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By C. S. Yust, J. W. Smith, J. R. Walsh, R. E. Simpson

This paper presents the results of a complete reservoir studv designed to determine a sound economic program for the conservation of oil and gas in the Pickton field, Hopkins County, Texas. The Pickton field produces from the Bacon Lime with all indications of the study being that production is predominately by dissolved-gas drive. Calculations of the total ultimate recovery to be expected under primary operations indicated only 16.7 per cent of the oil originally in place would be recovered. This unusually low recovery is due to the type of drive operating and the extremely high dissolved gas-oil ratio and shrinkage. Results are presented for six plans of returning gas to the reservoir, evaluated to determine (1) comparative recoveries and economics of (a) returning gas at a constant rate by supplementing Pickton gas with extraneous gas during the early portion of the operation, and (b) conventional gas-return operations without using extraneous gas, and (2) the optimum size of compressor plant for each type of pressure maintenance. The over-all economic program considers, for either type pressure maintenance operation. a gasoline plant to process the unusually rich casinghead gas. Since pressure maintenance will disturb equities, pooling of royalties is in the case of Pickton a prerequisite to conservation of oil by this type of operation, both from an economic and legal standpoint. In the event pooling of royalties cannot be achieved, the study considers a gasoline plant to operate under a modified primary production operation which will make the conservation of gas possible. INTRODUCTION The Pickton field, located in Hopkins County, Texas. was discovered in November, 1944. by the completion of Humble's C. D. Nichols 1, in the Bacon lime of the Lower Glen Rose formation, through perforations from 7,888 to 7.896 feet. The well initially produced 50.2 API gravity oil with a gas-oil ratio of 1,350 cubic feet per barrel. Subsurface samples of the reservoir fluid obtained soon after completion of the discovery well showed that the Pickton crude is unique in that it has an extremely high dissolved gas-oil ratio and is subject to very severe shrinkage. Calculations of the future behavior of the Pickton reservoir indicated that ultimate oil recovery by primary operations would be 3,269,000 barrels, representing only 16.7 per cent of the oil in place (19,577,000 stock-tank barrels), and that recovery could be substantially increased by returning the produced gas. The cumulative production of 1,382,694 barrels on November 1: 1947, amounted to 42.3 per cent of the estimated ultimate oil recovery from primary operations. The purpose of this study is to determine and evaluate the optimum program for conservation of oil and gas in the Pick-ton field, including the desirability of conducting gas-return operations and of installing a gasoline plant. LOCATION AND DESCRIPTION Pickton Field, The Pickton field, as shown in Fig. 1, is located in southwest Hopkins County, Texas, 12.5 miles southwest of the New Hope field, 2.7 miles northeast of the Coke field, 16 miles southwest of Sulphur Springs, and 8 miles northwest of Winnsboro, Texas.

Jan 1, 1949

By A. M. Gavdin, F. W. Bowdish

Mineral dressing is an industrial art concerned with the treatment and separation of solids suspended in fluids. Knowledge and evaluation of the area of solid-fluid interface is important in all cases except those involving only large pieces of solid. In fact, many problems relating to comminution, to flotation, to thickening and classification, could be dealt with more rationally if the interfacial area were known. A number of methods have been proposed for the measurement of the surface of certain finely divided solids. Among them are methods using rate of dissolution of the solid,? its magnetic remanence,³ the turbidity of its suspension," and the character of the size distribution of the material.9 The first two are limited to one mineralogical species per sample; the third has certain optical limitations, especially for mineral mixtures, and the fourth is based on an extrapolation of uncertain validity. The need of a better and more general method of surface determination has long been felt, therefore. The method of P. H. Emmett,4 based upon the low-temperature adsorption of vapors, appears to fulfill this need. This method consists in determining the amount of nitrogen that is adsorbed by a given sample of solid at the temperature of boiling nitrogen. The more surface there is on the solid—both internal and external—the more nitrogen is abstracted. In actual operation, the method is somewhat less simple than has been stated so far, in that the nitrogen is adsorbed in an incomplete layer, the completeness and thickness of the layer being related to the pressure of the nitrogen in contact with the sample.2 This circumstance makes it necessary to determine the nitrogen adsorption for three or more values of the nitrogen pressure. Apparatus In the Richards Mineral Dressing Laboratories an Emmett apparatus has been built and tested (Figs. I and 2). A mechanical vacuum pump B and a mercury diffusion pump A work in series to give a high vacuum. The sample, placed in bulb D, can be evacuated by this pump train by suitable operation of the stopcocks in the glass tubing that connects the various parts of the apparatus. C is a McLeod gauge, used to ascertain the order of magnitude of the vacuum obtained, and not for accurate pressure measurements. Pressure measurements are made in the mercury manometer F and gas-volume measurements in the gas burette E. Gases are stored in flasks L (nitrogen) and K (helium), arranged so that definite quantities of these gases can be introduced into

Jan 1, 1947

By A. M. Gavdin, F. W. Bowdish

Mineral dressing is an industrial art concerned with the treatment and separation of solids suspended in fluids. Knowledge and evaluation of the area of solid-fluid interface is important in all cases except those involving only large pieces of solid. In fact, many problems relating to comminution, to flotation, to thickening and classification, could be dealt with more rationally if the interfacial area were known. A number of methods have been proposed for the measurement of the surface of certain finely divided solids. Among them are methods using rate of dissolution of the solid,? its magnetic remanence,³ the turbidity of its suspension," and the character of the size distribution of the material.9 The first two are limited to one mineralogical species per sample; the third has certain optical limitations, especially for mineral mixtures, and the fourth is based on an extrapolation of uncertain validity. The need of a better and more general method of surface determination has long been felt, therefore. The method of P. H. Emmett,4 based upon the low-temperature adsorption of vapors, appears to fulfill this need. This method consists in determining the amount of nitrogen that is adsorbed by a given sample of solid at the temperature of boiling nitrogen. The more surface there is on the solid—both internal and external—the more nitrogen is abstracted. In actual operation, the method is somewhat less simple than has been stated so far, in that the nitrogen is adsorbed in an incomplete layer, the completeness and thickness of the layer being related to the pressure of the nitrogen in contact with the sample.2 This circumstance makes it necessary to determine the nitrogen adsorption for three or more values of the nitrogen pressure. Apparatus In the Richards Mineral Dressing Laboratories an Emmett apparatus has been built and tested (Figs. I and 2). A mechanical vacuum pump B and a mercury diffusion pump A work in series to give a high vacuum. The sample, placed in bulb D, can be evacuated by this pump train by suitable operation of the stopcocks in the glass tubing that connects the various parts of the apparatus. C is a McLeod gauge, used to ascertain the order of magnitude of the vacuum obtained, and not for accurate pressure measurements. Pressure measurements are made in the mercury manometer F and gas-volume measurements in the gas burette E. Gases are stored in flasks L (nitrogen) and K (helium), arranged so that definite quantities of these gases can be introduced into

Jan 1, 1947

By P. K. Foster, A. McNabb

A consideration of the literature shows the inadequacy of Fick's Laws to describe the diffusion of hydrogen in steels below 400°C. These laws are modified an the assumption that hydrogen is delayed at fixed sites in the lattice. Approximate and exact solutions of the resulting nonlinear system are derived for simple geometrical shapes. The results qualitatively account for the observed anomalous behavior. Experimental methods for verifying the theory are suggested. 1 HIS paper presents a new analysis of the diffusion behavior of hydrogen in steel based on a physical model which supposes that hydrogen atoms wander in a random manner through the crystal lattice, but tend to get trapped or delayed at certain fixed sites uniformly distributed throughout the metal. These sites, which will be called traps, are regarded merely as potential wells of significantly greater depth than those encountered in regular regions of the crystal lattices and no assumptions are made concerning their nature or origin. The results of experimental studies of the diffusion of hydrogen in iron and steel have usually been reported in the literature in terms of a diffusion constant D derived under the assumptions that the hydrogen concentration C is governed by Fick's laws.1 Fig. I is a composite of published graphs of the man. ner in which the values of D, so derived, vary with temperature. It is convenient to consider this material in two categories; the high temperature results above 400°C, and the results at lower temperatures. The graphs 2, 3, 4, 5 in the first class lie within a factor of three of each other and are relatively consistent compared with the low-temperature values. There is an increasing divergence in values of D with decreasing temperature till at room temperature they are spread over three orders of magnitude. Small values of D have been obtained for work-hardened specimens.' It is evident that D is a function of other variables besides temperature in this range and that these neglected variables are in some way connected with the work hardening experienced by the specimen. In view of evidence for an interaction between hydrogen in solution and dislocations9'10 and adsorption on crack surfaces,' some doubts must be entertained about the validity of Fick's laws and their associated physical model of noninteracting particles in random motion through the medium. More direct evidence of their inapplicability to the diffusion of hydrogen in steel was first produced by Darken and smith." Consider the permeation of hydrogen through a plate of thickness a under a boundary concentration Co at the ingoing, and zero at the outgoing, face. If Fick's first law1 is valid, the steady state flux P, through unit area is DCo/a. In addition, the concentration C varies linearly throughout and Qo, the mean quantity of hydrogen in the medium, is co/2. Compare Qo with Q1 the mean quantity required to saturate the same specimen to a uniform concentration G. In this case Ql = Co and hence the ratio

Jan 1, 1963

By Kyle Wightman

INTRODUCTION CRA Limited is the largest mining group in Australia by value of sales and the second largest company in Australia in terms of share market capitalisation. In the past 25 years, CRA, its predecessors and affiliates have been involved in a number of mining and further processing developments in Australia and elsewhere. Many of these have been financed using project financing techniques. These include Comalco's development of the Weipa bauxite deposits in Northern Queensland in the late 1950's, the Hamersley iron ore developments in the Pilbara region of Western Australia in the mid 1960's, the Queensland Alumina Limited alumina refinery in Gladstone, Queensland, at about the same time, and the Bougainville copper project in 1969/70. In the past three years CRA has again utilised project financing techniques to fund its Tarong steaming coal project in Queensland, the Blair Athol steaming coal project also in that State and CRA's interest in the Argyle diamond project in the Kimberley region of Western Austrlia. PROJECT FINANCE DEFINED Nevitt Definition Nevitt's is the most frequently quoted definition - "A financing of a particular economic unit in which a lender is satisfied to look initially to the cash flows and earnings of the economic unit as the source of funds from which a loan will be repaid and to the assets of the economic unit as collateral for the loan." Risk and Balance Sheet Treatment It is important to focus in more detail on two aspects of project financing, risk and balance sheet treatment. The assessment of the various elements of risk in a project and the sharing of that risk between sponsors and lenders is the most critical feature. At one end of the spectrum is full absorption of risk by the sponsor(s). This can be described as "on risk" or "on credit" or "full recourse" to the sponsor(s) and is effectively a corporate financing. At the other end of the spectrum the lenders absorb the whole risk in a non-recourse financing which is "off risk" or "off credit" for the sponsor. The other aspect is the sponsor's balance sheet treatment. If the balance sheet of the economic unit undertaking the project and the financing need not be consolidated into the balance sheet of the sponsor (because ownership does not exceed 50%) then the financing may be described as off-¬balance sheet. If consolidation is required then the financing is described as on-balance sheet. Most project financings involve some recourse to the sponsor, i.e. they are limited recourse. Very few are non-recourse or off credit to the sponsor. Limited recourse financings may be on-balance sheet although many may also be off-balance sheet insofar as consolidation is concerned. However, sponsor support may very well be a contingent liability to the sponsor and require disclosure by way of note to the balance sheet should consolidation not be required. CORPORATE FINANCE CONTRASTED A financing which is on credit or full recourse to the sponsor, whether it is directly borrowed or guaranteed by that sponsor, is a corporate financing. Lenders will tend to base their credit assessment on a historical assessment of the sponsor's activities and its financial results rather than an assessment of the project or a detailed assessment of the future activities and prospects of the sponsor. PROJECT FINANCE - A BORROWER'S PERCEPTION Although CRA could choose to arrange all finance on a corporate basis (except perhaps for the very largest projects or acquisitions), project financing techniques provide a number of specific advantages which CRA has noted and which should be carefully considered by a project sponsor. Advantages

Jan 1, 1985

By L. W. Holm

This study shows that in the presence of foam, gas and liquid flow separately through porous media representative of reservoir rock. These results were obtained by using tracer techniques to measure the flow of the gas and liquid comprising the foam. Foam does not flow through the porous medium as a body even when the liquid and gas are combined outside the system and injected as foam. Instead, the liquid and gas forming the foam separate as the foam films break and then re-form in the porous system. Liquid moves through the porous medium via the film network of the bubbles and gas moves progressively through the system by breaking and re-forming bubbles throughout the length of the flow path. The flow rates of the gas and liquid are a function of the number and strength of the films in the porous medium. There is no free flow of gas; i.e., no continuous gas phase. On the basis of these results, foam can be expected to improve a water flood or gas drive by decreasing the permeability of the reseruoir rock to a displacing liquid or gas. This improves the mobility ratio and thus the conformance of the flood. INTRODUCTION Foam is formed when gas and a solution of a surface active agent are injected into a porous medium either simultaneously or intermittently. During the past few years, several papers have been published on the subject of foam flow in Dorous media. Foam has been used successfully in the removal of capillary water blocks from producing formations.''2 The use of foam in gas storage reservoirs to reduce gas leaks and to increase storage capacity has been considered in recent years. Foam has also been investigated as an oil displacing agent,3-5 and as an agent to improve the mobility ratio in a waterflood.6-10 However, the mechanism by which the gas and liquid phases comprising the foam flow through a porous medium has nor been described adequately. Normally, when two immiscible phases (gas and liquid) flow concurrently through a porous medium, each phase follows separate paths or channels. At given saturations of the two phases, a certain number of channels are available to each phase, and as saturations change, the number and configuration of the channels available for each phase also change. The effective permeability of each phase is a function of the saturation of that phase only, and the flow of each phase can be described by Darcy's law. When foam is present, the effective permeability of the porous medium to each phase is greatly reduced compaced with permeabilities measured in the absence of foam.6,11-13 Based upon the observed flow of surfactant solutions and gas in capillaries, it has been concluded that the gas and liquid may flow separately or they may flow combined as foam. At least four mechanisms have been postulated to explain how fluids flow with foam present: 1. A large portion of the gas is trapped in the porous medium and a small fraction flows as free gas, following Darcy's law.9 2. The foam structure moves as a body; the rate of gas flow is the same as the rate of liquid flow. 6,13 3. Gas flows as a discontinuous phase by breaking and re-forming films. Liquid flows as a free phase.12 4. A portion of the liquid and gas move as a foam body while excess surfactant solution moves as a free phase.14 It also has been suggested that different flow mechanisms exist for high quality (dry) foams made from dilute surfactant solutions and for foams made from more concentrated solutions. Studies conducted on the flow of foam through capillaries have shown that a plug-type flow occurs and that foam flows as a body.6,15 Fried also has described the flow of foam through porous media as

Jan 1, 1969

By E. T. Turkdogan, P. Grieveson

Experimental results are given for the rate 0.f solution of nitrogen in y iron in the temperature range 1000° to 1200°C. It is shown that, when purified reacting gas is used, the rate-controlling process is the diffusion of nitrogen into the iron. The difhsiuity of nitrogen in y iron is calculated from the results and the equation logD = —(8800/T) — 0.04 is recommended to represent the temperature dependence of the diffusivity. In some experiments using unpurified nitrogen, solution rates are found to be slower than those attributable to a solely solid-state diffusion process. Indications are that in the presence of impurities in the gas, e.g., H,O, chemisorption of nitrogen at the surface is hindered and becomes a rate-controlling process for the transfer of nitrogen across the gas -metal interface. ALTHOUGH the solubility of nitrogen in y iron at known nitrogen activities has been well-established,'-a the kinetics of the solution of nitrogen in iron are not known. The work of Darken, Smith, and Filer' indicates that at temperatures below about 1300°C the rate of solution of nitrogen in y iron is controlled by a chemical reaction at the metal surface, while at temperatures above about 1300°C the rate-controlling process is the diffusion of nitrogen in the metal. Fast and verrijps studied the denitro-genization of y iron using wet hydrogen at 950°C and their results clearly indicate that the rate of nitrogen removal is controlled by diffusion of nitrogen in the metal. In Part I of this series of papers, the kinetics of the solution of nitrogen in y iron are discussed in the light of the present experimental work. EXPERIMENTAL Apparatus. The reaction chamber consisted of a platinum wire-wound resistance furnace with a re-crystallized alumina reaction tube. The temoerature of the furnace, which was automatically controlled to approximately 1°C, was measured with a Pt/Pt-13 pct Rh thermocouple and a potentiometer. The temperature distribution in the working zone of the furnace was determined using a calibrated Pt/Pt-13 pct Rh thermocouple and the hot zone was found to be approximately 3 in. long with a temperature variation of * 3°C. A series of experiments was also carried out at 1000°C and pressures above atmospheric using a pressure vessel which was similar in construction to that described elsewhere.1° Materials. Ferrovac E grade iron used in all ex-

Jan 1, 1964

L. C. Graton, Cambridge, Mass.—The subject of chalcocite occur; rence and its geological significance has, of course, a very important commercial bearing, as shown by the recent remark of a hard-headed mining .man: "This secondary enrichment business is one thing you geologists have put up which we can hang on to, and come out right." Most enrichments of copper ores depend upon the formation Of chalcocite from leaner sulphides. Recently it has been shown that not only does there exist this secondary or derived chalcocite, * but that in certain ores the mineral is present as an initial or original constituent, which therefore we may call primary. The desirability of distinguishing between these two kinds of chalcocite is evident and has recently been emphasized. That constitutes the first problem in this connection. I believe many who are working upon secondary enrichment of mineral deposits are giving much attention to that particular question. It is now possible to distinguish primary from secondary chalcocite in many cases. In such cases, what do we know of the' conditions under which this secondary or derived chalcocite was formed? , This is the second main question in connection with the subject. It is now plain, at least in many instances, that the formation of this derived chalcocite represents a phase of oxidation if we have in mind the primary ore as the thing acted upon. The next important question—and it is most important—is: does such oxidation go on above the zone where the rocks are saturated with water—that is, above the water level—or below, or indiscriminately above and below? Many of you have, or have had, opportunities to study at first hand, day after day, occurrences that' enable valuable conclusions to be drawn upon these and other important questions concerning the formation and significance of chalcocite. It is greatly to be hoped that your testimony will be made available and undoubtedly it will go far toward clearing up some of these doubtful points. John D. Irving, New Haven, Conn.—A short time before this meeting was called, H. V. Winchell, who was unable to be present, requested me to exhibit and describe these two samples of pyrite. (Exhibiting specimens.) They consist of fragments of pyrite inclosed in two small bottles. The first bottle shows fragments of pyrite which were immersed in water carrying copper sulphate but without SO2 for a period of two years. They remained comparatively clear and bright. No chalcocite has been deposited on them. The second bottle shows fragments of

Jan 1, 1915

By M. M. Rao, P. G. Winchell, R. J. Russell

A detailed analysis has been used to correlate the avalable thermodynami c da In on iron-ric11 Fe-Ni (41loys in the body-centered a, and the face-centered y phases. The inp ut injovrt~ation required by the a am lysis consists of tile heat of the a, to y transformation at 1123°K, the heat of mixing of y at 1123°K, tile specific heats of both a, and y (decomposed into Debye, electronic, and magnelic contributions), and the positional and magnetic entropies of both a, and y. PYLrrzary oirt.bul of the analysis is the free energy of each phase as a Junction of temperature and composition. FOr Fe-Ni alloys the adjustment of twenty-one parunletevs allows the accurate reproduction of enthalpy data for both phases, the heat of mixing- for y, the a/y equilibrinm compositions in the Fe-Ni phase diagram, and the usually accepted enthalpy and entropy of a and y iron. Also obtaitzed are fuirly accurate reproductions of electronic specific heat coefficients predicted from electron- to-atom ratio interpolations and To temperatuves eslimanted from transformation studies. Also considered in the calculation are the elastic constants, Curie temperatures, saturation magnlelizalion values, and indications of short- range order. The measnred activity coefficient of iron in anstetnite could not be accurately matched. The major source of uncertainty in the model is thought to be the magnetic contribution to the entropy of austenite. Calcrclations were extended to Fe-ni-C alloys using available carbon-acliuity data. The free energy of transformation from martensile to r at fixed composition was obtained as a function of nickel and carbon contetzt, and binary thetal-carbon phase diagrams Were estimaled as a function of nickel contenl. We needed thermodynamic information for Fe-Ni and Fe-Ni-C alloys at temperatures between 400" and 800°K in order to interpret the results of several phase-transformation studies. The most recent theoretical analysis of the thermodynamics of Fe-Nialloysl was based on a lumped-parameter, regular-solution model and used the Fe-Ni phase diagram available at that time.' Because significant difficulties were encountered in attempting to extend this analysis to Fe-Ni-C alloys, and because more experimental data has become available recently, we decided to attempt a new correlation. The analysis used here allows the extrapolation of measured and calculated thermodynamic values to lower temperatures and the extension of the thermodynamic analysis to Fe-Ni-C alloys. The structure of this correlation consists of expressions containing a total of twenty-one adjustable parameters. The forms of these expressions are discussed in the next section; however, a less formal summary is presented now to provide a physical overview of the model and to indicate its connections to prior work. Primary input information for this correlation is described below. The measured values of the specific heat of iron3 and its analysis475 and theoretical estimates of the specific heat of y* iron at low tempera- loys at 1123°K has been measured by solution calori-metry.7 The enthalpies of both a, and y have been measured most recently by Scheil and Saftig,B who used a dry-ice calorimeter. These data are used to formulate expressions for the heat of mixing of y and the heat of transformation of a, to y both at 1123°K. The a and y solubility limits in the Fe-Ni phase diagram have been redetermined recently9 by methods which assure a close approach to equilibrium. The a to y transformation can occur without change in nickel content or free energy at a temperature called TO; TO temperatures for various nickel contents have been estimated from transformation studies. The computed free-energy functions are adjusted by means of the parameters to fit both the phase diagram and the TO temperatures. Primary emphasis is placed on the phase diagram fit. Iron activities have been measured in Fe-Ni austenite10 between 973" and 1173°K. These activity data, which cannot be fitted accurately with our model, indicate that iron is substantially ideal in iron-rich austenite. Secondary, but helpful, information for the present correlation is provided by neutron diffraction and saturation magnetization measurements on both body-centered and face-centered Fe-Ni alloys."-'3 These results were interpreted11 in terms of composition-insensitive, localized magnetic moments on both iron

Jan 1, 1968

Jan 1, 1889

Jan 1, 1894

By S. D. Thompson

An AIME transaction by P.L. Allsman (1960), "Analysis of Explosive Action in Breaking Rock," contains many useful concepts applicable to blast design. Of special interest was the derivation of a heave blasting burden formula, which is important in establishing the maximum burden. Unfortunately, its derivation contains a fundamental error and then a compensating one. This formula was: [bImpulse _P d At max =nwuwu where: bmax = maximum burden in m (ft). P= average detonation pressure in N/m2 (lb per ft2). A= duration of the average detonation pressure in sec. n= 3.1416. w= specific weight of rock in N/m3 (lb per ft3). u= minimum velocity that must be imparted to the rock in m/sec (ft per sec). d= borehole diameter in m (ft).] The derivation used the impulse-momentum principle, with a 0.3 m thick (1 ft thick) radius of rock mass being acted on by an explosive impulse. However, the rock weight was not converted to mass by dividing by the gravitational constant. This mistake can be verified by checking the units in the formula, which resolve into m1/2-sec instead of meters. Adding the gravitational constant corrects this: [P d Atbmax =gu g = gravitational constant equal to 9.81 m/sect (32.2 ft per sec2).] If the minimum velocity is now taken as 0.3 m/sec (1 ft per sec), as was recommended, excessively large burdens result. Any appropriate rock velocity should be capable of throwing the rock mass a minimum distance so that the swell needed for breakage can occur. Unless the burden is extremely small and the bench height is very high, it is unlikely that a velocity of only 0.3 m/sec (1 ft per sec) will be sufficient. A review of the literature indicates that average rock velocities observed by camera studies typically range from 15 to 30 m/sec (50 to 100 ft per sec) (duPont deNemours and Co., 1977; Tansey, 1979). On this basis, a minimum rock velocity of about 15 m/sec (49 ft per sec) would be expected and not 0.3 m/sec (1 ft per see). When a velocity of 15 m/sec (49 ft per sec) is inserted into the corrected formula, the results approximate those of the original formula with a velocity of 0.3 m/sec (1 ft per sec). The errors were approximately self-compensating [(9 = 1.24)]. ? References Allsman, P.L., 1960, "Analysis of Explosive Action in Breaking Rock," Transactions, AIME, Vol. 217, pp. 475-476. E. I. duPont deNemours and Co., 1977, Blasters' Handbook, 175th Anniversary Edition, Dupont, Wilmington, DE, pp. 233. Tansey, D.O., 1979, "The DuPont Sequential Blasting System," CIM Bulletin, Vol. 72, July, p. 80. Thompson, S.D., 1981, "Critical Review and Revision of Surface Blasting Practice," MS thesis, West Virginia University, pp. 308-316.

Jan 1, 1986

By H. C. Vacher, C. J. Newton

EXTENSIVE investigations in the field of residual strain measurement by X-ray diffraction have been made by Bollenrath, Hauk, and Osswald,1 by Smith and Wood,2'3 by Greenough; by Rosenthal and Norton." and many others. Since X-ray strain measuremeits apply only to those crystals of the test body which are of the proper condition and orientation to diffract and since the residual strains revealed may be accompanied by either body or tex-tural stresses, there has been considerable disagreement among investigators with respect to the validity of conclusions in this field. Although the experi-mentors have employed a variety of loading schemes, surface preparations, and X-ray wave lengths, the observations almost invariably have been made only on the outer surfaces of the specimens. The present note is not to be construed as an exposition of a new method of stress analysis by X-ray strain measurements on sections but as a presentation of some results which point to interesting possibilities for further experiments with sections. The two test rods used in this study were of ingot iron annealed at 910°C. The initial length of the gage section was 2 in. and the diameter was 0.415 in. Cross-sections were cut from the ends of the annealed rods to provide strain-free material. The tensile rod was axially loaded the desired amount in a commercial testing machine. A 1 in. portion of the gage length was cut from the other rod and was subjected to compression in the same machine. Details of this plastic straining of each rod are given in the upper half of Table I. A half-cylinder piece about 1/4 in. long was obtained by making a short longitudinal plane cut containing the axis of the rod near the center of the gage length. From adjacent material a disk about 1/8 in. thick was cut to provide the cross-section specimen. Later another section was cut from this same region with an angle of 30" between the normal to its surface and the axis of the test rod. A cross-section and a longitudinal section were cut from the compression rod in a similar manner. All of these as well as the strain-free cross-sections were mounted in Bakelite and used as specimens for the following X-ray strain measurements. During the course of the study, it became apparent that the condition of the surface of a specimen was a highly critical factor. One of the annealed strain-free specimens as a control was subjected to about 24 hr of polishing with fine alumina, interrupted about every 2 hr for etching with 1 pct nital. Its lattice parameter was determined at intervals from measurements on back-reflection X-ray diffraction patterns, which were calibrated with diffraction from tungsten powder. The parameter gradually approached the value found in the literature for strain-free iron and remained there, within the limits of the experimental error. This determined a long polishing and etching procedure which was adopted for all the specimens and which gave X-ray results from the surfaces believed to be representative of each specimen as a whole. A large number of back-reflection patterns were made with cobalt and chromium radiation, all at normal incidence. Except for some preliminary stationary exposures made to monitor the removal of cold work from the surfaces, each exposure was made with the specimen slowly translating and the film slowly rotating. In appropriate cases a thin layer of a standard metal powder, tungsten with cobalt radiation and silver with chromium, was dusted over a film of vaseline on the surface of the specimen to serve to calibrate the X-ray patterns. After the preliminary work, four films were made,

Jan 1, 1956

Charles H. Morgan, Worcester, Mass. (communication to the Secretary): In connection with Mr. Douglas's mention of the continuous charcoal kiln used at Kopparberg, some further data concerning this important invention may be of interest. Before giving these, however, I will say a word or two concerning other features of Swedish practice. In 1894 I spent two days at Soderfers with Mr. Tom Bergendal, the manager of the works, and was specially interested in the gas-producers and wood-drying kiln, illustrated in the paper contributed to our Transactions by Mr. Odelstjerna in that year.* The wood-drying kiln is, however, quite different in design and construction from Ljungberg's charcoal kiln. In the summer of 1894 it was discovered that by placing the gas-producer as close as possible to the open-hearth furnace, and working the producer hot, ordinary weather-dried wood, still containing a considerable percentage of moisture, could be used to advantage in the melting-furnace. Hence, the dryingkiln was needed for wet wood only. One of the iron-works of the Udeholm Go. was the first to adopt the Lundin saw-dust gas-producer and condenser, enabling them to make gas from saw-dust containing 45 per cent. of moisture, and convey the gas from the condenser through wooden pipes to the Siemens steel-melting furnace.† This sawdust gas gave very satisfactory results in iron-works; but the proprietors experienced much trouble by reason of the pollution of rivers by the tar-water from the condenser. On my visit, in 1894,I found that the Udeholm Co. had put in for their steel-melting furnaces the same wood-gas producers

Jan 1, 1899

By B. R. Palmer, G. Gutierrez B., M. C. Fuerstenau

Selective flotation in nonmetallic systems is often complicated by the presence of iron-bearing silicates occurring as gangue. Minerals such as augite, diopside, hornblende, and tourmaline respond readily to flotation under the same conditions as ore minerals. Mechanisms by which these minerals respond to flotation with anionic collectors must be established if selective separations are to be made in these systems. It was the objective of this investigation to determine the mechanisms involved in the flotation of two pyroxenes, augite and diopside, with potassium oleate. Experimental Materials and Methods Pure potassium oleate, prepared by neutralization of oleic acid with KOH, was used as collector, while reagent-grade HC1 or KOH were used for pH adjustment. Conductivity water, made by passing distilled water through a mixed-bed ion exchange column, was used in this investigation. Two pyroxenes, [ ], were involved in this work. One member of this class of minerals was augite and was found to contain 3.3% calcium, 4.6% iron, and 9.6% magnesium. The source of this mineral was Tillamook County, Ore. The other pyroxene involved was diopside which contained 8.3% calcium, 2.7% iron, and 7.6% magnesium. The source of this sample was Bancroft, Ont. Microflotation experiments were conducted with a Hallimond cell. Mineral samples were ground dry and sized to 100 x 200 mesh. One-gram charges were conditioned for 3 min in the presence of various additions of potassium oleate. Flotation was conducted for 1 min with a nitrogen flow rate of 50 cm3/min. The electrophoretic mobilities of these two minerals were measured with a Zeta Meter in the absence and presence of [ ] salts and in the presence of an indifferent electrolyte, NaC1, added to maintain ionic

Jan 1, 1978

By E. A. von Hahn, T. R. lngraham

The rates of cementation of pd11 on electropolislzed copper cylinders were studied in aqueous perchloric acid solutions at pdII concentrations from 0.02 to 0.1 mM. The cylinders were rotated at various high speeds to reduce the diffusion layer to a minimum thickness. In 0.1 M HClO4 solutions, the cemented palladium is dense, adherent, and shiny. The rate data indicate that there are two stages in the deposition. In the initial stage, the rate of cementation is first order with respect to the pd11 concentration. The second stage is much slower. The first stage is consistent with rate control by the diffusion of pd11 ions to the copper surface, and/or chemical reaction at the surface, and the second stage is consistent with rate control by the diffusion of copper ions from the cop-per surface through the deposit of cemented palladium, out to the main body of solution. In 0.001 M HClO4 solution, only the first stage is evident and the rate is more rapid than at higher acidities. This rate enhancement is attributed to PdOH+ ions that predominate at low acidity and aye more reactive than unhydrolyzed pdII. The deposit is porous and loose. All of the cemented deposits are Pd-Cu alloys rather than pure palladium. Activation energies are 9.5 kcal per mole in 0.1 M HClO4 and 7.4 kcal per mole in 0.001 M HClO4. CEMENTATION or displacement reactions occur between aqueous solutions of metal salts and immersed metals according to the general equation: where M1 is electrochemically the more noble metal. Although these reactions find considerable application in metals recovery processes (e.g., the cementation of copper192 or gold3), in electrorefining processes (e.g., solution purification before electrolysis4,5), and in plating and metal finishing processes,6 few studies have been made of the kinetics of such reactions.7-9 The rates of cementation reactions will depend on one or more of the following factors: a) chemical reactions at the metal-solution interface; b) ionic transport to or away from the interface;'-' and c) the character and adherence of the cemented deposit on the substrate metal,6a,10 because the deposit will inhibit the rate of transport of dissolving ions (M2m+) into the solution. In this investigation, the kinetics of the early stages of cementation were studied to obtain an understanding of the reaction mechanism under conditions in which the deposit was sufficiently thin that its inhibiting effect could be disregarded. To achieve this, very dilute solutions in Mn+ were used. Cementation rates are often fast in the initial stages and transport-contr01led.9 To find conditions under which transport control would shift to chemical control, very high stirring velocities were used to minimize the diffusion-layer thickness. Of the many possible cementation reaction systems, the palladous perchlorate-copper system was chosen for this investigation because it was believed to involve simple ion-for-ion exchange. In addition, there are no interfering side reactions, such as the reduction of hydrogen ions, and anion effects are usually absent in perchlorate solutions. EXPERIMENTAL Materials. Reagent-grade chemicals and redistilled water were used in all experiments. Palladous perchlorate stock solutions (0.02 M) were prepared by dissolving 99.5 pct Pd sponge (Johnson Matthey and Mallory Ltd.) in concentrated nitric acid, adding concentrated perchloric acid, evaporating twice slowly (to prevent PdO precipitation) to a small volume, and diluting in a volumetric flask. To prevent gradual hydrolysis of PdII, the stock solutions were made 0.4 M in HC104. Tests for pdIV (Ref. 11) and C1- were negative. Copper strips were cut accurately from 0.025-in. electrolytic tough pitch sheet, Sample 1 (Mines Branch stock or Canadian Copper Refineries Ltd., Montreal), or from oxygen-free, high-conductivity sheet, Sample 2 (American Metal Climax O.F.H.C. brand, sold by Utility Brass and Copper Corp., Brooklyn). The strips were annealed for 1 hr at 335°C in a stream of purified nitrogen (Union Carbide, Linde Division) which had

Jan 1, 1967

By Rossiter W. Raymond

(Read at the Amenia Meeting, October, 1877.) IN the case of The Eureka Consolidated Mining Company v. The Richmond Mining Company of Nevada, recently tried at San Francisco, California, the real defendant was the Richmond Consolidated Mining Company, of London; but this being a foreign corporation, holds its mining property in Nevada through the Nevada corporation of similar name, in which the London Company owns all the stock, except the few shares necessary to "qualify" the American directors. The trial would naturally have taken place in the Circuit Court at Carson City, Nevada, and before a jury. But by stipulation of the parties, the case was tried in San Francisco, before Hon. Stephen J. Field, Justice of the Supreme Court of the United States, Hon. Lorenzo Sawyer, United States Circuit Judge of the Ninth Circuit, and Hon. E. W. Hillyer, United States District Judge, for the District of Nevada. The hearing began July 23d, 1877. The witnesses occupied two weeks, and the argument of. counsel three days. Very eminent lawyers were. engaged on both sides ; for the plaintiff, Messrs. Solomon Heydenfeldt, R. S. Mesick, John Garber, and H. J. Thornton ; for the defendant, Messrs. S. M. Wilson, Thomas Wren, and J. J. Williams. The court held the case under advisement until August 22d, when Mr. Justice Field delivered its unanimous opinion in favor of the plaintiff. The action was a complaint in ejectment, and an appeal was taken to the United States Supreme Court. The questions at issue between the Eureka and the Richmond Company in this suit, comprised several points in the construction of the mining law of the United States, and its relation to the customs and regulations of the mining districts, which possess an importance and an applicability far beyond the limits of the case in which they arose. It is my purpose to state these points, the arguments

Jan 1, 1878

By P. K. Koh, H. A. Lewis, H. F. Graff

New data on the distribution of silicon between slag and carbon-saturated iron at 1600Oand 1700OC are presented which, in combination with previously published data, permit the determination of silica activities over a broad range of compositions in the CaO-Al2O3-SiO2 system. The distribution of silicon between graphite-saturated Fe-Si-C alloys and blast furnace-type slags in equilibrium with CO has been described in previous publications.1"3 In this past work the silica-silicon relation was established at temperatures of 1425" to 1'700°C for slags containing up to 20 pct A12O3. This paper presents the results of additional studies at 1600" and 1700° C which extend the silicon distribution data at these temperatures for CaO-A12O3-SiO, slags over a range from zero pct Al2O3 to saturation with Al2O3, or CaO.2Al2O3. The upper limit of SiO2 is set by the occurrence of Sic as a stable phase when the metal contains 23.0 or 23.7 pct Si at 1600" or 1700°C, respectively. The activity of silica over the expanded range is determined directly from the distribution data.3 Recently4-7 other investigators have studied the activities of SiO, and CaO, principally in the binary system, using different methods and obtaining somewhat different results. EXPERIMENTAL STUDY The experimental apparatus and procedure have been fully described in previous publications.1, 3 Six new series of experimental heats have been made, four at 1600° and two at 1700°C. Master slags of several fixed CaO/Al203 ratios were pre-melted in graphite crucibles, and these were used with additions of silica to prepare the initial slag for each experiment. Slag and metal were stirred at 100 rpm and CO was passed through the furnace at 150 cc per min. The initial sample was taken 1 hr after addition of slag at 1600°C or 1/2 hr after addition at 1700°C. The run was normally continued for 8 hr at 1600°C or 7 hr at 1700°C, and the final sample was taken at the end of this period. Changes in Si and SiO2 content indicate the direction of approach to equilibrium, and in a series of runs where the approach is from both sides this permits approximate location of the equilibrium line. Fig. 1 shows the results of such a series of 15 runs at 1600°C for slags of CaO/Al,O3 = 1.50 by weight. Figs. 2 and 3 record other series at 1600°C and Fig. 5 a series at 1700°C with fixed CaO/Al0 ratios. The results of the experiments at 162003°C have been reported in part in a preliminary note.3 In the experiments recorded in Figs. 4 and 6, the slags were saturated with A12O3 (or with CaO.2A12O3 within its field of stability) by suspending a pure alumina tube in the melt during the course of the run. The final slag analyses were used to establish the liquidus boundaries8 in the stability fields of CaO.2Al2O3 and of Al20,. ACTIVITY OF SILICA The free-energy change in the reaction has been calculated by Fulton and chipman2 from recent and trustworthy data including heats of formation, entropies, and heat capacities. The more recent determination by Olette of the high-temperature enthalpy of liquid silicon is in satisfactory agreement with the values used and therefore requires no revision of the result which is expressed in the equation: SiO2 (crist) + 2C (graph) = Si + 2CO(g.) [1] &F° = + 161,500 - 87.4T The standard state for silica is taken as pure cristobalite and that of Si as the pure liquid metal. Since the melts were made under 1 atm of CO and were graphite-saturated, the equilibrium constant for Eq. [I] reduces to K1 = asi /asio2. The value of this constant is 1.77 at 1600°C and 16.2 at 1700°C. Through K1, the activity of silica in the slag is directly related to the activity of silicon in the equilibrium metal.

Jan 1, 1960

By F. S. Buffington, Morris Cohen

THERE is little quantitative information available concerning the effect of applied stress, in both the elastic and plastic ranges, on diffusion kinetics. Accordingly, a program has been undertaken to determine the rate of self-diffusion in high purity iron, with the specimens subjected to stress during the course of diffusion. Results are reported here for body-centered cubic iron at a diffusion temperature of 890°C. The iron used was 99.97 pct Fe, the principal impurities being 0.002 pct C, 0.008 pct 0, and 0.02 pct Si. The surface-decrease method of self-diffusion analysis was employed, and Fe55 Mn x-radiation, 2.9 years half-life) was the tracer element. Details of specimen preparation and equipment are given elsewhere.' Disks of the high purity iron, % in. diam x 1/4 in. thick, were annealed at 890°C for 18 hr in dry hydrogen to produce large grains of a ferrite. The faces of the disks were then surface ground, and possible grinding stresses were relieved by annealing at 890 °C for 45 min in vacuum. A layer of radioactive iron 0.00186 cm thick was electroplated on one face of each disk. The self-diffusion coefficient was calculated from the ratio of the radiation intensities emanating from each of these faces, as measured before and after diffusion.' The heating was carried out in a vacuum furnace (10-5 mm Hg) controlled to ±1.5°C. The specimens were loaded in compression between two quartz disks during the diffusion runs by means of a lever system operating through a vacuum seal. Thus one quartz disk was pressed directly against the radioactive face of the specimen, minimizing the vapor loss of radioactive iron. Steady-state creep occurred in all instances where permanent deformation could be detected, but the specimens did not exhibit appreciable transverse barreling until natural strains of 0.2 to 0.3 were attained. Essentially, the diffusion took place under uniaxial stress. The plastic strain in each case was obtained at the diffusion zone by measuring the diameter d there before and after the run: e = 2 In — do Let Du equal the self-diffusion coefficient which would have prevailed at the given temperature if no stress had been applied. This was calculated from the temperature-dependence equation which had been previously determined: —59,800 D, = 6.2 exp ( I sq cm per sec* [I]

Jan 1, 1953

By R. Schuhmann

Distribution of material in the fine sizes of a comminution product generally is well represented by the empirical equation' y = 100 (x/k)a [1] in which y — cumulative percent finer, x = particle size, a -= distribution modulus, and k = size modulus. Charles3 found that the energy consumption in comminution is usefully expressed by another empirical relation, E = Ak(1-D) [2] in which E = energy input per unit volume of material, A = a constant, k = size modulus based on Eq. 1, and n = a constant; (1-n) is the slope of a plot of log E vs log k. Holmes3 has presented energy equations similar to Eq. 2. The constants a and n in Eqs. 1 and 2 have been shown to depend both on the nature of the material and on the comminuting device. Moreover, Charles showed that within experimental error a and n are a — n+1 = 0 [3] Combining Eqs. 2 and 3, E = A k-a [4] In the first sections of this article it is shown that the energy equation, Eq. 4, can be derived directly from the size distribution equation for the fine sizes, Eq. 1. The derivations are made without assuming any of the specific relationships between energy and particle size which have been common in previous literature. For comminution processes in which Eqs. 1 and 4 adequately represent the experimental data, the constant A in Eq. 4 is found to be a simple and useful inverse measure of grindability. That is, A is the energy consumption per unit volume of comminution product finer than unit size as determined from the straight line portion of the log-log plot of the size distribution. These considerations all lead to a unifying hypothesis of comminution mechanism from which both Eq. 1 and Eq. 4 can be derived. Finally, it is pointed out that this hypothesis raises serious questions as to the significance of the Rittinger hypothesis, the Kick hypothesis, and other theories in which energy numbers are systematically assigned to various size fractions of comminution products in order to calculate theoretical energy consumptions. Derivation of the Energy Equation from the Size Distribution Equation: For simplicity, consider the comminution of 100 volumes of a feed material of relatively uniform particle size. The comminution process may be considered as the summation of many individual and independent comminution events. The extent of comminution is most easily expressed as the number of comminution events, z. In the first derivation, the key assumption is that the characteristics of the comminution events in a given crushing or grinding process are substantially constant and do not vary with the progress of the comminution process. Accordingly the characteristics of an average comminution event may be defined. In one such event, a quantity of energy $E is applied to a single particle of size f and volume $v. The crushing of this particle produces fine particles with a size distribution similar to that given by Eq. 1: yw=100(x/ka)a0 [51 In this equation yo, a0, and k0 are used to characterize the product of an individual comminution event rather than the product of the comminution process as a whole. In using Eq. 5, we will not be concerned with values of x close to the feed size f and will therefore assume only that the equation is applicable to the finest sizes of the material. In 100 volumes of total product, the actual volume of product finer than x from a single comminution event, or dy, is given by The total volume of material below size x, resulting from z events, is then given by y = z(dy) =z(dv) (x/ka)a0 =" Eq. 7 reduces to Eq. 1 when we let a, = a and [8a] z =100/dv (ka/k )1 or k = ka (zdv/100)-1/a [8b] Eq. 8a shows that the distribution modulus of the comminution product is the same as for the product of an individual comminution event. Eq. 8b shows how the size modulus of the comminution product k varies with the extent of comminution as measured by the number of events, z, or as measured by the fraction of the feed actually subjected to com- minution1 zdv/100. The energy input to 100 volumes of total feed, or 100E, is the sum of the energy inputs for all the comminution events: 100E =z (dE) [9]

Jan 1, 1961