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By C. H. Bowen

Industry needs a generally applicable means of defining average grain sire and grain size distribution. Students of sediments have explored this field, employing methods that might also prove useful in engineering problems. Before attempting to solve specific problems it is well to review the derivation of commonly used grade scales and the reasons for their selection. This aspect of the problem seems largely to have been lost, and a review of basic factors may suggest causes for failures in using size analysis data.

Apr 1, 1956

By K. Kobayashi, K. Ueda, K. Yamaguchi

Lead concentrates from Kuroko (black ore) mines, which contain 4-7% Cu, 55% Pb, 3-777, Zn, and 0.5-0.9% As, are pretreated by a hydrometallurgical process before electric furnace smelting with other lead resources from Kuroko. The hydrometallurgical pretreatment involves sulfuric acid leaching in the first stage and ferric leaching in the second stage. This paper describes the short history of lead recovery from Kuroko and the performance of laboratory tests and pilot plant and commercial operations.

Jan 1, 1985

By W. F. de Lange, M. I. Brittan

A mathematical model of the Western Holdings gold concentrator in South Africa was generated by multiple regression analysis of routine plant operating data. Interpretation of the computer results and application of the model indicated that significant economic improvement in gold recovery could be realized by relatively minor modifications to the circuit. The modifications made are described and the economic benefits resulting from the increased gold production are assessed. Comparison, of the projections of the mathematical model with actual plant performance is illustrated.

Jan 1, 1976

By K. Osseo-Asare

LIX63 In combination with DNNS selectively extracts nickel and/or cobalt from acidic leach liquors with pH values as low as 10 Nickel/cobalt and cobalt/nickel selectivities are achieved by varying the relative concentrations of LIX 63 and DNNS Increasing LIX63 concentration retards both extraction and stripping rates while DNNS has the opposite effect. Slope analyses of equilibrium data Indicate that both LIX63 and DNNS are present in the extracted complexes. Examples of possible flowsheets are presented.

Jan 1, 1981

By B. Yu, H. M. Lee, R. P. Gardner

Some preliminary results are given on the use of radioactive tracers for implementing the mechanistic approach to flotation. The process studied is an industrial one for the cleaning of sand for the production of glass. The radioactive tracers employed are those produced from intrinsic elements in the sand by neutron irradiation in a nuclear reactor. The results indicate that the technique will be useful for the determination of flotation simulation mechanistic model parameters on operating industrial processes without interruption of their normal operation.

Jan 1, 1980

By H. A. Guess

For a number of years I have used for the commercial wet assay of lead generally the ammonium molydate, and occa-sionally the ferrocyanide method. These well-known methods need no detailed description here. In the ore-selling and ore-buying establiahments of the West, 90 per cent. of all wet lead-assays are made by one or the other, and at least nine-tenths of this proportion by the molybdate method. A procedure so well-established must have merit; and, in

Jan 1, 1905

By William P. Blake

The phenomena of concentric arrangement of minerals in rock-masses, generally known as " orbicular structure," have of late received much attention from investigators. Lawson, of the University of California,' has described the orbicular gabbro at Dehesa, San Diego county, Cal. Kessler and Hamilton, of Stanford University, working independently upon the same subject, published their descriptions,2 giving also a list of many other localities in Europe and America where orbicular rocks are found, adding copious references to the literature of the subject.

Jan 1, 1906

By William J. Potter

The current financial environment differs markedly from past commodity price expansions, which have benefited the mining industry. Deregulation, financial innovation, and the globalization of capital markets in the 1980s have altered financing and investing patterns. Investment bankers and smart money within the industry have recognized the alterations and trends that facilitate fee revenue and profitable growth. This paper profiles transactions exemplifying change and documents financing techniques or instruments that have developed during the past half decade, emphasizing equity in the global marketplace.

Jan 1, 1990

By Marius R. Campbell

VArIoUs classes of coals are recognized in this country at the present time. These classes depend largely upon physical characteristics rather than upon chemical composition, and consequently they cannot be accurately defined. The divisions into anthracite, semi-anthracite and semi-bituminons are fairly satisfactory; but the term bituminous embraces so large a variety of coal that it is of little value, and the term lignite is so loosely applied that it has little or no place in a scientific classification.

Jan 1, 1906

By W. J. Maraman, D. R. Harbur, J. W. Anderson

A device for rapidly quenching liquid metals into thin platelets has been developed at the Los Alamos Scientific Laboratory. This rapid quenching equipment is built around the technique of catching a molten drop of metal between a rapidly closing plate and a stationary plate. The design and operation of this unit are described. The closing speed of the smasher plate at impact is 12.6 ft per sec. The quenching rate for this device is controlled by the interface resistance between the plates and the platelet, and is dependent upon the heat content and density of the material being quenched. The initial quenching rate down to the freezing point of the platelet material is lo5º to 106ºC per sec. After an isothermal delay, which is poportional to the heat of fusion of the platelet material, the final cooling rate down to the temperature of the smaslier plates is l04ºto 105cº per sec. RAPID heating of metals by capacitor discharge and other methods has provided the metallurgist with a useful tool for probing into the kinetics of phase changes and the many nonequilibrium phenomena which occur during rapid temperature changes. Equally interesting studies can also be made on metals and alloys which are rapidly cooled from the liquid state.' Studies in this field have been limited, however, because the rates at which metals could be cooled were many orders of magnitude slower than the rates possible for heating. In recent years many new laboratory methods have been developed to rapidly cool metals from the liquid state to ambient temperature and below.2"4 All of these methods involve spreading a liquid drop of metal into a thin foil in a very short time. The methods developed have varied from ejecting a drop of molten metal at the inside surface of a rotating cylinder or stationary curved plate to catching a falling drop of molten metal between rapidly closing plates. The equipment which has been developed at the Los Alamos Scientific Laboratory for rapidly cooling molten materials uses the latter of these two approaches. The basic design, operation, and initial results of this rapid quenching device are given in this report. APPARATUS The drop smasher, which is now being used to obtain rapidly cooled metal foils, is shown in Fig. 1. Basically the device consists of a smasher plate which is driven by a solenoid into a stationary plate. The solenoid is activated by a drop passing through the photoelectric cell and is powered by discharging an adjustable 350-v capacitor bank with a 66-amp peak current into it. This power supply is designed so that the solenoid is powered for 2 m-sec after plate closure to minimize the rebound effect. There is an adjustable time-delay mechanism between the photoelectric cell and the solenoid. Both smasher plates have changeable inserts so that a variety of materials can be used to smash the molten drop. The shaft of the moving plate is guided in an adjustable housing which has ball-bearing walls. The cabinet shown to the left of the drop smasher in Fig. 1 contains the power supply and receiver for the photoelectric cell, the time delay mechanism, and the capacitor bank. The drop smasher can be placed inside a vacuum chamber, for use with radioactive materials, with the upper plate forming the lid, as shown in Fig. 2. On top of the vacuum lid is an induction coil, powered by an Ajax induction generator, which is used to melt drops from the end of the rod extending through the vacuum seal on top the quartz tube. OPERATION The drop smasher shown in Fig. 2 is operated in the following manner. The smasher plates are separated and the unit is lowered into the vacuum chamber using a pressurized cylinder. The induction coil, quartz tube, and lid with sliding vacuum seal are then assembled on top the vacuum chamber. A rod of the material for rapid quenching studies is connected to the rod extending through the sliding vacuum seal. The vacuum chamber is then evacuated and the desired atmosphere established. The photoelectric cell is turned on, and the capacitor bank is charged and armed. Power is supplied to the induction coil, and the rod of material for rapid quenching studies is lowered into the induction field. A molten drop forms on the end of the rod, drops off, falls through the light beam of the photoelectric cell, and is then caught between the smasher plates. .

Jan 1, 1970

By V. D. Perry

Mineralized breccia pipes, because of their widespread occurrence and close structural relations to some of the world's great ore bodies, are objects of unusual interest for mining engineers and geologists. The literature contains many references to them, but it is questionable whether their genetic significance and economic importance have been sufficiently emphasized. The purpose here is to stress these features, relating them to the field facts, for the particular benefit of younger generations of geologists who, confronted with and sometimes confused by the growing flood of geochemical, geophysical, and other specialized research approaches, may be reassured that mappable field relations remain a foremost guide to a better understanding of ore deposits. A mineralized breccia pipe is a pre-mineral, breccia structure which has controlled the circulation and deposition of subsequently introduced mineralization. It is composed of relatively rotated angular or rounded rock fragments, set in a mineralized matrix. A pipe in plan outline may be circular, oval or approach polygonal form, with a steep to vertical axis proportionately much greater than its horizontal dimensions. The pipe is a steeply plunging, chimneylike mass of brecciated rock cemented with later minerals. Rock breaks in a variety of ways and complete fragmentation often occurs without rotation of individual pieces. A finely broken rock mass may fit into a tight jig-saw pattern, each fragment having mutually concordant boundaries with its neighbors. The result is a stockwork of innumerable reticulating cracks that, once cemented by mineralization, forms a complicated intersecting network of individually insignificant but collectively important seams and veinlets. Stockwork fracturing among its many forms takes the shape of domes of subsidence, fracture pipes, and related peripheral zones around and over breccia columns, or a combination of any of these structures. The significance of the mineralized breccia pipe is that it represents the extreme or climactic expression of a structural type which has a variety of mutations including subsidence domes, fracture pipes, and other stockwork zones all with related ancestry and similar to dissimilar characteristics. These allied and associated structures hold an answer to the fundamental question of the origin of many important ore deposits. CANANEA-TYPE LOCALITY FOR BRECCIA PIPES The Cananea district is characterized by an unusual development of mineralized breccia pipes. It is an important copper producer located in Sonora, Mexico, a short distance southwest of Bisbee, Arizona, and at the southerly limit of the great porphyry copper belt of the southwestern U.S. Cananea's rocks consist of Paleozoic quartzite and limestone capped unconformably by a thick series of volcanics including andesitic flows, tuffs, and agglomerates. These rocks have been intruded by a deep-seated granite with related basic and acid differentiates including dikes and plugs of quartz mon-zonite porphyry. Mineralization coincides with a northwesterly trending belt of these intrusives which break upward into and through the sedimentary-volcanic rock sequence. The district has weakly defined tectonic alignments in a northwesterly direction with subordinate intersecting fracture elements, but lacks important faulting or fissuring to provide throughgoing avenues for the upward circulation of mineralizing fluids. Thus, as will be discussed in subsequent paragraphs, the alternate way in which late magmatic and hydro-thermal derivatives of the parent magma reached the near-surface zone was by excavating their own breccia pipe channelways. There are numerous stages of breccia pipe development, related both in time and space to magmatic activity. A compilation of similarities and differences in various pipes suggests that proximity or remoteness of a demonstrable or inferred magmatic source provides an orderly genetic basis for describing the following representative types. Cananea Duluth Type: There are no intrusive rocks within or close to the Cananea Duluth pipe; therefore, the existence of any deep-seated magma that may have been related to its formation must be inferred. The structure is an oval-shaped ring 1200 x 300 ft in plan dimensions, cutting steeply across low angle, bedded tuffs, and other volcanics; it has been developed by drill holes to a depth of 2000 ft below the surface. The ore follows the periphery of the pipe and is composed of intensely brecciated rock which is cemented by minor galena, sphalerite, chalcopyrite, quartz, carbonates, and adularia. There is a definite vertical zoning of sulfides with less galena, continuing sphalerite, and increasing chalcopyrite at deeper levels. Within the interior of the ore ring, the brecciation becomes progressively weaker and coarser, the whole indicating relatively gentle slumping with broken, thin tuff beds pre-

Jan 1, 1961

By Dilip K. Das, Douglas T. Pitman

ONE of the major uses of barium in metallic form is as a getter material in vacuum tubes. Because of the high chemical reactivity of the metal, Ba-Al alloys are extensively used. Numerous methods for the preparation of Ba-Al alloys have been published, a few of which1-4 are cited here. Most of these methods were found to be quite elaborate, involving the reduction of BaO, and not too well adapted for the close control of the final composition of small amounts of alloys prepared for laboratory use. A simple laboratory method for the preparation of Ba-A1 alloys in small batches starting from pure metals was devised, so that it was possible to control the desired compositions to within 1 pct. The pertinent features of the alloy system Ba-Al5 are 1) an intermediate compound BaAl, with the melting point of 1050°C, and 2) a eutectic between aluminum and BaAl4 at 98 pct Al. The accompanying sketch shows the experimental arrangement for the preparation of the alloys. Weighed amounts of aluminum and barium were placed in an alumina and a stainless steel crucible, respectively. According to the supplier's specification, the purity of the metals used in the alloys is as follows: a) aluminum rods—99.9 pct Al, and b) barium rods—99.5 pct Ba. The stainless steel crucible, tapered at the bottom and having a 1/16 in. diam hole, rested on top of the alumina crucible. The assembly was placed inside a graphite sleeve which rested on a refractory platform. The platform moved the assembly up and down through the field of a radio frequency coil. A glass bell jar was placed between the crucible assembly and the radio frequency coil to maintain a steady flow of helium around the melt. A small window was cut out on the wall of the alumina crucible to observe the progress of the re- action and to record the temperature with an optical pyrometer. The platform was first raised high enough to move the barium out of the radio frequency coil field in order to allow only the aluminum to melt. The assembly was then lowered so that the barium began to melt and flow out through the small orifice into the molten aluminum. In order to keep the violence of the exothermic reaction under control, the rate of flow of barium was carefully regulated by raising or lowering the crucible assembly. All the samples prepared by this technique were examined by a Norelco X-ray diffractometer using CuKa radiation, The diffraction specimens were prepared by placing the finely powdered samples in flat specimen holders. The Ba-Al alloys prepared with a high barium content were found to consist mainly of BaAl4. The structure of BaAl4 has previously been reported by Alberti and Andress.8 They found that BaAl4 was body-centered-tetragonal with an a0 = b0 = 4.530Å and c0 = 11.14Å. An alloy whose composition was found by chemical analysis to be almost 100 pct BaA1, was used to determine the relative intensities. The d-spacings were obtained from the same alloy to which a small amount of tungsten had been added as a calibrating material. Accurate values for a, and c, were calculated according to the method proposed by Taylor and Floyd.' The calculated values are: a, = b, = 4.566Å and c0 = 11.250Å. The measured d-values for BaAl4 are shown in Table I along with relative peak intensities above background and hkl indices. Acknowledgment The authors are grateful to L. J. Cronin, the head of the Techniques Dept., for suggesting the problem and for his constant interest. References 1Froges and Camargue: German Patent No. 809107, 1951. French Patent No. 935324, 1949. 2E. Bonnier: Annales de physique, 1953, vol. 8, pp. 259-312. 3M. Orman and E. Zemhela: Prac Institute of Metals; 1952, vol. 4, pp. 437-445. 4E. Fujita and H. Yokomizo: Reports Gov. Chemical Industrial Research Institute, Tokyo, 1952, vol. 47, pp. 291-297. 5E. Alberti: Ztsch. fur Metallkunde, 1934, vol. 26, p. 6. 6E Alberti and K. R. Andress: Ztsch. fur Metallkunde, 1935, vol. 27, p. 126. 7 A. Tnslor and R. W. Floyd: Acta Crystallographica, 1950, vol. 3, p. 285.

Jan 1, 1958

By A. H. Heim

A method and apparatus for measuring gas porosities of rocks are described. The apparatus can be assembled from commercially available components. In principle, measurements are made by volume substitution at constant pressure. The maximum error is not more than 0.3 porosity per cent. Typical results are given. INTRODUCTION Determining the porosity of rock samples is one of the most important and yet most varied types of measurement in core analysis. Among the many techniques devised are the so-called "gas porosity" methods. An old and well known example is the Washburn-Bunting method.' The U. S. Bureau of Mines2-' described and later improved the apparatus for a now widely used method generally known as the "Boyle's law" method. In the present form of the Washburn-Bunting method,' the volume of air in the pores of a rock sample at atmospheric pressure is extracted and then collected in a graduated burette at atmospheric pressure. The volume of air is read directly as the pore volume of the sample. The absolute error in reading the collected volume of gas is independent of the total volume; thus, the relative error is larger when the volume is small, as it is for rocks of low porosity. In addition, the sample after measurement contains mercury, which limits its use for other analyses. The Bureau of Mines (or Boyle's law) method measures directly the solids volume of a sample from which the pore volume and porosity are derived, using a separate measurement of the bulk volume. Gas at a few atmospheres pressure is introduced into a sample chamber of known volume containing the rock sample. The pressure is accurately measured. Following, the gas is expanded into a burette at 1 atm, and the gas volume is read directly. From the initial pressure p, and the final pressure p2 and volume v,, the initial gas volume v1 is calculated using Boyle's law; that is, p1v1 = p2v2. Volume v, minus the volume of the empty sample chamber is the solids volume of the sample. The accuracy of the method is limited, unless corrections are made, by deviations of the gas from the "ideal" gas-law behavior assumed in the simple form of Boyle's law. The purpose of the present paper is to describe a method for measuring the gas porosity of a rock which avoids many of these difficulties. Gas volumes are measured directly with the same accuracy as the bulk volumes. Pressures of at least an order of magnitude larger than those of previous methods are employed to insure rapid penetration of the gas into the sample. While special equipment may be built to apply the method, the porosimeter may be constructed as well from commercially available components. For simplicity, the apparatus described will be referred to as the "Constant-Pressure gas porosimeter". THE CONSTANT-PRESSURE METHOD Fig. 1 shows schematically the arrangement of components comprising the present Constant-Pressure porosimeter. Briefly, the method is one of volume substitution and may be considered a null measurement. Omitting (for the present) some of the operational details, the method of measurement consists of the following three steps. 1. After evacuation, the volume of the measuring system (a ballast chamber, a manifold, two gauges and their connections) up to the sample chamber is filled with gas to a high pressure (- 1,000 psi). A sample of the gas at this pressure is trapped in one side of a sensitive differential pressure gauge to serve as the reference pressure for subsequent steps. 2. The evacuated sample chamber containing the rock sample is opened to the measuring system. As the gas expands into the chamber, the resulting decrease in pressure unbalances the differential pressure gauge. 3. The pressure is restored by means of a mercury volumetric pump. The volume of mercury injected exactly equals the free or void volume of the sample chamber (volume of empty chamber minus the solids volume of the rock within). From the injected volume and the known empty chamber volume, the solids volume is obtained and the porosity calculated. The pressure and the volume occupied by the gas are the same before and after opening the sample chamber. Expansion and compression of the gas are incidental operations and do not enter into the calculation of porosity. By the pressure balancing or nulling, the free volume of the sample chamber is merely substituted by an equal and measured volume of mercury. Since the measurements are at constant pressure, there are no compressibility corrections necessary for the sample chamber.

By D. R. Irving

Prior to this time, ample supplies of high grade mineral fillers, such as clay, have been available close to consuming centers. Now depletion of these accessible deposits, coupled with other factors such as increasing demand due to population expansion and standard of living rise, has made development of upgrading techniques attractive to producers. Various investigations being carried out by the U.S. Bureau of Mines are described. Factors making the development of improved methods for upgrading clays attractive to producers include: depletion of accessible deposits of high-grade clays, rising transportation and labor costs, more exacting specifications, and increased demand resulting from an expanding population and a constantly rising standard of living. Industry recognizes the need for upgrading presently unusable materials and has cooperated with the U.S. Bureau of Mines by providing samples from submarginal deposits and by evaluating the products that USBM upgrades. Following are some examples of recent clay beneficiation work by the Bureau. FIRE CLAY BENEFICIATION At the Rolla Metallurgical Center, Rolla, Mo., the Bureau is conducting research to develop technically and economically feasible mineral-dressing methods to remove quartz, pyrite, and other impurities from submarginal fire clays. The research has been spurred by the growing shortage of high-grade bur-ley, flint, and plastic clays in the Missouri fire-clay district resulting from increased consumption and the low rate of discovery of new deposits of adequate quality. There apparently is ample tonnage of submarginal flint and plastic clays to maintain the industry for many years if such material can be upgraded to commercial quality. Samples have been submitted to USBM by several major producers of refractories, including A. P. Green Fire Brick Co.; Harbison-Walker Refractories Co.; Mexico Refractories Div., Kaiser Aluminum and Chemical Corp.; and Wellsville Fire Brick Co. Research on some samples has been completed and still is in progress on others. The Bureau has found that specimens containing quartz or pyrite in grains coarser than the accompanying clay generally can be upgraded either with a gravity table or hydraulic cyclone. The improvement in quality is notable not only in chemical analysis but in an increase in pyrometric cone equivalent (PCE) of one or more cones. As an example, consider the results attained on a sandy flint—a fine-grained mixture of kaolin and halloysite with quartz and minor quantities of iron and manganese oxides. Chemical analysis was: 35.4 pct alumina (A12O3) and 47.8 pct silica (SiO2). The sample contained 9.2 pct free silica as quartz. The PCE was 33. The sample was crushed to -10-mesh, blunged with water, and then stage-ground to -48-mesh. The ground sample was tabled to yield a clay fraction containing 37.6 pct A12O3, and 45.3 pct SiO2 of which 2.4 pct was free silica. The PCE was 34. Recovery of alumina by this process was 73.6 pct. Concentration of the same clay in the hydraulic cyclone was even more effective in respect to quartz removal. The clay fraction analyzed 38.6 pct A12O3, 45.0 pct SiO2 of which 0.5 pct was free silica as quartz, and had a PCE of 34. Recovery of alumina was 71.9 pct. The hydraulic cyclone was also effective in reducing the pyrite content of a plastic clay which likewise was a mixture of kaolin and halloysite, plus some pyrite, quartz, and carbonaceous material. It analyzed 30.6 pct Al2O3, 52.3 pct SiO2, 2.3 pct Fe2O3, and 0.76 pct S. The sample was blunged and screened through 10-mesh to remove some coarse pyrite, then ground to -65-mesh and cycloned to remove most of the remainder. The final product recovered 81.8 pct of the alumina at a grade of 32.3 pct A12O3, 50.9 pct SiO2, 1.4 pct Fe2O3, and 0.1 pct S. The PCE was 32-1/2, compared with a PCE of 31-1/2 for the crude clay. The fine beneficiated clays, of course, must be pelletized and dried or fired to meet commercial acceptance. This operation has already been solved by industry. Little progress has been made on two remaining problems. One is that of fine-grained impurities, not separable by table or cyclone. Flotation is being investigated to solve this. Although fine pyrite is readily rejected, a satisfactory quartz-clay separation has not been attained. The second problem, a stubborn one, is that of alkali. Samples containing as much as 5 pct potas-

Jan 1, 1961

By D. Turnbull, J. H. Hollomon, J. C. Fisher

Application of the concepts of nu-cleation and growth to the analysis of experimental transformation data has led to valuable descriptions of phase transformations, an outstanding example being the transformation austenite —* pearlite which has been examined with particular care by Mehl and co-workers.&apos;-5 In addition to the pearlite transformation, the proeutectoid fer-rite and proeutectoid carbide transformations are known to proceed by nucleation and growth. Martensite, on the contrary, until recently was thought to form by a mechanism involving neither nucleation nor growth; however, extension of standard nucleation theory6 suggests that martensite, bain-ite, and the other products of austenite decomposition all grow from nuclei in the parent phase. The theory that martensite forms by nucleation and growth is strongly supported by recent experimental work of Kurdjumov and Maksimova.7 The concepts of nucleatioli and growth have been fruitful also in providing a sound basis for quantitative theoretical treatments of the kinetics of phase transformations. For example, Volmer and Weber8 and Becker and Döring9 developed the theory of nucleation from fundamental considerations to a point where excellent agreement was obtained with the results of experiments on the condensation of supercooled vapors. As a result of their analysis, the kinetics of vapor-liquid transformations now can be predicted. It seems probable that application of the theories of nucleation and growth to a quantitative study of austenite decomposition similarly will clarify the nature of the individual transfor: mations involved, and will enable the calculation of austenite transformation kinetics. In the present paper, the theories of nucleation and growth are applied to the austenite ? martensite transformation in steels. The analysis begins with a discussion of nucleation in single component systems. Martensite appears to be coherent with the parent austenite, hence the nucleation theory is modified to include the effects of elastic distortion. Nucleation in the two component iron-carbon system then is discussed, for most steels are primarily alloys of these two elements. Finally, M. temperatures and martensite transformation curves are calculated for each of several alloy steels of varying carbon and chromium content, and are compared with those determined experimentally by Lyman and Troiano10 and Harris and Cohen.11 Nucleation Theory NUCLEATION IN SINGLE COMPONENT SYSTEMS6,12-14 The work required for reversible formation of a region of phase within the parent a phase is expressed conveniently as the sum of two terms: W1 = Aa, the product of the area of the interface and the interfacial free energy, and W2 = VAf, the product of the volume of the region and the free energy increase per unit volume associated with the transformation. The total work is therefore W = Aa + VAf. When a is more stable than ß, Af is positive and W increases without limit as the volume increases. The transformation a ?ß does not occur. It is nevertheless true that small regions of phase ß enjoy temporary existence here and there in the a. The equilibrium number of ß regions of given size is proportional to exp(— W/kT) per unit volume of a, assuring that larger (ß regions occur with diminishing probability. When a is less stable than ß, Af is negative and W passes through a maximum as V increases. Assuming for simplicity that regions of ß are spherical, as is true when the interfacial tension is isotropic and there are no elastic strains, W = 4r2a + (4/3)*r3Af The maximum value of W is W* = 16iro3/3Af2 [1] for regions with radius r* = -2o/Af. [2] For single component condensed systems it has been shown14 that the steady rate of nucleation of 0 per unit volume of untransformed a is nearly proportional to exp[- (W* + Q)/kT] where Q is the activation energy for the unit processes of adding or removing one atom from an embryo or nucleus. If To is the temperature at which a and ß are in equilibrium, the rate of nucleation is a maximum at a temperature 0 < T < To where (W* + Q)/kT is a minimum. P regions smaller than critical size are called embryos; they tend to grow smaller and disappear, only exceptionally growing larger. Regions equal to or larger than critical size are called nuclei. A critical size nucleus may grow indefinitely large or may shrink back to a, either process decreasing the free energy of the region.

Jan 1, 1950

By R. H. Kolb

A long term project at Shell Development Co.&apos;s Exploration and Production Research Laboratory has been the improvement of the accuracy and the ease of BHP measurements. As a result of these efforts, two complete and separate systems have now been built for the automatic logging of BHP variations. The first of these is a small-diameter instrument suitable for running through production tubing on a single-conductor well cable. During the development of this instrument, as much emphasis was placed on providing a high degree of usable sensitivity and repeatable accuracy as on obtaining the advantages of surface recording. The second system combines the benefits of automatic, unattended recording with the convenience of a permanently installed Maihak BHP transmitter.&apos; THE CABLE INSTRUMENT For many years the standard instrument for BHP determination has been the wireline-operated Amerada recording pressure gauge or one of several other similar devices. This gauge records on a small clock-driven chart carried within the instrument, and although relatively precise readings from the chart are possible, they are difficult to ob-tain. a Both the maximum recording time and the resolution of the time measurements are limited by chart size, and when a slow clock is required for long tests, the precision of the time measurement is often inadequate. Since it is impossible to determine the data being recorded until the gauge has been returned to the surface, wasted time often results when a test is protracted beyond the necessary time or when it is terminated too soon and must be re-run. Clock stoppage or other malfunctions which would be immediately apparent with surface recording remains undetected with down-hole recording; the test is continued for its full term with a consequent loss in production time. As new uses for subsurface pressure data evolved, the shortcomings of the wireline instrument became increasingly apparent, and the concurrent development of a surface-recording pressure gauge and the associated high-pressure well cable service unit&apos; was undertaken. Description of the Instrument Because of its ready availability and advanced degree of development, the Amerada bourdon-tube element was chosen as the basic pressure-sensing device. This element converts a given pressure into a proportional angular displacement of its output shaft, and a suitable telemetering system was designed to measure accurately the extent of this displacement and to transmit the measurement to the surface and record it. The telemetering system furnishes a digital record printed on paper tape by an adding machine-type printer. The present arrangement provides a resolution of one part in 42,000 over the angular equivalent of full-scale deflection, giving a usable sensitivity of better than 0.0025 per cent of full scale. An additional refinement simultaneously records on the tape the time or the depth of the measurement, also in digital form. When the instrument is placed in operation, an adjustable programer can be set to initiate a read-out cycle automatically at selected time intervals. When subsurface pressures are changing rapidly, readings may be recorded as frequently as once every 10 seconds; when pressures are more nearly stabilized, the period between readings may be extended to as much as 30 minutes. Because the instrument is surface-powered as well as surface-recording, the maximum period of continuous logging is (for all prac. tical purposes) unlimited. The subsurface instrument is a tubular tool, 1 1/4-in. in diameter and 6.5 ft in length, operating on 12,000 ft of conventional 3/16-in. IHO logging cable. The transmitting section, mounted above the bourdon-tube element in place of the regular recording mechanism, contains no fragile vacuum tubes or temperature-sensitive transistors. This unit has been laboratory-tested to 1 0,000 psi and 300°F and has performed dependably during a number of field operations. The down-hole transmitting arrangement can be fitted to any standard Amerada pressure element, regardless of range and with no modification of the element itself. Calibration To obtain a repeatability commensurate with the sensitivity and resolution of the instrument, it was necessary to develop a special calibrating technique. The manufacturers of the Amerada recording pressure gauge claim an accuracy of only 0.25 per cent of full scale, which is a realistic figure for normal calibrating and operating procedures. An exhaustive investigation was made of the errors inherent in the bourdon-tube element, itself, independent

By R. L. Slobod, C. Gatlin

This .study defines the basic mechanism of the mis-cible displacerrzent of oil and writer from porous Medici by various water-driven alcohol .slugs. Three distinct alcohol slug processes were .studied. Considerable data concerning the quanity of alcohol required for oil recovery were also obtained. All data were obtained in a 1-in. diameter, 100-ft long, unconsolidated core. The porosity of this system was 35 per cent. and the permeability was approxitrlately 4 darcies. Total core pore volume wax 5,716 cc. All displacements were conducted at a constant injection rate of 5 to 6 cc//min, which corresponds to a frontal advance of 5 ro 6 ft/hr. The first portion of this paper is concerned with 111 use of one alcohol—isopropyl—a\. the slug material. Isopropyl alcohol (IPA) is completely miscible with both oil rind water; however, miscibility of the threc-component systems, oil-water-IPA, requires a relutively. high concentration of IPA. Hence, the displocement is not of the misoible type unless the IPA concentration is maintained above some critical value. A slug of IPA equal to only 13.5 per cent of the pore volume was jound to be sufficient to obtain complete recover?, of residua1 naphtha. In later studies two distinct process variations were developed. The firsr of these utilized methyl alcohol (MA) and IPA as slug materials. It was shown that methyl alcohol may he substituted for IPA at the front and rear of the slug with no loss of oil recovery. A .slug of 4 per cent MA-4 per cent IPA-4 per cent MA was sufficient for complere oil recovery. Because MA is considerably cheaper than IPA, this represents an important step toward economic application. A .second process variation used normal butyl alcohol (nBA) and MA as the composite slug, the nBA segnzent being injected first. This technique requires the smallest total slug size (approximately 10 per cent) of all processes studied. The high cost of nBA, however, precludes commercial application. It is possible that this basic process, subject to changes of alcohol type, may lead to a commrercicil process. INTRODUCTION Within the last 10 years, considerable study has been devoted to the general mechanics of miscible phase dis- placements in porous media. These studies have. in general, dealt with two-component displacernent. All reported field trials to date have been modified gas drives of one type or another. These utilize either lean gas at high pressure, rich gas at lower pressure or an LPG slug. The irreducible water content of the reservoir remains immobile during these processes. Although these techniques hold great promise. certain drawbacks do exist. Poor areal sweep efficiency, inherent in any displacement having a highly unfavorable mobility ratio, is one disadvantage. Furthermore, the miscibility of all processes which use gas is dependent on pressure. These pressure limitations may prohibit application to shallow reservoirs. There are also many areas where large quantities of LPG and natural gas are not readily available. These factors emphasize the need for improved techniques. The alcohol slug process is also a miscible-phase displacement process. It differs from the previously mentioned two-component techniques, however, in that both the reservoir oil and water are displaced by the slug. This behavior is a consequence of the miscibility of certain oil-water-alcohol systems. In the simplest case, a relatively small volume (slug) of an alcohol (such as isopropyl) is injected into the system. Water is then used to drive the slug through the medium. Thus. three components—-alcohol. oil and connate water-—exist at the front side of the slug. Miscibility is obtained at some alcohol concentration, this being dependent on the solubility of the particular system. Miscibility is maintained within the slug until the alcohol concentration falls below that value required to maintain miscibility. When miscibility is lost, the process reverts to a water flood. Certain inherent benefits of this technique are apparent. High pressures are not necessary to obtain miscibility in these liquid systems. Furthermore, water is a more desirable driving agent than gas because of the improved mobility ratio and the attendant improvement in areal sweep efficiency. The main disadvantage is, of course, the relatively high cost of alcohols. The use of an alcohol slug to recover reservoir oil is not a new idea." &apos; However, this process has received only limited study, presumably due to the lack of industrial interest caused by the seemingly prohibitive cost of alcohols. The main purpose of this study was to investigate the mechanism of the displacement of oil and water by various alcohol slugs and to develop process modifications aimed toward possible commercial application.

By William P. Blake

THE occurrence of enormous masses of pure copper has given the mining district of Lake Superior worldwide reputation. The first masses brought from there excited great attention, and directed the notice of the mining world to the few particular mines from which they were taken. It may not now be generally known that nearly all the veins which are worked, and which cut across the trap ridge, contain mass copper, and that large masses are continually being raised from them. The largest continuous mass which has been taken out was probably that from the Minnesota, in 1857, which is variously stated as weighing 420 tons and 470 tons. Its length was about 45 feet, its breadth or height 22 feet, and its greatest thickness 8 feet. All such masses are very irregular and ragged in their form and thickness, thinning out generally from a foot to a few inches, and straggling through the vein until they connect with other large masses. This was the character of a mass found in the Phoenix Mine, one of the oldest on the lake, which mass altogether weighed some 600 tons. But this was really a series of masses more or less connected by strings of metal, yet no one large part of it weighed, singly, over 200 tons. A similar series of masses, weighing about 600 tons, was extracted from the Minnesota. Some of the Phoenix masses were four to five feet thick of solid copper. The Cliff Mine has yielded masses weighing from 100 to 150 tons in one piece. One of 40 tons was taken out this year, besides numerous blocks weighing from 1 to 8 tons. This mine and the Central are now yielding mass copper in abundance. It is, of course, impossible to pick, or drill, or to break out such huge masses of solid metal when they are found, by drifting upon the course of the vein. The method of extraction is as follows The miner picks out or excavates a narrow passage or chamber upon one side of the mass, laying it bare as far as possible over its whole surface. It is usually firmly held by its close union with the vein-stuff, or by its irregular projections above, below, and at the end. If it cannot then be dislodged by levers, the excavation of a chamber is commenced behind the mass, and this excavation is made large enough to receive from 5 to 20 or more kegs of powder. In one

Jan 1, 1876

By J. Laskowski

J. Laskowski (Associate Professor, Dept, of Mineral Processing and Coal Preparation, Silesian University of Technology, Gliwice, Poland) -Referring to the papers by J. A. L. Campbell and S. C. Sun, I must say that I am very pleased to see that type of work, because it is the only way to progress towards an understanding of flotation mechanisms. All those interested in the science of the surface chemistry of coals would find these papers a valuable contribution to the literature. In their extensive research, the authors attempt to synthesize their findings into a theory of coal flotation. To do this, the zeta potential of bituminous coals and their lithotypes, as well as that of an anthracite coal, was measured and H+ and OH- ions were found to be potential determining ions. The measured ZPC of bituminous coals was at a pH range from 3.5 to 4.6 and for the anthracites between 2.0 and 4.5. The authors have pointed out that since the hydrophobicity is pH-controlled, the flotation mechanism should also be. The Campbell and Sun papers confirm a good many of the conclusions on surface properties of coals reported in recent years. It is noteworthy to point out that the ZPC found in the paper on bituminous coals was approximately pH 4, similar to the ZPC for the anthracite coal. In fact, we have been investigating different coals from low to high ranks. Thus, the plot of the pH for ZPC against rank could be derived and this curve-an electrocapillary one-indicates a pH near which the hydrophobicity of the coal surface should be at maximum. This can be proved by so-called salt flotation, which, in a sense, can be treated as method of surface charge measurement. It is obvious that the salt flotation experiment is possible when the native hydrophobicity of the mineral surface is high, e.g., when the solid surface does not have an orienting influence on an adjacent water layer and the hydration layers are controlled by the electrical double-layer potential. The addition of electrolyte or a change of pH which decreases the thickness of the stabilizing double-layer "opens up" the hydrophobic surface micro-area mosaic. Thereby the surface becomes hydrophobic and particles become floatable. The orienting influence of surface on hydration layer increases even after very slight oxidation and flotation is affected by it. It seems that such an explanation agrees reasonably well with those of Campbell and Sun.

Jan 1, 1972

By William P. Blake

The occurrence of enormous masses of pure copper has given the mining district of Lake Superior worldwide reputation. The first masses brought from there excited great attention, and directed the notice of the mining world to the few particular mines from which they were taken. It may not now be generally known that nearly all the veins which are worked, and which cut across the trap ridge, contain mass copper, and that large masses are continually being raised from them. The largest continuous mass which has been taken out was probably that from the Minnesota, in 1857, which is variously stated as weighing 420 tons and 470 tons. Its length was about 45 feet, its breadth or height 22 feet, and its greatest thickness 8 feet. All such masses are very irregular and ragged in their form and thickness, thinning out generally from a foot to a few inches, and straggling through the vein until they connect with other large masses. This was the character of a mass found in the Phœnix Mine, one of the oldest on the lake, which mass altogether weighed some 600 tons. But this was really a series of masses more or less connected by strings of metal, yet no one large part of it weighed, singly, over 200 tons. A similar series of masses, weighing about 600 tons, was extracted from the Miunesota. Some of the Phœnix masses were four to five feet thick of solid copper. The Cliff Mine has yielded masses weighing from 100 to 150 tons in one piece. One of 40 tons was taken out this year, besides numerous blocks weighing from 1 to 8 tons. This mine and the Central are now yielding mass copper in abundance. It is, bf course, impossible to pick, or drill, or to break out such huge masses of solid metal when they are found, by drifting upon the course of the vein. The method of extraction is as follows: The miner picks out or excavates a narrow passage or chamber upon one side of the mass, laying it bare as far as possible over its whole surface. It is usually firmly held by its close union with the veinstuff, or by its irregular projections above, below, and at the end. If it cannot then be dislodged by levers, the excavation of a chamber is commenced behind the mass, and this excavation is made large enough to receive from 5 to 20 or more kegs of powder. In one