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By H. M. Howe

It has seemed to the writer that one important, and indeed sufficient reason, for our slow progress in learning the relation between the chemical composition and the physical properties of cast-iron, has been that the problem has not been attacked properly. It would be well to select the most probable working hypothesis which we can find, and proceed to test that hypothesis by comparison with observed facts, and by making new observations specially designed for such a test. Our first step, then, is to select the most probable working hypothesis ; and to attempt this selection, to state the hypothesis and its immediate corollaries, and to take some first steps toward testing it, is the object of the present paper. Its chief purpose is to bring the hypothesis to the attention of those who are more familiar with the evidence than the writer can pretend to be, and in a better position both to present new evidence and to discuss it. The hypothesis here selected is, that composition governs properties in the case of cast-iron, in the same general way and for the same reasons as in the case of steel, mutatis mutandis. This hypothesis, which of course makes no claim to originality, certainly seems reasonable and probable; its exposition and discussion are made easy by our existing knowledge of the constitution of normal or " carbon " steel; it therefore seems worthy of consideration.

Jan 1, 1902

By J. Burns Read, Charles H. Fulton

A previous article1 by the authors contained a general description of the new roasting furnace herein described but it did not go into detail as to the metallurgical behavior or the results obtained. Believing that such information would be of great value, they have elaborated on the subject and have given many unpublished details. The furnace described applies the principle of roasting finely divided zinc-sulfide ores, now produced in large quantity by the flotation process, in gaseous suspension; that is, the ore particles are carried, in suspension, in a current of air and gaseous products of the roast. The relatively great fineness of flotation concentrate presents difficulties and problems of roasting in furnaces of the ordinary type; the fine ore is forwarded through the furnace in the form of a shallow bed and its very fineness leads to dense impervious bedding which prevents oxygen from reaching the interior of the bed, thus unduly lengthening the time of roasting and preventing the elimination of the last of the sulfur. The fineness of the concentrate, normally, should lead to a rapid and complete roast, for the speed of roasting is a function of the surface exposed to oxygen, which surface is greatest, per unit of weight, in very fine material. The difficulty in bed roasting is to get the oxygen to the particle. If the fine ore, during the roasting, could be freely suspended in oxidizing gases, full advantage could be taken of the great surface conferred by its fineness. This fundamental idea, of course, is not new, for the Stedtefelt furnace, familiar to the older metallurgists, is an example of it; but the manner in which this is accomplished may be new. The numerous efforts to roast in gaseous suspension show that the idea is attractive; in fact, an analysis would indicate that it is the most reason-

Jan 1, 1925

By W. E. Ruder

IT has been pointed out by Stead 1 that grains of considerable coarseness may be developed in steels containing from 3 to 5 per cent. of silicon, and in a previous paper 2 the present author has shown that under the proper conditions of annealing single grains having an area of 50 sq. cm. may be obtained. It is the purpose of this paper to discuss in more detail the conditions, promoting the growth of these grains, in the hope that the experiments described may throw some additional light upon the general problem of grain growth in metals. These silicon steels lend themselves particularly well to such experiments because of the ease with which the change in structure may be followed and because of the fact that the effect of the carbon present is largely obliterated by the high percentage of silicon. This forms a solid solution with the iron, which acts very much like a pure metal. This alloy has been found to have but one critical point, viz., Are. This point, determined by Roberts-Austen for Hadfield's 4 per cent. Si alloy, was found to lie at 703° C. Vigouroux3, in working with pure Fe-Si alloys, finds this point to rise from 750° C. for 0.5 per cent. Si to 860° for 6 per cent alloy, with a flat region in the curve from 3 to 4 per cent. Si. No accurate determination of this point has been undertaken by the present author, but it has been roughly determined to lie between 730° and 750°.

Jan 12, 1913

By G. R. Mansfield

THE third year of Government exploration f or potash by the U. S. Geological Survey and-the U. S. Bureau of Mines under the authorization of the act approved June 25, 1926 (Public 424-69th Cong.) is drawing to a close. The results thus far obtained are thought to be sufficiently interesting and satisfactory to justify the presentation of a brief preliminary account of the work. REVIEW OF EARLIER EXPLORATION The general geologic similarity of the Permian basin of Texas and New Mexico to the potash field of Germany had long ago suggested the possibility of the presence of potash salts somewhere in that basin, but petroleum exploration was then making little headway there and the necessary data could not be obtained. The discovery by Udden in 1912 of potash in brine from the Spur well in Dickens County, Texas, was the first direct evidence of its presence. In 1915-17 the U. S. Geological Survey drilled a test well with standard tools at Cliff side near Amarillo, but failed to find potash. Nevertheless, an observer has been kept in the field, at first in cooperation with the Texas Bureau of Economic Geology but since 1922 by the Survey alone, to `secure data and samples from oil and gas tests. Since the discovery of oil in Reagan County in 1923 exploration by drilling has been rapidly extended to many parts of western Texas and southeastern New Mexico. The identification of the potash-bearing mineral polyhalite was first announced by the Geological Survey in June, 1921, the material having come from cuttings from the Bryant well in Midland County and the Burns well in Dawson County, Texas. Successive discoveries and announcements of similar purport aroused widespread interest in potash exploration, which culminated in the action by Congress already noted.

Jan 1, 1929

Further discussion of the paper of JAMES JOHNSTON, presented at the New York meeting, February,. 1914, and printed in Bulletin No. 85, January, 1914, pp. 107 to 133. See also Bulletin No. 91, July, 1914, pp. 1473 to 1496. THOMAS CROWE,* Victor, Colo.-The interest manifested of late in the treatment of low-grade ores, together with Mr. Clevenger's discussion of the Mill and Metallurgical Practice of the Nipissing Mining Co., prompts me to acid a few remarks relative to concentration in connection with cyanide treatment of low-grade ores. Mr. Clevenger in this discussion does not condemn concentration in this connection, but, nevertheless, the tone of his remarks would lead one to believe that his conclusions are like those of many others: that concentration is often turned to as a last resort in an attempt to improve or obtain an extraction upon an ore by the recovery and sale of the refractory portion of the ore. This, I will attempt to point out, is not always the case. Concentration in connection with cyanidation often performs an entirely different function, i.e., one of saving fine grinding. Economy being the keynote of successful treatment of low-grade ores, the problem often becomes more commercial than metallurgical, and, as there is generally a definite ratio existing between cost of operation, degree of comminution, and percentage of extraction, the grade of ore under treatment usually imposes a limit upon these factors. With many ores grinding is the most expensive single item in their treatment; therefore, the degree of comminution is very apt to be governed by the allowable cost of operation. With most ores the degree of comminution controls to a great extent the percentage of extraction. So in the treatment of low-grade ore it often becomes necessary to sacrifice extraction, through coarse grinding for the benefit of cost, in order that the greatest ultimate profit may be obtained, and it is under these conditions that it is, possible for concentration to play an important part in overcoming to some extent the effect of mesh. The precious metals occurring in an ore are usually closely associated with the metallic portion of the ore, and as this metallic portion is generally fairly well liberated from the gangue at comparatively coarse meshes, further grinding of the ore is necessary only in order that the metallic portion may be reduced sufficiently fine that the precious metal part of it may be dissolved by cyanide solutions in a reasonable length of time.

Jan 11, 1914

By J. J. Crowe, G. K. Burgess

PAGE, Theories of Allotropy of Iron........... 667 Previous Determinations of A2 and A3 in Iron........ 668 Critical Ranges as Determined by Expansion........ 669 Critical Ranges by Thermoelectric Observations........ Critical Ranges in Terms of Crystalline Structure....... 670 Critical Ranges as Detected by Mechanical Methods...... 670 Critical Ranges as Given by Electrical Resistance....... 670 Critical Ranges as Determined Magnetically........ 671 Critical Ranges as Determined Calorimetrically....... 673 Critical Ranges from Heating and Cooling Curves....... 673 Summary of Previous Determinations of A3 and A2 in Pure Iron.... 675 The Present Investigation............ 678 The Experimental Method........... 678 Arrangement of the Apparatus.......... 679 The Measurements of Temperaturc.......... 679 The Measurement of Time........... 679 The Thermocouples............ 681 Temperature Scale and Calibration of Thermocouples...... 681 Mounting of Thermocouples........... 682 The Differential Measurements.......... 682 The Furnace and Accessories........... 682 The Vacuum Pump............ 683 The Energy Supply............683 The Rheostat.............. 683 The Materials Investigated............ 685 Sources of Iron............. 685 Preparation and Description of Samples......... 685 Chemical Analyses............. 687 The Experimental Data............. 688 The Preliminary Observations.......... 688 The Definite Series............691 Description of the Plotted Curves........... 694 The Effect of Plotting at Different Intervals........ 694 The Curves of the Definite Series.......... 695 . The Curves of the Preliminary Series......... The Existence of Other Critical Ranges......... 696 The Microscopical Examination........... 697 Summary and Conclusions............ 698 Bibliography............... 701 Plates................ 704

Jan 1, 1914

By K. P. Gupta, P. A. Beck, N. S. Rajan

By determining the a phase boundaries in the following ternary systems: V-Fe-Si (at 1175oC), V-Co-Si (at 1175°C), V-Ni-Si (at 1175oC), Cr-Mn-Si (at 1000°C), Cr-Co-Si (at 1175°C), Cr-Ni-Si (at 1175°C), V-Fe-A1 (at 1175°C) and Cr-Co-A1 (at 1175°C), it was found that Si exerts a stabilizing effect on these a phases, while A1 tends to destabilize them. Si atoms in solid solution occupy sites D in the a structure, The co/ao ratio increases with increasing Si-, Mn- or Fe-content. The volume of the unit cell decreases with increasing Si-content. THE stabilization of certain metal silicides (the Nowotny phases) by the addition of relatively small

Jan 1, 1961

By C. M. Schwartz, A. E. Austin, W. B. Wilson

High-temperature X-ray diffraction studies were conducted with Th-U alloys with up to 10 wt pet U. The solid solubility of uranium in thorium as a function of temperature was determined by the method of lattice parameters. Thorium will dissolve up to 2.5 wt pet U at 950°, 4.5 wt pet U at 1150°, and 7.5 wt pet U at 1250°C. Determinations were made of the temperature of the transition of thorium and of the effect of uranium upon the transition. The a to ß transition for thorium was observed to occur at 1330' ±20°C. Mean coefficients of expansion were calculated for thorium and two alloys, and for ThO2 in contact with the thorium, using X-ray lattice-parameter data. Values obtained at 950° C for thorium and Tho2 were 12.1 and 9.40 X 10-6 per OC, respectively. Impurities obtained during the X-ray exposure were identified by diffraction and were essentially Tho2 and ThC, with two additional unknown phases being detected. The effect of the impurities upon the results is discussed. DIRECT investigation (i.e., high-temperature X-ray diffraction studies) of the phase diagram of thorium-rich uranium alloys has been shown to be necessary since recent work1 - has disclosed the presence of an allotropic transformation near 1400°C in pure thorium with the room temperature face-centered-cubic phase transforming to a body-cen-tered-cubic structure at the elevated temperature. The effect upon the transition of the addition of uranium to thorium and of the solubility of uranium in thorium at high temperatures remained unknown, yet was of interest in understanding fabrication procedures and elevated temperature use. The present work was undertaken to provide information in this area by determining the transition temperature, the effect of uranium on the transition temperature, and the solubility of uranium in thorium as a function of temperature. Experimental Work The high-temperature diffraction data were obtained using a camera especially designed for the purpose3 and capable of reaching temperatures in excess of 2000°C at pressures as low as 1 x 10." mm Hg. Temperature regulation was provided by regulating the power input to ±0.1 pet variation, and by regulating the water flow through the camera jacket to provide a constant thermal load. The X-ray sample was a rod nominally 80 mil diam, which was further turned down to 20 mil and then etched to 18 mil over 1/2 in. of one end. This was placed in the sample holder and mounted on the camera so that the smaller part was surrounded by a cylindrical tantalum-sheet radiation-type heating element. Diffraction from the sample was recorded on film after passing through a slot in the heating element and radiation-baffle shield and through beryllium vacuum windows. The X-ray film mounting was of the Straumanis type4 with a camera diameter of 114.59 mm. Since previous work of Chiotti' indicated that impurities considerably alter the transition temperature, chemical analysis of the arc melted iodide crystal-bar thorium samples was obtained prior to testing. The analysis disclosed the material to contain as low as 0.001 ±0,0002 wt pet H and 0.007 ±0.001 wt pet 0. Carbon was 0.003 wt pet and nitrogen less than 0.002 wt pet. This material was sealed in mild steel in an inert atmosphere and subsequently hot rolled to 3/8-in. diam rods at a temperature of 732°C. Following removal of the jacket, the material was pickled and cold swaged to 1/8-in. rods, from which the diffraction samples were prepared. The alloys were similarly prepared, with the uranium being added during arc melting. The uranium analyses of the alloys prepared appear in Table I. The experimental procedure for diffraction examination of the three samples of high-purity thorium differed from those of the Th-U alloys. The original practice, later modified, consisted of pumping down the camera with the diffusion pump on and then admitting liquid nitrogen to the cold trap of the system. This was modified for the Th-U alloys by maintaining liquid nitrogen in the cold trap at all times before and while the diffusion pump was heated. This minor change produced a reduction in the amount of carbon pickup by the sample during exposure to the diffusion-pump vapors. The sample was brought to the desired test temperature and exposed for 21/2 hr at pressures which were usually 2 x 10-6 mm Hg, or lower. Exposures were made at

Jan 1, 1959

By R. E. H. Pomeroy

The statistical data given in this paper are taken from the actual performance of the No. 2 reverberatory furnace of the Nevada Consolidated Copper Co., Mc Gill, Nev., for a period of four months, from April to July, 1914. The principal furnace dimensions are: Length, 132 ft. % in. at the skim-line level; average width, 18 ft., 10 in. at the skim-line level. The roof is 7 ft. above the skim-line level at the firing end. The average area in the uptake flue is 36 sq. ft., and the area above the skim line under the vulcatory arch is 24.3 sq. ft. Fig. 1 shows a diagrammatic plan and sectional elevation of this furnace. The furnace is equipped with two 400-b.h.p. Stirling waste-heat boilers set in parallel. California crude petroleum is used for fuel and has a specific gravity of 16.5" B., flashing in open test at 199" F. The oil is heated to about 200" F. in a steam heater before going to the burners, requiring about 9 b.h.p. per furnace day to heat it from the line temperature to the burning temperature. Measurement is made by oil meter, checked daily by reservoir readings. The oil is fed by gravity (34 Ib. static pressure) to seven low-pressure blast burners of the Steptoe type (Fig. 2). The blast for these burners is supplied at about 40-08. pressure by a motor-driven Connersville blower of 42 cu. ft. capacity per revolution. The air supplied by the blower through the burners for atomizing the oil amounts to about 10 per cent. of the theoretical air necessary for complete combustion of the oil. The remainder of the necessary air enters the furnace through the burner openings in the firing wall. No checker holes are provided, and the charge holes in the roof are equipped with slide gates and " dog houses" to minimize air leakages. The combustion of the fuel, as shown by gas analysis at the front of the furnace, is practically complete, the carbon monoxide in the gases being less than 0.5 per cent. The draft at the firing end of the furnace is 0.18 in. of water. At the throat or in the uptake above the "verb" the draft is about 1 in.

Jan 1, 1915

By Charles W. Dickson

CONTENTS. [ ] I.THE RELATION OF NICKEL TO PYRRHOTITE. Introduction. The Sudbury district is to-day one of the two great sources of nickel in the world. The peculiar geological relations of

Jan 1, 1913

By George W. Toth

This paper describes the features of a computer cost model developed to estimate requirements and costs of individual coal mining projects. Detailed cost analysis procedures for both coal mining and preparation are incorporated into the model. This model has been developed over a period of seven years through funding provided by the Electric Power Research Institute (EPRI). The model follows a process engineering approach for the estimation of all project capital and operating costs. A discounted cash flow analysis procedure is also designed into the model to allow for the solution of cost/ton or cost/MMBtu of clean coal production. The model can be applied to most surface or underground mining deposits and can accommodate a wide variety of coal washing situations. This flexibility makes the model a particularly useful tool for preliminary project analysis, property screening, investment analysis, mining technology assessment, coal cleaning level assessment, and general property valuation.

Jan 1, 1983

By Nicholas J. Grant, Oliver Preston

PUBLICATION of data by Irmann' indicating outstanding thermal stability and elevated-temperature strength properties in a sintered aluminum powder product (SAP) stimulated interest in the strengthening of metals by means of a highly dispersed oxide phase. This material was produced by compacting, sintering and extruding a fine flake aluminum powder, resulting in a dense product containing 10 to 16 volume pct alumina, which arises from the thin oxide film on the starting powder, highly dispersed in a matrix of pure aluminum. The method of producing SAP, and the stable high-temperature properties obtained from it, introduced the possibility of developing superior materials for high-temperature service by powder metallurgy methods. The composition of the materials of this type which are presently under consideration is predominantly metallic, containing from less than 1 pct up to about 20 volume pct of the oxide. As a result, other properties of these materials, such as electrical and thermal conductivity, thermal shock resistance, and to a certain extent ductility, notch sensitivity, machinability and hot working properties, are also predominantly metallic. These alloys do not constitute, therefore, a completely new class of materials as do the cermets, but rather present a new means of modifying the properties of a metallic matrix. In this sense, SAP type alloys are more closely analogous to the alloy aging systems. While the strength properties realized in the oxide-pure metal systems at the lower temperatures are substantially less than the best attainable in the aging systems, the thermal instabilities in the latter make them of less value for use at temperature much above their optimum aging temperatures, as indicated in Fig. 1. While the means of obtaining an oxide dispersion are more difficult and costly than conventional aging processes, in the light of the as yet limited understanding of such systems there is considerable promise of improved high temperature properties arising from the thermal stability of these structures. Since the development of SAP in 1946, its properties and the properties of a series of similarAl,O,-A1 products containing from about 1 to 20 pct aluminum oxide have been fairly extensively studied and reported.'- "articular attention has been given to

Jan 1, 1958

By M. C. Fuerstenau, J. D. Miller

The response of calcite to flotation with saturated fatty acids and alkyl sulfonates of various chain lengths is presented. The amount of collector re-quired for flotation is shown to decrease systemati-cally with increasing carbon content from 8 to 12-carbon atoms per molecule. This systematic flotation response is correlated with the solubilities of the calcium-collector salts, which were established with a nephelometer. The 14-carbon collectors deviate from this systematic behavior, and no flotation is possible with the 16-carbon homologs. As determined by infrared analysis, the mechanism of collector adsorption involves a specific chemical reaction be-tween the collector and the surface. A reaction of the form CaCO3(s)+ 2 RCOO"=*=Ca(RCOO)2(s) + C03= is suggested. The pH of the system is also shown to be a most important parameter as it controls the carbonate, calcium, and collector ion concentrations in solution and thus controls flotation response. The importance of hydrocarbon chain length of collectors was recognized early, and various studies have been made on this aspect of flotation. Wilkinson, ' for example, noted that as the chain length of alkyl xanthates is increased, the amount of collector required for flotation of sphalerite is decreased. The same effect has been shown in the flotation of galena.2 Similar results were obtained when malachite3 and calcite4 were floated with various fatty acids. DeBruyn5 has shown that a similar phenomenon occurs when quartz is floated with amines at constant pH. Recently, Fuerstenau, Healy, and Somasundaran6 correlated this phenomenon with the van der Waals cohesive free energy of association of the hydrocarbon chains. It seems unlikely, however, that chain association could be involved in the sulfide and carbonate systems with the collector additions employed, especially with the short-chain xanthates. Rather, it would seem that the decrease in collector concentration with increase in chain length noted for flotation is related to the solubility of the metal-collector salt. The purpose of this investigation is to verify this premise and also quantify this phenomenon if possible. Calcite was selected for study with both alkyl sulfonates and saturated fatty acids as collectors. EXPERIMENTAL MATERIALS AND METHODS The collectors used in this investigation ranged from 8 through 14 carbon atoms per molecule. The fatty acids had a reported purity of greater than 99%. The sodium alkyl sulfonates were provided by the Marathon Oil Cot, Littleton, Colorado, and had the

Jan 1, 1968

THE primary interest in the subject of this chapter lies in the fact that various heats of steel made to the same chemical specification do not always have the same properties. The properties considered here, of course, are those inherent in the ingot immediately after solidification and not qualities imparted by variations in subsequent mechanical or thermal treatment. The expression "made to the same chemical specification" is used because some of the variations in properties are due to variations in chemical analysis within the specified ranges of those elements commonly specified and determined. Other variations in properties are due to variations in those constituents of steel (elements or compounds) that are not ordinarily included among the elements specified, thus not a part of the specified "composition." The term "constitution" is used to include not only the specified composition but also the nature and distribution of every element or compound contained in the steel entering the ingot mold ; also included are items such as aluminum oxides and nitrides, presence of soluble gases, and dispersion of nonmetallic particles. When it is considered that the constitution of steel is determined by the addition or absorption into the bath of all such constituents from whatever source, it follows that constitution is of necessity the final result of steelmaking practice. It is the agency through which steelmaking practice operates to control the properties of the steel. The term steelmaking practice is here used in the broad sense, meaning the control of all the materials entering the steel and of the conditions under which the process is carried out. Steelmaking practice, thus defined, establishes the chemical system within which the reactions between components must proceed in obedience to the laws of chemistry. Thus the chemical constitution of the steel is established and, through constitution, the properties of the metal are established. In the preceding chapters it has been shown how the constitu-

Jan 1, 1964

By P. A. C. Wilson

Instantaneous outbursts of carbon dioxide in coal mines have occurred in Germany only in one part of the Waldenburg-Neurode mining district.' This mining region comprises the northeastern fold of the "Innersudetian" coal basin. The basin (Fig. 1) is in the form of a geologic trough approximately 60 km. (37 miles) long and 30 to 35 km. (19 to 22 miles) broad and is enclosed on three sides by ancient truncated mountain ranges—the Riesengebirge, the Bober-Katzbachgebirge and the Eulenge-birge. Only the southeastern part of the trough is not enclosed by mountains of older rock formation. The floor of the basin before the building up of the coal measures was formed on the western, northwestern and northeastern borders by the material from Archean rocks (gneiss and mica schists); in the northern part over this was deposited the Silurian formation. The carboniferous period is represented both by the Lower ("kulm") and Upper Carboniferous, with an unconformity between the stages; that is, the kulm was tilted up and partly eroded before the Upper Carboniferous was deposited. The kulm is a salt-water formation (with marine fauna) but Upper Carboniferous rocks are nonsaline water deposits, with fresh-water flora only. The Lower Silesian coal measures were thus formed in a lime basin fed by the running water coming down from the mountains. As already indicated, the bottom series of the Upper Carboniferous formation, termed "Waldenburg strata" were laid down unconformably on the Lower Carboniferous. Over the Waldenburg strata there are the "Weisstein strata," an intermediate barren stage without coal beds, 400 to 500 m. (1300 to 1600 ft.) thick. Another unconformity followed, which is overlain by the '(Saarbrucken" series, which contain the upper coal measures, and the ('Ottweil" strata. In the last named, it is only on the southwestern fold that beds of coal are developed.

Jan 1, 1931

By William Phillips

THE earliest mention of the sulphur deposits in what is now Culberson County, Texas, seems to be contained in "Explorations and Surveys for a Railroad Route from the Mississippi River to the Pacific Ocean, United States War Department, 1853-54." Captain John Pope (he was not commissioned Captain until 1856) had charge of one of the divisions of the Survey. In his report on the geology of the route, William P. Blake noted the analysis of a greenish earthy powder from the bed of Delaware Creek, at the springs, which contained 18.28 per cent. of free sulphur. The report states: "From the chemical examination of the waters of the spring, by Dr. Booth, it appears that chloride of sodium is the principal solid ingredient, but considerable quantities of sulphide of sodium are present. * * * * * The waters from the springs examined by Dr. Booth were alkaline, but it is possible that some of the springs are acid; and in this case the precipitation of sulphur would ensue on the mixture of the acid waters with those charged with alkaline sulphurets and the origin of the deposits of sulphur would he thus explained." This is the first reference to the existence of sulphur in that region, the first mention of the character of the water found there and the first suggestion as to the' origin of the deposits. The possibility of the existence of acid waters was confirmed by E. M. Skeats, nearly 50 years later.1 In this publication, Skeats says that the water from the sulphur deposits in Section 11, Block 114,, Township 5, contains 79.08 grains of free sulphuric acid per gallon. This locality is about 13 miles (21 km.) south of Delaware Creek and about 35-miles (56 km.) east of the Delaware Springs. The next published reference to the existence of sulphur in Trans-Pecos Texas is in the First. Annual Report of the Geological Survey of Texas, 1889, page 226, where W. H. von Streeruwitz mentions that sulphur is found in that region, but gives no further information. In the

Jan 9, 1917

By J. E. McDonald, J. G. Eberhart

A model is discussed from which the work of adhcslon .tor liquid transition metals on aluminum oxide surfaces can he calculated, A close-packed (00011 oxygen surface on A12O3 is assumed with two different types of surface sites: one type involving metal-oxygen bonds and the other man der Waals into actions. The work of adhesion is thus expressed as the sum of these two bonsding free energies. Calculated works of adhesion for nickel, titanium, chromium, and zirconium on sapphire agree well with the experimentally determined quantities. The model is extentled to the calculation of the work of adhesion and shear stress required to remove a thin metal film from a sapphire substrate and is in good agreement with experimental values. The obsewed dependence of the work of adhesion on the free energy of oxide formation of the metal is shown to also provide an interpretation of the tittle dependence of thin-film adhesion. THIS paper presents a model for the type of bonding which occurs across a metal-A12O3 interface. The model is used to explain the results of two types of experiments in which such an interface exists: 1) the adhesion of thin metal films on Al2O3 substrates and 2) the wetting of A12O3 by liquid metal drops. The adhesion of thin films to various substrates has been the subject of a variety of investigations.'-' Benjamin and weaver3 and Bowie,6 using the scratch test developed by Heavens,10 studied the adhesion of metallic films to glass substrates. Their observations for noble-metal film adhesion agree well with an adhesion model involving a van der Waals type of bonding between the film and the substrate. For films of metals whose free energy of oxide formation. ?F°f, has a negative value. Benjamin and weaver3 and Bowie6 found a time-dependent adhesion with an initial value that can be interpreted in terms of van der Waals interactions but a larger terminal value which was related to ?F°f, Karnow-sky and Estill7 deposited films on sapphire at elevated temperatures and noticed no time dependence of film adhesion but a similar correlation with ?F°f. Because of the kinetic problems associated with thin-film adhesion it is desirable to examine adhesion in an equilibrium system. The wetting behavior of liquid-metal drops on Al2O3 provides such a system. Systems of this metal-ceramic type have been studied extensively.11 Humenik and Kingeryl2 have measured the wetting of A12O3 (and other substrates) by several metals and have pointed out that the wetting ability of these metals increases with increasing values of -?F°f. It is thus seen that thin-film adhesion and metal wetting on A12O3 are both related to the tendency of the metal to react with the surface oxide ions of the Al2O3 substrate and, because of this, both phenomena should be explainable by an appropriate model for the metal-Al2O3 interfacial bonding. In the sections that follow, wetting and adhesion data on A2O3 are reviewed and a model is presented by which these phenomena can be interpreted. ANALYSIS OF WETTING EXPERIMENTS In an equilibrium system involving a liquid-metal drop on a solid Al2O3 substrate, the work of adhesion, WAD, is defined by the Dupre, equation as WAD = ?s + ?L -?sL [1] where ?s and ?L are the surface free energies of the solid substrate and the liquid drop, respectively, and ?sL is the interfacial free energy. The work of adhesion is the work required to separate a unit area of the solid-liquid interface into two surfaces. The work of adhesion is usually determined from a sessile-drop experiment in which yL and the contact angle, ?, are measured. The Young-Dupr6 equation is then used to calculate WAD Wad = ?L (1+ cos ?) [2] The literature of this subject has been examined and Table I shows work of adhesion data for various liquid metals as measured on A12O3 substrates. The standard free energy of oxide formation of the metal at the temperature of the wetting experiment, ?F°f . is also tabulated in kcal per g-atom of oxygen. The data is grouped according to the gaseous atmos-

Jan 1, 1965

Shoemaker: We've all heard a lot about epoxy liner backings. This brings up the question-do zinc furnaces still have a place in a new plant? Meaders: I would, you must understand, be prejudiced in this question because we introduced epoxy backing into the industry. Naturally, we wouldn't have done so if we didn't think it should be done. With that background maybe I could give a little more information on this particular subject than some of the others, because we now have been in this business for some three or four years.

Jan 11, 1967

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 Charles N. Bell

The Telluride mining district of southwestern Colorado is defined by the 37" 45' and 38" parallels of latitude and 107" 45' and 108" meridians of longitude. Telluride was never a boom camp, but has had a steady growth. In recent years, notwithstanding the business depression of 1920, the business has been the same as in normal years. The first prospector is said to have appeared in 1875, in which year locations on the Smuggler vein were made. Shipments were made in 1877 and 1878, and in 1879 milling the ores was attempted. While the district produced high-grade ores, it did not become important until 1890, when the Rio Grande Southern R. R. was completed from Ridgway to Telluride. The railroad has since been extended to Durango. In the fall of 1896, 400 stamps were in operation, and the annual production was $3,000,000.00, two-thirds of which was gold. The total production from 1875 to 1923 was: gold $58,274,527; silver 41,-830,920 oz., valued at $31,016,893; copper 15,258,866 lb., valued at $2,533,291; lead 166,056,484 Ib., valued at $8,324,910; zinc 18,141,182 Ib. valued at $1,323,787; or a total production of $101,473,408. All claims are held in fee. Most of them are 1500 by 300 ft. but claims located within the last few years are 1500 by 600 ft. General supplies are obtained at Telluride, Denver, and Salt Lake. The largest mines are within 6 miles of the town of Telluride. Denver is 422 miles and Salt Lake is 439 miles, by rail, from Telluride. One-half of the distance to Denver and one-sixth of the distance from Telluride to Salt Lake is by narrow-gage railroad. The labor is efficient. The best miners are Italians and Austrians, then Slavs, Greeks, and Mexicans follow in the order mentioned. There are no labor unions. There are no serious mine pumping problems, the drainage being through adits. The Tomboy and Smuggler companies pump water from their reservoirs, the former for milling and domestic purposes and the latter for milling, power, and domestic purposes. BIBLIOGRAPHY A partial bibliography of the Telluride District is: Geologic Atlas Telluride No. 57; Preliminary Report on the Mining Industries of the

Jan 1, 1925