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By Milton E. Wadsworth, Edward M. Eyring

BETTER understanding of solid surfaces and their associated adsorption products is of both academic and practical value. The study of detergents and their behavior in cleaning surfaces is fundamentally related to the nature of the products adsorbed and their ability to compete for certain surfaces. Similarly in flotation, the nature of the adsorbate before and after adsorption is basic to clear understanding of the process. The recently developed pellet technique1,2 employing infrared spectroscopy provides a powerful tool for the study of solid surfaces. Absorption bands, which are infrared-active, may be observed for adsorbed products. Also any changes in the surface substrate that occur as a result of adsorption may be detected by means of differential spectra. In applying the pellet technique to solids of large surface area, French and his coworkers3 have surveyed the adsorption of organic flocculants on clay minerals, oleic acid on fluorite, and ammonia on cracking catalysts. Recent work on application of differential infrared spectroscopy to the study of solid surfaces' has demonstrated that the difference between a sample and a reference can be obtained with double-beam instrumentation. In this way displacement of surface products, adsorption of new products, and differences in the substrate, if any, may be detected. Experimental Procedure: Potassium iodide pellets were used in this study, prepared from recrystallized analytical reagent grade KI. Grinding was carried out in a Fisher mechanical agate mortar. Two-gram plates containing the solid under study were pressed in a special evacuated die constructed in the laboratory at the University of Utah." Concentration depended on the solid in question. Zinc sulfide and willemite are sufficiently transpar- ent in the infrared region for concentrations as high as 20 mg of mineral in 2g of KI to be used. Zinc oxide is even more transparent, permitting concentrations as high as 60 mg in a 2-g plate. For non-differential operation, however, much lower concentrations (2 to 10mg/2g KI) had to be used. Spectra were obtained on a Per kin-Elmer 21 double-beam recording infrared spectrophotometer. A sodium chloride prism was used giving a spectral range of approximately 2 to 15 v wave length. For differential runs a resolution of 1000 was used and the scanning speed was controlled commensurate with instrument response. The response was checked continuously and each spectrum was repeated several times. For nondifferential runs a resolution of 927 was used. Zinc oxide used was analytical grade oxide fume. The zinc sulfide was precipitated from solution with analytical grade zinc sulfate and sodium sulfide. The precipitate was washed and centrifuged several times and dried. Before use the precipitate was washed in dilute HCl and then treated with saturated NH4Cl to remove any bulk oxides and sulfates. X-ray patterns of the precipitate were comparable to that of the natural mineral sphalerite. The precipitate was much more satisfactory than finely ground natural ZnS because of its very large surface

Jan 1, 1957

By Pradeep K. Rohatgi, David N. French, Surendar M. Jain, Clyde M. Adams

The effect of solute concentration and diffussivity on dendritic solidification of dilute binary aqueous solutions has been investigated; chlorides of sodium, potassium, lithiurn, and hydrogen were used as solutes. Dendrite spacings were measured in spherical droplets and in unidirectionally solidified specimens. In the droplets, the freezing rate is uniform over the entire specimen and remains constant from the beginning to the end of solidification. In the unidirec-tionally frozen specimens the freezing rate varies within a given volume of liquid during the solidification cycle; in addition, it varies with location uithin the specimen. Mass transport analysis has been used to calculate the supersaturation, AC, supercooling, AT, and transcerse growth velocity, V , of ice dendrites during solidijication from the dendrite spacings measured in the droplels. The ice dendrite spacing in a given solute increases lineary with the solule concentralion at a fixed freezing rate. The ualues of AC, AT, and V increase with an increase in solule concentration. The value of AT in the aqueous solution is of the same order of magnitude as in Al-Cu alloys of the same concentration; the dendrite spacings in Al-Cu alloys also increase with an increase in solute concentralion. For the jamily of aqueozrs solulions incestigaled, the dendrite spacing increases linearly with solute diffusivity at fixed values of concertralion and freezing ,rate. The values of ?C and ?T decrease, whereas the value of V increases with an increase in solule diffusicity. The measured dendrite spacings , L, can be expressed by the relatiun: L = K;(dfa/db) 4 K2C +K3D - K4 where dfs/d? is-change in fraction solid with time (freezing rate), C is solute concentration, D is solute diffusivit K1 = (14 * 4)pmin1'2, K2 = (70 ± 10) pl (moles)- K3 = (24 r 3) . l05 psec (cm)-~. K. = -132 ± 10) 1. FREEZING of solutions is almost always an ehunmix-ing" process because the composition of crystallizing solid generally differs from that of the parent liquid. " Solute concentration and transport are therefore in]portant considerations in solidification of solutions. The influence of these factors on the dendritic solutions produced from metallic solutions is of practical significance since the properties of the solid aggre-gate are often strongly influenced by dendrite spacing.''' Alexander and Fthines3 found that dendrite spac- ings generally increase with solute concentration in several metallic systems. Michael and Bever1 have observed an increase in a aluminum dendrite spacings in dilute A1-Cu alloys. Rohatgi and AdamsJ have reported a linear increase in a aluminum dendrite spacings with increasing copper contents up to 28 pct in A1-Cu alloys. Bolling and Tiller"' have theoretically examined the effects of solute concentration and diffusivity on the growth of cells and dendrites. Their analysis of dendritic growth assumes a steady-state growth and the maximum possible velocity for dendrite propagation. In addition, the quantitative analysis is restricted to dendrites of rotational symmetry and is therefore not directly applicable to the plate-shaped dendrites of ice obtained in the present study. There are practically no experimental observations of the effect of solute diffusivity on dendrite spacings in metallic systems. The reason appears to be the lack of experimental data on solute diffusion coefficients in liquid metallic solutions. The present work is concerned with the effect of solute concentration and diffusivity on dendritic solidification of dilute aqueous solutions: the solutes examined are potassium chloride. sodium chloride, lithium chloride. and hydrogen chloride. There were several reasons for selecting these solutes. The variation of dendrite spacing with freezing rate in these solutiolls is similar to that observed in A1-Cu alloys.8 These aqueous solutions have almost identical phase diagrams at dilute concentrations. Fig. 1. and the diffusion coefficients show very little variation with solute Concentration.9,10 Dendrite spacings were measured as a function of freezing rate. solute concentration. and solute diffusivity. Dendrite spacings were measured in two different types of freezing systems. droplet and unidirectional, respectively. In the droplet freezing system

Jan 1, 1970

By E. Martinez

Samples of chrysocolla, a hydrated copper silicate, from several sources were submitted to differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). Pure samples of chrysocolla are difficult to obtain, but comparison of the thermograms revealed that certain reactions occurred in all the samples and it is believed that these are due to chrysocolla. Endothermic reactions occurred at 50' to 175°C, 350° to 650°C, and 980° to 1100°C each of which caused a weight loss. The first was due to loss of absorbed water, the second to a dehydroxyla-tion, and the last to conversion of cupric oxide to cuprous oxide. In addition, two exotherms were detected at 685° to 695°C and 935° to 950°C. Infrared spectra of heated samples indicated the exotherms were due to changes in the Si-O bonds leading to the formation of cristobalite. The results suggest that thermoanalysis may be a more sensitive and reliable method for detection and identification of chrysocolla than X-ray diffraction, infrared spectroscopy, or optical techniques. The recovery of copper from oxide ores has been the subject of much research in recent years. One of the principal oxide copper minerals is chrysocolla, a hydrated copper silicate. The information available indicates that it has widely varying properties depending on the origin of the sample. Chrysocolla usually is found associated with cuprite, malachite, azurite, and native copper. Most of these other minerals are recoverable by present day flotation practice, but chrysocolla is lost in the tailings.1,2 Reagent combinations that are successful in laboratory chrysocolla flotation with ore from one source have been found to be ineffective with another. 3 The copper segregation process offers an altemative to beneficiation of oxide copper ores.4'5 The process is of particular interest in processing ores that cannot be treated by conventional hydrometal-lurgical methods because of high acid consumption.6 Fuller understanding of the properties of chryso- colla may prove of value in the search for improvements in both the flotation and segregation processes. Chrysocolla samples from Arizona, Nevada, Chile, Australia, and South Africa were studied by differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). In addition, a sample from Miami, Ariz., was submitted to X-ray diffraction, infrared spectrophotometry, and surface area determination. EQUlPMENT Differential thermal analysis (DTA) detects, amplifies, and records exothermic-endothermic reactions occurring in a sample as its temperature is raised at a constant rate, usually 10°C per minute. A unit made by the Robert L. Stone Co. was used in this study. The tests can be run if desired with a gas streaming through the sample. A thermobalance records weight losses or gains in a sample as its temperature is raised at a uniform rate. The gravimetric analyses (TGA) were run on a Chevenard thermobalance converted electronically for graphic recording. A heating rate of 5°C per minute up to 1100°C was used in these tests. A Perkin Elmer Infrared Spectrophotometer, Model 221, was used with sodium chloride optics obtaining IR spectra in the 2 to 15 region. A pressed pellet technique with potassium bromide was used in preparing the samples. DESCRIPTION OF SAMPLES Chrysocolla is found in the oxidation zones of copper deposits commonly associated with malachite, azurite, and limonite. It is described as varying in composition and in color from bluish green to brown or black. Inclusions of other minerals are usual so chemical analysis of chrysocolla samples may be suspect. However, it is considered by many to be a solid solution of CuO, SiO2 and H2O with a general formula of CuO.SiO2.2H2O or 2CuO.2SiO2. 3H20. Chukhrov7 has described a sample from the Urals as CU3,5(OH)2 (A1Si3) O10.nH2O and stated that chrysocolla is a montmorillonite-type mineral. On the basis of X-ray analyses, DTA, and infrared spectra of chrysocolla from the Inspiration Mine, Ariz., Sun8 concluded that there was no substantial evidence to classify it as a montmorillonite mineral. Chrysocolla samples from many sources throughout the world were used in this investigation. The following is a brief description of each:

Jan 1, 1963

By M. J. Marcinkowski, E. N. Hopkins

An investigation has been made of the ß(fcc) — a(hexagonal) transformation which occurs in lanthanum using both electrical resistivity and transmission electron microscopy techniques. It has been shown that the ß phase can be retained below the transformation temperature by rapid quenching but that the sample immediately begins to transform to the a phase. The transformation is observed to nucleate in the vicinity of inclusions. Based on the above observations, a detailed model of the transformation has been advanced which involves the nucleation of an extrinsic stacking fault bounded by a pair of Shockley partial dislocations in the vicinity of some heterogeneity, i.e., an inclusion. The stress field of the resultant dislocation pair acts to nucleate extrinsic faults in adjacent planes and leads quite naturally to the B-a conversion with a minimum of strain energy induced in the crystal. LANTHANUM possesses an fcc structure ß) (8) upon cooling transforms to a hexagonal modification (a) in much the same way as cobalt. The one exception, however, is that the stacking sequence of the closest packed planes in a La is ABAC ABAC, and so forth,1 whereas in cobalt it is ABAB, and so forth, i.e., hep. Mainly on the basis of transmission electron microscopy techniques, there seems to be little doubt that the 0 — a transformation in cobalt involves a dislocation mechanism2 although its exact nature still remains obscure. Although the ß - a transformation in lanthanum is somewhat more complex than that occurring in cobalt, it was thought that its very uniqueness would be helpful in understanding fcc — hexagonal transformations in general. Such a general understanding of these transformations is important since they represent what are perhaps the simplest of the martensitic class of transformations. The experimental techniques used were those of electrical resistivity and transmission electron microscopy. EXPERIMENTAL PROCEDURE The lanthanum used in this investigation was prepared by the calcium reduction of lanthanum fluoride in a tantalum crucible under an argon atmosphere as described by Spedding et al. The residual calcium was removed by vacuum remelting in a tantalum container. Portions of the metal were then analyzed by emission spectroscopy as well as vacuum fusion. The amounts of the various impurities that were found are listed in Table I. A portion of the lanthanum ingot was swaged at room temperature into 0.030-in.-diam rod for the resistivity samples while the remainder was rolled into 0.010-in.-thick sheet for the transmission electron microscopy phase of this investigation. In order to eliminate the plastic deformation induced in the samples during fabrication, they were sealed in evacuated tantalum lined quartz capsules and annealed for 1 hr at 700° C. Specimen resistances were measured using the conventional "four-wire" technique described by MacDonald, 4 employing a type K-3 Universal Potentiometer and a standard 0.001-ohm resistor, both manufactured by Leeds and Northrup Co. By taking into account all of the possible errors in the apparatus, it was felt that the absolute resistivities of the approximately 0.87-in.-long specimens measured are reliable to 3 pct. Resistances from room temperature to 700°C were measured using a vacuum furnace. In order to avoid sample contamination by the thermocouple, chromel-alumel leads were spot-welded into a tantalum shield which in turn was welded to the lanthanum specimen. Resistances below room temperature were obtained by transferring the sample to a helium gas-filled quench tube and slowly dripping liquid nitrogen into a surrounding dewar flask. A steady reduction of temperature to about —190°C was completed in about 23 hr, and the resistances were measured at various temperature intervals. As will be shown shortly, rapid quenching from above about 350°C was sufficient to suppress the B -a transformation initially but subsequent annealing at lower temperatures leads to a partial ß --a conversion. To investigate this aspect of the transformation, the samples were suspended in the hot zone of a helium-filled furnace from which they could be rapidly dropped into the quench tube mentioned previously which was now

Jan 1, 1969

By R. Stickler, A. Vinckier

An optical and electron microscope study was made on a commercial 302 stainless steel heat treated for massive carbide precipitation. Convincirg evidence was obtained that the grain boundary precipitate does not grow away from the grain boundary into the matrix, but grows as a network of large thin dendrites in between the grains. IN austenitic stainless steels the carbon in supersaturated solution precipitates when the steel is heated in the temperature range 450" to 1000°C. During such heat treatments the chromium-rich carbide occurs primarily at the grain boundaries and has adverse effects on the corrosion resistance and low-temperature ductility of the material. It has been shown that the morphology of the precipitated particles differs widely depending on the time and temperature of the heat treatment, the nature of the boundary, the misfit between the grains, and so forth.1"5 It was assumed by Mahla et al.,' Streicher,' and Mc Nutt' that the carbide particles which nucleate in the grain boundary grow in various geometric or dendritic forms away from the boundary into the matrix. However, Kinzel,' Hatwell et a, and Plateau et aL4 found that the particles nucleate in the grain boundary and grow as a network of thin dendrites in the grain boundary interface. We have made a comprehensive studyg of the precipitation occurring in a commercial 302 austenitic stainless steel heat treated for times ranging from 0.15 to 1500 hr at various temperatures from 480" to 1065"~. This study was made to elucidate the influence of heat treatments on both the mechanical and the corrosion properties of this steel. Part of this investigation which is pertinent to the morphology of the grain boundary carbides referred to above is separately reported here. We found that the particles which nucleated in the boundaries grew in the interface of these boundaries, thus supporting the viewpoints of Kinzel,' Hatwell et al.,3 and Plateau et al.4 Furthermore, when carbide particles nucleated in the matrix very close to the boundaries, they possessed a morphology distinctively different from the particles growing in the grain boundaries. MATERIAL A study of metallographic samples and of fracture surfaces of a 302 stainless steel is reported in this paper. The composition and heat treatments are listed in Table I. Polished and etched samples were examined und813r the optical microscope, and carbon extraction replicas of etched micrographic samples and various fracture surfaces3'8'9 were examined under the electron microscope. RESULTS AND DISCUSSION A representative optical micrograph of the 302 steel, condition A, is shown in Fig. l(a). Particles can be seen on the grain boundaries but no traces can be found of particles which grow from the grain boundaries into the matrix. A carbon extraction replica of this sample shows numerous large thin dendrites, Fig. l(b). The lateral dimension of such carbide particles vary up to 100 p, and their thickness estimated from the amoun! of electron penetration i:; between 500 and 1000A. Such large dendrites are extracted from almost all grain boundaries and, if they had grown into the grains, they would definitely be revealed by etching traces in the matrix, Fig. l(a). The reason why these large dendrites on the extraction replica appear to be grown into the grain is due to the mechanism of the extraction replica process. Thus, these dendrites are supported by the carbon replica film only at the edges originally along the grain boundary trace A-A, Fig. l(b), in the polished metal section and have subsequently fallen over onto the carbon replica film during handling. Although such dendrites generally fall only to one particular side of the grain boundary trace, one finds occasionally that parts of a dendrite have fallen to both sides, as shown in Fig. l(b). Further evidence for the growth of carbide in the grain boundary can be obtained from the appearance of fracture surfaces. A small impact specimen of the 302 steel, condition A, was broken at liquid nitrogen temperature. The fracture path follows the

Jan 1, 1962

By J. U. Messenger

A technique is described whereby the resistance of an emudian to breaking can be quantitatively determined. Produced ailfield emulsions are usually the water-in-oil type and, accordingly, do not conduct an electrical current. However, there is a threshold of A-C voltage pressure above which an emulsion will break and current will flow. The more stable an emulsion, the higher the required voltage. A Fann Emulsion Tester, modified so that low voltages (0 to 10 v) can be accurately measured, is suitable. This technique has application in evaluating the effect of a demuksifier on the stability of an emulsion. Emulsions can, in essence, be titrated with demulsifiers by adding a quuntity of demulsifier, stirring, and measuring the voltage required to cause current to flow. Any synergistic effect of two or more materials added simultaneously can be followed accurately. A demulsifier that significantly lowers the threshold voltage (from 100 to 400 v to 0 to 10 v for the emulsions in this study) is effective and can cause the enlulsion to break. A demulsifier that will bring about this drop in the threshold voltage at low concentration ir very desirable. The technique is also well adapted for rapidly screening demulsifiers. INTRODUCTION Stable emulsions in produced reservoir fluids resulting from certain well stimulation and completion procedures are common problems. The use of suitable demulsifiers can often mitigate these difficulties. At the present time, a rapid and efficient method for selecting satisfactory demulsifiers is not available. It is badly needed. Reliance is now placed primarily on trial-and-error procedures. A new test method has been developed which permits a more rapid and precise selection of demulsifiers. It involves measuring the electrical stability potential of an emulsion before and after a demulsifier has been added. This paper describes this method and shows where it should have application in field emulsion problems. NATURE OF OILFIELD EMULSIONS Two immiscible components must be present for an emuhion to form; we are concerned here with crude oil and water. An emulsifier must be present for tin emulsion to be stable. J Emulsifiers can be substances which are soluble in oil and /or mter and which lower interfacial tension. They can be colloidal solids such as bentonite, carbon, graphite, or asphalt which collect at the interface and are preferentially wet by one of these phases. Unrefined crude oils can contain both types of emulsifiers, A popular theory is that, of the two phases in an emulsion, the dispersed phase will be the one contributing most to the interfacial tension.' Usually this phase contains the least amount of emulsifier. The stability of a water-in-oil emulsion is affected by the fol1owing: l) viscosity; (2) particle or droplet size; (3) interfacial tension between the phases; (4) phase-volume ratios; and (5) the difference in density between the phases. A stable emulsion is usually characterized by high-viscosity, small droplets, low interfacial tensions, small differences in density between its phases, and slow separatian of the phases. It also has low conductivity (high electrical stability potential). Water-in-oil and oil-in-water emulsions"' are both common; however, oil field emulsions are predominantly water-in-oil emulsions. The emulsions which commonly occur during oompletion and stimulation operations contain a combination of several of the following: acids, fracturing fluids (oil, water, acid), and formation water and oil. Produced emulsions usually contain formation water and oil. Emulsions form in oil wells because oil and water are mixed together at a high rate of shear in the presence of a naturally occurring or unavoidably produced emulsifier. During the completion and stimulation of productive zones, and while formation fluids are being produced, oil and water are very often commingled. These mixtures are formed into emulsions by agitation which occurs when the fluids are pumped from the surface into the matrix of the formation or produced through the formation to the surface. Restrictions to flow (such as perforations, pumps, and chokes)".'" increase the level of agitation; tight emulsions are more likely to form under these conditions. Often an emulsified droplet is an emulsion itself.'" Therefore, emulsion-breaking problems can be quite complex. The complexity can be even greater if a third phase (gas) is included. Demulsifiers operate by tending to reverse the form of the emulsion. During this process, droplets of water become bigger, viscosity is lowered, color becomes darker, separation of the phases faster and electrical stability potential approaches zero. Any of these effects could be followed as a means of determining emulsion stability. However, electrical stability potential is the most reproducible and most easily measured parameter for following the stability of a water-in-oil emulsion.

Jan 1, 1966

By Leonard R. Weisberg

HE procedure of directional freezing by the Bridgman technique1 is frequently used in crystal preparation. On those occasions where the crystal is regrown, it can be advantageous to Crop part of the ingot before regrowth to achieve purification. This note describes some simple, yet interesting, observations concerning the effects of cropping an ingot between successive freezes. First, it is not effective to Crop the front end of an ingot, whether or not the distribution coefficient, k , of the impurities is greater or less than unity. This can be shown as follows. The concentration C, of an impurity in a directionally frozen ingot of length d with a uniform cross section is given by where x is the distance along the ingot, and C0 is the initial concentration per unit length. It is assumed in deriving this equation that diffusion is negligible in the solid, is complete in the melt, and that k is constant. Consider that a section of the ingot Ad is removed from the front end. Then the average impurity concentration in the remaining (d- Ad) section of the ingot can be shown by integration to be given by When the ingot is remelted and refrozen, the new impurity distribution is given by where xl is the distance along the refrozen ingot. Substituting the value of c into Eq. [3], one finds This is identical to Eq. [11 when x = (x, Ad), which represents the original impurity distribution in the (d - Ad) section of the ingot after the first directional freeze. Therefore, the cropping and re-freezing accomplished nothing. This can also be seen physically by realizing that the average impurity content in the melt after the first Ad section is frozen, is identical to that after the resulting ingot has been cropped and remelted. Hence, it is assumed in the following sections that only the tail end of the ingot is cropped. However, it must be realized that for impurities with k greater than one, the pieces cropped from the tail end are purer, and are therefore saved. After cropping an amount Ad from the tail end of an ingot, the average impurity concentration of impurities in the remaining portion of the ingot is given by wheref= d/d. For the case of k < 1, the purification is defined as c,/c. It is obvious from Eq. [5] that the purification increases asf increases, but the increase in purification is not large. For example, iff is doubled from 0.1 to 0.2, the purification increases by only 10 pct for k = 0.5, by only 24 pct for k = 0.1, and by 32 pct for k =0.01. Much smaller values off than 0.1 are not desirable since insufficient purification is achieved. These figures indicate that much larger values off do not lead to substantial improvement, especially considering that much of the original ingot is lost. Therefore, it is generally useful to Crop about 1/10 of the ingot to achieve purification. As compared to doubling the value off, it is much more helpful to remelt, refreeze, and crop the ingot twice. Using Eq. [51 reiteratively, and assuming f= 0.1, it is found that the purification after this process is found to be increased over the purification after a single freeze and cropping by 33 pct for k= 0.5, 450 pct for k = 0.1, and 4100 pct for k = 0.01. This indicates that considerable purification can be obtained by this procedure. However, if purification is the main goal, one should resort to zone refining,3

Jan 1, 1962

SEC. 1. This Institute is incorporated under the Membership Corporations law of the State of New York; its corporate name is American Institute of Mining and Metallurgical Engineers, Inc.; and its abbreviated title A. I. M. E. SEC. 2. The objects of this Institute, as set forth in its certificate of incorporation, are: "To promote the arts and sciences connected with the economic production of the useful minerals and metals, and the welfare of those employed in these industries by all lawful means; to hold meetings for social intercourse and the reading and discussion of professional papers, and to circulate by means of publications among its members the information thus obtained, and to establish and maintain a place for meeting of its members, and a hall for the reading of papers and delivery of addresses, and a library of books relating to subjects cognate to the sciences and arts of mining and metallurgy." ARTICLE II MEMBERSHIP SEC. 1. The membership of this Corporation shall include all those who on the third Monday in February, 1928, were members and all others subsequently elected and qualified in accord with the By-laws of the Institute at the time of such election. SEC. 2. The membership shall be divided into such classes as may be from time to time fixed by the By-laws. ARTICLE III DIRECTORS SEC. 1. The business, financial, professional, technical, scientific and social interests of the Institute shall be managed by a Board of Directors, elected annually by letter ballot in the manner specified in the By-laws, to serve for the terms as set forth in the Certificate of Incorporation. ARTICLE IV AMENDMENTS SEC. 1. Proposals to amend this Constitution may be made by resolution of the Directors or by written petition signed by at least ten members. Such proposals must reach the Secretary not later than October fifteenth. The Board of Directors shall consider them and, in case of petitions, the proposers shall be notified of the opinion of the Board in regard to them, when they may cither withdraw their proposals, or accept any changes suggested, or insist on the original form. All proposals when in final form shall be mailed to all members on or before January first, with the election ballots, and with a ballot in proper form for voting on the amendment in its original or amended form. Ballots shall be received by the Secretary until the second Tuesday in February. The Tellers of the election shall count these ballots,

Jan 1, 1929

By S. Sumski, M. B. Panish, R. T. Lynch

The liquidus isotherms in the gallium-rich corner of the Ga-Al-P phase diagram have been determined from 1000" to 1200°C and at I100°C the corresponding solidus isotherm was obtained. A simple thermody-namic treatment which permits calculation of the solidus and liquidus isotherms is discussed. A technique which was previously used for the growth of GaxAl1-xAs was used for the preparation of solution epitaxial layers of GaxAl1-xP and ALP. An approximate value of 2.49 i 0.05 ev for the band gap of Alp at 300°K was obtained and the ternary phase data were used to estimate a value of 36 kcal per mole for the heat of formation 0f Alp at that temperature. The Gap-A1P crystalline solid solution is one in which there exists the possibility of obtaining crystals with selected energy gaps, within the limits imposed by the energy gaps of Gap and Alp. Such crystals are of considerable interest because of their potential value for optoelectronic and other solid-state devices. Furthermore, it has been amply demonstrated for GaAs and GaP,&apos;-7 that device, or bulk materials grown from gallium solution generally have more efficient radiative recombination than materials prepared in other ways. This presumably due to the lower gallium vacancy concentration in such material.= Small crystals of GaXAl1-xP and A1P have been grown from solution,8-10 and A1P has been grown from the vapor," but neither have previously been grown by liquid epitaxy. In this paper we present the ternary liquidus-solidus phase diagram of the Ga-A1-P system in the region of primary interest for solution epitaxy, and discuss the thermodynamic implications of that phase diagram with particular reference to the liquidus and solidus isotherms in the gallium-rich corner of the GaxAl1-xP primary phase field and to the A1-P system. Several measurements of the absorption edge of GaxAl1-xP crystals have been made and the width of the forbidden gap of A1P has been estimated from these measurements. EXPERIMENTAL The differential thermal analysis technique used to determine the liquidus isotherms and the optical measurements used in this work are similar to those described previously12 for the Ga-Al-As system, ex- thermocouples in the thermopile for added sensitivity. The materials used were semiconductor grade Ga, Gap, and Al+ The composition and temperature range at which DTA studies could be done was quite restricted. The upper temperature was limited by the chrome l-alumel thermopile to about 1200°C, and the highest aluminum concentration to about 5 at. pct by low sensitivity caused by the reduced solubility of Gap with increasing aluminum concentration in the liquid. DTA studies were not possible at 1000°C and below because of the low sensitivity caused by low solubility of Gap in the Ga-A1-P system. The cooling rate for these studies was about 1°C per min. No heating studies were done because of limited sensitivity. Supercooling probably does occur, but our experience with other 111-V systems indicates that it is no greater than about 10 to 15.c. Solid solubilities were determined by analyzing epitaxial layers of GaxAl1-xP grown from the liquid, with an electron beam microprobe. The layers were grown on Gap seeds by a tipping technique in which the layer is grown over a short-temperature range (20" to 50°C) on the seed from a solution of known composition. The tipping technique reported by Nelsson1 for GaAs could not be used, particularly for solutions containing appreciable amounts of aluminum, because of the formation of an A1203 scum on the liquid surface. A system was therefore designed, which would effectively remove the oxides mechanically, so that uniform wetting and crystal growth could occur. This tipping technique has already been described in detail." The best control over the composition of the re-grown layer was obtained when the tipping was done at a temperature which corresponded to the temperature of first formation of solid for the solution being used. Generally, therefore, a solution was prepared by adding the amounts of Ga, Gap, and A1 required to yield a solution which would be completely liquid above the tipping temperature with solid precipitating below that temperature. For most of the work reported here, the 1100°C isotherm of the ternary was used. It was generally necessary to heat the solution to 50" to l00. C above the tipping temperature to dissolve all of the Gap in a reasonable length of time. The epitaxially grown layers were used both for optical transmission measurements to aid in the estimation of the way in which the absorption edge changed with aluminum concentration, and for the electron beam microprobe analyses to provide data for the determination of the solid solubility isotherm. RESULTS AND DISCUSSION Liquidus Isotherms in the Ga-A1-P Ternary Phase Diagram: Thermodynamic properties of the system. The only thermal effect studied in this work was that

Jan 1, 1970

By A. M. Skov, L. F. Elkins

Inclusion of anisotropic permeability in mathematical analysis of pressure transients observed during development of the huge Spraberry field indicates a major fracture trend which is in good agreement with that observed by fluid-injection tests spread over a 12- by 17-mile area. Delineation of this trend is important in selecting a pattern of injection for the pending large-scale water flooding in this field. Determination of reservoir parameters yielding best agreement between calculated pressures and observed reservoir pressures in newly completed wells was made using an IBM 650 computer. INTRODUCTION The Spraberry field covering 400,000 acres is a tight sand of less than 1-md permeability cut by an extensive system of vertical fractures. Primary recovery dominated by capillary retention of oil in the fractured sand matrix blocks is less than 10 per cent of oil in place. Strong forces of capillary imbibition of water into the sand, coupled with water flow under dynamic pressure gradient, indicate considerable increase in oil recovery can be achieved through water flooding. Best results will occur if the pattern of water injection is selected to force the water flow across the grain of the major fracture system. Existence of an oriented vertical fracture system in the Spraberry, observed first in cores, was highlighted more recently by the 144-fold contrast in permeability along and at right angles to the major fracture trend required to match relative water breakthrough times in Humble Oil & Refining Co.&apos;s waterflood test there. Spraberry operators since have conducted two gas-injection tracer tests for further areal confirmation of the fracture trend. Re-analysis of early reservoir pressure transients for evidence of anisotropic permeability has permitted many more local determinations of major fracture trend without resort to further field tests. This paper is limited to updating analysis of reservoir pressure transients to include anisotropic permeability as a test for orientation of the major fracture trend in the Spraberry. The reader is referred to Refs. 1 and 2 for information about general Spraberry reservoir performance and to Refs. 3 and 4 for information about significance of fracture orientation in selection of the injection-well pattern for water flooding the Spraberry. RESERVOIR PRESSURE DATA—DRIVER AREA During early development of the Spraberry Driver area, Sohio Petroleum Co. made the extra effort to measure the initial pressure in each of the 71 wells in a 5-mile-long area immediately after completion. Progressively greater reductions in pressure ranging up to 400 psi were observed throughout the six-month development period. Detailed data are presented in Ref. 1. Since the reservoir oil was undersaturated some 300 psi initially, early reservoir performance involving 55 new well pressures is subject to analysis as flow of a single compressible fluid in a porous media. Assumption of uniform permeability in all directions yielded good agreement between calculated pressures and observed pressures of these wells in the earlier study,&apos; but subsequent, additional, mathematical development to include anisotropic permeability in the transient pressure considerations and present availability of electronic computers to perform the much more extensive arithmetical calculations now yield even better agreement. The previous analysis, assuming uniform permeability, consisted essentially of calculating pressure reduction expanding circularly around each producing well and summing these effects at the time and location of each newly completed well for comparison with the measured pressure reduction. Permeability, effective fluid and rock compressibility, and permeability X thickness were varied until the best match with measured pressures was obtained. The present analysis, assuming anisotropic

By G. R. Fitterer

Trends in slag composition in acid open hearth practice, particularly the variation in iron and manganese oxides during refining, are reviewed. A procedure which is currently being used to control the refining reactions is described and partially explained through slag phase diagram considerations. In addition, the ionic nature of these slags is considered and it is proposed that silica combines with the oxide ion and forms a series of complex silicate ions. The effect of basic oxides such as FeO, MnO, and CaO is apparently additive in furnishing the oxide ion for this purpose. IT is now possible to control192 the refining of steel in an acid open hearth furnace to a surprising degree. This control has been brought about through the knowledge and use of several facts and tests. These are: 1—A planned charge analysis based on a knowledge of the type of fuel, the bath depth, etc. 2—Knowledge and control of rate of fuel input as well as its method of atomization, if any. 3—Determination of the slag fluidity. 4—Bath temperatures (use of the Pt-Pt-Rh thermocouple). 5—Periodic determination of carbon content (use of the Carb-analyzer or Carbometer). Through the use of these control methods, a heat may be made to "melt-in" with or without residual manganese and silicon. The rate of refining or carbon elimination may be controlled accurately, and the desired tapping (or "go-ahead") carbon may be approached at a rapid or slow rate according to preference and type of steel being made. Thus operating time may be predetermined and greatly reduced. Further, all of the refining can be done without any ore or other oxidizing additions, and the heat may be brought to the desired tapping temperature simultaneously with the attainment of the desired carbon analysis. This control procedure is being used in most acid plants in the United States today and has been de- scribed.&apos;, &apos; Although the slag metal relations are sufficiently well known to control the heat as stated, yet it is possible to account for only about two-thirds&apos; of the 0, which must have been used for the elimination of the carbon and other metalloids. Phase diagram studies&apos; of the slags, slag weights, the metal particle theory,&apos; ore additions, limestone additions, etc., may all be taken into consideration; yet, the mechanism of oxidation and source of all the oxygen remain to be explained. This paper reviews some of the principles upon which the control methods were based and proposes other possibilities regarding the unexplained phenomena. Old and New Acid Open Hearth Practice Some of the recent statements in the literature regarding acid open hearth operation are based on old heat data which are not typical of modern American practice. These old heat logs have been responsible for many misconceptions regarding the acid hearth practice and represent heats which do not coincide with modern methods. In recent years, American practice has been altered materially and these changes will be briefly described. Modern American Practice: A typical log of a modern American acid open hearth heat&apos; is shown in Fig. 1 which indicates that the refining time was only two hours, during which the carbon was eliminated rapidly and the bath temperature increased at a fast rate. The manganese and silicon contents of the metal were essentially eliminated and their oxides had become constituent parts of the slag at the "melt-down" period. During the course of the heat, the MnO content of the slag remained practi-

Jan 1, 1954

By Pedro L. Lizaur

INTRODUCTION The degree of success of an association between parties in establishing a new venture ultimately depends on three factors: a. the venture&apos;s underlying economic strength, which is based on the complementarity of the comparative advantages brought by each party to the negotiating table; b. the ability to reach an agreement which satisfies each party&apos;s objectives and constraints; and, c. the capacity to design and implement a funding structure which is consistent with the project economics. A thorough assessment of the venture&apos;s profitability and associated risks under alternative technical and economic scenarios is the basis for a sound "go" or "no go" decision. In-depth evaluation of the risks and rewards to each of the parties involved under alternative legal and financial structure must be the foundation for a long lasting "how to go" decision. The allocation of risks and rewards should be consistent with the objectives and constraints of all parties and the sharing mechanisms, established in the contract, should be flexible to assure the long-term stability of the agreement. Rapidly changing economic conditions during the last decade have had a dramatic impact on the envisaged allocation of risks and rewards between host countries and private investors. The effects of these changes, and the fact that the relative strengths of the parties involved may shift during the life of a project (e.g. before and after major capital investments have been made), have forced the renegotiation of a multitude of contracts. Therefore, the present and future stability of an economic agreement would depend not only on the originally designed provisions, but also on provisions which allow for the automatic adjustment of rewards to project sponsors under a variety of future economic situations. A pre-condition for the allocation and quantification of risks and rewards is the definition of standards of measurement used by each of the parties. This is critical in international negotiations when one of the parties represents the national interests of a country. The understanding and use of different standards for the measurement of rewards for risk taken between a government and private enterprise facilitate the negotiation of a satisfactory agreement. This is possible because certain trade-offs between the negotiating parties may have different relative values. STANDARDS OF MEASUREMENT OF REWARDS FOR RISK TAKEN The negotiating process takes a step forward when the parties are able to focus on their interests, explore different alternative solutions and then base results on a set of objective standards. Unfortunately, the parties frequently put more effort into "staking out" and defending positions, than into understanding their intrinsic interests. Moreover, when one party, such as a governemnt owned corporation, represents a country&apos;s national interests, the negotiation process increases in complexity. Private firms focus on commercial profitability, using discounted cash flow techniques such as NPV, IRR, or ROE. In contrast, the government is also concerned with the project&apos;s impact on the local socio-economic environment. Without entering into a discussion of alternative economic development theories and approaches, there exist several possible measures that could be pragmatically utilized by each party in evaluating the socio-economic impact of a project. The more complete measure is the National Profitability (NP). The NP is a discounted cash flow procedure similar in structure to IRR or NPV but in which the project&apos;s financial cash inflows and outflows and discount rates are adjusted to take into consideration the local conditions. The NP is calculated on an unlevered basis and all taxes and duties are removed from the project

Jan 1, 1985

By Herman Garlichs

The development of the extensive Southeast Missouri deposits greatly preceded that of the Iowa and Wisconsin deposits. It began about 1720 at Mine La Motte and other localities, and has continued uninterruptedly to the present time. It is estimated that this district produced about 184,000 tons of lead in the year 1916, having a value of approximately $25,000,000. This is a new high record. The Southwest Missouri orebodies were hardly known before 1845 and were not extensively developed until 1870. Lead production in Southwest Missouri for 1916 was 38,788 tons. Oklahoma produced 14,399 tons and Kansas 2,345 tons, making a total for Southwest Missouri, and the adjoining districts in Oklahoma and Kansas, of 55,532 tons of lead. The first metallurgists in Missouri were the Indian and the hunter. The early settler learned to procure his bullets either by melting ore in his camp fire or by throwing pieces of galena on an old stump and depending on the usual roasting and reaction method to obtain the metal. A little more refined method was to arrange two flat stones in the form of a, V. Wood and galena were placed in the furnace and ignited.. As heat developed, some of the metal was extracted and molded into bullets. The next step in utilizing the lead ores was the log hearth. All lead in Missouri was smelted in this crude affair before 1820. It was built on sloping ground, and consisted of a hearth of stone, surrounded on the front and two sides by a stone wall. The wall was 7 it. high in front. The top and rear end were left open and in front an arch or opening was made, forming the eye of the furnace. In front of this a pit was dug in the ground, to receive the molten metal. Large logs were rolled in at the back and made to rest upon ledges formed inside, to raise them from the hearth and to give a draft. These logs filled the entire width of the furnace. Small split logs were then set up around the two sides and the front, and the ore was piled on until the furnace was full. Finally, the mass was covered with logs and fuel until the ore was completely surrounded. A gentle heat was started, which was raised very gradually. After 12 hr. the heat was increased and continued for 12 hr. more, 24 hr. being required for each smelting. The furnace treated about 5,000 lb. per 24 hr. and the ore yielded about 50 per cent. of its metallic lead. A considerable quantity of the ore was not desulphurized, and fell between

Jan 1, 1918

By R. H. Schnitzel

Internal-friction peaks have been observed in tungsten single crystals at about 300° and 400°C. The characteristics of these peaks are similar to interstitial peaks observed in other bee metals; therefore, the origin of these peaks appears to he the Snoek mechanism. The interstitial responsible for the peak at about 300°C has not been identified. Carburizing increases the magnitude of the peak at about 400°C; consequently, it appears reasonable to suppose that the specific interstitial associated with this peak is carbon. The activation energies associated with the 300° and 400°Cpeaks are about 35,000 and 45,000 cal per mole, respectively. INTERNAL - friction peaks resulting from the stress-induced diffusion of interstitials (Snoek relaxation peaks) have been frequently observed in bee metals.1-5 Attempts to detect Snoek relaxation peaks in tungsten have, however, not been fruitful.&apos; Failure to find Snoek peaks in sintered tungsten can perhaps be attributed to one or more of the following difficulties: a) the relatively low purity of the sintered tungsten; b) the lack of extensive metallurgical knowledge about tungsten-interstitial alloys, such as suitable interstitial dosing and quenching procedures; and c) the inconsistency of some of the interstitial analyses of tungsten, which reflects itself in one&apos;s inability to be sure of the nature of the specimens. This present investigation did not overcome all of these difficulties for successful tungsten internal-friction measurements. Some of these difficulties still persist and new difficulties were encountered during the course of this investigation. Nevertheless, the use of electron-beam tungsten single crystals having somewhat greater purity levels than sintered tungsten combined with appropriate carburizing and quenching procedures permitted a reasonable attempt to be made. As a consequence, internal-friction peaks were observed in these tungsten single crystals at about 300° and 400°C. These peaks were found to be unstable, since they annealed rapidly away during a sequence of internal-friction measurements. Hence, it was necessary to construct an apparatus having a faster heating rate to study some of the details of these peaks. From the behavior of these peaks as well as our knowledge of similar peaks in other bee metals, one can reasonably conclude that these peaks are caused by residual interstitial impurities within these crystals. Further investigation of these peaks after the application of various metallurgical treatments lent credence to this supposition. EXPERIMENTAL TECHNIQUE The internal friction of tungsten single crystals was measured using two different pieces of apparatus both of which are of essentially the same conventional design, namely the KE type of torsion pendulum. The important difference between these two types of apparatus was in the attainable heating rate and method of protection of the specimen from atmospheric contamination. The apparatus designated "number 1" was enclosed in a vacuum chamber which was heated by an externally mounted furnace. It had a slow rate of heating which was estimated to be about 4°C per min from room temperature to about 350°C and then about 1°C per min to 600°C. The internal friction of tantalum was measured with this apparatus and the established Snoek peaks were found.&apos; These tantalum peaks in the temperature range from room temperature to 400° C served as a check for the apparatus. The apparatus designated "number 2" having a faster heating rate than number 1 was not elaborate. It consisted of a mounted nickel tube to which split heating elements were attached. Argon was used as the protective atmosphere. The measured heating rate was about 12° to 15°C per min whereas the cooling rate was somewhat slower at about 10° C per min because of the increased difficulty encountered in stabilizing the temperature. No surface oxidation of the specimen was noted after any test. This apparatus was also checked with the known peaks of tantalum.1 The preparation of the single-crystal specimens for internal-friction measurements consisted of centerless grinding the crystals from an approximate 0.200 in. diameter to 0.030 to 0.040 in. in diameter, and then electropolishing them to about 0.020 in. in diameter. Single crystals processed in this manner are designated as being in the virgin condition. Since the length of crystal varied from 3 to 9 in., the test frequency varied from about 1 to 2 cps. The frequencies of measurement, axial orientations, and chemical analyses for the various crystals are listed in Table I. The controlled addition of carbon into tungsten is a difficult problem. Attempts to find the critical conditions necessary for an equilibrium treatment were not fruitful. Therefore, a simple nonequi-librium method was used. The addition of carbon to these crystals consisted of appropriately combining three treatments—carburizing to achieve a case, annealing to partially dissolve the carbon into the

Jan 1, 1965

By W. T. Thom

ALL engineering education is faced by certain basic problems, three of which seem to have particular present importance in geological engineering training in general, and in respect to training for oil field geoexploratory work in particular. PROBLEM I The first of these problems has to do with present and future educational objectives and with the numbers and qualities of the men who should be coming out of our geoexploratory training programs. Before the war we needed ever-increasing numbers of graduates at the Bachelor&apos;s level and a very much smaller number of men who had reached the Doctorate degree. Now, with more difficult, more extensive, and more costly exploratory work; with a rapid expansion of company "staff" activities, and with the initiation of many new research organizations and laboratories; it is clear that men of exceptional ability will be more and more in demand, and that the schools will need to carry a greater proportion of their students through to the Ph.D. degree. PROBLEM 2 Assuming that the mineral industries will need an increasing supply of well-qualified Ph.D.s for future geoexploratory work (staff, line and research), can the schools expect to provide this supply of able Ph.D.s merely by expanding the proportion of B.S. and B.A. majors who go on through to the doctorate stage of training? And the answer is definitely "No "-as the situation stands at present. Most A.B. graduates are years short of the preparations in basic science and elementary engineering prerequisite to effective graduate study in the geoexploratory fields (paleontology excepted), and similarly many of the annual crop of B.S. graduates lack adequate training in English; in ancient and modern history; and in the modern principles of labor and public relations. Indeed, several basic problems of undergraduate curricular organization and integration remain to be solved before most recipients of a Bachelor&apos;s degree will have that sound and broad educational foundation prerequisite to graduate training on a really effective basis. It is for these reasons that we have continued to experiment with our geological engineering program at Princeton, in an endeavor to provide a pilot-plant demonstration of a suitably broad and flexible undergraduate curriculum. PROBLEM 3 But assuming that the schools can and do get undergraduate curricula set up in proper phase and scale to meet needed enrollment quotas for graduate training, what about the most urgent part of our whole mineral-industry educational problem? What about finding and bringing into mineral-industry training those youngsters of superior ability who are, by potential or known inclination, especially well-qualified for geoexploratory work?

Jan 1, 1947

By Suresh P. Babu, Joseph W. Leonard

The ultimate objectives of comminution should be to reduce material to some specified size while producing a minimum of undersize or fines, with less power, higher throughputs, and with more compact machinery. Attempts to achieve these objectives have been only partially successful, since gains in some areas are achieved at the cost of concessions in other areas. An example of some of these trade-offs can be found in the closed circuit crushing operations of the anthracite and crushed stone industry where, in order to produce a minimum of unprofitable fines, unfavorable concessions must be made in the size of the crushing facility where 2 or more crushing stages are interphased by 2 or more screening operations. This paper discusses experiments with a new process which attempts to achieve some, if not all, of the comminution objectives in a single pass operation without undesirable concessions; or, at the very least, to achieve more than is possible with systems in use today. These objectives are sought by use of water-flushing to enhance comminution. The crushing of coal and other minerals is a mature technology that is long overdue for a careful re-examination. Crushing of coal is generally achieved through the use of rotary breakers and roll crushers. Water-flushing, as envisioned here, appears to have potential application in the following areas: 1) For primary raw coal crushing or for secondary crushing of rotary breaker products. 2) For use as a size reduction and/or concentrating step for crushing coal mine refuse from present production or from existing refuse dumps. 3) For possible future application in underground preparation interphased with continuous mining machinery. Size reduction with conventional methods is known to be an inefficient operation when the increase in surface energy of the material crushed is compared with the input energy. A simple breakdown of the energy consumption in size reduction, given by Orr, is shown in [Fig. 1]. It is believed that most of the energy supplied is lost in the form of interparticle friction.2 Hence, the removal of fines immediately after their formation or the implementation of steps to prevent their formation, based on reduced friction, will reduce the energy requirements of the communition operation.3 A detailed discussion of the mechanism of size reduction is available in other literature.3-5 Even though the closed circuit crushing operation is designed to carry the fines away from the crushing zone, it is still inadequate for instantaneous removal of fines. The present investigation advocates the use of a flowing liquid medium to remove the crushed product immediately after size reduction. Unlike the wet-grinding methods, no constraints are required for the liquid flow rate, and, also, the liquid medium can be used in primary crushers like jaw crushers, hammer mills,

Jan 1, 1978

By B. H. Caudle, A. B. Dyes, R. A. Erickson

The study of the influence of fluid mobilities on the sweepout pattern resulting from the injection of gas or water has been extended to cover the production period which follows breakthrough of the injected material. Mobility ratios over the range common in field operations (0.1 to 17) were studied for several pattern floods (five-spot, staggered, and direct line drive). The experimental data required for these studies were obtained by the use of the x-ray shadowgraph technique using miscible oil phases of different viscosities in porous plate mode1s of a reservoir element. From the shadowgraph pictures obtained before and after breakthrough of the injected fluid, flowing ratios at the producing well and cumulative volumes injected were calculated. The method for applying such data in predicting field behavior is illustrated for a water flood of a five-spot. For this case a range of mobility ratios of 0.5 to 5.0 results in: (I) nearly complete (95 to 100 per cent) sweepout pattern efficiencies at abandonment conditions, (2) production after breakthrough being responsible for as much as one-third of the total recovery at the lower mobility ratios, and (3) a twofold variation in the operating life of the reservoir. In determining the merits of a secondary recovery operation, the fraction of the reservoir which is ultimately to be swept by the injected fluid is of major importance. Because of its significance a large amount of research has been applied to the study of areal sweepout efficiency. Muskat, Wyckoff and Botset1,2 have presented the classic analysis of the pattern efficiency at breakthrough for several injection patterns in which the mobility of the fluids ahead of the injected phase front was equal to the mobility of the fluids behind the front. Aronofsky3 as extended this analysis of recovery at breakthrough through numerical computations and by the stepwise use of the potentiometric model to include the effect of different fluid mobilities ahead of and behind the invasion front on the line drive performance. Fay and Prats&apos; have also employed numerical computations to show the influence of one other condition of fluid mobilities on the five spot flood. In a previous paper&apos; a new method of attack on this problem which employed x-ray and porous plates was described. At that time experimental results were also presented which described the effect of fluid mobilities on the reservoir area contacted by the injected fluid at breakthrough for the five spot and direct line drive patterns. Most of the literature pertaining to sweepout pattern efficiency has emphasized the pattern which is obtained at breakthrough of the injected phase. The increase in the sweepout pattern which occurs after breakthrough

Jan 1, 1955

By H. A. Wheeler

The great depths attained by some of the older mines, and the milch greater depth at which they will have to he worked in the not distant future, strongly emphasize the imperfect and inadequate character of our present hoisting-practice. The depth of 3000 feet having been exceeded at several places, and 4000 feet almost reached

Jan 1, 1891

By H. W. Turner

The axis of the middle portion of the Ural mountains is made up chiefly of highly compressed igneous and sedimentary schists, considered of Devonian age by the Russian geologists, with large areas of serpentine (peridotite originally) gabbro, etc,, intrusive in the schist series. In addition there are large areas of probably older granitic and gneissic rocks. The nickel deposits referred to in this paper are found in the Devonian schists and their associated igneous rocks. The gabbro-peridotite intrusions probably took place in late Devonian or early Permian time, inasmueh as the Permian and Carboniferous beds lie at gentle angles on the Devonian series on the west slope of the Urals. Perhaps the first attempt to work a nickel deposit in the Urals was made about 1866 in the Revdinsk district, which is situated southwest of Ekaterinburg. 3 was informed by a Russian that a wet method of extracting the nickel was tried but was not a commercial success. This deposit has been described by Muller,l Foullon, and Karpinski.3 Beck4 gives an abstract of these papers. ; Lying to the southeast of the Revdinsk district, the Sissert estate intervening, is the Verkhne-Ufalei district, which is traversed by the railroad from Ekaterinburg to Cheliabinsk, as shown on the map, Fig. 1, there being a station on this railroad at the iron-smelting town of Verkhne-Ufalci. About 7 versts (4.6 miles) north of this town is the Nijni-Karka-dinsk iron mine, which is a limonite deposit. In one of the shafts in this mine a serpentine rock showing a green mineral was encountered. A sample of this mineral collected in 1910 was tested by Mr. Wyatt, chief chemist of the Karabash laboratory of the Kyshtim Mining Works, and determined as nickel ore. A thin section of one piece of the serpen-

Jan 1, 1915

By V. B. Kurfman

Grain refinement of Mg-Al melts by carbonaceous additions has been attributed to nucleation by aluminum carbide. The effects of process and alloy variables are interpreted and predicted in terms of the dispersion and chemistry of this phase. The grain coarsening action of Be, Zr, Ti, R.E., chlorination, temperature extremes, and prolonged holding times is described. Measures necessary to insure an adequate dispersion of the catalyst are discussed. CARBON inoculation treatments have become fairly well known and used for grain refinement of magnesium alloys containing Al. Although there is general agreement that a nucleation process occurs, the process is not understood and the inoculants are used in a rather empirical fashion. The treatment is applied to the class of alloys containing 3 to 10 pct Al, i.e., AZ31A to AM100A. Typical methods involve melting, alloying, and adjusting the temperature to 1400° to 1450°F. Then 0.01 to 0.5 pct C as CaC2, C6C16, or lampblack is added by any convenient means, and the melt poured within 10 to 30 min. Investigators generally have been impressed by an assumed similarity of this refinement process to superheat grain refinement, which depends on heating approximately the same alloys to a temperature in the range of 1550" to 1650°F, then pouring promptly after the melt is cooled to the pouring temperature. Various predictions have been made that carbon refinement would replace superheating in commercial practice due to reduced process costs, but this replacement has not fully taken place because of production difficulties and conflicting observations. Davis, Eastwood, and DeHaven1 agree with Nelson2 and wood3 in suggesting that an excess of inoculant may be harmful. Wood however says that overtreat-ment is not a problem in production use of hexa-chlorobenzene inoculation, and Hultgren and Mitchell4 claim no evidence of harm from excess additions. Various grain coarsening reactions are known to occur, including the possibility of overtreatment mentioned above. Trace amounts of Be,2 Zr, and Ti may prevent refinement by either a carbon treatment or a superheat. Occasionally treatment with cl25 may cause coarsening, although the Battelle refinement process&apos; uses a CC14-C12 blend. Grain coarsening also tends to occur on holding at temperatures below 1350°to 1400°F, especially after a superheat treatment, and for this reason Nelson2 stresses the desirability of a refinement method useful at lower temperatures for open pot melting practice. Since a carbon treatment can be made to work at temperatures below 1400°F, it seems desirable to investigate the mechanism of the refinement and the mechanisms of the coarsening reactions in order to establish control conditions for use in commercial production. The identity of the nucleating phase must first be established and then the factors affecting its chemistry and physical dispersion must be determined. THE IDENTITY OF THE NUCLEATING PHASE Davis, Eastwood, and DeHaven suggested that the nucleating phase in this system is Al4c3,1 but Mahoney, Tarr, and LeGrand8 disagree, largely because they found no evidence of the compound in alloys after carbon treatment and because there is no indication that aluminum carbide should be unstable over the temperature range used in the superheat treatment. This latter objection is based on the assumption that both the carbon treatment and the superheat treatment introduce the same nuclei. Electron diffraction studies have been made to identify the nucleating phase. Samples of grain refined A292 have been selectively etched SO that clean surfaces are obtained and so that secondary phases are in relief. Electron diffraction patterns from these surfaces have established that the carbon treatment of A292 introduces into the metal a large number of small, plate-like particles with a structure very similar to Al4C3. In most cases, the plate-like nature of the particles prevented positive identification but in the cases where the identification could be made the particles proved to be AIN A14C3. However, enough variation in lattice constants was observed so that all compositions from pure A14C3 to the 50:50 solid solution A1N.Al4C3 were probably present.14 In A14C3 and especially AlN.Al4C3 the A1 atoms occur in layers within which they have the same hexagonal symmetry and spacing as the Mg atoms in a single basal plane of a magnesium crystal. The solid solution spacing lies between the 3.16 of AIN and the 3.3? for Al4C3, in satisfactory agree-

Jan 1, 1962