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By E. I. Alessandrini, A. U. Seybolt

Selective oxidation (preferential oxidation of a single alloy component) can be an important oxidation mode in the case of alloys such as Si-Fe, Al-Fe, and so on, when heat-treating in atmospheres of low oxygen potential. It was the purpose of this work to identify the oxide films formed on iron containing 31/4 pct Si at low oxygen potentials, and to make some observations on the H2O/H2 ratios required to form them. EXPERIMENTAL METHOD HYDROGEN of varying water content offers a very convenient method of establishing a wide range of oxidizing power, or oxygen potential. The method chosen to provide a desired H2O/H2 ratio was to nearly saturate hydrogen at room temperature by bubbling the gas through water at room temperature, and then to wring out the excess water by passing the wet gas through a long glass spiral immersed in a refrigerated liquid at a desired dew point. After oxidation, the samples were examined by electron diffraction in order to identify any film which might be present. PREPARATION AND TREATMENT OF SAMPLES The samples were prepared from a Si-Fe alloy made in the laboratory using electrolytic iron and 96 pct ferro-silico11, vacuum-induction melted, hot-rolled then cold-rolled to 0.015-in. thickness. After the cold-rolling the samples were annealed at 1000°C. Transmission Laue X-ray patterns showed very little evidence of preferred orientation, but it is likely that a weak texture could have escaped notice. The chemical analysis was as follows: 3.34 Si, 0.01 Al, 0.001 0, 0.006 C, 0.002 N. Before each sample was oxidized, it was polished through 4/0 emery paper, cleaned and dried using benzene, carbon tetrachloride, acetone, absolute alcohol, and ether. The method of oxidizing the samples was as follows: Samples about 1/2 by 1 by 0.015 in. were held in the upper, cool part of a vertical vacuum furnace until the desired temperature was established in the furnace, Fig. 1. The sample was then lowered into the uniform hot zone where it was heated quickly to the desired temperature, and subjected to hydrogen of controlled moisture content (dew point) as mentioned previously. Temperatures from 400" to 1000°C were used, and dew points from room temperature to —78°C were explored. In general, the runs lasted about 6 hr, but a few runs were of different duration, as will be indicated later. After the predetermined period of time had elapsed, the specimens were withdrawn by the hollow stainless steel-quartz holder to a cool zone at the top of the furnace. EXPERIMENTAL RESULTS The results are summarized in Table I. Most of the electron-diffraction patterns were obtained by glancing-angle reflection, but in a few cases it was possible to strip the oxide films from the surface by a total immersion in a 3 pct bromine-methanol solution. Some of the thinner stripped films yielded quite satisfactory transmission patterns. However, both diffraction techniques yielded the same results; the patterns while most frequently showing a (low) tridymite, also showed a (low) cristobalite in some cases. A few patterns showed evidence of both phases. Because of the known nonequilibrium behavior of silica, it is not surprising that both forms of silica could coexist on one sample. It was noted that at fairly low dew points such as —40°C, there was a tendency for diffuse diffraction rings, suggesting a very small crystallite size. Also some subsequent experiments to be reported later show that thin silica films can be amorphous.

Jan 1, 1959

By Lewis T. Wright

(Pittsburg Meeting, March, 1910.) I HAVE long been aware that ferruginous copper furnace slags if fused in the electric arc will yield metallic iron containing copper, and in order to confirm this knowledge, and to obtain further information of the behavior of such slags in the high temperature and reducing conditions of the electric furnace, a number of samples of slag were fused in an experimental electric furnace. The results obtained, given in Table I., show that a very large amount of metallic iron was produced, and that this iron carried with it practically all the copper, gold, and silver, and more than 50 per cent. of the sulphur, of the original slag. The metallic buttons formed in the electric furnace were clean, hard, but not brittle.

Mar 1, 1910

By J. H. Brophy, A. L. Prill, H. W. Hayden

An error lzas been found in the conventional way of determining the time exponent of linear shrinkage for the solution-precipitation stage of liquid-phase sintering. Large amounts of shrinkage due to initial rearrangenzent result in erroneously low exponents and tni si dentification of the rate-controlling process. Two alternative, mathematically correct, methods of calculation are applied to existing data on Fe-Cu, WC-Co, and Tic-Ni-Mo. This results in reidentifi-cation of the rate-controlling process and somewhat better agreement with related data. In each case the solution-precipitation process is solution-controlled and not diffusion-controlled. THE liquid-phase sintering process has been the object of a considerable amount of research for many years. Linear shrinkage vs time data at various sintering temperatures have been used recently in an attempt to identify the prevailing mass-transport processes in a number of metallic and nonmetallic systems. There is an analytical error inherent in the methods previously used for handling data during the "solution-precipitation" stage of shrinkage which must be recognized before the correct rate-controlling processes can be determined. It is the purpose of this paper to show how the error has affected previous conclusions and to suggest corrections. A number of mechanisms have been proposed to explain experimental observations during sintering in the presence of a liquid phase. The earliest of these is due to Price, Smithells, and williamsl who attributed the observed growth of the solid phase to the simultaneous solution of smaller particles and growth of larger particles. From the work of Lenel et al.2,3 and Gurland and Norton4 has come the suggestion that the liquid-phase sintering process may be divided for analysis into three steps: 1) rearrangement upon formation of the liquid phase; 2) solution and reprecipitation of the solid phase in the liquid; and 3) "coalescence" or a final stage of sintering, characteristically slower than the solution-precipitation process. The sequence of steps is shown schematically in Fig. 1. Kingery5 presented a thermodynamic and kinetic analysis of the first two "stages" of the liquid-phase sintering process in which the functional dependence of lineal shrink- age on time at temperature was used to identify the rate-controlling mass-transport process. Table I summarizes the time dependences and processes considered by Kingery.5 This method of data presentation has been employed by Kingery and coworkers for Fe-CU,6 WC-Co, and a number of nonmetallic systems," and bv Whalen and Humenik for Tic-Ni-Mo and Fe-cu.8 In each of these studies, the rate-controlling step during the "solution-precipitation" stage was identified from the slope of the curve in that stage on a logarithmic plot such as Fig. 1. However, in all of the previous studies, at a certain composition, relatively large amounts of shrinkage due to rearrangement preceded the solution-precipitation stage. Under these conditions, the larger the amount of rearrangement shrinkage the

Jan 1, 1965

By E. E. Donath

THE coal hydrogenation process is well known as a means for the production of liquid fuels -from coal. In this paper the possibilities of the coal hydrogenation process as a source of chemical raw materials will be discussed. The recovery of chemicals from coal hydrogenation products necessitates some modifications and additions to the equipment used for the production of fuels. The conversion of coal into liquid fuels such as gasoline requires two steps: liquid phase and vapor phase hydrogenation. Intermediate oils obtained in the liquid phase contain oxygen and nitrogen compounds, especially aromatic compounds, since the coal itself is composed mainly of cyclic compounds. These oils are the raw material for the separation of high molecular weight aromatics and of tar acids and tar bases. The relative amounts of heavy and middle oil-boiling above and below, e.g., 325°C-can be influenced by temperature, residence time, and catalyst of the liquid phase hydrogenation. In the vapor phase hydrogenation a solid bed catalyst is used to convert the intermediate oil from the liquid phase operation into hydrocarbons of the gasoline boiling range. Essentially pure hydrocarbons with a low content of sulphur, oxygen, nitrogen, and olefines are obtained. Depending mainly on the catalyst, the high ring compound content of the liquid phase oil can be preserved and gasoline rich in aromatics obtained. However, with other catalysts, these ring compounds can be split into gasoline with a high content of isoparaffins.1 Again, depending on the operating conditions, products of varying boiling range can be obtained. Selection of catalyst and operating conditions therefore makes possible the production of different grades of motor fuel and also variations in the relative amounts of benzene, toluene, and xylene when aromatic hydrocarbons are produced. The schematic flowsheet, Fig. 1, shows the main steps of the coal hydrogenation process, and the product streams used for the recovery of chemicals are indicated. In the liquid phase hydrogenation stage, coal is made into a paste with recycle heavy oil. The coal paste is mixed with hydrogen and preheated at a pressure of 300 to 700 atm in heat exchangers and preheaters. The coal paste and hydro¬gen enter high pressure converters where the liquefaction of coal, conversion of the high boiling liquid materials initially obtained, into intermediate oils is performed at a temperature around 470°C. The reaction products enter the hot catchpot in which lower boiling oil vapors are separated from the residue containing unreacted coal, ash, and heavy oil. This residue, usually called H.O.L.D. (heavy oil let down), is processed to separate solid and liquid material. By thermal treatment of the residue, e.g., a coking process, distillate oil is obtained, which can be recycled as part of the pasting oil. This stream is rich in polynuclear aromatics and can be, and has been, used for the recovery of such material. The oil vapors and hydrogen from the hot catch-pot are cooled in heat exchangers and a cooler, and the condensed oil is separated from the recycle hy-

Jan 1, 1952

By J. Bruce Wagner, Roger L. Levin

Integrated forms of two solutions of Fick's second law for the movement of a plane interface through a sample of wustite, and for diffusion into a semi-infinite slab of wustite, are shown to yield nearly identical values of the chemical diffusion coeffcients of cation vacancies in wustite, over the temperature range 900° to 1100°C. The chemical diffusion coefficients, the values of D obtained for the propagation of a concentration gradient through samples of undoped and doped wustite, are obtained from the equations It is becoming increasingly important in metallurgical practices to understand the role of the chemical diffusion coefficient, i.e., the diffusion coefficient of a species across a concentration gradient. During the first stages of sintering, one of the mechanisms by which the bonds between neighboring particles develop is by volume or bulk diffusion. This diffusion coefficient as deter- where ?m is the weight change at any time t, ?W is the total weight change at t =8, A is the area of the specimen, and AC is the total change in the cation concentration after the establishment of equilibrium, as determined by reduction experiments in different carbon monoxide -carbon dioxide mixtures within the limits of existence of the single-phase field. mined from the standard equations for volume diffusion during sintering is actually a chemical diffusion coefficient, and it has been observed to be many times larger than the self-diffusion coefficient as determined on the same materials by experiments using radioactive tracer techniques. Kuczyn-ski1 has noted that, if the controlling mechanism of sintering of A12O3 in an oxidizing atmosphere is the diffusion of oxygen, then this diffusion coefficient as measured from sintering rates is about 2.2 x 104 higher than the self-diffusion measurements obtained by tracer techniques. He has also reported the diffusion coefficient obtained from the rate of sintering of Fe2O3 powder to be about 10 6 times faster than the self-diffusion coefficient of

Jan 1, 1965

By W. Rostoker, D. W. Levinson, A. Yamamoto

The influence of carbon on tensile strength, tensile ductility, transformation kinetics, and grain growth characteristics of selected Ti-Mo base alloys was studied. No systematic influence of carbon in tensile strength or significant deleterious effect on tensile ductility was observed. There was a marked increase in transformation rate due to carbon. Dispersed carbides exert a marked inhibiting effect on grain boundary migration, and thus effectively prevent grain coarsening during solution treatment in the ß phase field. AS part of a research program directed toward the illumination of factors governing modes of transformation, transformation kinetics, and mechanical properties obtainable through these transformations by heat treatment, Ti-Mo base alloys were selected for study. The binary system is a characteristic phase diagram type which has been studied in some detail', ' in relation to transformation kinetics and mechanical properties. Although carbon bearing alloys have acquired a bad reputation, the possibilities of melting titanium under conditions which occasion some carbon pickup are very attractive. It is therefore of considerable importance to know whether carbon, present as a dispersed carbide phase, is actually deleterious when all other detrimental factors are minimized. Basic alloy compositions containing nominally 3, 5, 7, and 11 pet Mo were prepared with systematic carbon addition up to 1 pet by weight. Various of these alloys were subjected to a series of critical and definitive experiments to delineate the effect of carbon on the transformation behavior and associated mechanical properties. Experimental Procedure Alloys were prepared from 115 Bhn magnesium-reduced sponge titanium. This sponge analyzed ap- proximately 0.05 pet C. Ti-Mo and Ti-C master alloys were made by arc-melting the sponge with high purity (99.9 + pet) molybdenum and spectro-scopic grade graphite, respectively. Alloys were then prepared from the master alloys and sponge by double are-melting. One kg ingots were prepared by melting in a nonconsumable electrode furnace. These ingots were forged at 1000°C to '/z in. rods, and cleaned and processed into electrodes for the second melting operation. The final ingots were ground to remove surface defects, then forged again to 1/2 in. or 3/8 in. diam rods for processing to test samples. It is significant that all of the alloys at all carbon levels forged satisfactorily. For convenience, the alloys will be referred to throughout the text by their nominal analyses. Samples for the study of transformation rates were prepared from 1/2 in. diam round stock. They were then solution treated in a helium filled tube furnace at 1000°C for 30 min prior to the isothermal transformation treatments in lead bath furnaces. Temperature control in both cases was within ±3oC. Following the isothermal transformation treatments the samples were water quenched. These experiments were carried out before the general adoption of the resistometric procedure for kinetic studies. The data were therefore obtained entirely by metal-lographic analysis. M, temperature was also determined by the metallographic method. Shoulder-type tensile test pieces were machined from heat treated, 1/2 in. diam slugs to provide a 0.252 in. test diam and a 1 in. gage length. The isothermal-type heat treatments were chosen from previous data' to provide three levels of strength and ductility.

Jan 1, 1957

By Alwyn Birchmore Cox, Ian William Wark

In defending the chemical theory of flotation, Taggart, del Giudice and Ziehl have criticized1 the views of those who prefer to attribute the effects of certain flotation agents to adsorption. Perhaps with some justification, they describe the latter term as the "haven of refuge of writers lost in a morass of shaky experiment and muddy thinking." We prefer to regard it, however, as a haven of refuge for writers who seek a conventional term to describe the formation of films of flotation reagents on solid surfaces, because in many cases it is not yet possible to specify the forces that hold them there. Originally, as Taggart and his associates state, adsorption connoted a concentration difference and nothing more. In recent years, workers in the field of surface chemistry have tacitly added other meanings, and they now speak of orientated adsorption of unimolecular films on a solid sub-strate, of chemi-adsorption, and of exchange adsorption. Thus the term adsorption may connote simply the Gibbs layer of excess concentration at the surface of a solution, or a unimolecular film at the surface of a solid. Perhaps this has led to the misunderstanding of Taggart, del Giudice and Ziehl concerning the relationship between surface tension and adsorption at solid surfaces. The change in "surface tension" accompanying adsorption at a liquid surface can be used as a measure of the adsorption, and the Gibbs equation as quoted by these authors correlates these two conceptions. But, to correlate two conceptions docs not necessarily imply an attempt to explain either, although sometimes such an "explanation" is carelessly inferred. Use of "surface energy per unit area" instead of the numerically equal but more difficult and less definite conception of "surface tension per unit length " would lessen many of the present difficulties. (Compare with Adam.2) At interfaces involving a solid phase, neither '" surface tension " nor " interfacial tension "can have any meaning, but the conception "interfacial energy per unit area" call be understood by anyone who is familiar with the concept of free energy. While it is true that surface energy cannot be directly measured at a solid surface,

Jan 1, 1939

By Ian William Wark, Alwyn Birchmore Cox

In defending the chemical theory of flotation, Taggart, del Giudice and Ziehl have criticized1 the views of those who prefer to attribute the effects of certain flotation agents to adsorption. Perhaps with some justification, they describe the latter term as the "haven of refuge of writers lost in a morass of shaky experiment and muddy thinking." We prefer to regard it, however, as a haven of refuge for writers who seek a conventional term to describe the formation of films of flotation reagents on solid surfaces, because in many cases it is not yet possible to specify the forces that hold them there. Originally, as Taggart and his associates state, adsorption connoted a concentration difference and nothing more. In recent years, workers in the field of surface chemistry have tacitly added other meanings, and they now speak of orientated adsorption of unimolecular films on a solid sub-strate, of chemi-adsorption, and of exchange adsorption. Thus the term adsorption may connote simply the Gibbs layer of excess concentration at the surface of a solution, or a unimolecular film at the surface of a solid. Perhaps this has led to the misunderstanding of Taggart, del Giudice and Ziehl concerning the relationship between surface tension and adsorption at solid surfaces. The change in "surface tension" accompanying adsorption at a liquid surface can be used as a measure of the adsorption, and the Gibbs equation as quoted by these authors correlates these two conceptions. But, to correlate two conceptions docs not necessarily imply an attempt to explain either, although sometimes such an "explanation" is carelessly inferred. Use of "surface energy per unit area" instead of the numerically equal but more difficult and less definite conception of "surface tension per unit length " would lessen many of the present difficulties. (Compare with Adam.2) At interfaces involving a solid phase, neither '" surface tension " nor " interfacial tension "can have any meaning, but the conception "interfacial energy per unit area" call be understood by anyone who is familiar with the concept of free energy. While it is true that surface energy cannot be directly measured at a solid surface,

Jan 1, 1939

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

The Colorado School of Mines, Golden, Colo. M F Coolbaugh, President. Since 1906 the School of Mines has issued a journal, known as the Quarterly of the Colorado School of Mines, which carries many articles on matters of general interest as well as other articles of a technical nature There is no regular subscription price to the School of Mines publications Anyone interested in back numbers should write and find out the conditions under which individual copies may be obtained, whether a price is set on them or whether they are free Some back numbers are not now available but efforts will be made to supply copies from the files of alumni or other friends of the School Vol 23, No. 3 of the Quarterly (July, 1928) is an index of the publications complete from July, 1906 to July, 1928. A selected list of the technical articles appearing in the Quarterly is given here: Vol 3, No. 3, Rare metals. uranium and vanadium, by H. Fleck (1909), vol 3, No 4, Tungsten in Colorado, by H R Van Wagenen, vol 4, No 3, Preliminary report of the radioactivity of the carnotite of southwest Colorado, by H Fleck and W. G Haldane (1909), vol. 8, No 1 (1913), Some recent developments at Leadville, by G. M Butler, vol 8, No. 3, Physiography of

Jan 1, 1933

By Haley, D. F.

WHEN operations were first started at Climax in 1917 by the Climax Molybdenum Co., they were pioneering in the molybdenum industry for little was known relative to the uses of molybdenum or the metallurgy of molybdenite concentration. Concentration of molybdenite is relatively simple today but in 1916, when the Climax deposit first attracted attention, it presented serious difficulties. Little was known, in fact, even about the assaying of such low-grade molybdenum ores. Mine samples were sent to at least a dozen of the best laboratories in the United States and average values reported varied from 0.4 per cent to 1.0 per cent MOS2. Owing to the wide variations in MoS2 content obtained from reliable chemists, the actual value of the ore was most uncertain. This variation occurred repeat¬edly over a period of six months in 1917. It was finally decided, as a last resort, to cut several tons of sample from the tunnel and have a mill test made, using the recovered MoS2 per ton as the grade of the ore, for a small error in the assaying of the concentrate would not materially affect the results. These mill tests were made by the General Engineering Co. (Callow) at Salt Lake City. The results proved an ore of commercial grade and indicated the flotation process for the best metallurgy. Based upon these tests, the decision was made to build a 200-ton flotation plant. At this time, the art of flotation was

Jan 1, 1946

By A. L. Jr. Pozzi, A. O. Garder, D. W. Peaceman

A new numerical method is proposed for the solution of multidimensional miscible displacement problems. Besides the usual stationary grid associated with numerical procedures, the method uses moving points for which positions and concentrations are computed each time step. Based on the method of characteristics for treating combined transport and dispersion, the method applies equally well to any number of dimensions and, in contrast with other numerical procedures, properly takes into account the physical dispersion, no matter how small. Extensive tests show that accurate solutions of one-dimensional problems can be obtained over a wide range of values of the dispersion coefficient, including zero. They also show that the moving points do not need to be uniformly spaced, and that increasing the number of moving points beyond 2/grid interval does not significantly improve the accuracy of the solution. Two-dimmsional calculations using the new method were carried out to simulate laboratory model displacements in which gravity caused overriding of solvent. Good agreement between observed and computed profiles and measured and computed concentrations of produced fluid was obtained for a viscosity ratio of 1.89; at higher viscosity ratios, fair agreement was obtained Computed results were found to be significantly affected by vertical dispersion, and negligibly affected by dispersion in the direction of flow, in agreement with conclusions based on experimental observations. INTRODUCTION Although miscible displacement processes are potentially of great economic significance, limited progress has been made in developing mathematical methods for predicting the outcome of a solvent flood. Because of the complexity of the partial differential equations which describe multidimensional miscible displacement, numerical methods are a natural approach to their solution. The task of finding suitable numerical approximations to one of the partial differential equations, which involves both dispersion and convective transport, has been particularly difficult. Dispersion in the absence of transport is described by the heat flow equation, a second-order equation of parabolic type. This equation has been very successfully treated by numerical methods. Transport in the absence of dispersion is described by a first-order equation of hyperbolic type. This equation has been treated numerically with some success in one dimension, both by Lagrangian and Eulerian techniques, 1.2 but extension to two or more dimensions has not been satisfactorily accomplished. Usually one of two things happens: either the numerical solution develops oscillations or it becomes smeared by artificial dispersion resulting from the numerical process. When transport and dispersion are considered simultaneously, this numerical dispersion may dominate the low physical dispersivicy that generally characterizes miscible displacement. Stone and Brian2 have developed a new difference equation for treating combined transport and dispersion in one dimension. By suitable choice of certain parameters, they succeeded in markedly reducing both oscillation and numerical dispersion. However, a satisfactory extension to higher dimensions has not yet been found. Peaceman and Rachford3 presented a centered-in-time and centered-in-distance difference equation combined with a 1,transfer of overshoot" procedure which was demonstrated to work well in one dimension. The technique was applied to the two-dimensional miscible displacement problem, but subsequent calculations with zero dispersivity showed little change in results compared with the calculations they presented. This indicates that their method involved a numerical dispersion of the same order as the physical dispersion. The present paper describes an alternate method for solving the combined transport-dispersion

Jan 1, 1965

By E. B. Hunt

Paraffin deposition has been studied in the laboratory under conditions simulating deposition in well tubing. A theoretical analysis has been made of the cooling of the oil and the precipitation of paraffin from the oil as it flows up the well tubing and through surface flowlines. It is proposed that paraffin deposits are initiated by the precipitation of paraffin directly on or adjacent to the pipe wall and grow by diffusion of paraffin from solution to the deposit. This mechanism is consistent with laboratory and field observations, and has proved useful in the design and interpretation of laboratory paraffin-deposition tests. Tests have been made of the effect of plastic pipe coatings and chemical additives on paraffin deposition. INTRODUCTION Paraffin deposits which form in well tubing and surface flowlines interfere with production and must be removed. Over the years much progress has been made in developing and improving methods of removing these deposits after they form. Much less progress has been made in developing methods of preventing or inhibiting the formation of paraffin deposits. This is due, it is believed, to the lack of knowledge of the mechanism of paraffin deposition, the absence of satisfactory laboratory testing methods and the difficulties in evaluating the results of field tests of preventive treatments. The present investigation was undertaken to elucidate the mechanism of paraffin deposition and to develop suitable laboratory tests for studying the inhibition of paraffin deposition in well tubing and surface flowlines. Current theories on the mechanism of paraffin deposition have been evolved from field observations, from laboratory studies of various factors which might be involved in paraffin deposition, and from laboratory paraffin-deposition tests.1-9 Paraffin deposits have been formed in the laboratory by immersing a cold finger into a hot wax-oil solution and by flowing hot wax-oil solutions through cooled pipe or over cooled plates. These laboratory conditions differ in important features from field conditions, and the observed deposition behavior is not entirely field-like." Thus, there is reason to question the field applicability of the results of these tests. The present investigation was undertaken to determine how to perform and interpret laboratory paraffin-deposition tests to obtain information on the inhibition of deposition in the field. The paraffin problem in the broadest sense encompasses the formation of any predominantly organic deposit in well tubing, surface flowlines and other equipment in contact with crude oil or gas. The present investigation was limited to paraffin deposition involving the precipitation of paraffin wax from solution by cooling and its concentration in a deposit on a cooled surface. This probably excludes its applicability to those problems arising from asphaltic-base crudes, but not those arising from paraffin-or mixed-base crudes. This also excludes its applicability to emulsion and congealing oil problems which are often included as part of the paraffin problem. The phenomenon of cooling appears to be the controlling factor in paraffin deposition involving the precipitation of paraffin wax and its concentration in the deposit. Deposits of this type are usually found in the field only where cooling occurs. Early in this laboratory investigation, it was not found possible to form deposits under constant temperature conditions from a wax-oil slurry, either by steady flow through pipe or by gas-lift up a pipe. Thus, the investigation was limited to situations involving cooling. THEORY The relationships involved in establishing the temperature profiles in an oil stream as it flows up well tubing with a linear (geothermal) pipe-wall temperature distribution or through surface flowlines with essentially constant pipe-wall temperature are presented in the Appendix. The relationship between radial distance in the pipe and the rate of cooling of the oil is then combined with a relationship between cloud point and rate of cooling to develop the pattern of formation of a wax cloud in the oil. The following discussion of paraffin deposition under various laboratory and field conditions is based upon this development which is presented in the Appendix. PARAFFIN DEPOSITION IN SURFACE FLOWLINES The average temperature of the oil coming out of a well is somewhat higher than the ground temperature. Thus, the oil continues to cool on its trip through the surface flowline, and wax deposition can occur. The temperature distributions calculated from Eq. A-4 are given in Fig. 1. As can be seen, almost all the cooling occurs in the first 500 ft from the wellhead. In addition, the radial temperature gradient near the wall decreases rapidly with distance and becomes very small after a few hundred feet. Thus, growth of a paraffin deposit would be expected to decrease rapidly with distance from the wellhead and become negligible after a few hundred feet, since growth is dependent on concentration gradient. Wax precipitation and diffusion of wax to the already

By Joseph P. Hodgson

JOSEPH P. HODGSON.-As to ".Safety First," I did not deal with that, but I will say that in 1913, the number of .men killed was nine, and that year the "safety first" program was commenced; the next year, 1914, the number was reduced to five. In 1915, I am pleased to say that the number was reduced to two in the Copper Queen's entire property, and we have none so far this year. THE CHAIRMAN (G. F. G. HERMAN, Bisbee, Ariz.).-I can say, further, that we have from eight to nineteen men per month incapacitated for more than 14 days. Those are classified in this State as serious accidents. The number of men injured has apparently increased, -but that is clue to our improved method of recording and classifying accidents, no matter how slight. C. W. GOODALE, Butte, Mont.-The importance of cooperation among the members of the staff of an industrial organization is well brought out by Mr..Hodgson's paper.

Jan 12, 1916

By Y. L. Yao

It is suggested that the binary alloy systems of transition metals may be classified into groups according to "excess energy"E. For systems with positive ?E, the Laves phase, the TiNi3-, the TiCu3- and the Cudu-type rich in the smaller atom and the TizNi-type rich in the larger atom may exist. For systems with negative ?E and composed of two components of different crystal structures, the X, the Cr3O and the phase may exist on the side of the phase digrattz rich in the component with the higher "solubility factor" value am! the Cudu-type and the disordered hcp phase on the other side; if the crystal structure of two components is the same, the Cudu-type may exist on both sides. For systems with weakly positive ?E and cotnposed of different crystal structures, the u phase and the MgCd3-type may replace the Laves phase and the other types; the X, the Cr3O and the a phase may also exist. Finally, the equirnolar compounds of the CuAu- and the CsC1-type may exist irrespective of the sign of ?E. THERE are many factors which play a major role in the formation of binary intermediate phases in alloys, such as the crystal structure, the electronic structure, the atomic size and the electrochemical factor. To find the simultaneous effects of all these factors on the formation of intermediate phases of every metal would be a difficult task, especially because only a small fraction of experimental facts necessary for the complete formulation is known at present. Thus the past surveys of intermediate phases have been usually confined to few metals, several types of intermediate phases and some but not all controlling factors. In a previous paper1 the idea of "solubility factor" of metals was introduced. Although the suggested values are tentative and empirical, the formation of a continuous series of solid solutions in metals could be correlated with the interplay among the atomic size factor, the solubility factor and the crystal structure factor. The purpose of this paper is to demonstrate qualitatively the interplay of these factors in the formation of binary intermediate phases among transition metals. FACTORS CONSIDERED The Crystal Structure Factor. With rare earths excluded, the transition metals are classified into three common crystal structures listed in Table I. There is arbitrariness in the present classification of several allotropic elements. However, out of seventy-odd continuous solid solutions formed among transition metals, only six of them, namely, those

Jan 1, 1962

E. D. TILLYER,* Southbridge, Mass. (written discussion?).-It is quite generally known that there is very little that is standard about a mercurial thermometer at temperatures above 212° F. (100° C.) because so many precautions must be taken-precautions that are rarely realized in practice-such as depth of immersion, aging, elastic fatigue, separation of mercury column, and accidental deformation from very slight excess temperature. One cannot help wishing that Mr. Brown would dwell at greater length on the practical side of both radiation and optical pyrometey, both of which have great possibilities as commercial instruments. In the radiation pyrometer we have ideal conditions for a permanent instru-ment, no materials being exposed to excessive temperatures or subjected to contamination from the furnace fumes which may raise such havoc with an ordinary pyrometer. The development of a radiation pyrometer requires a thermocouple having a relatively high electromotive force but which need stand temperatures of only 200° F. or 300° F. instead of 1500 to 2000° F., which is required of even a base-metal couple. The galva-nometer, if located near the thermocouple, does not need to have a high resistance as at such low temperatures no changes can occur in the thermocouple that will affect its resistance and, consequently, the in-dicated temperature.

Jan 11, 1919

By Carl L. Renzoni

INTRODUCTION This paper defines equity as the issuance of a permanent interest in the business on a broadly distributed basis. As such, it excludes the issuance of equity to either a merchant bank or to another corporation. Nearly twenty years ago the equity markets were very simple: The instruments used were primarily common shares, convertible debentures or convertible preferred shares. Another equity-type option often used, especially by junior companies, was the sale of joint venture interests. Issue sizes were generally in the order of $25 - $100 million and issues were syndicated primarily in North America and Europe by one or two investment dealers. Mining corporations today benefit from a market with much more depth. Issues are syndicated by dealers on a truly international basis, and issue sizes now often range up to $300 million. Moreover, dealers are now willing to take significant risk in buying the issues for redistribution. This discussion of trends in equity markets will encompass: 1) common shares 2) warrants to buy common shares 3) convertible debentures 4) commodity backed instruments A review follows of events that affect the mining industry and investment dealers as they have a bearing on the equity markets for the metal producers. FACTORS AFFECTING THE MINING INDUSTRY The current business cycle, up to October 1987, had been characterised by a buoyant stock market and depressed base metal prices. Mining companies entered this period with weak balance sheets and little prospect of cash flows meeting capital needs. The issuance of equity and the sale of assets were used extensively to reduce debt to manageable levels. During this period, the relative high price for gold, and more important, the very high earnings and cash flow multiples afforded to gold producers, caused companies to target gold as the only game in town. The need for capital to acquire and develop gold properties prompted an unprecedented volume of equity issues. (Burns Fry led or co-managed over $1 billion of mining equity issues per year during this period). This high demand for equity capital by the industry prompted an increase in the use of equity instruments, such as commodity backed instruments. In addition, government tax incentive programs in Canada, such as flow-through shares, allowed smaller companies to raise significantly more equity than would otherwise have been possible. Over $1 billion in flow-through equity was raised in 1987 alone. The abundance of flow-through capital in Canada made it easy to form a new company. One flow-through share fund developed a system of providing the working capital required for a company to be eligible to receive flow-through share capital so that an entrepreneur required only a mining property to get started. Many new companies were formed and several flourished in a buoyant stock market environment to the point that market capitalizations grew to $100 million or more. The current period is in stark contrast to that before October 1987. The equity markets are generally available to the resource industry only on a window basis and only for senior companies and for special situations. The industry is benefitting from buoyant metal prices, and bankers are anxious to provide debt capital. Investment dealers previously processing several equity issues

Jan 1, 1990

The Arizona Committee, consisting of GERALD F. G. SHERMAN, Chairman, ARTHUR NOTMAN, Secretary, NORMAN CARMICHAEL, B. BRITTON GOTTSBERGER, W. L. CLARK, J. C. GREENWAY, W. G. MCBRIDE, FOREST RUTHERFORD, has arranged the following program for the Arizona Meeting, which has been approved by the President of the Institute and by the Executive Committee. It is printed herewith for the information of members, and probably will not be changed in any material respect. Sunday, September 17, 1916.-Arrive at El Paso, Texas, 2.40 P.M., leave 10.20 P.M. Monday, September 18, 1916.-Arrive at Deming, N. Mex., .12:47 A.M. Arrive at Santa Rita, N. Mex., 4.00 A.M., where luncheon will be served, after which there will be a visit to the Chino mines. From there the train will proceed to Hurley, N. Mex., where a visit will be made to the mill of the Chino Copper Co.

Jan 7, 1916

By John McCoy, Edward Thimons, Kenneth Heller

As the working levels in domestic mines are developed to greater depths and work areas move further from the shafts, maintaining a safe and healthful working environment becomes more difficult. Increased temperature and humidity at greater depths becomes first a factor in productivity and then a threat to the miner's safety. Initially, a miner might develop listlessness leading to reduced productivity and reduced alertness. Continued overexertion can lead to heat stroke and possibly death. Mine ventilation engineers, therefore, must not only provide clean air to work areas, but also must provide cooled air. The following article describes the United States Bureau of Mines (USBM) and Foster-Miller's successful development of a high performance, low maintenance direct water to air contact heat exchanger for mine cooling. While heat problems frequently do not develop until mining operations descend below sea level, problems will arise any time mining penetrates high temperature rock. Hot fissure water will increase the severity of the situation, causing increases in wet bulb temperature - the temperature to which perspiring miners reject metabolic body heat. All energy expended in mining adds to the heat load which must be absorbed by the ventilation air. Just when the cooling capacity of ventilation air is needed most, adiabatic compression (autocompression) of air descending the shaft raises air temperatures 1.3g°C (2.5'F) to 2.94"C (5.3OF)/305m (1000 ft) depending on humidity. Increased temperatures decrease the ability of the air to absorb heat from the mine, and work area temperatures rise. Once forced ventilation air can no longer maintain safe work area temperatures, refrigeration methods must be employed. Many mines now use cooling coils for this purpose. A cooling coil uses refrigerated mine water to cool the air by passing the air through banks of copper tubing filled with cold water. Heat from the air is transferred to the water through the pipe with the aid of fins. Conventional water to air heat exchangers prove troublesome for many mines be- cause of the high levels of dust that are encountered, causing these exchangers to operate at relatively low efficiencies. A more satisfactory approach to work- place cooling is desired - one that offers reduced maintenance and increased cooling efficiency.

Jan 1, 1982

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members.) Members and guests who registered at Institute headquarters during the period Nov. 10 to Dec. 10, 1915: F. Lynwood Garrison, Philadelphia, Pa. E. Fleming l'engle, Costa Rico, C. A. William J. Lakeland, Burma, India. Fred Maccoy, El Oro, Mexico. Dwight E. Woodbridge, Duluth, Minn. 0. N. Scott, Toronto, Ont., Canada. Chester A. Fulton, Yonkers, N. Y. K. P. Swenson, Tokyo, Japan. Willet G. Miller, Toronto, Canada. - H. L. Mead, New York, N. Y. L. G. Huntley, Pittsburgh, Pa. E. DeGolyer, Norman, Okla. L. E. Howard, Lockport, N. Y. J. S. Lane, New York, N. Y. H. W. DuBois, Philadelphia, Pa. T. V. Nonactre, Argentina. Howard R. Stewart, London, England. N. H. Darton, of the U. S. Geological Survey, has returned to Washington after a long season of field work in New Mexico investigating the prospects of finding potash deposits in the Red beds.

Jan 1, 1916