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By F. E. Turton

THE town of Rancagua, at the junction of the state and Braden Copper Co. railroads, is located 82 km south of Santiago, the capital of Chile. From Rancagua 70 km to the east, situated in the Andes at an elevation of 7000 ft, is the town of Sewell, the location of a millsite. Two and one half km east of Sewell by underground railroad at an elevation of 7500 to 10,000 ft is the Teniente ore-body. The history of El Teniente dates from the eighteenth century, when according to legend a Spanish lieutenant, or teniente, a fugitive from justice, escaped to the Andes and camped at what afterwards became known as the Mineral El Teniente. This man reputedly discovered a vein of high grade copper ore. The first official records date from 1819, when some exploitation was begun, and continue until 1870. The orebody was large and of relatively low grade and was beyond the capabilities of the small groups attempting to operate it. No effort was made to erect a concentrator until William Braden became interested in the property. In 1901 Mr. Braden promoted the necessary capital for the first practical exploitation of the ore-body. Barton Sewell and E. W. Nash, both of the

Jan 1, 1953

By John H. Walthall, Raymond L. Copson, Travis P. Hignett

In October 1942, the War Production Board requested the Tennessee Valley Authority to undertake investigations to determine the feasibility of producing alumina suitable for reduction in aluminum cells, from clays and other domestic materials, by a lime-sintering, soda-ash leaching process. The work was undertaken by the chemical engineering staff of the Authority under the general direction of the War Metallurgy Committee of the National Academy of Sciences. The investigation included small-scale tests to determine the most suitable conditions for the process, and construction and operation of a pilot plant to obtain data for evaluation of the process and for design of a plant. The results of this investigation are described in the present paper. Sources of Alumina Alumina for the commercial production of aluminum is obtained from bauxite by the Bayer process. The tremendous demand for aluminum for wartime uses is causing rapid exhaustion of the high-grade bauxite deposits in the United States. On the other hand, there is an abundance of aluminous materials such as clay and lower grades of bauxite, which are not suitable for treatment by the Bayer process because of their high silica content. The Tennessee Valley Authority has conducted research and pilot-plant work for more than 5 years on methods for the production of alumina from clay and low-grade bauxite. Particular attention has been given to the high-grade white kaolin found in Carroll County, Tennessee. Exploratory drilling has demonstrated that at least 4 1/2 million tons of kaolin containing in excess of 34 per cent AlzOI is available in this area by strip-mining methods. It has been estimated that hundreds of millions of tons of clay of similar quality occur in the Tennessee Valley region. The Process The process is illustrated in the flowsheet (Fig. I), and consists essentially of the following steps: I. Heating a mixture of clay and limestone to form a sinter containing calcium aluminate and dicalcium silicate. z. Leaching this sinter with a dilute sodium carbonate solution, to form a sodium aluminate solution and a calcium carbonate, calcium silicate residue, which is discarded. 3. Treating the sodium aluminate solution with carbon dioxide to precipitate aluminum trihydrate and regenerate the sodium carbonate solution, which is recycled. 4. Heating the aluminum trihydrate to produce alumina. The process was considered promising because of the abundance and cheapness of the two raw materials, clay and limestone; and because, as compared with an acid process, smaller amounts of critical

Jan 1, 1944

By Charles Barrett

THE copper-silver system presents several points of special interest in the study of segregate structures. The system is simple eutectic, with limited solid solutions terminal with the pure component metals. The extent of solid solubility decreases with decreasing temperature for both the copper-rich and the silver-rich alloys, thus offering a possi-bility for the formation of Widmanstätten figures and also a possibility for aging after quenching. In contrast to the structures studied previ-ously the structures in this system are unique in their; origin, for one terminal solid solution will precipitate the other, and ice versa. In most of the other systems for which crystallographic data on the precipi-tation (or transformation) process are available, either intermetallic compounds or intermediate phases partake in the decomposition process; the absence of such phases thus distinguishes this system. The lattice structures of the two solid solutions are identical in type, differing in lattice spacing by approximately 10 per cent; because of this it seems difficult if not impossible to predict on the basis of present theory either the outward form of the precipitate or the lattice orientation relationships between matrix and precipitate. The eutectic temperature in the copper-silver system1 is 779°C. At this temperature copper -dissolves 4.3 atomic per cent (7.0 weight per

Jan 1, 1935

By E. K. Soper

It has been observed that where veins or other types of orebodies are intersected by cross faults, the continuation of the ore deposit below the fault is often of lower grade than that portion above the dislocation.' In some mines, the reverse of these conditions has been noted, and the richest ore is found to occur in that portion of the vein beneath the fault intersection. Such instances seem to be less frequent than those where the richest ore is above the offset. The important and widespread influence of fault and vein intersections upon the localization of ore shoots is well known,2 but the factors that govern the position of the ore shoot relative to the fault intersection seem to be less clearly understood. The richest ore may be above or below the fault, or it may occur at the point of intersection, or there may be no change. Recent observations made by the writer in mines in Idaho and Montana suggested a possible explanation for the changes in the richness of ore below certain types of fault intersections. These observations have been supplemented by a study of the literature containing detailed descriptions of ore deposits at a large number of mines in North America. The results of these studies are presented herewith in the hope that they may lead to further discussion of this important phase of ore deposition. Relative Age oF Faults Faults which intersect veins and other ore deposits may be either pre-mineral or post-mineral in age—that is, they may be older or younger than the deposits which they intersect. Many veins are formed along

Jan 1, 1918

Endurance Properties of Non-ferrous Metals Discussion of the paper of D. J. McADAM, JR., presented at the Syracuse Meeting of the Institute of Metals Division and issued, as Paper No. 1506-E, with Mining AND METALLURGY, October, 1925. H. F. MOORE,* Urbana, Ill. (written discussion).-This paper says that the results of tests of some non-ferrous metals made at the University of Illinois and in the testing laboratories at McCook Field are abnormal when they do not agree with results obtained by the author. The writer can see no inherent reason why results of the type uniformly reported in this paper are any more normal. The knee of the stress-cycle, or S-N, diagram comes at different lengths of life for different metals. For steel, the knee occurs after from 1,000,000 to about 4,000,000 cycles, and for some non-ferrous metals not before 20,000,000 of 30,000,000 cycles. The writer can see nothing inherently abnormal in finding certain nonferrous metals for which the knee of the stress-cycle curve occurs at 1,000,000,000 cycles or higher. The writer has had experience with both the cantilever and the rotating-beam testing machine, and thinks that the chance of whipping action in the cantilever machine is a more serious handicap than the action the author has pictured. Furthermore, the writer questions whether the author has shown the existence of a clearly marked and definite endurance limit for all the non-ferrous metals he has tested including the following: Nickel (CT and A-16, Fig. 1), monel (CS-5.5 and BK, Fig. 2), bronze (F and CK, Fig. 4), aluminum bronze ( BJb-1, Fig. 6).

Jan 12, 1925

By Neil Johnson

IN the cyanidation of gold, silver and mixed ores, the solids suspended in the pulp after fine grinding, primary settling and series agitation are subjected to a washing step known, generally, as countercurrent decanta-tion, abbreviated C.C.D. The conventional C.C.D. plant consists of a series of separate thickeners-three to five in number-arranged in series on slightly different elevations. Solids settled in the first thickener are pumped at maximum density into the second thickener, where they are diluted with weak solution overflowing the third. After settling in the second thickener they are pumped to the third, where the process of repulping with still weaker solution is repeated, and so on throughout the system, until they reach the last thickener and are repulped with barren solution or water. Recently there has been developed a new type of thickener, known as the Dorr Washing Tray Thickener, consisting of up to five individual thickeners, which performs in a single unit all the functions of a conven-tional C.C.D. plant. Fig. 1 illustrates the essential features. It is a multicompartment tray thickener, in which the trays operate in series instead of in parallel for countercurrent washing. Feed enters the top compartment via a central, semisubmerged feed well. Strong solution overflows into a peripheral launder. Solids settle to the bottom, are raked to the center and flow into the top of the second compartment, directly below, via an inverted cup and seal. Solids pass downward, compartment by compartment, against a counter flow of wash solution and finally of fresh water. Thus, in accord-ance with the basic C.C.D. principle, the solids transfer the dissolved metal content to the wash solution and finally are removed by a dia-phragm pump from the bottom compartment virtually free of valuable material. Similarly, the wash water, as it flows through the system, becomes increasingly enriched in dissolved metal until it overflows from compartment two and returns to the process.

Jan 1, 1939

By Sydney H. Loram

TEIS paper, which is merely an arrangement of data collected during several hurried journeys, is offered to serve as a record, until such time as a better substitute be compiled. My observations were confined, as far as possible, over the entire distance, to the actual river valley; because near the Central Cordillera the country is so mountainous as to be im; passable in any direction but that of the dominant valleys. The river is not navigable anywhere, and for the first part of its course is a mountain torrent that runs down the bottom of narrow, almost vertical-sided valleys, through which the only road requires repeated fording, and often following up the bed of the stream ; but the rock-walls, standing clean and free from debris on either side, present the different formations with remarkable distinctness. A topographical map and a cross-seetion of the Rio Huasco is given in Fig. 1. The Rio Huasco practically rises from Laguna Grande, a lake about 17 km. from the Argentine boundary, and 3,135 m. above se-level, which is fed by direct snow-water, and by a few streams varying from a considerable volume, when supplied by the melting snow, in late spring, to little or nothing during the rest of the year. It is a somewhat pear-shaped body of water, about 1.5 miles in length and half a mile in average width, with a reported maximum depth of 45 meters. It was formed by the choking up of a narrow continuation of the same valley with blocks of an agglomerate mentioned later. The present level is some 5 m. below high-water mark (to which point, according to local accounts, it has not been filled for 35 years). In the intervening margin is a calcareous deposit about 4 m. thick, formed by the rapid evaporation of the water in the exceedingly dry air, and aided by the capillary action of an aquatic plant, growing in thick masses around the edge of the lake. These masses, dying and banking up, form

Jan 1, 1905

By J. R. Stack, H. H. Alexander

Prior to 1915, numerous attempts were made to treat tin concentrates in the United States, but for various reasons they were unsuccessful. Tin ore is said to have been found in nearly every state, but none of the deposits has proved to be of commercial importance. An annual output of a few hundred tons in Alaska is the only domestic production; hence any considerable production of tin in the United States must be from foreign ores. The most promising occurrence of tin was found in the Black Hills, S. Dak.; in the early development stage, it was called the Cornwall of America. Associated with the tin is tungsten The story is told that an exceedingly fine specimen of the Black Hills ore was sent to England to encourage stock promotion; the desired effect was produced until a skeptic chipped off a small piece, which the analysis showed to be wolframite. First Attempts at Smelting One of the first promising attempts at tin smelting in the United States was made by R. T. White at Bayonne, N. J., in 1903. Mr. White, after spending some time in England studying the methods of tin smelting, organized a company called the International Tin Co., and erected a plant to treat tin concentrates from the Straits of Malacca. About the time the plant was completed, the English Government placed an export duty of 40 per cent. ad valorem on tin concentrates exported to other than British smelters, which duty made it impossible to operate this plant so the enterprise was abandoned, As this export duty is still effective, the only source of tin-ore supply for the United States is the Bolivian concentrates. Bolivian Tin Concentrates Unlike the alluvial placer deposits, nearly all Bolivian tin occurs in lode deposits and some of the highest grade ores contain only a small

Jan 1, 1924

By A. M. Rowe, I. H. Silberberg

A computer program was written to predict the phase behavior generated by the enriched-gas-drive process. This program is based, in part, on a new concept of convergence pressme, which is then used to select vapor - liquid equilibrium ratios (K-factors) for performing a series of flash calculations. The results of these calculations are the equilibrium vapor and liquid phase compositions which define the phase envelopes. The program was used to predict phase envelopes for 11 different hydrocarbon systems on which published experimental data were available. The predicted and experimental results compare favorably. INTRODUCTION The reservoir engineer is frequently faced with the problem of predicting what will happen if gas is injected into a reservoir. One aspect of this, general problem is predicting the phase changes that will occur when a non-equilibrium gas displaces a reservoir fluid. In particular, a "dry" gas, upon displacing a volatile oil, will pick up intermediate components from the oil. On the other hand, a "wet" gas, containing a high concentration of intermediates, will lose some of these components to a relatively low-gravity, non-eouilibrium1- crude. It is this latter Drocess. occurring in the enriched-gas displacement, which is treated in this paper. In the past, these phase changes have been determined experimentally and the results incorporated into various modifications of the Buckley-Leverett analysis.112 Such experimental work is time consuming, and the results are sensitive to numerous experimental errors. With the wide availability of high-speed digital computing equipment and numerous correlations pertaining to the vapor-liquid equilibria of hydrocarbon systems, it is now practical to calculate such phase behavior. This paper describes a computer program for performing these calculations. THE ENRICHED GAS DISPLACEMENT PROCESS Experimental results have shown that oil recovery can be significantly increased by enriching the displacing gas with intermediate hydrocarbon c0m~onents.3 The essential features of the phase behavior generated by this enriched-gas-drive process are commonly illustrated with ternary diagrams such as Fig. 1.4 In this figure, Gas D, which contains a high concentration of intermediate hydrocarbons with respect to the undersaturated Crude A, is injected into the reservoir. When D contacts A, gas goes into solution until the oil becomes saturated (Point. B). Further contacting of Gas D and saturated Oil B results in a Mixture C which separates into Vapor Y(c) and Liquid X(c). Liquid X(c) is contacted by additional Gas O, resulting in Mixture E which separates into Vapor Y(e) and Liquid X(e). Repeated contacts of the liquid by the injected gas will eventually result in Liquid X(4 of maximum enrichment existing in equilibrium with Gas Y(d). The equilibrium tie-line X(4 Y(4, when extended, passes through the Point D representing the enriched injection gas. For systems of more than three components, the predicted equilibrium states are dependent upon not only reservoir temperature and pressure, but also the compositions of the crude oil and injected gas. If the gas is sufficiently enriched, a miscible displacement is generated. Line If is tangent to the phas,e envelope at the critical point (Point Z) and represents the limiting slope of the tie-lines as the critical state is approached. Point 1 therefore represents the minimum enrichment of injection gas required to generate a miscible displacement. Point G represents the minimum enrichment required for initial miscibility of the injection gas with Crude A. Accra has presented a method to be used for prediction of oil recovery by the enriched gas displacement process.l To develop the phase behavior data needed, he designed the experimental procedure described in the following quotation from his paper: The original liquid was contacted by a volume of displacing gas and allowed to come to equi-

Jan 1, 1966

By C. D. Gilpin, Franklin Moeller

The application of electric power for driving mine hoists handling heavy loads at high speeds has recently been extended by the installation of what is probably the largest electrically driven hoist in this country at the Granite Mountain shaft of the North Butte Mining Co., Butte, Mont. While the weight of rock which is hoisted by this machine is not the largest now being handled by electric mine hoists, the speed of hoisting is so, and the combination of the high speed with the heavy load has resulted in a machine of considerable interest to all those actively engaged in mining. Aside from mere considcration of size, this installation deserves attention because of the careful attention given, not only to the question of economy of operation, but to the details of construction and installation of the entire equipment. The conditions to be met in this installation were as follows: Weight of rock to be raised per trip, 7 gross tons........... 15,680 1b. Weight of skip.......................................... 8,000 1b. Weight of cage.......................................... 1,800 1b. Maximum depth of hoisting.............................. 4,000 ft. Diameter of rope.......................................... 15/8 Total weight suspended on one rope from drum............. 42,000 1b. Normal hoisting speed.................................... 2,700 ft. per minute. Maximum hoisting speed.................................. 3,000 ft. per minute. Desired capacity-200 tons per hour from 4,000 ft. depth. The ore is mined in several levels and hoisting is carried on from the 800-ft. level down to the 2,700-ft., which is at present the maximum depth from which the ore is raised regularly. Development is proceeding and a depth of 2,900 ft. has already been reached. The rock is handled underground in cars holding % ton, and about 10 cars are the usual load for a skip. All of the ore is dumped into underground bins, which are of diffcrent capacities varying up to 250 tons. From the bins the ore is fed into the skips without passing into measuring pockets. At the surface the

Jan 1, 1916

By Dorsey Hager

The information given in the accompanying table is submitted as evidence confirming the application of the anticlinal theory and the value of geology in the Kansas and Oklahoma oil fields. The term anticline has been used to define a particular type of arched fold. The anticlinal theory of oil accumulation should, however, be broadened to include any structural fold of an arched type even if not a distinct anticline. A terrace may very properly come under the heading of the anticlinal theory of accumulation, as the folding is closely related to that of the anticline; in fact, in many cases is an arrested anticline, though not completely closed in all directions. Stratigraphic forms due to lensing or irregular cementation of the sands certainly cannot be considered to fall within the anticlinal theory, though the laws of accumulation may be similar. A dome is similar to an anticline and belongs to the same class. A dome is broader in proportion to its length than an anticline. Many anticlines undulate along their axes to form domes. The anticlinal theory in this discussion will then be applied to anticlines, domes and terraces. In the following list, the writer has tabulated the main oil fields of Oklahoma, and a few recently discovered fields in Kansas. The fields discovered within the past 4 years are listed with the date of their discovery. Under "How found," the writer puts "Wildcat" where a geologist has not been employed, "Geology" where it has been used, and "7" where there is doubt. In some places the geologists have claimed pools that may rightly belong to them, but their claims have been questioned, so that they belong in an unsettled category. Unless one has mapped all the old pools, it is not possible to say just how far they are dominated by structure, but from our own work, and from discussions with others, it is safe to venture that nearly all the "shallow-pool" districts, Nowata, Bartlesville, and the Eastern Osage, are controlled by structure; domes, noses, and terraces are the main structural features. The "shallow pools" of Kansas show the same relation. At Peru and at Sedan, domes are evident, though gas occurs high on the domes, and oil well down the flanks, leading some to believe

Jan 1, 1917

By Fred H. Poettmann

An equation has been derived for use in calculating the sandface pressure of flowing gas wells in which the variation of the compressibility factor of the gas with pressure is taken into consideration. This variation due to compressibility has been put into both graphical and tabular form. Comparison of calculated results with field measured results were made on 20 dry gas wells from a given field and 11 distillate wells from different fields. The agreement between calculated and observed results is good. In addition to their use in the calculation of sandface pressures of flowing wells, the factors can be used in the direct calculation of the static bottom hole pressure of gas wells, the capacity of gas transmission lines, and in the calculation of the theoretical isothermal horsepower necessary to compress a natural gas. Examples demonstrating the use of various equations are given. INTRODUCTION Many of the equations used to calculate the sandface pressures of flowing gas wells from well head data do not take into consideration rigorously the deviation of the natural gas from ideal gas behavior. For low pressure wells this error is not serious. For high pressure wells flowing at high rates this error call be serious. Sandface pressures are used to determine the producing capacity of gas wells as shown in the U. S. Bureau of Mines' Monograph 7.' An equation has been derived for use in calculating the sandface pressure of flowing gas wells in which the variation of compressibility of the gas with pressure is taken into consideration. This variation due to compressibility has been put into both graphical and tabular form. In addition to their use in the calculation of sandface pressures, these "factors" can also be used to give a direct solution in the calculation of the static bottom hole pressure of gas wells, the calculation of the capacity of gas transmission lines, and the calculation of the isothermal horsepower necessary to compress a gas. CALCULATION OF SANDFACE PRESSURE OF FLOWING GAS WELLS The starting point in the derivation of any specific flow equation is an energy balance on the fluid flowing between any two points in the system. This energy balance based on one pound of flowing fluid is expressed by the well known general flow equation: jp~- vdP+ Ah + -— + wt + r. = o . . (i) P, 2 g. where V = specific volume of flowing fluid in cu ft/lb P = pressure in Ib per sq ft ah = difference in height above datum plane in, ft ------ = kinetic energy change of one lb of flowing fluid, v equals velocity in ft/sec and g. = 32.174 Ws = Work done by fluid while in flow (similar to shaft work in driving a turbine) W, = Znergy losses due to the irreversibilities of the flowing fluid This equation contains no limiting assumptions and can be made the basis of any fluid flow relationship by limitations or substitutions. The energy units are usually expressed in term* of foot-pounds of energy per pound of mass. Considering the vertical flow of gas through tubing or annu-lus, the external work W, done by the gas is zero. Let us also assume that the value of the kinetic energy function is small and can be neglected. Equation (1) is reduced to: /P: VdP + Ah+Wt = 0 .......(2) Pi The energy loszes PI can be expressed in terms of the well known Fanning equatinn: 4/Lf: rf = —— ............(3) 2g,D where L = the integrated average velocity in ft/sec of vertical flow in a uniform flow string -~h = L v = the integrated average velocity in ft/sec / = dimensionless correlating function

Jan 1, 1951

By Fred H. Poettmann

An equation has been derived for use in calculating the sandface pressure of flowing gas wells in which the variation of the compressibility factor of the gas with pressure is taken into consideration. This variation due to compressibility has been put into both graphical and tabular form. Comparison of calculated results with field measured results were made on 20 dry gas wells from a given field and 11 distillate wells from different fields. The agreement between calculated and observed results is good. In addition to their use in the calculation of sandface pressures of flowing wells, the factors can be used in the direct calculation of the static bottom hole pressure of gas wells, the capacity of gas transmission lines, and in the calculation of the theoretical isothermal horsepower necessary to compress a natural gas. Examples demonstrating the use of various equations are given. INTRODUCTION Many of the equations used to calculate the sandface pressures of flowing gas wells from well head data do not take into consideration rigorously the deviation of the natural gas from ideal gas behavior. For low pressure wells this error is not serious. For high pressure wells flowing at high rates this error call be serious. Sandface pressures are used to determine the producing capacity of gas wells as shown in the U. S. Bureau of Mines' Monograph 7.' An equation has been derived for use in calculating the sandface pressure of flowing gas wells in which the variation of compressibility of the gas with pressure is taken into consideration. This variation due to compressibility has been put into both graphical and tabular form. In addition to their use in the calculation of sandface pressures, these "factors" can also be used to give a direct solution in the calculation of the static bottom hole pressure of gas wells, the calculation of the capacity of gas transmission lines, and the calculation of the isothermal horsepower necessary to compress a gas. CALCULATION OF SANDFACE PRESSURE OF FLOWING GAS WELLS The starting point in the derivation of any specific flow equation is an energy balance on the fluid flowing between any two points in the system. This energy balance based on one pound of flowing fluid is expressed by the well known general flow equation: jp~- vdP+ Ah + -— + wt + r. = o . . (i) P, 2 g. where V = specific volume of flowing fluid in cu ft/lb P = pressure in Ib per sq ft ah = difference in height above datum plane in, ft ------ = kinetic energy change of one lb of flowing fluid, v equals velocity in ft/sec and g. = 32.174 Ws = Work done by fluid while in flow (similar to shaft work in driving a turbine) W, = Znergy losses due to the irreversibilities of the flowing fluid This equation contains no limiting assumptions and can be made the basis of any fluid flow relationship by limitations or substitutions. The energy units are usually expressed in term* of foot-pounds of energy per pound of mass. Considering the vertical flow of gas through tubing or annu-lus, the external work W, done by the gas is zero. Let us also assume that the value of the kinetic energy function is small and can be neglected. Equation (1) is reduced to: /P: VdP + Ah+Wt = 0 .......(2) Pi The energy loszes PI can be expressed in terms of the well known Fanning equatinn: 4/Lf: rf = —— ............(3) 2g,D where L = the integrated average velocity in ft/sec of vertical flow in a uniform flow string -~h = L v = the integrated average velocity in ft/sec / = dimensionless correlating function

Jan 1, 1951

By J. M. Toguri, H. Flood

The application of the mass action law to the thermodynamic treatment of metal-slag equilibria is discussed. The consideration of the reactions essentially as ionic exchange equilibria is shown to be both an advantage and an aid for the elucidation of the theoretical treatment. This is illustrated by several examples. In general two different methods of application of the mass action law to metal-slag equilibria have been used by different groups of investigators. These could be called the oxide reaction and the ionic reaction approach respectively. At the recent discussion in the metallurgical section of the I.U.P.A.C. Congress in Montreal, 1961,' divergent opinions prevailed regarding the most rational way of applying the mass action law to metal-slag equilibria. This question is of fundamental importance in the treatment and understanding of theoretical chemical metallurgy. Consequently, the following is an attempt to contribute towards its clarification. As an example, the distribution of iron and manganese between molten iron and slag will be considered. I) THE OXIDE EXCHANGE REACTION APPROACH The equilibrium between iron and manganese between molten iron and slag is frequently formulated as an oxide metal exchange reaction as follows:

Jan 1, 1963

By R. K. Datta

Eluropium -activated yttrium vanadate, excited by short- and long-wavelength ultraviolet radiations, shows enzission lines near 6100A, the principal ones correspondirzg to transitions of EU+3 ions from 5Do to the F2 energy level. The ~neclmlallistns of absorption and etnissiorz of this phosphor have been empirically studied. The absorption is caused by two separate processes in the matrix. The phosphor YVO4:Eu and tlie matrix YVO, haue essentially the same resectance spectra in the region 2500 to 4000if. There are two broat ah~o?~ption bands: natnely, around 2600 and 3600A regions. Whet? compared with the reflectance spectra of the constituent oxides, namely, Y2O3, V205, Eu2 03, the absorption bands of the tnatvix and the phosphor in the short- and long-wavelength ultraviolet regions can be interpreted as due to charge-transfer processes involving i) Y-O and ii) 17-0, respecti~~ely. The excitation spectrum' of the phosphor has two broad bands with peaks at about 2600 and 3600A regions. U can be postulated that enevgy absorbed under short- crud long-wavelength ultraziolet excitatzon, respectzcely, by Y-0 and V-O parts of the niatrix is transferred by radcatio~zless process to EU+3 ions. Thzs postulate can empirically be proved on the basis of the spectra of the systems (YVO4,-YPO4,):Eu. PO? ~ons do not have' any appreciable absorption in the short or long uv regions. When P0't3 ions are substitlited for v0i3 ions in YVO,:Eu phosphors, the absorption and excitation in the lo~zg uv region are gradually reduced. Ailoreover, the £«+3 emission under 3650A excitation is decreased zuitlz increase in PO^ content, lt~lzereas the emission under 253711 excitation remains esserztially constant with as IILUCIL as 60 mole pct of YPO, in YVO,:En. EUROPIUM-activated yttrium vanadate (YV04:Eu) is a well-known phosptor.'-3 When excited by cathode rays, 2537, or 3650A radiations, YV04:Eu emits typical narrow-band spectrum of EU'3 fluorescence in the region of 5900 to 7100A, a very strong maximum occurring at about 6190A. This emission is considered to be due to 5Do — 7F2 transition of excite: EU*3 in 4f state. Moreover, the emission under 3650A excitation increases with temperature markedly. Because of these properties, YV04:Eu phosphor finds wide application in industries, namely, in color television tube, laser, and high-pressure mercury-vapor lamps. It is the purpose of this paper 1) to present the empirical study of the mechanism of absorption and excitation of YV04:Eu phosphor by ultraviolet radiation, and 2) to offer an explanation for the process of emission. It should be mentioned that a theoretical discussion on the mechanism of absorption in terms of the crystal or ligand field theory is beyond the scope of this paper. Empirical studies presented here are based primarily on spectroscopic and crystal-chemical investigations. EXPERIMENTAL i) Preparation of Materials. The synthesis of vanadate phosphorinvolves preparation of (Yi-.tEuj^Oj, blending the mixed oxide with an oxidic compound of vanadium, such as V205 or NH4V03, and firing the mixture at about 1000°C for several hours when YVO4:Eu forms as a primary phase. (Y1-xEux)203 compositions are prepared by coprecipitation of oxalates, and igniting them at about 1000°C. The vanadium compound is added in excess of the stoichiometric proportion for fluxing purposes. The charge is cooled, ground, and the excess of vanadium is removed by a hot wash (-80°C) of alkali or ammonia. Y(VP)04:Eu samples are prepared by mixing (Yi-xEux)203 with stoichio-metric proportions of (NH4)2HP04 and the vanadium compound. The mixtures are prefired at 700" to 800°C for 1 or 2 hr, then ground and refired at 1150°C. The firings of the phosphors are done in silica crucibles, and the homogeneity of the final products checked by X-ray diffraction analysis. ii) Spectroscopic Measurements. Diffuse reflectance sqectra of the samples within the range 2500 to 7000A are obtained by using CaF2 as standard in Cary Recording Spectrophotometer, Model No. 14. The emission spectra from phosphor plaques, excited under different ultraviolet sources, are obtained by a direct-recording spectroradiometer4 adapted with a grating monochromator with nearly constant dispersion. Maximym sensitivity in the spectral region from 2500 to 7000A is obtained with a quartz-windowed, S-20 response p$otomultiplier. The total' band pass is kept about 30A. The spectra are calibrated against the light from a standard tungsten filament lamp reflected from a magnesium-oxide plaque. Brightness data given throughout this report $re measured from the height of the main peak (6190A) of the emission spectra. The excitation spectra are measured using sodium salicy-late as standard. RESULTS AND DISCUSSION The diffuse reflectance spectra of both pure and activated YV04, along with their constituent components, are shown in Fig. 1. YVO4 shows two broad absorption bands, namely, around 2500 and 3600A, respectively. Since there is little difference between the reflectance spectraoof YVO4 and YVO,:Eu in the uv region (2500 to 4000A), it can be postulated that excitation of the phosphor is mainly due to absorption by the matrix, i.e., YVO4. The question, now, is whether the matrix (Yv04) is excited as a whole, or different components are responsible for the two absorption bands. The characteristic absorption spectra of molecular ions involving transition metal ions, both in aqueous solutions and in crystals, are due to electronic transi-

Jan 1, 1968

By John Langton

In determining what kind of pourer should be adopted for the works of the Moctezuma Copper Co. at Nacozari, Sonora, Mexico, certain considerations imposed by local conditions had to be taken into account. Water.—During most of the year the water-supply is abundant for all purposes, but it dwindles rapidly when the dry season sets in, reaching a minimum flow which is entirely undergrouad. It was evident, that with the greatest care in keeping down the unavoidable loss of water in milling and smelting, these operations and hence the capacity of the works mould ultimately be limited for about two months of the year by the small watersupply available at the period of minimum flow. Transportation.—The nearest railway terminus was in Arizona, at the international boundary-line; and the price of supplies at that point would be enhanced at Nacozari by the additional cost of a 90-mile wagon-haul. During the rainy season, transport to Nacozari was much impeded, and at times made impossible, by the condition of the roads. Hence, to insure continuous operation at the works, it would be necessary to provide for hauling the year's supplies, including fuel for power and coke for smelting, in less than eleven months. In other words, the average freight delivered daily at the works should be at least 10 per cent. more than the average daily consumption. For moderate quantities of freight, pack-carriage by burros is astonishingly cheap. But it has a capacity-limit which is generally very soon reached. A 200-lb. load, and 10 miles a day, 5 with and 5 without load, is the full capacity of a burro. This means one burro per ton-mile of the round trip; and,

Jan 1, 1904

By C. G. McLachlan

THIS paper outlines a series of tests carried out during the first six months of 1927, in the laboratory and mill of the Moctezuma Copper Co. The object of the tests was to determine whether the soluble salts present in the mill circuit water were having a detrimental effect on the recovery made by flotation. To accomplish this object a series of water analyses were made, followed by flotation experiments in which definite quantities of the salts found were added as addition agents. Before proceeding to describe the results obtained in the course of the investigation, reference will be made to five articles that have appeared during the last two years in which the action of such salts is discussed. Two of these are by A. T. Tye1,2 and describe flotation practice at Cananea and the way in which water high in ferrous and ferric salts is conditioned for differential flotation. Two, one by A. C. Munro and H. A. Pearse3 and the other by H. A. Pearse,4 outline Britannia milling methods, and the advantages that have been derived from ore washing; while in the fifth, A. W. Hahn5 summarizes the results of laboratory experiments in which ferrous, ferric and aluminum sulfates have been added in varying amounts. The mill of the Moctezuma Copper Co. has a daily capacity of 3000 tons, and is situated about 75 miles south of Douglas, Arizona, on the Rio de Nacozari, in the Mexican state of Sonora. The ore treated is mined from the company's mine at Pilares, about 5 miles southeast of the Concentrator. This ore contains about 2.5 per. cent. copper -- present almost entirely as chalcopyrite-and 10 per cent. iron, of which

Jan 1, 1928

By N. H. Murlenberg, T. M. Drown

It is often a tedious matter to get a solution of pig iron or steel, for the determination of phosphorus, which is absolutely free from silica. Where pig iron rich in silicon is dissolved in hydrochloric or nitric acid in the usual procedure, it is necessary, not only to evaporate the solution to complete dry ness, but to heat the dry residue for some beam in an air-bath to a temperature of about 120° C. The oxide of iron is thus rendered insoluble in nitric acid, and is only slowly dissolved by hydrochloric acid. In the method of determining silicon by nitric and sulphuric acid, described in the Transactions of the Institute, Vol. VII, page 346, arid Vol. VIII, page 508, we obtain in one or two hours a solution of the iron in the form of ferric sulphate entirely free from silica, and containing free sulphuric acid. It occurred to Us that this solution might be made available for the determination of the phosphorus by the molybdate method. The following experiments mere tried with unsatisfactory results. 1st. The iron was precipitated by ammonia, the precipitate filtered, washed, and dissolved in nitric acid. 2d. The iron was precipitated as basic acetate and dissolved in nitric acid. 3d. The solution was neutralized by ammonia, and nitric acid added in small excess. In all these cases the phosphorus obtained by precipitating by ammonium molybdate and magnesia-mixture was too low. The following method was then tried with success. The filtrate from the silica and graphite was evaporated to small bulk and heated in a porcelain dish on a sand-bath. until fumes of sulphuric acid ceased to escape. The dry residue was taken up with dilute nitric acid and the solution precipitated by ammonium molyldate. The phosphorus was weighed as magnesium pyrophosphate. The results were satisfactory. To save time, the original solution of the iron in nitric and sulphuric acids was evaporated to dryness and heated as before until

Jan 1, 1882

By W. A. Anderson, R. F. Mehl

RECRYSTALLIZATION of cold-worked metals has long been known to proceed by a process of nucleation and growth.1 When a cold-worked metal is heated to a temperature at which recrystallization will ensue, nuclei of new grains, essentially strain-free, appear and grow. As the process proceeds, nuclei continue to appear and to grow, until the cold-worked matrix has been entirely consumed and recrystallization has been completed (Fig. I). Conducted isothermally, a measurement of the fraction of the matrix recrystallized plotted against time, yields an isothermal recrystallization curve, showing the time course of the recrystallization process (Fig. 2).2 Evidently, then, the rate of recrystallization is determined by the rate at which nuclei form and the rate at which they grow. The rate of nucleation N is the number of nuclei that form in unit time in unit volume of the unrecrystallized matrix, and the rate of growth G is the increase in radius of the recrystallized grain per unit time. In recent years attempts have been made to determine N and G as these vary with the well-recognized variables affecting recrystallization: time, temperature, degree of deformation, etc.' Such studies yield information that is more fundamental than that conveyed by the conventional recrystallization diagram,' since the rate of recrystallization is thus analyzed into its two component rates.2 Methods are now available by which N and G can be measured, and analytical expressions have been developed for the interrelationships among N, G, the isothermal recrystallization curve, and the final grain size, which greatly facilitate analysis.2-4 The application of these methods has been demonstrated recently for the recrystallization of silicon ferrite.2 Data on N and G in dependence upon the recognized recrystallization variables are, however, very fragmentary;* values of N and G have been determined for some metals, but the effect of temperature, which would yield the fundamentally important activation energies, has been too little studied. Thus far there has been no detailed study of the recrystallization of any one metal in terms of N and G over appreciable ranges of the variables time, temperature, degree of deformation, and original grain size. It is the purpose of the present paper to provide such a study, employing aluminum.

Jan 1, 1945

By F. Gordon Smith

ALTHOUGH several geological indicators of the critical type are known, including quartz inversions and decomposition of hydrous minerals such as serpentine, there are very few of the general type. Solid solutions are excepted, but the limitations of use are very restricted and interpretations are sometimes ambiguous. General methods for determining temperature and pressure conditions during the crystallization of minerals would have considerable scientific and economic value. It is not the purpose of this paper to discuss the various methods of geological thermometry and barometry, but to present one general method, applicable to all minerals, and to describe what progress has been made in the methods of measurement. The general method, in brief, is a study of the stress conditions in and around various types of foreign inclusions which are trapped in minerals during growth. The method depends upon the fact that any homogeneous gas, liquid, or solid will in general have coefficients of thermal expansion and volume compressibility different from those of any given mineral. Therefore stress must develop in and around all types of inclusions in minerals if the temperature or the pressure, or both, are changed from the conditions which prevailed during the growth of the mineral. The methods of measurement consist of determinations of the temperature-pressure conditions of fit of the inclusions in the host mineral. The types of inclusions in minerals are: I—gas, or liquid plus vapor, when observed at room temperature, due to crystallization under pneumatolytic conditions; 2—liquid, or liquid plus vapor when observed at room temperature, due to crystallization under hydrothermal conditions; 3—glassy solid, or devitrified glass, due to crystallization under magmatic or high temperature metamorphic conditions, in a siliceous liquid; and 4—crystals, due to overgrowth of other minerals crystallizing simultaneously or of other minerals which crystallized previously. A survey of the literature shows that much valuable earlier work on inclusions, especially that car- ried out in England in the last century, has dropped out of current knowledge. The following is a brief summary of the significant contributions to the problem up to the present day. Davy in 1822 asserted that fluid inclusions in minerals consist of an aqueous solution of salts and a gas bubble, the whole being either at lower or higher pressure than atmospheric.' At intervals from 1823 to 1862, Brewster contributed information concerning other types of inclusion consisting of 1—aqueous solution, a much more expansible liquid, and a gas; 2—aqueous solution, salt crystals, and a gas; and 3—the very expansible liquid and a gas. The very expansible liquid fills the gas space between 20" and 30°C. Compression strain effects were seen around inclusions in diamond, topaz, and other minerals.'-" Sorby in 1858 and 1869 further advanced the study begun by Davy, stating that fluid inclusions represent a sample of the mother liquor of crystallization and that the degree of filling of aqueous inclusions at room temperature defines the temperature-pressure relations during formation of the host. The degree of filling may be measured by determining the minimum temperature of filling of the inclusion by the liquid phase. The very expansible liquid in some fluid inclusions is liquid carbon dioxide. The temperature at which salt crystals in fluid inclusions completely dissolve in the fluid is the minimum temperature of formation. Inclusions of glass or devitrified glass indicate crystallization from a melt. Inclusions of crystals in minerals are often centers of strain, which may be seen by optical effects or by radial tension cracks. Sorby realized that an analysis of stress-strain relations about inclusions could be used to provide precise data on the temperature of crystallization, but the matter was never pursued.' , Hartley (1876, 1877),".'" Hawes (1881)," Wright (1881),'V ohnsen (1920),I3 and Holden (1925)"

Jan 1, 1953