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By J. R. Cahoon, W. V. Youdelis

In a recent publication by Flemings and Nereo, equations for the calculation of the solute distribution in castings were developed, and the solute distributions for unidirectionally solidified A1-4.5 pct Cu ingots cast under various thermal conditions were calculated. The equations derived by Flemings and Nereo for the dendrite "expansion" and "steady-state" zones are essentially equivalent to those previously published by Kirkaldy and Youdelis, 16 for, although the flow velocity cooling rate, and temperature gradients appear in the fundamental differential equations, calculation of the solute distribution requires that the above be explicitly related to the assumed or measured solid-liquid mass distributions during solidification. In the treatment of Kirkaldy and Y-oudelis the mass distributions are simply assumed or measured without any prior and explicit association of the mass distributions to a velocity parameter. The treatment of Flemings and Nereo permits solidification conditions more complicated than the simple unidirectional case to be considered (although in principle the treatment of Kirkaldy and Youdelis could also be extended to include the more general solidification case); however, we note some limitations in the treatment of Flemings and Nereo, and the purpose of this discussion is to point these out and also to indicate those points of similarity in the mass distribution models used which make the two treatments equivalent. Both the Kirkaldy-Youdelis and Flemings-Nereo treatments consider a zone of dendrite "expansion" followed by a "steady-state" zone. However, Flemings and Nereo have failed to consider a zone of "collapse" which begins at the base of the first dendrites to reach the top of the ingot. The omission of this zone of "collapse" results in too high a value for the solute concentration in the latter portion of the ingot to solidify and the conservation of total solute is not possible. In the zone of "collapse" the solute concentration rapidly decreases, which may be accounted for as follows: consider a mushy zone of length X,, shown schematically in Fig. 11 (a), which develops at the chill face and then moves as a steady-state configuration along the length of a solidifying ingot. The solute distribution in this zone, when it first attains the steady state, is shown qualitatively in Fig. 11(b). The segregation is positive (above Co) in the region ab because this region contains primary dendritic solid, ranging from kco to kcE in composition (where k is the partition coefficient and CE is the composition of the eutectic liquid), and liquid metal near eutectic composition. The segregation is negative (below Co) in the region bc because it contains primary dendritic solid only slightly above kco in average composition and liquid metal only slightly above Co in composition. As the zone X, moves as a steady state

Jan 1, 1969

By Arthur F. Taggart, A. W. Thomas, T.C. Fitt

It was noticed early by operators that high recoveries and flocculation of the sulphide minerals were closely correlated in agitation-froth flotation. Later, this readily visible flocculation was found almost invariably to be due to the binding together of the oiled sulphides by minute air bubbles, and is now known to be characteristic of pulps in which at least one of the mineral species is coated with an insoluble collecting oil. In 1930 it was reported1 that in differential flotation a correlation exists between Brownian movement of particles in the pulp and their nonfloatability, and that Brownian movement and dispersion are likewise correlated, whence it would appear to follow that dispersion of a mineral particle in a flotation pulp denotes a particle condition unfavorable to flotation. In 1934 it was postulated2 that Brownian movement, dispersion and nonfloatability all flow from the condition of the surface of the dispersed particles. It was also postulated at that time that the surfaces of dispersed particles are ionized, the ionized compound being a product of reaction between a component of the particle and a component of the pulp, of a mass solubility of the general order of a fraction of a milligram to I 5 to 20 mg. per liter. It was then further asserted, and has since been confirmed by Bankoff,3 that sulphides so conditioned with soluble collectors as to be floatable flocculate without the intervention of air bubbles as binding media. The present paper comprises an inquiry into the nature of the bound and counter ions in zinc sulphide dispersed by sodium arsenate. A part of its findings was mentioned in the 1934 paper above cited.= The tests show that: I. When powdered granular zinc sulphide is immersed in aqueous solutions of sodium arsenate, arsenate ion is abstracted from solution and anchored to the solid surface, while sulphate and lower sulphoxy ions are concurrently displaced therefrom in substantially stoichiometric quantities. 2. The ion counterbalancing the anchored arsenate ion is zinc. 3. Dispersion and Brownian movement of zinc sulphide are concurrently maxima at an arsenate-ion concentration lying between 0.01 and 0.001-molar sodium arsenate. 4. Any condition or reaction that tends. to remove the zinc arsenate coating from the zinc sulphide particles decreases dispersion and Brownian movement concurrently. Experimental Three samples of zinc sulphide were used. Lot I was C.P. zinc sulphide, washed well be~ond absence of chloride, as shown by test with silver ion. Lot 2 was prepared by precipitation from hydrochloric acid solution of arsenic-free zinc, and was washed as lot I. Lot 3 was prepared by heating a portion of lot 2 in absence of air at 1200° to r300°C. for one hour."

Jan 1, 1943

By Clarence Zener, Howard Clarke, Cyril Stanley Smith

The importance of cold-working in the fabrication of metals is in marked contrast with our ignorance as to the nature of the accompanying internal changes. The failure of the usual methods of testing to provide a consistent picture of these internal changes has given the incentive for the present program of investigating the effect of cold-working upon the internal friction of metals measured at small strain amplitudes. It has previously been shown1,2,3, that the internal friction introduced by cold-work is removed by annealing at comparatively low temperatures. In the present paper the following additional factors are investigated: (I) frequency of measurement, (2) amount of cold-work, (3) temperature of measurement. Special care was taken to minimize the internal friction due to causes other than cold-work. The present paper is purely experimental, the authors believing that any conclusions drawn from this work as to the nature of the internal changes accompanying cold-work would be premature.'l PrEpaRations oF Specimens In this study of cold-work it was desirable to eliminate as far as possible all other sources of internal friction. One disturbing source is the lack of temperature equilibrium between adjacent crystallites of a vibrating specimen.4 Temperature equilibrium is aided by small grain size and by the use of low-frequency vibrations. Unless unduly long specimens are used, low frequencies can be obtained only in transverse vibrations. But in transverse vibrations a second source of internal friction is present, that arising from transverse thermal currents.5 The effect of these may be reduced by increasing the transverse dimensions. The grain size and transverse dimensions of the specimens were thus so chosen as to render the vibrations simultaneously nearly isothermal with respect to intercrystalline thermal currents, and nearly adiabatic with respect to transverse thermal currents. The material for this investigation was a 70-30 brass, part of the same lot of material that was used for some earlier studies on the effect of strain on proportional limit.10 It had the following composition: copper, 70.59 per cent; zinc, 29.39; lead, 0.01; iron, 0.01. This material was received from the brass mill in the form of 3/4-in. rod, cold-drawn to final size by a 65 per cent reduction of area from material that had been annealed to give a grain size of 0.060 mm, Rods of appropriate length were annealed for 2 hr. at 400°C. and cooled in air. The annealed rods (grain size, 0.012 mm.) were then stretched in a tension-testing machine, using special grips1' to ensure axial application of the load. The rate

Jan 1, 1942

By Fred C. Bond

AN improved method of measuring the surface area of a comminution product down to any desired particle size has been developed. The method is largely graphical, and requires relatively little calculation. It can be used with materials containing large amounts of clay, or excess fines of any kind. The surface area S is expressed in terms of square meters per 100 c.c. of solids. This expression is based upon volume rather than weight, and is considered to be more suitable for crushing and grinding problems, where the machines ordinarily are operated under constant volume conditions. It has the advantage that surface areas of different materials can be compared directly, even though their specific gravities may be unknown. The "specific surface" of a material, or the number of square centimeters of surface area per gram, is equal to 100S divided by the specific gravity. Particle diameters are expressed in microns, K being the diameter of the largest particle present and L the grind limit, or lower size limit of the particles formed directly by grinding. The value of K does not always coincide exactly with the diameters of the largest particles retained on the coarsest testing sieve, since the largest particles formed in crushing and grinding are often slabby, or have other irregular shapes. L has been chosen as 0.700 microns, or number 27.5 in the size number series, for reasons to be explained later. S is the total surface area of all particles larger than L microns in diameter. When a homogeneous comminution product is separated into fractions whose diameters bear a constant geometrical relationship p to each other, and the log per cent weight retained upon each size and passing the next larger size is plotted against the log diameter, a straight line results, which is called the distribution line, and which has a slope in called the distribution modulus. The distribution line can be extended to any desired limiting size, and the total surface area of all particles larger than that size can be calculated. The equation of the distributi0n line is [w = Cx" [I]] where w is the per cent weight retained on each successive sieve; x is the particle diameter; and C is the per cent weight retained on an opening of unit diameter.2 Theoretically, the distribution line can be extended to include infinitely small particles. When it is so extended, and the assumption is made that no fine particles are present other than those accounted for by the equation; the log per cent cumulative weight passing any series of sizes, plotted against the log diameter passed, will result in a straight line lying parallel to and above the plotted distribution line.

Jan 1, 1941

By John P. Bryant

Plant nutrients are obtained by plants from both the air and the soil. Carbon dioxide, a gaseous form of carbon and oxygen, supplies the carbon which usually makes up 50% or more of plant structure. Plants are capable of absorbing carbon dioxide directly from the air. Most of this nutrient comes from the air, although some carbon dioxide is absorbed by soil water and taken into the plant as liquid. Growing plants use more water than any other substance. Plant nutrients in the soil dissolve in soil water; soil water entering the plant carries nutrients into the plant structure. Water is then given off into the air as the plant breathes or transpires. The inorganic or mineral portion of the nutrients which plants require comes from the soil. Inorganic or mineral composition of plants is usually less than 5% of their weight, and this mineral requirement, usually lacking in the soil, must be provided by fertilizers. Proper fertilization of a soil to improve its mineral level and productivity is the basis for the fertilizer industry (Thomas, 1960). There are 13 essential plant nutrients which often must be added to soils or plants and are generally considered as fertilizer minerals. These nutrients are divided into the categories: primary minerals (nitrogen, phosphorus, potassium); secondary minerals (calcium, magnesium, sulfur); and micro or trace minerals (boron, iron, manganese, copper, zinc, molybdenum, chlorine). Further, cobalt is often added to fertilizers. Although it is not considered to be an essential plant nutrient, it is essential to animal health and is often applied to forages as a fertilizer constituent. One point of major significance to the fertilizer industry is that not all nutrient carriers supply that nutrient in a chemical form which will be available to the plant. Thus, a product which may be considered a fertilizer mineral may require substantial processing or treatment before it becomes useful as a nutrient carrier. Fertilizer Industry Scope Until about 1900 demands for higher crop yields were met simply by bringing new agricultural lands into cultivation. Since that time great progress has been made in increasing yields through fertilization and improved varieties and cultural practices. The importance of the fertilizer industry to the economy and welfare of the U.S. is widely recognized. [Fig. 1] illustrates the relationship of lime and fertilizers to crop yields. In terms of tons of fertilizer products, the growth of the industry has been phenomenal, particularly between 1950 and 1970. Table 1 shows the increase in fertilizer usage. Primary Plant Nutrients in Fertilizers Primary minerals (nitrogen, phosphorus, potassium) are designated as such because of their significance to plant growth. Practically all soils are deficient in both nitrogen and phosphorus, and most of them are also deficient in potassium. Consequently, these nutrients

Jan 1, 1975

By G. D. Van Arsdale

THE paper of Mr. Posnjak presents a laboratory confirmation of the well known facts that air ox-idation of pure solutions of ferrous sulfate is slow and difficult and that, like many other similar reactions, the speed, may be greatly accelerated by the presence of other substances, often in very small amounts, the effect of the presence of copper being determined ex-perimentally in this case. However, it should not be. overlooked that copper is always present in heap leach-ing solutions in amounts equal to or greater than those in the experiments described; therefore the paper may be considered as an explanation of present results rather than a possible improve-ment to be added to present practice. It is not practicable and it does not pay to precipitate copper by ce-mentation below a point about 5 lb. per 1000 gal., equivalent to about 0.0005 mol. Cu. per liter, compar-ing with the approxi-mately 0.0009 mol. per liter of curve 2 in the diagrams given of course, also, in the heaps local concentrations are usually very much higher than this, which is also true of the effluent li-quors, so that I feel that it is safe to say that copper is already present in amount sufficient to realize, as large an accelerating effect as is practicable. Too much im-provement or refinement cannot be expected in a method of this kind, due to commercial limitations. It should be remembered that chemically and physically there is no sharp dividing line between leaching in place, heap leaching, and the usual tank leaching practice, practi-cally the same reagents being used in all three. From the viewpoint of extractions, etc., it is not common sense to apply leaching in place to an orebody carrying enough copper to pay for mining; and the same is true of heap leaching, for an ore carrying enough to pay for the crushing, handling, etc., of ordinary leaching. That is to say, leaching in place should properly be consid-ered only for an ore too low-grade to pay for mining, and heap leaching for the next higher grade, still how-ever too low-grade to pay for crushing and other re-finements. There is no advantage in leaching without mining or in heap leaching except lower cost of in-stallation and handling; on the other hand there are very distinct disadvantages which are inherent and which should prohibit their use except where necessity requires. The object of metallurgy is to make money out of the handling of ore, and it is purely a question of money as to how far we can go in "improving" or

Jan 7, 1927

By A. M. Gaudin

IT is only in recent years that substantial progress has been made in developing a physico-chemical picture of the solid state. The molecular concept, so useful in dealing with gases, was naturally carried over to the field of crystalline solids; it has resulted in the firm implanting of erroneous concepts that only now are being eradicated successfully. Two simply written and effective books on the subject are Crystal Chemistry by Stillwell1 and An Introduction to Crystal Chemistry by Evans.' A more complete treatment of the subject is available in a book by Wells.' The monograph by Hückel4 also touches on a subject most easily perceived by reference to the brief introduction by Bragg,5 that master of the field. These texts make it clear that while some solids are built of molecules, many are built of ions, others of atoms connected in the form of giant molecules, and still others of cations and electrons. The various lattices in which these entities are systematically arranged, the joint use of several of these entities, and the transitional character of some of the bonds make for the great variety of crystalline solids. The purpose of this paper is to point out a most important corollary of present views on the structure of solids. In this connection the classification of solids in Table I is helpful. Atomic crystals are those formed by the noble gases, e.g., helium and argon. They are soft, sublime at very low temperature, of very low specific gravities, and not encountered in ores. Molecular crystals are uncommon among inorganic materials, common among organic materials. Typical examples from both inorganic and organic fields are sulphur, iodine, naphthalene, benzene, and carbon tetrachloride. These crystals are soft and have low specific gravities; where the molecules are small, the sublimation temperature is low. Filament and sheet crystals are rare. They are typified by elemental selenium and elemental arsenic, respectively. Graphite and molybdenite come near being sheet crystals. These crystals are soft in some directions, tough in others, sublime at various temperatures. Diamantine crystals, typified by diamond, are very few in number, stable at high temperatures, and extremely hard. Ionic crystals are common. Most salts, acids, and alkalies belong in the two classes of ionic crystals; examples are rock salt, fluorite, calcite, and angle-site. The salts, acids, and alkalies that do not belong in these classes are more properly regarded as transitional between ionic crystals, framework crystals, and diamantine crystals, e.g., ice and quartz. Fiber crystals are relatively uncommon mineral-ogically speaking, but common in the fields of living processes. Examples are asbestos, silk, cellulose, and wool. Many fiber crystals are so little known even now that their crystallinity may be doubted. Layer crystals, among the more interesting and useful of solids, include a wide variety of substances

Jan 1, 1956

By Nathaniel Arbiter, Arthur F. Taggart

THE fact that the floatability of minerals with fatty-acid collectors changes as the pH of a pulp varies was utilized in the early days of flotation, when sulphuric acid was used with oleic acid to float sphalerite and galena from gangues which themselves float with fatty acids in alkaline pulps. Gaudin1 showed that this difference in floatability is a regular function of the extent of the change in pH. The present paper offers an explanation of the phenomenon, and on the basis thereof sets up recommendations for control of soap-flotation operations. EXPERIMENTAL Parallelism between floatability of a mineral in a given environment and its contact angle in that environment is so well established,' and the contact angle is so readily and rapidly measurable, that contact angles have been used throughout the experimental work to indicate relative floatability. Experiments comprised contact-angle measurements on a number of representative minerals and metals, and a variety of subsidiary tests designed to check and to amplify the contact-angle indications. Contact-angle measurements were made by the method described in detail by del Giudice.3 Sequence of procedure for determination of the points of Fig. I was: 1. Polish specimen. Most specimens yielded zero contact angle after polishing; a few showed a slight "cling." Cling is characteristic of specimens that pit on polishing; it is due to a residue of organic contamination, originally on the particle surface, which persists in the pits. The cling did not change total contact angle after conditioning, and is not, therefore, additive in the upper part of the curves of Fig. I. It may have broadened the bases of the curves for the affected minerals slightly. 2. The specimen was next conditioned in soap solution for 5 minutes. 3. The conditioned particle was transferred, under conditions that precluded surface drying, to an aqueous solution of the pH desired and contact angle determined. 4. The particle was thereupon transferred, again without surface drying, to water. The confirmatory tests will be described at the places pertinent in the argument. DISCUSSION OF RESULTS Gaudin and Vincent4 have shown that contact angles with heptoic acid as a collector decrease for a given specimen when the concentration of collector present falls below a certain value. A similar reduction in angle occurs with collector-conditioned particles that are visibly slime-coated, and varies roughly with the extent of coating. Since in the last case the reduction in angle is certainly due to reduction in the proportion of total conditioned mineral surface presented to the bubble, the authors believe that the same condition prevails in the first case cited, and that similar reduction in angle and floatability will occur whenever starvation quantities of collector are present, whether

Jan 1, 1943

By Grover J. Holt

IN order to provide a clear picture of the development of the sink-and-float process of concentration as applied to the iron ores of Minnesota, a few pertinent facts should be brought out concerning the ores and the products of concentration. Iron ore is primarily a cheap commodity handled in immense quantities. The price of iron ore at present, based on a natural iron content of 51.5 per cent, varies from $2.55 to $2.70 per gross ton f.o.b. cars at the mine or washing plant in Minnesota. Last year 92,000,000 gross tons were shipped from the Lake Superior district (Minnesota, Michigan, and Wisconsin) to the furnaces. Concentrated iron ores have no greater value per unit of iron content than ores that can be mined and shipped direct from the shafts or open pits. For years only the higher grades of concentrating ores could be treated and sold in competition with the immense reserves of direct shipping ore available. These higher-grade "straight wash" ores required only the simplest treatment; namely, the washing out of fine sand from coarse ore particles. As the exhaustion of the "straight wash" ore is reached, rock is found replacing part of this sand, and the ore no longer responds to the former sizing treatment. Substantial tonnages of this marginal (jig ore) remained to be treated. Because of the limitations placed on concentrates by the furnaces-namely, low price of product and minimum amount of fines-iron-ore concentration has been and must continue to be a one-pass process. Only an increase in price or a change in structure of concentrates allowed by the ore consumer will encourage departure from this practice. Faced with the necessity of handling large tonnages, with the limitations mentioned, iron-ore research men have found their search for new and more efficient methods of treatment seriously handicapped and removed from the field of fine crushing. Sink-and-float treatment appeared to offer the best field in coarse concentration and has been proved by several plants to be well adapted to our problem. The use of ferrosilicon as a medium solid was decided upon. In our present practice, the ferrosilicon metal, carrying about 83 per cent iron, 15 per cent silicon and 2 per cent carbon and nonmagnetics, is crushed to pass 65 mesh and used without further sizing. When mixed with water the specific gravity of the medium may be controlled to within 0.02 per cent above or below the required gravity. Table I shows examples of a change in solid content of the medium for varying gravities. [ ] Table I is based on clean ferrosilicon, whereas some contamination is always present in the mill circuit, tending to

Jan 1, 1943

By J. Murray Riddell, George A. Morrison

This paper is a companion to the one by George A. Morrison on Mining a Deep Limestone Mine in Ohio.‡ Barberton is 8 miles west of Akron, Ohio, and 23 miles south of Cleveland. The underground mining of limestone at Bar-berton constitutes the world's deepest limestone mine. The stratigraphy is as follows: 0-20 ft. Loam, clay, sand and gravel. Water bearing. 2-40 ft. Fractured sandstone. Water bearing. 40-110 ft. Sandstone with interbedded shale, slightly fractured. Water bearing. 110-314 ft. Sandstone with interbedded shale, slightly fractured. Water carrying. 314-2197 ft. Shale with occasional seams of sandstone, which varies in thickness from a few inches to 4 feet. Dry. 2197-2247 ft. Limestone. Dry. 2247-2742 ft. Dolomitic limestone. Dry. 2742-2767 ft. Salt. Dry. 2767- Dolomitic limestone. Dry. All of the strata dip to the southeast, about 0.5 per cent from the horizontal. The top 110 ft. of the crust is water-bearing. The rock strata are naturally fractured to a depth of 314 ft., sufficient to allow the passage of water. In the shaft-sinking operations, a stra- turn of oil-bearing sandstone one foot thick was encountered at a depth of 520 ft., and flows of methane gas were pierced at depths of 1350 and 1952 feet. Specifications for the mine plant called for, in part, the sinking of two vertical shafts and a hoisting plant capable of producing at the rate of 300 tons per hour. No. I shaft is 550 ft. west of No. 2 shaft. Each shaft measures 8 by 17 ft. outside of steel. General features of the design (Fig. I) are: Principal set members, 6-in. H-section; connecting angles (studdles), ? by 4 by 4-in. angle irons; spacing of sets. 8 ft. centers; spacing of bearer sets, generally, 160 ft.; bearers, of 12-in. I-beams. Each bearing set featured a concrete ring about the periphery of the shaft, steel to rock, and 8 ft. in height; permanent guides, 6 by 10-in. long-leaf yellow pine, 85 per cent heart. The Shaft-sinking Operation The preliminary shaft-sinking work consisted of driving interlocked steel piling about the exterior of the shafts to depths of 35 and 32 ft., respectively, and of such horizontal dimensions as to ultimately permit the pouring of a concrete collar 2 ft. in horizontal thickness. Following the pouring of a shaft collar, a temporary wooden headframe for shaft-sinking purposes was erected. The head-frame, while ordinary, featured: (1) a storage pocket of 300 cu. ft, capacity with truck servicing facilities, and (2) pneu matically operated dump doors, which mere actuated by the hoistman, thus caring

Jan 1, 1946

By Arthur F. Taggart, T. C. Fitt, A. W. Thomas

It was noticed early by operators that high recoveries and flocculation of the sulphide minerals were closely correlated in agitation-froth flotation. Later, this readily visible flocculation was found almost invariably to be due to the binding together of the oiled sulphides by minute air bubbles, and is now known to be characteristic of pulps in which at least one of the mineral species is coated with an insoluble collecting oil. In 1930 it was reported1 that in differential flotation a correlation exists between Brownian movement of particles in the pulp and their nonfloatability, and that Brownian movement and dispersion are likewise correlated, whence it would appear to follow that dispersion of a mineral particle in a flotation pulp denotes a particle condition unfavorable to flotation. In 1934 it was postulated2 that Brownian movement, dispersion and nonfloatability all flow from the condition of the surface of the dispersed particles. It was also postulated at that time that the surfaces of dispersed particles are ionized, the ionized compound being a product of reaction between a component of the particle and a component of the pulp, of a mass solubility of the general order of a fraction of a milligram to I 5 to 20 mg. per liter. It was then further asserted, and has since been confirmed by Bankoff,3 that sulphides so conditioned with soluble collectors as to be floatable flocculate without the intervention of air bubbles as binding media. The present paper comprises an inquiry into the nature of the bound and counter ions in zinc sulphide dispersed by sodium arsenate. A part of its findings was mentioned in the 1934 paper above cited.= The tests show that: I. When powdered granular zinc sulphide is immersed in aqueous solutions of sodium arsenate, arsenate ion is abstracted from solution and anchored to the solid surface, while sulphate and lower sulphoxy ions are concurrently displaced therefrom in substantially stoichiometric quantities. 2. The ion counterbalancing the anchored arsenate ion is zinc. 3. Dispersion and Brownian movement of zinc sulphide are concurrently maxima at an arsenate-ion concentration lying between 0.01 and 0.001-molar sodium arsenate. 4. Any condition or reaction that tends. to remove the zinc arsenate coating from the zinc sulphide particles decreases dispersion and Brownian movement concurrently. Experimental Three samples of zinc sulphide were used. Lot I was C.P. zinc sulphide, washed well be~ond absence of chloride, as shown by test with silver ion. Lot 2 was prepared by precipitation from hydrochloric acid solution of arsenic-free zinc, and was washed as lot I. Lot 3 was prepared by heating a portion of lot 2 in absence of air at 1200° to r300°C. for one hour."

Jan 1, 1943

By G. L. Craig

In order to meet the unprecedented demand for copper it has proven necessary not only to develop every primary source, but also thoroughly to exploit the vast reservoir of metal in use that is not directly serving the war effort. To accomplish this, industry has been called upon to use its resourcefulness for developing methods of recovery that have not been previously utilized. It is in this connection that we have been asked to review the methods suggested for recovering the basic constituents of various types of the so-called clad or composite steels. As a background for a discussion of recovery processes, it seems appropriate to consider clad materials in general and their processes of manufacture. A composite steel has been defined as one consisting of two or more component parts of which the smallest shall comprise at least 3 per cent of the total mass. Clad materials or composites are produced commercially by several different methods of which the most important may be classified as: I. The Blacksmith or Forge Weld Method. This method is limited to carbon steels or low-alloy steels as the presence of even small amounts of common alloying metals prevent the formation of a satisfactory weld. The principle is the application of pressure to sections in contact at elevated temperatures. Because of the tendency of the iron to oxidize, borax is generally used as a flux to absorb the iron oxide. 2. Casting Process-In this method a composite ingot, billet or cake is produced by pouring one metal onto or about another. The bond may be accomplished by the action of the molten metal against a solid, in which case the bond may be referred to as mechanical; while in other instances alloying occurs at the interface producing an anchor by the formation of component parts of the two materials. 3. Cementation Process.-In this process any number of combinations of metallic and nonmetallic constituents which are mixed together may be used as a bonding agent. The combinations, whatever they may be, are placed between the materials to be joined and subjected to pressures at elevated temperatures to produce the desired bond. 4. Fusion Welding Processes.-Gas and electric joining for direct use or subsequent fabrication. 5. The, Assembly Process.-This method involves the joining together of prefabricated bars or plates followed by hot and/or cold working the assembly to the desired finished form. This method is advantageous in many cases because of its flexibility on small quantities as compared to the casting method. It is also possible to control the relative proportion of components more accurately. In this discussion we are concerned only with the scrap resulting from the manufacture of clad materials and our interest,

Jan 1, 1943

Boiler-Room Economy "Establishing and Maintaining Boiler-room Economy" is the title of a paper presented before the Ohio Society of Mechanical Electrical and Steam Engineers by Geo. H. Gibson, of which the following is an excerpt: Boiler-room economy depends less upon equipment than upon operation, i.e., it depends largely upon the condition in which the apparatus is maintained and how it is used. A given boiler may operate this week with an efficiency of 78 per cent., and next week with an efficiency of 65 per cent., while using the same fuel and developing the same rating. If there are variations ii; character of fuel and in load and other factors, the falling-off may be even greater, possibly to less than 60 per cent. The steam produced may cost twice as much per 1,000 lb. at one time as at another. Most steam plant managers know from their own experience that these statements are not exaggerated. It does not take much of a plant to run up a coal bill of $5,000 per year, many "spend $10,000 for coal, and fuel bills of $50,000, $100,000, or $200,000 per annum are not uncommon. As it call be shown in the majority of these plants that 10 per cent. of this amount may be saved, and in large numbers of them 25 per cent., while in some the expenditure can be cut in half, there is no disputing that we have here a subject worthy of attention. In the production of steam the greatest variable is the human factor. Before we can pass judgment, however, we must first have standards. This implies accurate quantitative knowledge of fuel consumption and steam production. We must measure the output and know how much the steam costs per thousand pounds, and how many pounds of steam are obtained from a pound of coal. We can then begin to analyze the problem, and find where and how methods and conditions can be improved, and how much. Many favor buying coal on a B. t. u. basis. This is advisable where the amount purchased warrants the considerable expense involved in systematically gathering samples that: are. truly representative and in having analyses made, of every carload. Coal analyses, combined with. an honest endeavor on the part of the miner to ship good coal, should insure the receipt of the heat units paid for. , It often happens, however, that the coal which is cheapest on a B.t.u. basis is not the cheapest or most suitable for producing steam, because of peculiarities of the plant in which it is to be burned, or conversely, the fuel which furnishes cheap B.t.u. may require special methods or equipment for its economic utilization.

Jan 2, 1916

By James E. Berryman

A method is presented for calculating the pressure depletion performance of a gas-condensate reservoir from the original reservoir fluid composition using the laboratory determined pressure-production history and retrograde liquid accumulation as guides. Equilibrium vaporization ratios for this calculation were modified from published data until the calculated dew point pressure and retrograde liquid accumulation agreed with the values observed in the laboratory. The calculated results are compared with the produced gas composition determined by low temperature analysis during constant volume laboratory experiments of pressure depletion behavior. This comparison shows that the calculation procedure is adequate for determination of gas phase composition. Data from field separation tests in low temperature separators are presented which verify the applicability of published equilibrium vaporization ratios for a wide range of separator conditions. INTRODUCTION A reliable prediction of the pressure depletion performance of a gas-condensate reservoir is necessary in determining reserves and evaluating field separation methods. The predicted performance is also used in planning future operations and studying the economics of projects for increasing liquid recovery. Because the flow of fluid in a volumetric gas-condensate reservoir is usually single phase flow, the pressure-depletion per-formake is primarily a function of the phase behavior of the reservoir fluid. The properties of a gas-condensate system of major importance are: (1) compressibility factor at reservoir temperature and pressure; (2) dew point pressure; (3) composition changes of the vapor phase with pressure depletion; (4) recovery of original in-place hydrocarbons at any pressure; and (5) retrograde condensate accumulation. These properties are most generally determined by a pressure depletion-type experiment on recombined separator gas and liquid samples in the laboratory. ldeally the pressure-depletion performance can be calculated from the composition of the original reservoir fluid if the reservoir temperature and initial pressure are known.1,2,3 It has been reported "... comparison of such computations with depletion-type ex-periments on recombined samples in the laboratory have yielded results that appeared to be entirely adequate.". The success of such calculations is determined by the equilibrium vaporization ratios chosen, especially those for the higher boiling point hydrocarbons. It is the purpose of this paper to present a method for computing the change in composition of the vapor phase during pressure depletion by production using laboratory determined properties of the system to guide the calculation and to illustrate the use of the method with data from the Cockfield "D" sand of Washington field, St. Landry Parish, La. Results of field tests and laboratory analysis are included. As a result of this reservoir fluid study, a cycling program has been evaluated, the fidd has been unitized, and the cycling started in July, 1956.

Jan 1, 1958

By Herman Garlichs

The development of the extensive Southeast Missouri deposits greatly preceded that of the Iowa and Wisconsin deposits. It began about 1720 at Mine La Motte and other localities, and has continued uninterruptedly to the present time. It is estimated that this district produced about 184,000 tons of lead in the year 1916, having a value of approximately $25,000,000. This is a new high record. The Southwest Missouri orebodies were hardly known before 1845 and were not extensively developed until 1870. Lead production in Southwest Missouri for 1916 was 38,788 tons. Oklahoma produced 14,399 tons and Kansas 2,345 tons, making a total for Southwest Missouri, and the adjoining districts in Oklahoma and Kansas, of 55,532 tons of lead. The first metallurgists in Missouri were the Indian and the hunter. The early settler learned to procure his bullets either by melting ore in his camp fire or by throwing pieces of galena on an old stump and depending on the usual roasting and reaction method to obtain the metal. A little more refined method was to arrange two flat stones in the form of a, V. Wood and galena were placed in the furnace and ignited.. As heat developed, some of the metal was extracted and molded into bullets. The next step in utilizing the lead ores was the log hearth. All lead in Missouri was smelted in this crude affair before 1820. It was built on sloping ground, and consisted of a hearth of stone, surrounded on the front and two sides by a stone wall. The wall was 7 it. high in front. The top and rear end were left open and in front an arch or opening was made, forming the eye of the furnace. In front of this a pit was dug in the ground, to receive the molten metal. Large logs were rolled in at the back and made to rest upon ledges formed inside, to raise them from the hearth and to give a draft. These logs filled the entire width of the furnace. Small split logs were then set up around the two sides and the front, and the ore was piled on until the furnace was full. Finally, the mass was covered with logs and fuel until the ore was completely surrounded. A gentle heat was started, which was raised very gradually. After 12 hr. the heat was increased and continued for 12 hr. more, 24 hr. being required for each smelting. The furnace treated about 5,000 lb. per 24 hr. and the ore yielded about 50 per cent. of its metallic lead. A considerable quantity of the ore was not desulphurized, and fell between

Jan 1, 1918

By Howard Clarke, Cyril Stanley Smith, Clarence Zener

The importance of cold-working in the fabrication of metals is in marked contrast with our ignorance as to the nature of the accompanying internal changes. The failure of the usual methods of testing to provide a consistent picture of these internal changes has given the incentive for the present program of investigating the effect of cold-working upon the internal friction of metals measured at small strain amplitudes. It has previously been shown1,2,3, that the internal friction introduced by cold-work is removed by annealing at comparatively low temperatures. In the present paper the following additional factors are investigated: (I) frequency of measurement, (2) amount of cold-work, (3) temperature of measurement. Special care was taken to minimize the internal friction due to causes other than cold-work. The present paper is purely experimental, the authors believing that any conclusions drawn from this work as to the nature of the internal changes accompanying cold-work would be premature.'l PrEpaRations oF Specimens In this study of cold-work it was desirable to eliminate as far as possible all other sources of internal friction. One disturbing source is the lack of temperature equilibrium between adjacent crystallites of a vibrating specimen.4 Temperature equilibrium is aided by small grain size and by the use of low-frequency vibrations. Unless unduly long specimens are used, low frequencies can be obtained only in transverse vibrations. But in transverse vibrations a second source of internal friction is present, that arising from transverse thermal currents.5 The effect of these may be reduced by increasing the transverse dimensions. The grain size and transverse dimensions of the specimens were thus so chosen as to render the vibrations simultaneously nearly isothermal with respect to intercrystalline thermal currents, and nearly adiabatic with respect to transverse thermal currents. The material for this investigation was a 70-30 brass, part of the same lot of material that was used for some earlier studies on the effect of strain on proportional limit.10 It had the following composition: copper, 70.59 per cent; zinc, 29.39; lead, 0.01; iron, 0.01. This material was received from the brass mill in the form of 3/4-in. rod, cold-drawn to final size by a 65 per cent reduction of area from material that had been annealed to give a grain size of 0.060 mm, Rods of appropriate length were annealed for 2 hr. at 400°C. and cooled in air. The annealed rods (grain size, 0.012 mm.) were then stretched in a tension-testing machine, using special grips1' to ensure axial application of the load. The rate

Jan 1, 1942

By Blake M. Loring

Recently the S-curves for 30 to 40 alloy steels have been pub1ished.l.2 These steels show individual characteristics, which make each additional S-curve of great interest. There are important differences in the mechanism of the transformation process, the type of transformation product, and the influence of alloying elements. Steels of the same general alloy composition may possess such variable characteristics with regard to the length of time of isothermal transformation that an S-curve for each heat of steel may be desirable. In the present work the isothermal transformation of a steel having the following composition and grain size was studied: 0.29 per cent carbon; 0.21 manganese; 0.026 phosphorus; 0.017 sulphur; 0.056 silicon; 1.45 chromium; 3.25 nickel; austenite grain size, 7. The progress of the isothermal transformation was followed by several different methods, including hardness measurements, dilatometer observations, and examinations of the microstructure. It was not expected that these methods would be in precise agreement.3 Accordingly, the changes in microstructure and hardness were given additional weight in determining the initial stage of transformation and the dilatometer measurements were relied on in estimating the completion of the process. The beginning of transformation was indicated by I per cent of transformation products and the end of transformation by about 99 per cent. The reproducibility of the various methods in the ranges of highest sensitivity was checked by several observations at each time and temperature. The steel used in this investigation was annealed for 24 hr, at 925°C. Macroetching revealed no serious segregation. The specimens for the metallographic and hardness investigations were 1¼ by ½ by ? in. Wires attached to the samples were used for handling. instead of tongs, to avoid chilling. The specimens were heated at 845°C. for ½ hr. and quenched into constant-temperature salt baths held at various temperatures from 205' to 650°C. The time required to transfer the specimens was found to be about 1½ sec., and nearly 5 sec. more was required for them to come to the temperature of the bath. After various lengths of time in the constant-temperature baths the specimens were quenched in water at 2I°C. The specimens were cut in half for the metallographic examination, to provide a surface free from decarburization. To determine the beginning and end of the transformation the percentage of transformation determined metallographically and by hardness was plotted against time. A planimeter was used in the metallographic determination. The hardness and metallographic determinations made at room temperature were confirmed reasonably well by dilatometer measurements taken during the process of transformation at the various temperatures. Two dilatometers were used to

Jan 1, 1942

By R. K. McGeary, B. Lustman

Orientation relationships and rates of annealing of 97 pct cold rolled zirconium have been studied by X-ray techniques, metallography, and by hardness measurements. The process of annealing occurring by the formation of domains, and their subsequent growth without recrystallization, is demonstrated. NUMEROUS investigators1-' have revealed sub-grain formation after annealing cold worked metal single crystals and have generally described the results in terms of a dislocation mechanism of polygonization.5,6 in heavily cold rolled polycrystal-line aluminum the first stages of heating cause an apparently spontaneous subdivision of regions of the deformed matrix into a great number of slightly disoriented domains followed or accompanied by rapid growth of certain domains to form a recrystallization texture.7,8 In the present investigation the isothermal rate of annealing of cold worked polycrystalline zirconium has been studied by X-ray techniques, metallography, and by hardness measurement. It will be shown that, rather than by the usual nucleation and growth mechanism,"12 the process of annealing can best be explained by the formation of domains early in the annealing treatment and the subsequent growth of these domains without recrystallization. Experimental Procedure All the experimental work was performed on an arc-melted ingot of high purity zirconium crystal bar made by Westinghouse in a production scale deBoer unit. The weight percentage of impurities in the zirconium were as follows: C, 0.04; Fe, 0.05; Hf, 0.014; W, 0.01; Ti, Ni, and Al, 0.003; Si and N, 0.002; Cr and Cu, 0.001. Metallographically the zirconium showed only a single phase. The 4 in. diarn ingot was forged at 760°C to a 1 1/2x3 in. plate and was then rolled at 760°C to 0.150 in. thickness and annealed at this temperature for 20 min to produce an equiaxed grain structure of about 0.1 mm average grain diameter. The hot rolled plate was roller-leveled, surface ground to 0.135 in., cold rolled 83 pct reduction in thickness on a two-high mill, and then to a total reduction of 97 pct on a Sendzimir mill. The 0.004 in. strip material so produced received no subsequent mechanical treatment. Specimens % in. square were sheared from the rolled strip and isothermally annealed at 104 mm Hg in an all glass vacuum system equipped with a Vycor furnace tube. The temperature data presented are the average temperatures during the runs and did not vary more than about k3"C. X-ray Diffraction Methods: When zirconium is drastically cold rolled, a high degree of preferred orientation results in which prism poles, {1010}, are perpendicular to the rolling direction. After fully annealing this material an entirely new texture develops which corresponds to a 20" or 40" rotation of the deformation texture about hexagonal axes of

Jan 1, 1954

By E. P. Abrahamson II

The effect of transitiorz element bitzary solid solution additions upon the recrystallization temperature of columbium has been investigated. The elements Mn, Fe, Co, Ni, W, Re, and 0s OWY the yecystallization tempel-aturye, while Ti, V, CY, zr, Mo, Ru, Rh, Pd, Hf, Ta, W, Ir, and Pt mise it. A correlation is kloted between the rate of chatzge of recyystallization tewaperature with atomic hercent solute and the free atom electron configuration of the solute element. The work of Abrahamson and Grant1 has indicated a correlation between the free atom ground-state electron configuration and the change in brittle-ductile transition temperature per atomic percent solute in chromium base alloys. A similar correlation was observed for the change in the recrystallization temperature of iron base alloys by Abrahamson and Blakeney and Abrahamson. It was also observed that the limit of rapid change in recrystallization temperature also Correlated with the electronic configuration of the free solute atom. A further study by Abrahamson4 established the generality of the phenomenon by yielding similar results for vanadium base dilute alloys. It has been inferred that a peri- odicity might be expected with changes in the free atom electron configuration of the solvent element. This study is the third set of transition base metal systems to be studied. It is the object of this and further studies on transitional metal systems to detect any systematic variations in the observed correlation which might contribute to the understanding of the electron interactions which are evidently exhibiting themselves. PROCEDURE All alloys were made using 99.9 pct Cb with 0.030 Ta, 0.016 0, 0.0025 H, 0.003 Mo, 0.021 Fe, 0.005 C, and 0.002 N. The solute elements were 99.9 pct pure. According to the published binary phase diagrams5 and metallographic examinations at X750, all additions were in solid solution. The alloys were arc melted and remelted 6 times in the form of cubic 400-g buttons under an argon atmosphere. They were then hot forged at 1200oC to 0.6-in. diameter, annealed for 3 hr at 1200o under argon, and furnace cooled. The specimens were then machined to 0.400 -in. diameter. Grain size was checked and found to remain essentially constant at 150 i 30 grains per sq mm. The specimens were then cold swaged to 0.187-in. diameter, yielding 46 i 1 pct cold work. All alloys were chemically analyzed for the major solute. Analyses of random samples indicated that the impurity content remained at the values of the starting material. Tungsten contamination was held to 0.007 pet.

Jan 1, 1962

By M. R. Hatfield, F. J. Vosburgh

IN a recent article,† it was shown that in the blast furnaces in Germany that are lined with carbon blocks no cooling plates are used, and that shower cooling is employed on the hearth and bosh sections. While one of the authors was in Germany he was told that one furnace was being operated without even the shower cooling on the bosh section, though the hearth section was shower-cooled. In discussion of this interesting situation with a number of blast-furnace operators in this country, it was made clearly and promptly evident that shower cooling was very unpopular, probably because of its messiness and its ineffectiveness. Both of the causes for the dislike of shower coolings are reasonable ones. Shower cooling can be and frequently is messy, but the present cooling of blast furnaces leaves much to be desired on that score. Shower cooling is ineffective as compared with plate cooling, so far as its usefulness in keeping the bricks cool enough not to melt or fall to pieces is concerned. However, the introduction of carbon linings changes the situation. No one is concerned with keeping a carbon lining cool, for no temperature in the blast furnace has any effect on carbon, which is just as stable at 3000°F. as it is at 70°F. The only concern is for the shell-to keep it cool enough for safety and comfort and for that shower cooling is sufficient. Of course, with only the shell to cool, instead of the shell plus all the refractory material, much less water would be required, and the necessity for constant attention to the flow would be lessened, as the hundreds of inlets and outlets would be eliminated. Probably half of the water used in cooling a blast furnace is used for cooling the shaft and tuyeres and the remainder for the bosh and hearth sections. However, in view of the dislike of shower cooling in the United States, and particularly because at least one German blast furnace is operated with no cooling of the bosh section, thought was given to the possibility that a carbon-lined blast furnace might be operated without any cooling of the entire carbon-lined portion. For that reason a series of experiments was performed to determine what might be the temperature of the shell of a blast furnace protected by a carbon lining and operated under varying conditions up to a maximum inside temperature of 3000°F. EXPERIMENTAL PROCEDURE A schematic diagram of the experimental setup is shown in Fig. I and a photograph of the entire assembly in Fig. 2. The heating element was a carbon tube nominally 2 5/8 in. o.d. by 2 in. i.d. by 30 in., used as a resistor. Power was furnished by a 15-kva. transformer operating

Jan 1, 1941