ores, have devised machines for separating the impurities from the ore by means of the electric current; and a greater or less degree of success has rewarded their painstaking and persevering efforts. We are now fairly in position to judge of the value of the process as applied to such material. It is not my purpose to speak of this matter further than may be required by the emergencies of the case. I shall assume that most engineers and metallurgical chemists are already acquainted with what has been done at the Chateaugay mines, at Mineville, at the Benson mines, at the Weldon and Ogdensburgh mines, and at Cranberry; although, at this latter place, there has not been so much done as we could wish. I shall not now speak of the various types of separators. From the time of William Fullarton, to whom was granted an English patent, in 1792, for separating iron-ore by the application of magnetic attraction, down to the present time, a great. many devices have been suggested, and a great many patents taken out for this purpose; but it is not necessary now to enter upon a discussion of their merits. Perhaps, at some future meeting of the Institute, after we shall have experimented further with some of the machines on the market, there may be an opportunity to contribute something to the current knowledge of the efficiency and economy of separating-machines. In this paper I propose to give, as briefly as possible, the results already reached in converting a non-magnetic ore into magnetic ore, and then concentrating it over a magnetic separator of the alternate-polarity type. I am aware of the work

Jan 1, 1896

By F. S. Knoll

The expanding role of electrostatics as applied to minerals and related fields is covered in this paper. New and existing forms of electrostatic separation are classified into two broad groups: separation of charged particles and separation of neutral particles. The basis for each form of separation is discussed along with particle examples and results obtained.

Jan 1, 1986

By E. B. Ekren, F. C. Frischknecht

Recently released results of surveys employing the slingram and turam methods show the applicability of electrornagnetics in mapping new areas containing both oxidized and unoxidized iron in the Lake Superior region.

Jan 10, 1961

By J. A. Berger, G. W. Wiener

Several transition metal nitrides have been prepared and their saturation magnetization determined. On the basis of an atomic model of ferromagnetism involving a consideration of nearest neighbor interactions and the assumption that all atomic moments of the metal point in the same direction, it appears that the nitrogen interacts with d-shell of the transition metal in such a way as to reduce the magnetic moment. THERE is a large class of materials having metallic properties which are formed by a combination of hydrogen, boron, carbon, oxygen, or nitrogen with the transition metals. Several attempts have been made to establish the type of metal-nonmetal bonding in these interstitial alloys because it is believed that many of the physical properties of these materials are determined by the characteristics of this bond. Several of these alloys are ferromagnetic, and thus a powerful method is available for investigating the structures in a direct manner by measuring the saturation magnetization. The latter is a fundamental property of ferromagnetic metals and alloys which depends primarily on the electron distribution surrounding the atom. For the first row of transition metals, this refers specifically to the 3 d-shell. Since bonding involves the electronic configuration between atoms, there is reason to suppose that a relationship exists between ferromagnetism and bond type. In the case of the interstitial structures studied in this work, bonding will refer to the distribution of electrons between the transition metal and the nonmetal. Since these alloys have metallic properties, it is further proposed that any bonding interactions will involve the outer p-shell of the interstitial element and the incomplete d-shell of the transition metal. If this is the case, then the relationship between ferromagnetism and metal-non-metal bonding is established qualitatively. In order to investigate the subject quantitatively, certain transition metal nitrides were chosen because they have simple crystal structures, are ordered alloys, and are ferromagnetic. They also have sufficiently high saturation magnetization to be of technical interest. Currently there are two major theories of ferromagnetism, each of which has been applied to the interpretation of the saturation magnetization in terms of atomic structure. They are usually referred to as the band theory and the atomic theory. The former has found widespread application to the study of pure metals and certain solid-solution allays. However, it has not been applied to the interstitial structures or ordered alloys because it does not interpret the properties directly in terms of the crystal structure. The atomic theory on the other hand is especially suited to the study of interstitial structures because it permits an interpretation of ferromagnetic phenomena in terms of the crystal geometry. As has been pointed out previously, the nitrides have simple ordered crystal structures and, therefore, the choice of the atomic theory for the interpretation of the data is a natural one. One of the prime difficulties with the atomistic theory is that its mathematical justification is much more difficult, and for this reason its general acceptance will depend to a large extent on the value it has in explaining and predicting the results of experiment. Before the presentation of the theoretical basis for understanding the metal-nonmetal bond, it is useful to review the ideas existing prior to this work. Four different interpretations have been given to the metal-nonmetal bond. These are summarized as follows: 1—acceptance of electrons by the nonmetal from the incomplete d-shell of the transition metal, 2—transfer of electrons from the nonmetal to the incomplete shell of the transition metal, 3—no exchange of electrons between the two atoms, and 4— a resonating type of bond involving the p electrons of the interstitial atom giving rise to half bonds. Zener'-4 in a recent series of papers has proposed a new theory of ferromagnetism and has developed an explanation of the observed saturation magnetization of iron nitride (Fe,N) using the concept that nitrogen accepts electrons from the 3d-shell of iron. Jack," on the basis of atom size considerations in iron carbonitrides, has proposed that nitrogen transfers or donates electrons to the inner 3d-shell. He found that the effective size of the carbon atom was less than that of nitrogen and thus suggested that the interstitial atoms give up electrons. Kiessling" has studied the borides of several transition metal atoms and proposed that boron loses one p electron to the transition metal. He postulated that the additional electron added to the metal lattice compensates for the loss in metallic properties which results from the increased metal-metal atom separation. GuillaudT3" has proposed similar arguments from some recent magnetic studies he had made on manganese nitride. However, he did not base his conclusions on a quantitative argument. Pauling," in a recent paper, discussed electron transfer in in-termetallic compounds. He classified nitrogen as a hyperelectronic atom which can increase its valence by giving up electrons. He classified the transition metals as buffer atoms which are capable of either accepting or giving UP an electron. He pointed out that two factors are operating which promote electron transfer because they lead to increased stability. The first is an increase in the number of bonds, and the second is a decrease in the electric charges on the atoms. These ideas when applied to the interstitial nitrides would indicate a viewpoint favoring electron transfer by nitrogen to the transition metal. Hagg7s arguments in favor of no exchange are adequately summarized by Wells." Implicitly, Hagg

Jan 1, 1956

By B. L. Landrum, J. Simmons, J. M. Pinson, P. B. Crawford

Patentiometric model data have been obtained to estimate the effect of vertical fractures on the areas swept after breakthrough in water flooding and miscible displacement programs such as gas cycling where the mobility is near one, The data are presented for the case of the fire-spot pattern in which the cemer well is fractured various lengths and orientations, the data indicate that for 10-acre spacing, fractures extetidirrg over 1300 ft in either directior1 from the fractured well may re.srrlt in reductions in sweep efficiencics from 72 to approximately 34 per cent. However. the area swept after break through may be quite largr and only 10 or 12 per cent 1ess than would be obtained if the reservoir were trot fractured. For the specific case when the volume of fluid injected is equivalent to 100 per cent of the pattern vol-unie, the swent area may vary from 80 to 88 per cent, depending on the lenght of the fracture. The former value is that which occurs when the break through or sweep efficiency was orrly 34 per cent and the latter figrrre of 88 per cent is that which is obtained if the reservoir were unfrac-ttm'd. It is pointed out that although the sweep efficiency may he very low in vertically fractured five-spot patterrz.s, the area swept at low water-oil ratios may be only 5 to 10 per cent less than those achieved if the reservoir were unfractured. INTRODUCTION Since the initiation of commercial reservoir fracturing techniques it has been desirable to determine the effect of fractures on the areas swept after breakthrough. Most water flooding or gas cycling projects are continued for substantial periods after the brcakthrough of the injected fluid. Although the sweep efficiency serves as one criterion for rating various flooding patterns. the area swept after breakthrough for various water-oil ratios or percentage wet gas, if cycling. is of perhaps more importance than the sweep efficiency alone. Sweep efficiency data on the vertically fractured five-spot have been presented3. Previous work on the line-drive pattern has shown the effect of vertical fractures on the area swept after breakthrough for the case in which the distance between injection and producing wells divided by the distance between adjacent input wells was equivalent to 1.5 (see lief. 2). The data indicated that for the line-drive pattern it may be desirable to flood or cycle substantially perpendicular to the fractures in order to achieve the greatest recovery for the smallest volume of fluid injected. For this study the center well of a five-spot is assumed as the fractured well. All fractures were assumed to originate at this well and extend into the reservoir for various distances and orientations. All the fractures are straight and are of large permeability compared to the matrix proper. These data are presented to aid the engineer in estimating fractured five-spot pattern performance. ANALOGY The potentiometric model was used in making this study. The model used was 20 20 in. by approximately 1-in. deep. For certain portions of the study one corner of this model was considered to be an injection well and the opposite corner a production well. To simulate vertical fractures a copper sheet was soldered to the wire well and made to conform to the desired length and orientation. In other studies the same model was used except that the four corners of the model might be considered as the corner wells of a five-spot pattern and a fifth well was placed in the center of the model. The well placed in the center of the model was fractured. The total fracture length is L and the well spacing. d. The complimentary fracture angles will be obvious from Figs. 3 and 4. The data obtained on the potentio-metric model assumes the pay to be uniform and homogeneous, the mobility ratio is one, steady-state conditions exist and gravity effects arc neglected. The permeability of the fractures is very great compared to that of the matrix proper. The po-tentiometric model has been used widely both in water flooding and gas cycling projects, and may be used for miscible displacement; how-ever. it is believed that the poten-tiometric model data are more properly applicable to gas cycling than water flooding because the model as-

By M. Shelef, A. W. Fletcher

The effect of alkali sulfates in promoting the sul-fation of nickel and copper in a bulk sulfide flota -tion concentrate by fluidized bed roasting has been studied in the laboratory, and it was shown that the various alkali sulfates promote sulfation to approximately the same extent. The sulfation of a mixture of synthetically prepared iron and nickel oxide and of nickel ferrite has also been studied. Nickel sulfation was promoted by high ratios of Fe:Ni and by the presence of sodium sulfate. THE work described in this paper was a continuation of earlier studies into the role of alkali sulfates in promoting the sulfation roasting of nickel sulfides1,2 in an endeavor to determine how the system was affected by the presence of compounds of iron and copper. The earlier work1 showed that, in the sulfation of NiO at 680°C, the reaction was limited by the formation of an impermeable film of nickel sulfate on the oxide surface. The relative effect of the various alkali sulfates in promoting nickel sulfation varied in the order: Li > Na >Cs > Rb > K A study of alkali sulfate/ nickel sulfate interactions at high temperatures showed that the promoting action was due to the fact that the nickel sulfate product layer sintered and agglomerated only when the more active additives were present. This resulted in the formation of discontinuities in the nickel sulfate layer so that diffusion of the sulfating gases to the NiO surface was no longer impeded and the reaction could proceed to completion. A similar explanation was used for the observation that sodium and lithium sulfates promote the oxidation of NiS to NiO at temperatures below 750°C since small amounts of nickel sulfate were formed during oxidation.2 It was of interest to study the effect of alkali sulfates on the sulfate roasting of a sulfide flotation concentrate which is typical of material treated commercially. In order to control temperature it is essential to roast sulfides in a fluidized bed and this technique was therefore used, although the batchwise operation of a small-scale laboratory reactor does not reproduce all conditions which prevail in full-scale continuous plant. The results obtained are therefore only comparative, and cannot be used for predicting the optimum conditions for metal extraction. The sulfation of synthetically prepared mixed oxides of nickel + copper and nickel + iron and of nickel ferrite was also studied to evaluate the relative effects of alkali sulfates with more complex systems. SULFATION ROASTING OF A SULFIDE FLOTATION CONCENTRATE The bulk sulfide flotation concentrate used in this work contained 7.92 pct Ni, 1.74 pct Cu, 35.66 pct Fe, and 31.28 pct S. The sulfide minerals present in order of abundance were pyrrhotite FeS, pyrite FeS2, pentlandite (FeNi)S, and chalcopyrite CuFeS2. Two samples described as coarse and fine were used. The coarse sample, which was a flotation concentrate (58 pct plus 300 mesh), was ground to 100 pct minus 350 mesh to produce the fine sample. Before roasting, the sample of sulfide concentrate was agglomerated by wetting witli a solution of the alkali sulfate (or water), thoroughly mixing, and drying at 110°C. This gave a cake which was gently crushed and screened, the -18 +100 mesh fraction being used for fluidized bed roasting. A similar-size fraction had been used by the authors in pilot plant work with a 4-in.-diam fluidized bed reactor.' In this work it was found that the molar ratio of additive to the total iron + nickel + copper content of the sulfide sample should be adjusted to a value of approximately 0.06, as this was the optimum amount necessary for nickel sulfation. Experimental. The fluidized bed reactor consisted of a quartz tube approximately 60 cm long and 30 mm in diameter resting in a vertical tube furnace. The sulfide bed (30 g) was supported on a bed of -4 +12 mesh quartz particles 3 cm high, which rested on a sintered quartz disc welded to the tube. The temperature of the furnace was controlled with a variable transformer to give a final bed temperature of 680°C. The bed was fluidized with air or mixtures of air + 10 pct v/v SO2, at a total apparent gas velocity of 60 to 65 cm per sec at 680°C. The SO2 was introduced into the fluidizing air stream only when the oxidation of the sulfides was completed. At the end of the roasting period the calcine was leached with boiling water and the

Jan 1, 1964

By W. Rostoker, R. F. Domagala, R. P. Elliott

The phase equilibria of the Hg-Th system over the composition range 0-100 pct Th and temperatures up to 1000°C have been studied for a small-volume, closed system. The solubility of Th in liquid Hg is about 5 pct at 300°C and decreases sharply with decreasing temperature. Two intermediate phases occur, Hg3 Th and HgTh. The structures of these are hexagonal (nonideally close-packed) and face-centered cubic, respectively. The HgTh phase decomposes eutectoidally at 400°-500°C. The solubility of Hg in solid thorium seems to be negligible. AFULL-phase diagram for this system would have to be defined on temperature-composition-pressure co-ordinates. This paper describes the pseudo phase diagram of a closed system, that is, where the alloy enclosed in a small volume equilibrates with a vapor pressure of mercury dictated by composition and temperature. Because of the experimental difficulties in studying a system of this nature, many of the phase relations can only be sketched. Alloy Preparation Alloys over the full range of composition were made from triple distilled mercury and one of two grades of thorium. For the bulk of the work, a calcium-reduced metal in sintered pellet form of reported 99+ pct total thorium content was used. Arc-melted specimens of this thorium gave a hardness of 135 VPN. The microstructure showed small primary dendrites of ThO2. A number of alloy compositions were made with a high-purity, iodide-decomposition thorium metal. The are-melted hardness of a button of this material was 35 VPN. Although the microstructure of the arc-melted specimens showed no dendrites of ThO2, there was definite evidence of an unidentified phase enveloping the grain bound-aries. There were no distinguishable differences between the constitution of alloys made with the two grades of thorium metal. Under normal conditions thorium is not wetted by liquid mercury. The film of ThO2 on all thorium metal cannot be penetrated by either liquid or vaporous mercury. It was therefore necessary to comminute thorium in the presence of mercury under such conditions that oxide films could not reform on the newly exposed metal surfaces. This was accomplished by the use of a high-speed, carbide-tipped rotary cutter incorporated in a chamber purged with argon and connected at the bottom to a demountable Vycor bulb containing a weighed amount of mercury. This experimental device is fully described in a separate paper.1 Alloy compositions were calculated by weighing the empty bulb, the bulb containing the mercury, and the bulb containing the mercury and the thorium chips. Many alloys were analyzed chemically for thorium and/or mercury after subsequent homogenization; the agreement between analyzed and calculated compositions was invariably very close. Bulbs containing the requisite amounts of mercury and fine thorium chips were clamped off, removed to a sealing unit, evacuated and sealed. Amalgamation under these conditions proceeded rapidly even at room temperature. To insure homogeneity, the specimens were annealed to 300-400°C. Alloys containing less than 30 pct Th remained pasty after all treatments, indicating an equilibrium condition of liquid plus solid. Alloys with more than 30 pct Th were transformed into a dark powdery product. These latter specimens were annealed for times of up to 1 week to complete interdiffusion. Many of the alloy compositions are pyrophoric. On exposure to air they oxidize with considerable evolution of heat to a mixture of ThO2 and free mercury. It was mandatory that alloy specimens be handled in a "dry box" purged thoroughly with argon. All X-ray diffraction specimens were powdered, screened, and sealed in capillary tubes within the dry box. Experimental Procedures Thermal analysis experiments, useful only in the mercury-rich region of the system, were conducted with the alloys in their original containers. A reentrant thermocouple well formed an integral part of the bulb. These bulbs were heated in a silicone oil bath and cooled in a dry ice-acetone mixture. The rates of heating and cooling were slowed by immersing the specimen bulb in a larger tube containing silicone oil. This provided a suitable thermal lag. In all tests, pure mercury was run as a basic standard. While the invariant reaction at about the melting point of mercury was detected by thermal analysis, the heat effect at the liquidus was not sufficient to produce an inflection in the cooling curve. It was necessary to determine the liquidus temperatures at the mercury-rich end of the system by "breaks" in electrical reslstivity versus temperature curves for individual alloys. The apparatus for this purpose consisted of a pyrex tube about 2 in. diam and 12 in

Jan 1, 1959

By H. G. Doll

A new electrical logging method called Laterolog is described which provides for better recording of formation resistivity. In this method a current, preferably of constant intensity, is forced into the formation perpendicularly to the wall of the hole as a sheet of predetermined thickness by means of a special electrode arrangement and of an autonlatic control system. The essential advantages of the Laterolog over the regular resistivity logs are explained. With the Laterolog, the mud column has much less influence than with conventional methods. The Laterolog is, therefore. particularly useful in wells drilled with highly conductive mud. Moreover. when the electrode system is located opposite a bed of moderate or small thickness, the disturbing effect of the adjacent formations becomes practically eliminated, provided the bed is thicker than the sheet of current. which itself is usually a few inches to a few feet thick. The sequences of beds are. therefore, much more sharply differentiated, and, in many cases, it is possible to read directly from the logs values close to the true resistivities of the formations without further corrections. Field examples are shown to illustrate the results of the method in various types of formations. INTRODUCTION As soon as it was introduced into the petroleum industry, electrical logging roved to be a powerful instrument for the delineation of the strata traversed by bore holes and for correlation of such strata." Research and engineering efforts were mostly devoted at this early time to the design of the techniqurs which could provide the best data for these purpoes. Later, attention was directed toward the quantitative analy5i.s of electrical logs, in order to obtain information on. reservoir characteristics, and, in particular, on oil and water saturation.3,4 Efforts have been made, accordingly, with a view to improving the already existing methods, or to finding new methods which could satisfy these new requirements." Quantitative analysis implies a determination as accurate as possible of the true resistivity of the formations. In fact, however; the "apparent resistivity" recorded in front of a given bed by a conventional electrical logging method is frequently quite different from the true resistivity of this bed. This is due to the combined influence of the mud column, of the adjacent formations both above and below the bed, and of the invaded zone, in which the original fluid has been more or less replaced by mud filtrate. When the beds are thick enough, and, as is frequently the case in sand and shale formations, when their resistivity is not much greater than that of the mud, it is generally possible to obtain their true resistivity directly on the electric log, or at least to obtain an approximate value which can be corrected without undue difficulty by means of recently published charts known as "departure curves."" When the beds are thin, and particularly when, in addition. their resistivity is substantially greater than that of the mud column, the apparent resistivities recorded on conventional logs are seriously affected, and it is generally very difficult, if at all possible, to estimate their true resistivity with a good enough accuracy. In the most severe cases, such as are encountered in holes drilled through hard formations with muds of high salinity, the conventional logs are so distorted and rounded that they do not even show clearly the houndaries of the different beds. In order to overcome the effect of the mud column and of the adjacent formations, it is possible to make use of appro. priate systems whereby the measurements involve a comp3ratjvelv thin slice of space at the level of the measuring device. A mention is due, in this respect, to a measuring system. called the "guarded electrode;" invented by C. Schlumberger over 20 years ago. The system, schematically represented in

Jan 1, 1951

By H. G. Doll

A new electrical logging method called Laterolog is described which provides for better recording of formation resistivity. In this method a current, preferably of constant intensity, is forced into the formation perpendicularly to the wall of the hole as a sheet of predetermined thickness by means of a special electrode arrangement and of an autonlatic control system. The essential advantages of the Laterolog over the regular resistivity logs are explained. With the Laterolog, the mud column has much less influence than with conventional methods. The Laterolog is, therefore. particularly useful in wells drilled with highly conductive mud. Moreover. when the electrode system is located opposite a bed of moderate or small thickness, the disturbing effect of the adjacent formations becomes practically eliminated, provided the bed is thicker than the sheet of current. which itself is usually a few inches to a few feet thick. The sequences of beds are. therefore, much more sharply differentiated, and, in many cases, it is possible to read directly from the logs values close to the true resistivities of the formations without further corrections. Field examples are shown to illustrate the results of the method in various types of formations. INTRODUCTION As soon as it was introduced into the petroleum industry, electrical logging roved to be a powerful instrument for the delineation of the strata traversed by bore holes and for correlation of such strata." Research and engineering efforts were mostly devoted at this early time to the design of the techniqurs which could provide the best data for these purpoes. Later, attention was directed toward the quantitative analy5i.s of electrical logs, in order to obtain information on. reservoir characteristics, and, in particular, on oil and water saturation.3,4 Efforts have been made, accordingly, with a view to improving the already existing methods, or to finding new methods which could satisfy these new requirements." Quantitative analysis implies a determination as accurate as possible of the true resistivity of the formations. In fact, however; the "apparent resistivity" recorded in front of a given bed by a conventional electrical logging method is frequently quite different from the true resistivity of this bed. This is due to the combined influence of the mud column, of the adjacent formations both above and below the bed, and of the invaded zone, in which the original fluid has been more or less replaced by mud filtrate. When the beds are thick enough, and, as is frequently the case in sand and shale formations, when their resistivity is not much greater than that of the mud, it is generally possible to obtain their true resistivity directly on the electric log, or at least to obtain an approximate value which can be corrected without undue difficulty by means of recently published charts known as "departure curves."" When the beds are thin, and particularly when, in addition. their resistivity is substantially greater than that of the mud column, the apparent resistivities recorded on conventional logs are seriously affected, and it is generally very difficult, if at all possible, to estimate their true resistivity with a good enough accuracy. In the most severe cases, such as are encountered in holes drilled through hard formations with muds of high salinity, the conventional logs are so distorted and rounded that they do not even show clearly the houndaries of the different beds. In order to overcome the effect of the mud column and of the adjacent formations, it is possible to make use of appro. priate systems whereby the measurements involve a comp3ratjvelv thin slice of space at the level of the measuring device. A mention is due, in this respect, to a measuring system. called the "guarded electrode;" invented by C. Schlumberger over 20 years ago. The system, schematically represented in

Jan 1, 1951

By R. L. Wilcox, M. L. Fuller

Owing to the nature of the die-casting process, fresllly cast alloys are undoubtedly not at equilibrium from the standpoint of alloy phase relationships. After casting, therefore, they tend to undergo phase changes, with the ultimate effeet of reaching a state of equilibrium at the aging temperature, beyond which no fnrther change takes place. This phase alteration undoubtedly is one of the primary causes of the changes in dimensions and physical properties that zinc-alloy die castings undergo during aging. It is planned to report on this problem in a series of papers of which this is the first. The writers have made a study of commercial zinc die-casting alloys over a period of several years, utilizing the X-ray diffraction technic of determining the phase composition changes in the alloys. Up to the present, two principal phase changes have been observed which are capable of causing dimensional changes: (I) the segregation of secondary constituents from the zinc-base solid solution and (2) the beta aluminum-zinc decomposition. The latter is the subject of the present paper and studies on the former will be reported upon at a future time. Scope of Study In the present investigation a special technic for the study of the beta phase in zinc-alloy die castings has been developed, making possible the determination of the period of existence of the beta phase after casting. The pure beta constituent and its decomposition have been studied in detail. The effect of magnesium and copper on the velocity of the decomposition is reported. The heat of decomposition, the eutectoid temperature arid the accompanying density change have been measured. The density change lias been calculated from data on crystal structure and the result thus obtained has been compared with the actual change.

Jan 1, 1935

By H. A. Schwartz, W. Kenneth Bock

In this paper it is shown that when the tensile strength of a given steel in various states of heat-treatment is plotted against its elongation, a straight line results. The equation of this straight line can be computed with considerable accuracy from its chemical composition. The appropriate equations are given. The logarithm of the slope of the tensile-strength locus is shown to be proportional to the cumulative effect of the total alloy addition and the vosition of the line to be directly proportional to the cumulative effect of the alloy content. It is further pointed out that heat-treatment is more effective than composition in determining yield ratio. The latter enters mainly by its effect on hardenability, which is briefly discussed. Reduction of area and Brinell number are given some incidental attention. The data are applicable only to steels that have been normalized and/or quenched. The steels, if normalized, may or may not have been tempered. If quenched they must have been tempered at or above 4oo°C. (75o°F.). Introduction Cast steels vary in composition and frequently are used in various states of heat-treatment. It is obviously important to be able to predict the compositions that might accompany specific engineering properties by suitable selection of heat-treatments. For cast steels, which are of necessity produced heat by heat in accordance with the particular requirements of the castings to be poured, there has been, happily, much less tendency to standardization than for rolled products, whose destination is not necessarily known when particular ingots are made or rolled. It is of distinct advantage to the steel foundry-men to be able to make steel of given properties, using alloys that can be recovered from scrap, or most conveniently or cheaply bought, rather than a particular formula adopted in the interest of standardization. The heat-treatment appropriate to securing a given result in a given steel is well known to be closely related to composition. For example, molybdenum steels are not much softened by tempering except at rather high temperatures. Highly alloyed steels are "air-hardening," and on cooling in air behave like carbon steels that have been quenched. With these matters, we do not concern ourselves in this paper, although we recognize their importance. The entire picture evidently will be very complex and can be brought within accurate understanding only if our knowledge of test results can be coordinated in terms of general principles.

Jan 1, 1944

By Charles C. Rodd

Prior to 1938, proration procedure in Kansas required the physical testing of wells in order to set up a basis for allocating production. Subsequently the use of liquid-level data and bottom-hole pressure data was authorized on certain types of wells as a basis for calculating well capacities, thereby permitting wells to be tested at low rates and with small volumes of production. This paper gives some attention to the equipment used for obtaining liquid-level data but in general it is devoted to the theoretical and physical factors involved in well testing by drawdown methods. These tests are divided into two classifications: (I) liquid-level data used directly to calculate capacities, and (2) liquid-level data and liquid-level measuring equipment used in connection with other data to determine bottom-hole pressure. Equations and calculations for both types are shown. Well capacities calculated from fill-up data have not been used generally but offer a simple means of testing some wells. Theoretical factors and calculations for such tests are shown. In the state of Kansas, proration laws required that the "ability of a well to produce" be given consideration in state allocation orders and for many years this was the only factor used in prorating the allowed oil. The "ability of a well to produce", was the quantity of oil that could be obtained from a well in a prescribed period, usually 24 hr. Early in the history of State-regulated proration, Kansas operators realized that, unless some restriction were placed upon equip- ment, the competition between producers to obtain large well "potentials" might result in a race to install the largest pumping equipment. Consequently, restrictions were placed upon the size of tubing and length of pump stroke that could be used in pumping wells during potential tests. Later, restrictions were placed also upon the size of tubing and chokes that could be used in flowing walls. Despite the restriction setup, better pumping equipment was designed and installed, pumps were improved, and various devices were invoked to obtain high rates of production for short periods of time. By 1937 pumping cycles of forty to forty-five 54-in. strokes per minute were not uncommon, and numerous wells had produced at the rate of 3500 bbl. per day for short periods. Such production was far beyond any rate that could be long sustained. Equipment necessary to take "potentials" was several times larger than that needed for normal producing purposes, and repairs and replacements required by the high pumping speeds were excessive. Also, many operators suspected that the high rates of production main tained during '"potential" tests were conducivc to early water encroachment. By 1938 large-scale physical testing of wells in Kansas ended, the use of the bottom-hole pressure gauge had become common, engineers and operators were becoming familiar with the term ''productivity index," and bottom-hole pressure was being used as a factor in allocation in many areas. There were many drawbacks, however, to large-scale use of

Jan 1, 1943