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By E. S. Machlin

The wzodel of Blandin and Diplunt;, generalized to include a phase factor, is applied to the carbon-carbon interaction in iron. Darken&apos;s "energetic" model is generalized to include not only first neighbor interactions but further neighbor interactions as well. On the bases of these generalized models relations are derived for the activity of carbon in both austenite and ferrite in terms of the carbon-carbon Pair interaction energies. A single function then yields the pair interaction energies consistent with the experimental activities of carbon in both ferrite and austenite. Thus, a simple explanation is given for the observation that the nearest-neighbor interaction between carbon is repulsive in austenite and attractive in ferrite. Certain consequences of this approach are explored. OnE object of the present paper is to attempt to take into account the consequences of electrostatic contributions to the carbon-carbon pair interaction energy for carbon as a solute in iron. Friedel&apos; has shown that oscillations in electrostatic potential are to be expected about a solute atom in a metallic solution. Blandin and 6lant6&apos; have shown that such oscillations yield an interaction energy between pairs of solute atoms that obeys the relation: W{ = A cos(2ftFri + 4>)/(kFri)3 [l] where kF = Fermi wave vector, ri = distance between solute atoms comprising the pair7 <p = phase factor dependent only on electronic nature of solute and solvent, A = coefficient dependent only on electronic nature of solute and solvent. Machlin3 found that Eq. [I] accurately described the pair interaction energy derived from short-range order measurements based on field ion microscope observations of dilute alloys of platinum. He also found that the value of the phase factor $ derived from residual resistivity measurements agreed well with that obtained from the analysis of the short-range order data. Harrison and paskin4 were able to predict the long-range ordering energy of 0 brass using Relation [I] and residual resistivity values to predict the value of the phase factor $. Machlin5 has repeated their analysis and applied it to the prediction of the long-range ordering energy in AgZn and AgCd with excellent agreement between prediction and experiment. Both A and $ are independent of the crystal structure. The Fermi wave vector depends uniquely upon the conduction electron concentration per unit volume in the spherical approximation of the Fermi surface. Thus, Eq. [I] is expected to apply to both fer- rite and austenite with only one set of values of A and $. Mossbauer studies6 yield the result that iron has one 4s electron. We shall make an assumption found to hold previously for platinum3&apos;7 and nikel, which is that only the s electrons are involved in shielding the perturbing potential of carbon. With this assumption, kF = 1.35 A-l. Although A and $ may be obtained from certain mdels&apos;&apos;&apos; we shall take A and $ to be empirical constants in the spirit of Kohn and osko.&apos; Thus, Eq. [I] involves two adjustible parameters. Consequently, two independent relations in A and $I are required in order to evaluate them for carbon as a solute in iron. We may use a recent analysis of Aaronson, Domain, and poundg who showed that Darken&apos;s energetic model,1° as well as others, can be used to describe the activity-temperature data for carbon in iron in both the aus-tenitic and ferritic phases. Darken&apos;s model takes into account only first neighbor pair interactions. For our needs, all neighbor pairs need to be taken into account. It is convenient to generalize Darken&apos;s model. The result for the partition function for austenite is: over the temperature range 800" to 1200°C and where the uncertainty corresponds to one standard deviation. Eq. [4] effectively yields only one relation. Another relation is required to obtain unique values for A and $. One property of Eq. [4] is that it is independent of crystal structure. Hence, data for a iron can be used to obtain another relation. To arrive at this relation we must generalize Eqs. [2] and [3] so that they may be applied to the bcc a iron. The result is that:

Jan 1, 1969

By Alan Morris

Season cracking of brass has received wide attention and there is a wealth of technical literature on the subject. Its causes arc fairly well understood and means for its prevention are inexpensive and effective, so that the frequency of failures from this source has diminished of recent years. But its sister phenomenon, the failure of annealed brass by reason of applied tensile stress plus a certain type of corrosion, has received less attention, though it has been responsible for occasional more or less troublesome cases of cracking of brass in service. The work described in the following pages was undertaken about two years ago to determine the relative resistance of various commercial brass mixtures to stress-corrosion cracking, and to learn something of the controlling factors. By stress-corrosion cracking we mean the cracking of brass free from internal stresses by reason of applied tensile stress and simultaneous attack by certain corrosive agents. Rogers,&apos; in discussing a paper by Hatfield and Thirkell, says: " He had also applied a solution of mercuric salt to tensile test pieces of brass whilst they were under stress in the testing machine. At very moderate stresses such test pieces cracked, and very readily broke." Moore, Beckinsale and Mallinson2 subjected test pieces to simultaneous corrosion and tensile stress. In order to determine the minimum stress detectable in brass by the mercurous nitrate test, tensile samples were placed under stress and treated with mercurous nitrate solution. They found that brass stressed below a minimum did not crack. Dr. McAdam3 has investigated the effect of corrosion on the fatigue limit of brasses, among other materials. He directed a stream of either fresh or salt water against the specimen while it was undergoing fatigue test. The corrosion-fatigue limits thus determined may be considerably lower than the endurance limit without coincident corrosion. The exact

Jan 1, 1930

By E. R. Macgregor, J. Halpern

The kinetics of the reduction of cupric salts in aqueous solution by molecular hydrogen to metallic copper are described. The rate of reduction appears to be homogeneously determined and shows a marked inverse dependence on the hydrogen-ion concentration. Precipitation of copper is more rapid and complete in sulfate than in per-chlorate solution. A mechanism is proposed which accounts for this behavior. IN recent years a number of important hydro-metallurgical processes have been developed in which metallic salts in aqueous solution are reduced by gaseous hydrogen, usually at elevated temperatures and pressures, and thereby precipitated either in metallic form (e.g. Ni, Co, Cu) or as an oxide or salt of lower valence (e.g. VO, and VA).1 ; In connection with applications such as these, most of which involve heterogeneously catalyzed reactions, recent demonstrations"-" that salts of certain metals, e.g., Cu", Ag&apos; , Hg" , and Hg,+ can activate molecular hydrogen homogeneously and thus catalyze hydrogenation reactions in aqueous solution, are of considerable interest. For example, cupric salts catalyze the otherwise slow homogeneous reduction of dichromate and ceric salts by hydrogen, i.e. Cr,O; + 3HL. + 8H1 ? 2Cr&apos;- -- 7H,O [1] 2Ce &apos; ! H.. ? 2Ce" | 2H . [2] In perchloric-acid solution, where Cu" is not appreciably complexed, the kinetics have been found" " to be of the form -d [H,] _- k,[HJ [CU"]&apos; dt -LCu+&apos; l+ (k ,/k,) [H] [3] where, K = 1x10"&apos; exp [—26,600/RT] 1, mole-&apos; min-&apos; ... [4] and (k ,/k,) - 0.25 at 110°C. This kinetic behavior suggests that the reaction proceeds by a mechanism involving the following sequence of steps kt Cu" +H1CuH&apos; 4-HA [51 k., CUH + CU" ? + 2Cu f H&apos; [GI 6Cu&apos;+ Cr,07 + 14H&apos;+ 2Cr- (¦ 7H,O + 6Cu" [&apos;i] fast The catalytic activities of the undissociated cupric-sulphate and cupric-acetate complexes are somewhat greater (by factors of 6.5 and 120, respectively) than that of the simple hydrated Cu" ion.&apos;" These considerations suggest that, in contrast to the other hydrometallurgical hydrogenation reactions, referred to previously, reduction of cupric salts in aqueous solutions by molecular hydrogen, should proceed homogeneously, and in the absence of an extraneous catalyst. This has already been demonstrated" for acetate-buffered solutions where the product of the reaction is a precipitate of cuprous oxide (Cu,O). In the present paper, an investigation of the reduction of cupric salts in perchloric-acid and sulphuric-acid solutions, leading to the precipitation of metallic copper, is described. Some results for the sulphate system, which is of considerable hydrometallurgical interest, have been reported previously by Ipatieff",&apos; " and by Schaufel-berger&apos; but these do not give a quantitative account, of the kinetics and mechanism of the reaction. Experimental The reduction experiments were conducted in the 1-gal, titanium-lined autoclave described in connection with earlier related investigations," " and using a similar procedure. The solutions were made up by dissolving known amounts of CP grade Cu(ClO,), and HC10, (or CuSO, and HISO,) in dis-tilled water. While in the autoclave, the solution was stirred and maintained at a constant temperature (±loc) and under a constant partial pressure of hydrogen gas. It was ascertained that the agitation (provided by two 3-in., four-bladed stirrers, rotating at 900 rpm) was adequate so that at no time was the rate of reaction limited by solution of hydrogen. During each experiment, samples of the solution were withdrawn periodically, allowed to cool, and the concentration of copper remaining in solution was then determined electrolytically. Some Cu&apos; is formed during the reaction, but undergoes disproportionation when the solution is cooled to room temperature. For purposes of kinetic calcula-

Jan 1, 1959

By Thomas L. Garrard, James A. Sprague, Rex B. McLellan, Samuel J. Horowitz

A simple rnodel for interstitial solid solutions has been devised in which each solute atom interacts with the solzlent lattice in such a way as to exclude an integral number of nearest-neighbor sites from being occupied by solute atoms. The vemaining interstitial sites ave not affected. In calculating the entropy of such a solution the increase in the number of interstitial sites available to solute atoms due to the ozlerlap of blocked sites is taken into account. The ther-modynamic functions and the solute activity fov the solution rnodel are calculated. It is shown that considevation of the overlap sues vise to a correction term of the order 8&apos; ( where 0 is the ratio of solute to solvent atoms) in the thevmodynamic functions of the solution and the solute activity. The theo,uetical equation for the solute activity was used to analyze the available data for the activity of carbon in austenite at three different temperatures. The use of a computer enabled many comparisons to be made between the experimental activity data and those predicted by both the complex blocking model and the simple, widely used blocking model in which the ozierlapping of blocked sites is not taken into consideration. Even though at the highest concentvations oj carbon the value of 0 is small it is shown that the best fit to the experimental data is found with the complex blocking model. RECENTLY it has been shown by analysis of gas-solid equilibriums that many interstitial solid solutions can be described by the quasi-regular solution model in which the partial energy of solution E, is independent of composition and, apart from a composition-independent term due to nonconfigurational factors, the partial entropy is that of an ideal solution. Dilute solutions of nitrogen in both bcc and fcc iron,&apos; dilute solutions of oxygen and silver,&apos; carbon in a Fe,&apos; and dilute solutions of carbon in ? Fe2 are all quasi-regular. In addition many hydrogen-metal solutions, both dilute and concentrated (with the notable exceptions of the H-Ni and H-Pd systems), can be described by this model.3 However, it has been shown that, at various temperatures, solutions of carbon in ? Fe begin to depart strongly from quasi-regular behavior at low concentrations. A plot of the activity of carbon in ? Fe relative to pure graphite vs atom fraction of carbon (Cc) calculated from Smith&apos;s data4 begins to depart from the (nonlinear) plot for a quasi-regular solution at about Cc = 0.02. Several statistical models have been proposed to account for the thermodynamic behavior of carbon in y Fe. Darken and smith4 set up a model in which a carbon atom in its octahedral site in the fcc lattice has either one or no neighboring carbon atoms in the twelve nearest-neighbor octahedral sites. It is assumed that the number of carbon atoms having more than one nearest neighbor is negligibly small and that a solute atom does not interact with another solute atom located at a greater distance than the first shell of interstitial sites. Thus this model contains two characteristic interaction energies. Darken and Smith showed that this model gives reasonable agreement with the measured variation of carbon activity ac with composition. It is noteworthy that Darken and Smith concluded from their analysis of the activity data using this model that there was a repulsive force between carbon atoms in austenite which reduces the concentration of C-C pairs below that corresponding to random mixing. Recently Aaronson, Domian, and pound5 have considered in detail the statistical model developed by Lachere and by Fowler and Guggenheim7 and have shown that it is compatible with the activity data for carbon in austenite. In Darken&apos;s model the energy of solution of carbon in austenite is dependent on temperature and concentration; the departure from Henry&apos;s law arises from the concentration dependence of the energy of solution. In Aaronson, Domian, and Pound&apos;s discussion of the Lacher, Fowler, Guggenheim model the interaction energy wy between adjacent carbon atoms in austenite is strongly temperature-dependent. Aaronson et al . suggested that this temperature dependence of wy and hence the energy of solution of carbon could be explained either by the formation of clusters of carbon atoms (despite the repulsive nature of wy) or by the dual occupancy of the octahedral and tetrahedral sites by the carbon atoms. However, a temperature-dependent heat of solution

Jan 1, 1968

By J. R. Kyte, L. A. Rapoport

The material balance equation for partiai or complete 1:trter-drivc reser1,oir.s been re-arranged to include a pressure irrferferencr ternr. This pressure interfernce term was ohtained from the theory established hy Morinda. A .successful progranl deissed to solve the resrclritlg c,qrration in a few hours on a nleelitr .sizeti, digital compuier. No prior knowdelge of the properties of the eqrrifer is required in the solution. 7&apos; ri~rl calculations areatle using various assumed con!binuiions of value of the constant expretsing the qquifer properties correspoinds to the best fit ohtained between observed and calculated field history. Details of the method of calculaion are illus trated by an example. INTKCDUCTICN A method 01&apos; calculating the material balance equation for a partial water-drive reservoir completed in an aquifer has been described in the literature." Pressure interference i&apos;rc,m other pools iocated in the same nquiucr is not taken into account in this solution. When present, the pres- sure interference effect must be included in order to make a complete performance analysis. A correction for this effect has been developed using the theory cstahlished by Mor-tada.&apos; Manual calculation of the material balance for water-drive reservoirs is a formidable task. Such manual ca1culation when interference eflects are includcd would be impossible to completc in any reasonable time period. However, a medium-sized stored program, digltal conlputer can he used satisfactorily. The method is described in the following sections. THECKETICAL CONSIDEKATIOhS The material balance equation for a reservoir producing by partial or total water drive, as proposed by Van Everdingen, This relationship is linear for Z/a from which thc slopc, Z, and the intercept, N, can be obtained by the least-squares method from the data points. It is not necessary lo know the aquifer properties to uktain oplimum values tor 2nd IV. Various assumptions are made tor At,,: where 11 is production time, seconds (oilfield between the equal successive time intervals into which the history is divided. t,, h It, times the number of equal time periods from i.e.. the total dimen-sionless time interval from It is noted that the dinlensionless time interval, At,,, involves all the relevant aquifer properties. Accordingly, any assunlption of is an assumption of the combined aquifer properties which pertain to the solution of the equation. Deviations of the data points from a straight line arc calculated for each assumption of and the value of A, correspond ing to the minimunl deviation is chosen as the optimum solution. This method is described in Ref. 1 and 2. Thc material balance solution is usually made with an initial assumption that the reservoir being studied is located in an infinite aquifer from which there are no other withdrawals. Deviation of the points by amounts greater than can be attributed to inaccuracies in field data may be the result of: (1) boundary effects of a limited aquifer, (2) pressure interference from othcr pools completed in the .sarne aquifer, and (3) a combination of these effects. Differentiation of these effects can be made only on the basis of geologic data. Pressure interference from other fields will result in a pressure drop at the original oil-water boundary having an interference component, The measured instantaneous pressure drops at the oil-water

By W. S. Owen, A. R. Rosenfield

The measured changes in the yield stress of a poly crystalline Ta-O alloy after strain aging at 100°C have been separated into two components; the change inflow stress and the change in dislocation locking parameter. These two components vary independently indicating that at least two separate recovery processes take place during strain-aging. Variations in the locking parameter can be accounted for by segregation of oxygen atoms to dislocations, but variations inflow stress cannot be explained by current theories. STRAIN-AGING in Fe-C and Fe-N alloys has been studied extensively.&apos; The kinetics of the removal of the interstitial solute from solution appear to agree with the predictions of the cottrell-bilby2 model or a variation of it proposed by harper.3 Solute segregates to the dislocations under the influence of the elastic strain field of the dislocation and the rate of depletion of the solute can be measured by following the change in electrical resistivity4 or internal friction.5 On reloading a prestrained specimen, plastic flow starts at Fig. 1, but after aging the reloaded specimen yields discontinuously at a higher stress The aging index reflects the extent to which the yield has returned. Until recently it was usual to assume that ? is a result solely of the pinning of dislocations by the segregated solute atoms, that is, that op and oj coincide and the strain hardening curves AB and CD are continuous. Thomas

Jan 1, 1963

By R. D. Carter

Nurnerical .solutions are presented to some problems of unsteady-state radial flow of gas in which Darcy&apos;s law holds. These solutions are intended to aid in explaining the observed behavior of gas wells during drawdown tests. The variation of viscosity and Z-factor with pressure is accounted for in the solutions. Results are presented for three types of problems: (I) unfractured wells producing at a constant rate, (2) fractured wells producing at a constant rate and (3) unfractured wells producing through a critical flow prover. In the critical-pow-prover solutions, a correction of the calculated well-bore pressure to account for non-Darcy flow is made. A good correlation is shown between the solutions to the problem of Type 1 and the corresponding diffusivity-equation solution. Using this correlation, the diffusivity solution may be used to obtain gas-well solutions. The solutions to the problems of Type 2 illustrate the difference in drawdown-curve behavior to be expected between fractured and unfractured gas wells. Methods for estimatting fracture radius and flow capacity are presented and verified from solutions of Type 2. The solutions to the problems of Type 3 illustrate the differences to be expected between critical-flow-prover drawdown tests and constant-rate tests. An equation is presented for correcting critical-flow-prover data to constant-rate conditions. A description of the methods used in obtaining the solulions appears in the Appendix. INTRODUCTION It is necessary for many engineering purposes, such as predicting future deliverability performance, to be able to relate bottom-hole flowing pressure, formation pressure and flow rate for conditions of stabilized flow in gas wells. This information is customarily given as a plot of on logarithmic co-ordinates. It is desirable to be able to predict stabilized performance curves for gas wells based on data obtained from drawdown tests of short duration. Tests of long duration may be wasteful of gas, and low-permeability wells do not stabilize in a short-duration test. Although it is now commonly recognized that non-Darcy flow plays a significant part in gas-well behavior, it is believed that an understanding of transient behavior of systems obeying Darcy&apos;s law is still important in the interpretation of short-term test data, and the prediction of stabilized performance curves therefrom. In this connection, an equation for correcting Darcy flow It seems likely that solutions of the type presented herein, combined with the non-Darcy flow correction of the type of Eq. 1 and the usual laminar-flow skin factor, could provide a model which would adequately explain transient gas-well behavior for times after the non-Darcy flow region (which should be confined to a small area surrounding the well) has been established. The solutions presented in this paper are for three types of problems: (1) unfractured wells producing at a constant rate, (2) fractured wells producing at a constant rate and (3) unfractured wells producing through a critical flow prover. In the problems of Types I and 2, no corrections for non-Darcy flow were made in the results presented, since it was reasoned that the constant-rate boundary condition would facilitate such a correction if it was desired later. For the problems of Type 3, however, a condition of varying flow rate required that a non-Darcy flow correction of the type of Eq. 1 be included. This was done. Based on the numerical results presented, a number of approximations and a correlation are presented which may be useful in analyzing gas-well test data. It is assumed that the system can be described as a finite cylindrical gas reservoir produced by a single cylindrical well located at the center of the reservoir. Flow is strictly radial.

By L. Moyd, P. Moyd

The first commercially available portable gamma ray-neutron beryllium detector, the Rerylometer, was developed by the same group that developed the first practical portable scintillation counter, the Scintillo-meter. This group includes Professor George Brownell, of the Geology Department of the University of Manitoba in winnipeg, and his associates, K. I. Roulston, R. w. Pringle, and R. L. Funt, of the Physics and Engineering Departments of the University of Manitoba. A prototype model was tested in the field by Dr. Brownell during the summer of 1958. Commercial production was undertaken shortly thereafter by Nuclear Enterprises Ltd., of Winnipeg, and a license for manufacture and distribution in the U.S. was granted to Isotopes Specialties Co., of Burbank, California, a division of Nuclear Corporation of America. Early in 1959, we were retained by the &apos;Mining Division of Minerva Oil Co. to Legin a search throughout North America for minable deposits of beryllium, and to train members of their permanent staff to continue the program. The project included literature sur-veys, interviews with members of various federal, state, and provincial agencies, scanning of our own collection of suites of specimens from various mineral occurrences, and the examination of deposits in the field. The value of a beryllium detector to this program was obvious and arrangements were made to procure one as soon as possible, which resulted in our obtaining and using the first instrument that was produced commercially in the U. S. In addition to the commercially available Berylometer, Mr. William Vaughan and his associates, of the U. S. Geological Survey Geophysics Division, in Denver, have developed and tested several experimental instruments based on the same principles. DETECTOR Principles The detection of beryllium is based on the fact that "hard" gamma rays (1.6 MEV and geater), such as those produced by Antimony convert ordinary beryllium (Be9) to Be8 , with the release of a neutron. The neutrons are counted by a scintillator designed to favor neutron responses while suppressing those of gamma rays. &apos;The instrument is completely selective for beryllium. No other element can interfere. Instrunlentation The Rerylometer itself, which is cylindrical, is about 8 inches in diameter, 13 inches high, and weighs about 11 pounds. (Figs. 1, 2). The principal components include: 1. A disc of wax to moderate (or "thermalize") neutrons. 2. A boron-enriched polyester-zinc-sulphide fluorescent screen. This material produces strong flashes when struck by thermalized neutrons but only weak flashes from gamma rays. 3. A photomultiplier tube. 4. An electronic circuit, complete with one srnall 71/2-volt dry battery. The photomultiplier tube and electronic circuit convert neutron flashes to electrical impulses, but gamma ray effects are almost

Jan 1, 1961

By B. Mueller

Altered concepts regarding the raw material used in conventional blast furnace plants as well as new technologies for the reduction of iron ores make it necessary to reconsider the design of pelletizing plants. The incorporation of a pelletizing plant within a conventional integrated steel mill involves considerations of the problems of using in-plant fines. A modern pelletizing plant in Mexico serves as an example of the technical solution. In recent times, pelletizing plants are also being integrated within steel mills based upon direct reduction processes. The design of such pelletizing plants must take into account special product quality requirements.

Jan 1, 1977

By L. S. Darken

IN the study of reactions occurring in liquid iron, alone or in contact with a liquid oxide or slag phase, it has been found that the experimental data over a limited range of concentration can in some cases be repre-sented satisfactorily by the simple equilibrium expression K - (p1)p1 (p2)p2 . (R1)r1(R2)r2 . where (P) denotes the concentration of a product and (R) the concentra-tion of a reactant in the reaction r1R1 + r2R2 + . . . Some of the reactions for which it holds are listed in Table 1. For others, however, the simple equation apparently does not hold. This has been attributed to an improper method of expressing concentration (for instance, weight per cent instead of mol fraction); or it has been supposed that the solutions are not ideal in the sense that the activity of a com-ponent is not proportional to its true mol fraction, But it may be that the problem has been oversimplified by neglecting some molecular species actually present; that is, by considering only the ostensible simple com-ponents and thus leaving out of account possible compound formation. It is the purpose of the present paper to point out how, in a group of related cases, a reasonable consistent assumption relative to the presence of a compound makes it possible to express the experimental data satis-factorily by the simple equilibrium expression when this compound is taken into account, and to bring into harmony data referring to different reactions in liquid iron. There are several a priori reasons for believing that solutions in liquid iron should not deviate far from ideality, provided that the concentration of solute is not too great and is expressed in proper terms. The factors that commonly lead to nonideality in systems at ordinary temperature as ionization or the occurrence of polar and nonpolar molecules-are presumably less effective in metal and in slag systems at high temperature. Again, the type of equation commonly used to express the value of

Jan 1, 1940

By A. J. Weinig

The method described is a modification of Schutzenberger&apos;s whereby the solution in titrations and the standards are protected from the atmosphere by a layer of kerosene. Indigo-disulfonate is the indicator and sodium hydrosulfite the standard. The method is rapid and delicate. It has been tried on a variety of mill solutions and mill men have found the method of value. THE important part that dissolved oxygen plays in the cyanide treat-ment of gold and silver ores is commonly recognized by most metallurgists and mill men.. But heretofore there has been no simple method on which the mill man could rely for determining the amount of oxygen in the various mill solutions. A few methods are adaptable to the, laboratory, such as the gasometric1 determination by actually measuring the oxygen. Winkler&apos;s2 iodometric method, and Schutzenberger&apos;s3 method, which depends on the reducing action of sodium hyposulfite on a blue solution of indigo carmine; but these are not readily adaptable to the needs of the mill man and cannot be applied to cyanide solutions without modification. The gasometric method is the most accurate but it takes too long to complete a determination. White&apos;s&apos; method (a colorimetric method that depends on the degree of coloration imparted to a solution of pyrogallic acid in the presence of caustic soda) although much more rapid than any of the methods named, often gives misleading results on account of grading of colors of different solutions, which nearly always contain various kinds of salts. The method herein described was devised for the use of the mill man, the aim being to develop a simple, practical, accurate method. It is a modification of the Schutzenberger method and depends on the reducing

Jan 8, 1924

By T. PH. D. Egleston

THE origin of gold both in placer deposits and in veins, and especially the origin of nuggets, has been the subject of repeated discussions and investigations, which have been recently brought to my attention by several extremely interesting specimens sent to me for examination, and more especially by the one exhibited at the meeting of the Institute in February, 1880.* In the year 1874 I made some examinations of the hydraulic mines of Califor¬nia, and was very much struck with the distribution of the gold throughout these deep placers, which were almost invariably poor on&apos; the surface, while gradually growing richer towards" the bed¬rock. The constant presence of fossil wood, and the large quantity of organic matter contained even low down in these beds, was also remarkable. Not being satisfied with the various theories advanced to account for the formation of these deposits, I began an investiga¬tion early in the year 1879 on the conditions of solubility of gold and the causes of the loss in working gold ore in a large way: The researches which I have undertaken show that gold must be considered a soluble rather than an insoluble metal, and that the conditions of solution are such as will be found anywhere where gold is likely to occur, and the solution may take place even under the ordinary cir¬cumstances of surface drainage, and may be going on freely even where the presence of gold has never been suspected, and that there are causes enough in nature to produce the solution of the gold in sufficient quantities to account for all the phenomena of both the vein and placer formations. The general theory with regard to the formation of these placer deposits and nuggets has been that they were the result of the de¬struction of pre-existing- vein-matter, which does not accord with the facts as shown in the deep placer deposits. The gold in such case would be distributed in layers of unequal richness throughout * Transactions of the American Institute of Mining Engineers, vol. 8, p. 451.

Jan 1, 1881

By T. H. Aldrich

There are two conditions generally prevailing upon the earth—those within atmospheric influence, tending towards oxidation, and those away from atmospheric influence, tending towards reduction. Practically all mineral substances from mines of any depth a.re in a reducing condition. Since the cyanide process, in order to dissolve silver or gold, requires that the prevailing conditions under which it operates shall be oxidizing, and the materials usually acted upon bei~lg of a reducing character, it becomes necessary to supply oxygen to the solution carrying the cyanide. This oxygen is usually supplied through the medium of dissolved air in the solation, or through the medium of various chemical compounds, which upon combining vith the solution or the ore give off a part of their oxygen. Strange as it may seem, practically all mineral substa~~ccs are partly soluble in water, especially water carrying alkali or cyanide. The greater the surface exposed and the finer the material is ground, the greater mrill be the rate of dissolving of the reducing-agents from the ore into the cyanide solution. In most cases, if the solution carrying the ore particles is agitated with air, the air will dissolve into the solution faster than will the reducing-agents; but in some cases the reducing-agents will dissolve more rapidly on account of easy solubility or greater surface exposed. It is a dissolving race between the oxygen from the air and the reducing-agents from the ore, and if the reducing-azents predominate, cyanide will not dissolve the gold from the ore. In many cases it will dissolve some of the gold, because in a mass of irregular shape some of the gold particles might be exposed upon the outside surface of a particle of rock; but if the solution had to penetrate through cracks, the side-walls of which were lined with reducing-agent-

Jan 1, 1912

By William F. Boericke

KIRKLAND LAKE and Porcupine in 1931 accounted for more than $41,625,000 of Ontario&apos;s total gold production of $43,117,688. For the first time, the younger camp surpassed the older in gold output, producing $21,734,000 against $19,891,000 for Porcupine. Present output of both camps is increasing, and should pass the record figures of 1931 before the year is out. In May of this year, Porcupine mines milled 285,759 tons, with a bullion value of $1,810,009; the corresponding figures for Kirkland mines are 149,188 tons and $2,104,757. A much higher average value per ton for Kirkland ore, $14.10 against $6.33 average for Porcupine accounts for the difference. The two fields are about 100 miles apart by rail, and there are important differences in the character of the ores, which accounts largely for the difference in milling costs and in final tailing values, despite excellent metallurgical work in both the fields.

Jan 1, 1932

By Harlowe Hardinge

THE sound made by ball, pebble and rod mills has long been used by the operator as the "telltale" of their operation. The nature of this sound depends upon local conditions and the type of mill used. By experience an operator can tell whether the mill is running properly or not. Some operators are able to detect the difference in sound much better than others and get better results running the same mill tinder the same conditions. The automatic operation of a mill using sound as the fundamental means for maintaining control presents many problems. The satisfactory solution of these problems requires, for given operating conditions, a greater average output, with improved product for subsequent processing, than can be obtained by manual control.

Jan 1, 1939

By G. W. Binkley, R. E. Collins, G. K. Dumbauld

A mathematical analysis has shown that the primary factors affecting the deposition of cement in unfractured perforations during squeeze-cementing operations are: the properties of the cement slurry, the geometry of the perforations, and the filtration time. The validity of the analysis has been substantiated by laboratory investigations. The information presented in this paper makes possible the prediction of the rate of deposition of cement in and about unfractured perforations under given squeeze-cementing conditions, the proper filtration time to control the amount of deposition to any desired value, and the deposition properties needed in cement slurries to restrict to any desired degree the formation of nodes of cement .Solids inside the casing. INTRODUCTION The deposition of solids against a permeable medium by the process of filtration is an important property of a cement slurry. General recognition of the role of filtration in the use of cement in wells is evident in view of the fact that several patents on low-water-loss cements have been issued during the past few years. In the conventional, high-pressure squeeze-cementing technique, a large volume of cement slurry is usually displaced into the area surrounding the perforated interval after the formation has been fractured hydraulically.&apos; Near the end of the job, the pumping rate is slowed or stopped intermittently in an effort to obtain a high pressure in the wellbore. The way in which a high pressure is obtained is not understood thoroughly. but it is be- lieved to be caused by the deposition of a rigid mass of compacted cement particles either in the fractures of the formations or inside the casing opposite the perforated interval. In a method of squeeze-cementing introduced several years ago, a small amount of cement slurry is squeezed into the perforations at a low pressure to avoid fracturing the formation. The filling of the unfractured perforations with cement particles by the process of filtration is important to the success of this technique. Early in the development of this low-pressure squeeze-cementing technique, laboratory and field-size experiments showed that conventional, neat cement slurries were unsatisfactory if the tubing was extended into or through the perforated section of the casing. The extremely high filtration rate of neat cement slurries caused the deposition of a compacted mass of cement inside the casing and made it impossible to remove excess cement by reverse circulation and difficult to withdraw the tubing. Because the need for cements with a reduced filtration rate was obvioils and urgent, modified cements containing 12 per cent bentonite were used until research was completed on modified cements containing 25 per cent bentonite.< These modified cements were useful in the solution of the immediate problem, but the following questions remained unanswered: (I) what is the optimum filtration rate of cement slurries for this application, (2) how long should the squeeze pressure be applied. and (3) how great are the effects of squeeze pressure and well temperature on the rate of deposition? Furthermore, the relationship of the filtration properties of cement slurries to the dimensions of the perforations and the wellbore was unknown. In order to obtain information relative to these basic considerations, a systematic evaluation of all the factors involved in the deposition of Cement during low-pressure squeeze-cementing operations was initiated. Although the work was directed toward an evaluation of the factors influencing the deposition of Cement in the low-pressure squeeze-

By D. G. Westlake

The electrical resistance of a series of V-H alloys (0 to 3.5 at. pct H) has been measured over the temperature range G° to 360°. Interstitial impurities made contributions to the residual resistivity, but not the ideal resistivity. The contribution of hydrogen in solid solution is expressed by Ap = 1.12 microhm-cm per at. pct H; but the contribution of precipitated hydride was negligible. A portion of the so1vu.s for the V-H phase diagram is presented. The solubility limit is given by In N (at. pct H) = (5.828 i 0.009) - (2933 i 44)/RT. Comparison of critical temperatures joy hydride precipitation and published critical temperatures for hydrogen embrittlement suggests the two are related. ThiS study was initiated as part of an investigation of the mechanism by which small concentrations of hydrogen embrittle the hydride-forming metals at low temperatures. It has already been shown that, in the case of hcp zirconium, a reduction in ductility accompanies the strengthening resulting from precipitation of a finely dispersed hydride phase.&apos;&apos;&apos; Our attempts to detect a similar precipitation of a second phase at low temperatures in V-H alloys by transmission electron microscopy have been thwarted because we have been unable to prepare thin foils that are representative of the bulk material with respect to hydrogen concentrati~n.~&apos;~ The present investigation establishes the solvus of the V-H system at subambient temperatures. Subsequently, we hope to be able to determine whether the embrittlement temperature is related to the critical temperature for precipitation of the hydride in a given V-H alloy. veleckis5 has proposed a partial phase diagram for the V-H system based on extrapolations of the pressure-composition relations he measured at higher temperatures. Kofstad and wallace&apos; conducted a similar study of single-phase alloys but did not attempt to establish the phase diagram. Zanowick and wallace&apos; and ~aeland&apos; have studied a portion of the phase diagram by X-ray diffraction, but they investigated no alloys in the hydrogen concentration range 0 to 3 at. pct, the range of interest to us. EXPERIMENTAL PROCEDURE The vanadium was obtained from the Bureau of Mines, Boulder City, Nev., in the form of electrolytic crystals. The analyses supplied with them listed 230 ppm by weight metallic impurities, 20 ppm C, 100 ppm N, and 290 ppm 0. The crystals were electron-beam-melted into an ingot that was rolled to 0.64 mm. Strips, 60 mm long and 4.2 mm wide, were cut from the sheet, and both rolled surfaces were ground on wet 600-grit Sic paper to produce specimens 0.4 mm thick. They were wrapped in molybdenum foil, vacuum-encapsulated in quartz, and annealed 4 hr at 1273°K. The specimens were annealed in a dynamic vacuum of 2X lo-&apos; Torr for 30 min at 1073°K for dehydrogenation, and charged with the desired quantity of hydrogen by allowing reaction with hydrogen gas at 1073°K for 2 hr and cooling at 100°K per hr. Purified hydrogen was obtained by thermal decomposition of UH3. Sixteen specimens were studied: two contained no hydrogen and the others had hydrogen concentrations between 0.5 and 3.5 at. pct (hydrogen analyses were done by vacuum extraction at 1073°K). Electrical resistances were measured by the four-terminal-resistor method on an apparatus similar to the one described by Horak.~ The specimen holder was designed so that both current and potential leads made spring-loaded mechanical contact with the specimen. The potential leads were 30 mm apart, and the current leads were 55 mm apart. The current was 0.10000 amp. We used the following baths for the indicated temperature ranges: liquid nitrogen, 77°K; Freon 12, 120" to 230°K; Freon 11, 230" to 290°K; and ethanol, 290" to 340°K. Temperatures lower than 77°K were achieved by allowing the specimen to warm up after removal from liquid helium. Temperatures above 77°K were measured by a calibrated copper-constantan thermocouple (soldered to the specimen holder) and below 77°K by a calibrated carbon resistor. The temperature of the bath changed less than 0.l0K between duplicate measurements of the resistance. RESULTS AND DISCUSSION Typical plots of resistivity p vs temperature T are shown in Fig. 1. In the interest of clarity, only five curves are presented and the data points have been

Jan 1, 1968

By David R. Maneval, W. E. Foreman, J. Richard Lucas

INTRODUCTION The objective of this chapter is to inform the industry, as well as the public, of the challenges in dealing with problems associated with air and water contamination by coal preparation plants. The need for an informed industry is most important. It is hoped that some contribution may be given to a more efficient and economical approach to the problems of plant waste contaminants at individual plants. The problem has many facets, and consideration should be given to specific areas before any significant problems develop at a given plant. It is then possible to have a reasoned approach before the pressures of an emergency environment force hasty and incomplete solutions. It will be necessary to anticipate these problems in the design of new preparation plants, and advance consideration should be given to all problems concerned with contaminants.

Jan 1, 1979

By George F. Weaton, Carleton C. Long, H. I. Najarian

Partial descriptions of the operation of the St. Joseph Lead Company&apos;s Joseph-town smelter have been published. In, 1936 the electrothermic production of zinc oxide was described;&apos; in 1939 appeared a description2 of the electrothermic method of producing zinc metal. Inasmuch as the plant capacity has more than doubled, and in view of the fact that operating practices have improved greatly since these publications, it seems worth while to prepare a fresh description of the present-day elec-trothermic zinc plant and practice. Josephtown smelter is situated on the south side of the Ohio River about 3 miles below its confluence with the Beaver River. In addition to river barge, the smelter is served by Pennsylvania state highway No. 18 and by a spur line of the Pittsburgh and Lake Erie Railroad (N.Y.C.). A recent extension of this spur line connects with the Pennsylvania Railroad. As originally contemplated the plant was to handle only the product of the com-pany&apos;s own mines in St. Lawrence County, New york, but owing to the incessant demand for zinc and zinc oxide, it has been necessary to supplement New York concentrates with foreign ores (principally from Quebcc and the Argentine). The general operational procedure followed comprises roasting the sulphide con-centrates, converting the sulphur dioxide into sulphuric acid, preparation of a strong-structure sinter from the calcine, crushing &lid sizing of coke, reduction of coke-sinter mixture by electrothermic means, condensation of the evolved zinc vapor to make zinc metal or burning of the zinc vapor to make zinc oxide, collection and packing of the zinc oxide. Dusts recovered by the roaster and sinter Cottrells are treated in the leach plant for separation of lead sulphate, cadmium metal and zinc sulphate. The general flowsheet is shown in Fig. I. Principal Items OF Equipment Roaster Plant Concentrate drier, 6-ft. &apos;ia. by 4O ft. 5 in., countercurrent, direct gas-fired. 3500-~on concentrate storage in three vertical steel tanks. Five modified Nichols-Herreshoff twelve-hearth roasters, 21 ft. 6 in. in diameter. Four fans for shaft-cooling air. One threedrum Stirling water-tube waste-heat boiler, 4&apos;8 hp., 200 1b. Per sq. in., with connections to upper and lower balloon flues. Direct gas-fired countercurrent rotary-kiln roaster for Cottrell dust. Necessary conveying equipment, described below. Instrumentation consists of: draft indicators, (3d hearth); various manometers; pyrometer served by thermocouples in each hearth, entrance and exit of waste-heat Joseph. entrance and exit of each hot Cottrell; roaster draft recorder and shaft air-pressure controller; temperature recorder and controller (10th and 12th hearths); SO* recorder (waste-heat boiler n

Jan 1, 1944

By T. H. Aldrich

(San Francisco Meeting, October, 1911.) THERE are two conditions generally prevailing upon the earth-those within atmospheric influence, tending towards oxidation, and those away from atmospheric influence, tending towards reduction. Practically all mineral substances from mines of any depth are in a reducing condition. Since the cyanide process, in order to dissolve silver or gold, requires that the prevailing conditions under which it operates shall be oxidizing, and the materials usually acted upon being of a reducing character, it becomes necessary to supply oxygen to the solution carrying the cyanide. This oxygen is usually supplied through the medium of dissolved air in the solution, or through the medium of various chemical compounds, which upon combining with the solution or the ore give off a part of their oxygen. Strange as it may seem, practically all mineral substances are partly soluble in water, especially water carrying alkali or cyanide. The greater the surface exposed and the finer the material is ground, the greater will be the rate of dissolving of the reducing agents from the ore into the cyanide solution. In most cases, if the solution carrying the ore particles is agitated with air, the air will dissolve into the solution faster than will the reducing-agents; but in some cases the reducing-agents will dissolve more rapidly on account of easy solubility or greater surface exposed. It is a dissolving race between the oxygen from the air and the reducing-agents from the ore, and if the reducing-agents predominate, cyanide will not dissolve the gold from the ore. In many cases it will dissolve some of the gold, because in a mass of irregular shape some of the gold particles might be exposed upon the outside surface of a particle of rock;&apos; but if the solution had to penetrate through cracks, the side-walls of which were lined with reducing-agent-

Feb 1, 1912