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By G. A. Beiswenger

The application of the law of supply and demand to the sale of crude oil is generally conceded, but the motives underlying the buyer's (refiner's) demands are not always obvious to the seller (producer). In some cases this obscurity has led to the conclusion that the refiner may be unnecessarily particular when he selects one crude and rejects another. This preference, however, is very largely the reflection of the refiner's product demands and the quality of the stocks obtainable from the selected crude. The purpose of this paper is to point out critical characteristies of the major classes of refined products and to show how crudes vary in their suitability for such products. With relatively few exceptions, available processing methods and addition agents make it theoretically possible to produce any type of refined product from any crude source, although it may not be economically sound to do so. The widespread application of thermal cracking for converting higher boiling stocks into gasoline is well known. More recently cracking and refining in the presence of catalysts9 have been developed, as well as various processes for polymerizing lighter hydrocarbons into gasolines having desirable characteristics.6 For several years, selective solvents have been applied commercially to refining inferior quality kerosene, Diesel fuel and lubricating oil distillates.3 Improved methods for refining lubricating oils from crude residual4 formerly suitable only for fuel, are now in use and a number of special solvent processes are available for dewaxing lubricating oils to low pour point.5 These improved refining methods have been developed not only to meet the demand for improved product quality but also to enable the refiner to obtain quality products from crude sources that would not yield such products by the older refining methods. In many cases, the utilization of these modern refining tools necessitates an appreciable expenditure for equipment as well as added manufacturing costs, and their application therefore must be justified economically. Despite the availability of such tools, the added processing costs involved and yields obtainable may render their application entirely impractical. To illustrate this point, inspections of typical cuts from various crudes

Jan 1, 1940

SAMUEL L. HOYT.-The question of adding the ferromanganese to the ladle or to the furnace involves both theoretical and practical questions and its discussion might very easily occupy the rest of the day. One of the points to be kept in mind is the desirability of obtaining uniform steel. If ferromanganese is added to the ladle, it is necessary first to melt the manganese and then to distribute uniformly throughout the heat. The only heat available for this purpose is that of the molten steel itself. No doubt sufficient heat is present, but in our desire to pour the steel as quickly as possible there is hardly sufficient time allowed, many times, for the proper distribution of the manganese. In other words, this is an operation which takes a certain amount of time and any undue shortening of the time allowed must affect the quality and uniformity of the steel. Again, this particular method does not lead to as efficient a use of the manganese as might be desired; a contention which is based on theoretical grounds. In concentrated solution, manganese will completely reduce all the ferrous oxide, the presence of which I hypothecate and produce, as the reaction product, manganese oxide. In dilute solution, the manganese only partly reduces the iron oxide, but the manganesee oxide which does form dissolves the iron oxide in simple solution. The dissolution of ferrous oxide in the manganese oxide will result in a more economical utilization of the manganese and an equal purification of the heat. This whole point, at present, has not been definitely proved and its answer will involve very difficult research work. On the other hand, if the manganese is added to the furnace, the heat of the furnace is used to melt the alloy and there is plenty of time during tapping for the manganese to be very uniformly distributed throughout the steel. By distributing the alloy throughout the charge we can secure a better utilization of the manganese than is possible if the addition is made to the ladle. Certain other points, such as the recovery, have been dealt with at greater length in the paper.

Jan 4, 1919

By B. M. Larsen, T. E. Brower

A perspective is presented of the steel plant sulphur distribution and elimination problem from coal to liquid steel ready for teeming, giving distributions of sulphur over a range of coke sulphur content, and some methods of sulphur control, in the blast furnace, external desulphuriza-tion between blast furnace and open hearth, distribution between fuel, slag, and metal, and methods and limitations of control of sulphur in the open hearth furnace. AS a part of the 1951 AIME symposium on sulphur in steelmaking, it was thought that a discussion of the distribution of sulphur throughout the whole series of operations, from coal and ore to finished steel ingots, might have some value in giving a perspective on the whole problem. The following discussion is an attempt to present such an overall picture. The order is that of the actual plant operations, beginning with a very brief consideration of the coking process. Sulphur in Coal and Coke Since by far the largest source of sulphur entering the steelmaking cycle is in the coal used to make coke for the blast furnace, it would seem reasonable to eliminate some of it, either from the coal, or the coke, or during the coking process. This has appeared impracticable up to the present, at least, for two main reasons: the low activity of the organic sulphur in either coal or coke, and because of price limitations involved in treating a low cost material such as coke. A variable portion, usually M or less, of the sulphur is present in coal in the form of pyrites or similar compounds, and a large part of this sulphur may be removed in the coal washery. Most of the sulphur, however, is normally present as "organic" sulphur, intimately associated with the coal structure. Its distribution prevents any separation by mechanical means. Its low activity makes improbable ' any rapid chemical removal, although hydrogen will remove sulphur from both coal and coke. Thus, prolonged recirculation of coke oven gas in the coking process would tend to leave a smaller percentage of the total sulphur in the coke residue. Table I shows a typical distribution of sulphur from coal into products in the coking process. As the sulphur in the coal increases, the sulphur in the coke tends to increase in about the same proportion. Sulphur in the Blast Furnace The best picture of the situation in the blast furnace is provided by a sulphur balance of raw materials entering, and of products leaving, the furnace. The difficulties in accurate weighing and sampling of the variable solid materials entering this process, and the number of hours required for the raw materials to descend through the furnace under variable operating conditions, make it difficult to obtain an accurate balance. However, balances made over periods of weeks or months tend to average out some of these uncertainties. Table I1 presents three typical sulphur balances similar to a number that the writers have calculated. In most of these the slag volume calculated from the sulphur balance is, in some instances more, and in other instances less, than the value corresponding to the best input and output balances of the other slag constituents (lime, silica, alumina, etc.). Probably the greatest source of error in these calculations is the sulphur content of the slag. Despite some possible inaccuracies the balances of Table II show rather definitely the following points: 1—That 87 to 95 pct of the total sulphur input is in the coke and 95 to 97 pct of the total sulphur output is in the slag. Also, that if any sulphur leaves the furnace with the gas it is relatively small, amounting to a possible 1 pct or less. 2—At the lower sulphur coke level of 0.86 pct the total amount of sulphur charged is 15 Ib of sulphur per ton iron increasing to 26 lb per ton at the higher sulphur, intimately associated with the coal struc-rare burdens containing sulphur-rich ores will the total sulphur burden fail to be nearly proportional to the content in the coke used. 3—The 7 to 9 pct of the total sulphur input from the limestone of furnaces B and C is due to the relatively high sulphur content of the stone, 0.226 and 0.265 pct, respectively. In the case of furnace A, the sulphur content of the limestone was only 0.06 pct which resulted in only 3 pct of the total sulphur input coming from this source. It is rather interesting to compare the sulphur balances of a typical ferromanganese furnace with

Jan 1, 1952

By Eugene H. Cowles

The German silver industry of the United States amounts in value to upwards of $6,000,000 or $8,000,000 annually. Several thousands of people earn a livelihood pursuing it, and the beautiful goods and articles manufactured from this time-honored and valued alloy are everywhere visible. German silver enters largely into our street signs, harness and house hardware, and all manner of table-ware, solid or plated. There is scarcely an hour in the day that German or nickel-silver is not before our eyes. The composition of this alloy is a very uncertain thing, and depends largely on the honesty of the manufacturer and the price the purchaser is willing to pay. It is composed of copper, zinc and nickel in varying proportions. The best varieties contain from 18 to 25 per cent. of nickel, and from 20 to 30 per cent. of zinc, the remainder being copper. The more expensive nickel-silver contains from 25 to 33 per cent. of nickel, and from 75 to 66 per cent. of copper. The nickel is used as a whitening element; it also strengthens the alloy and renders it harder and more non-corrodible than the brass made without it, of copper and zinc. Moreover, it reduces the odor emanating from brass, which is so disagreeable if it occurs about the dining-table. Of all troublesome alloys to handle in the foundry or rollingmill, German silver is the worst. It is unmanageable and refractory at every step in its transition from the crude elements into rods, sheets or wire. As a white-headed furnace-man recently said to the writer, in one of our large mills, " you can put eight crucibles into the fire, each containing exactly the same mixture of German silver, and when you take them out and pour them into slabs for rolling, seven will be a mass of scum or slag, or the stuff will swell up like rising bread and overflow the moulds, and be so full of blow-holes that it will look like a sponge. The eighth crucible will contain perfectly good metal. On remelting the next day, the bad stuff will, in nine chances out of ten, come out just as good metal as the eighth pot the day before, and under apparently the same conditions." With nickel at seventy or eighty cents per pound, German silver

Jan 1, 1890

By R. W. Smith, G. W. Delamore, J. A. Spittle

RECENT work by the authors1 has demonstrated that the crystals constituting the equiaxed zone in small ingots originate, on quenching, in the chilled liquid. Whether any partial remelting2 takes place of the den-drites nucleated in the chilled region was not examined. However, the claim3 that this normally occurs, leading to crystal multiplication, has been disputed.4 Thus, for an equiaxed zone to form in the central region of an otherwise columnar ingot, it is necessary to transport crystallites from the chill zone to this region. In view of the work of Uhlmann et al.,5 it was considered desirable to examine the transport process further. Experimental Technique and Results. In the earlier experiments by the authors.1 a stainless-steel crucible 17/8 in. diam, 41/2 in. high, ad containing an alloy of A1-4 wt pct Cu, was quenched from 660°C into a bath of Wood's metal maintained at 100°C. Under these conditions a central zone of equiaxed crystals was obtained. However, if a 2250-G unidirectional magnetic field was applied for 2 sec immediately following the instant of quenching, or subsequently, the equiaxed zone did not appear. Careful thermal analysis showed that the short application of the field had virtually no effect on the thermal conditions of the melt. It thus appeared that the crystallites which were ultimately to grow large enough to form the equiaxed zone existed in the liquid immediately ahead of the interface, occlusion being prevented by the convective fluid flow induced by freezing from the walls of the cylinder. When this relative movement was prevented by the Lorenz forces induced by the application of the magnetic field, the crystallites were caught up in the rapidly advancing dendrite solid-liquid interface. To test this assumption, a small ingot of super-purity aluminum was partially melted and poured into a heated stainless-steel mold which was then immediately quenched into molten Wood's alloy. The resulting structure is shown in Fig. 1, and consists of columnar grains with a central fine-grained zone. Thus the unmelted solid present at the beginning of solidification had been transported ahead of the columnar interface. Discussion. There appears to be little or no information available on the interaction of suspended particles with a metallic solid/liquid interface. However, some information is available for transparent organic sys-

Jan 1, 1969

Consolidated Gold Fields Limited published annually an excellent reference, GOLD 1978, GOLD 1979, giving the Supply and Demand for Gold, Recent Developments and Prospects, Soviet Gold Production, etc. This outstanding reference is authored by Christopher Glynn, Investment Department, London, Great Britain. The 1978 Report marked the tenth anniversary of Gold Field's review of world gold market developments; and from it and the 1979 report, the following information was derived. The recovery of gold is widespread in the Soviet Union. Originally, gold was mined principally in the Urals, but in the last few years several major deposits have been discovered in the southwestern areas of the Soviet Union. One of the most dramatic discoveries has been the Muruntau deposit in Western Uzbekestan. This deposit, discovered in 1958, is reported to be the largest and among the lowest cost producers in the Soviet Union. It is located in Armenia, approximately 750 km (465 miles) northeast of the Iran-Afghanistan border, lying in the center of the Kyzylkurn (Red Sands) desert at the foot of Muruntau Mountain. Free gold occurs in both fine and coarse size in quartz veins up to 20 m (66 ft) thick associated with a small percentage of sulfides, mainly arsenopyrite. The ore zone constitutes a large gold-enriched stock work of about 4 sq krn (1.5 sq miles). The development of Muruntau was a major undertaking with open -pit development and construction of the mill and refinery complex started early in 1967, and the first gold bar poured in mid-1969. At the end of the first construction stage in 1970, the mill building was an imposing structure about 38 m (125 ft) high and 330 (1,080 ft) in length housing, probably, 11 parallel milling circuits. The first construction stage also included six 50 m (165 ft) diameter thickeners and 30 Pachuca tanks. The original mill complex was tripled in size after large additional gold reserves were discovered at a depth of 600 m (1,970 ft); and the deposit is now being exploited by both open- pit and underground workings. Ore is ground in semi-autogenous mills with the free gold being recovered into a high-grade concentrate on shaking tables. Table tailings are purnped to duplex spiral classifiers in closed circuit with the grinding mills. Classifier overflow is then thickened before being transferred to the Pachuca building where cyanidation takes place. An ion exchange resin is then added in a countercurrent

Jan 1, 1981

THERE have always been in this world men of such keen intelligence that with their discourse they have been capable of infinite and various inventions that are as beneficial as they are simultaneously harmful to the human body. Wherefore, from day to day, we see unfolded before our eyes some of these that greatly astound our minds, and we remain so stupefied that when-we think of them we are not able to control our faculties for some time, both from considering by what necessity or purpose these men were goaded, as well as from contemplating the profound subtlety of their discoveries, which, in truth, are such that they are awarded the greatest commendation by noble minds. By following their counsels and with their aid, there have been* some astute and lever captains who have had certain pots or balls of earthenware carried by their infantry, expressly filled with compositions of powder or other unctuous liquors disposed to ignite easily. When they meet the enemy in battle and come up close to them, they try to strike vigorously with these in the first assault in an effort to throw them into disorder and to make them give way by breaking them up and drawing them out of formation. The smoke is harmful, but the fire very much more so. These are made in this way. Take the number of vessels that you have to make-it does not matter whether they are raw or baked as long as they are well freed from the moisture of the clay-and fill them a little more than half full with coarse gunpowder which has mixed in it pounded Grecian pitch and at least a third of crushed sulphur. Then pour in a covering a dito thick of strained pig fat mixed with powder. This keeps it from falling out when it is thrown and keeps the fire slower until it reaches the enemy. When this has been made, open up the pig fat a little at one side when you wish to throw it and put in a little fuse or a little good powder and apply fire, holding it in your hand until you see that the fire has taken hold well. Then throw it, choosing your time. A liquid composition is also made in a kettle in which are put pork fat, petroleum oil, oil of sulphur, live sulphur, [163] doubly refined saltpeter,

Jan 1, 1942

After the close of the Revolution, settlers began to pour over the mountains, to settle in the western parts of Pennsylvania, of Virginia, to move down the Ohio into Kentucky, and in the late seventeen-eighties to settle on "the Indian side" of the river, now Ohio. With the growth of population the interest in coal increased and it was not long before the production of coal west of the mountains was larger than that east of them. Foreign nations, too, became interested in the young republic and in 1783, at the instance of the Swedish government S. A. Hermelin, an engineer, visited this country to investigate its iron industry. He made a very interesting report, not published until 1931, in which he gave many details of the iron plants in the eastern United States; apparently he was not west of the mountains, but was well informed about conditions there. He says, "that some coal near the first branches of the Schuylkill River has been mined and utilized by the blacksmiths," referring, of course, to anthracite; again that "coal mines have also been worked for several years near Pittsburg," and that "great supplies of iron ore are available at the Ohio Falls and further to the west, at Coney Creek, a part of the Green River, where there is also coal."' In 1788, Dr. Johann David Schoepf, who came to this country with the Hessian troops, visited Pittsburgh. He was an intelligent man and acquainted to some extent with minerals and methods of working them. In speaking of Coal Hill on the south side of the Monongahela he mentioned several strata of marble in the lower part and that

Jan 1, 1942

By C. H. Herty, J. L. Keats

In the literature on the elimination of metalloids in basic open-hearth practice, there are a great many heats recorded in which excellent data on changes in slag and metal composition during refining are given, but in almost all of these heats either temperature data or weights and analysis of charge are unrecorded and observations on the physical characteristics of the slag are almost always lacking. With these points in mind, a test heat was made in which as complete data as possible on all the factors that affect the elimination of metalloids were obtained. The Test Heat The test heat was made in a standard 100-ton stationary furnace at the Lackawanna Steel Co., Lackawanna, N. Y., on January 17, 1922. The Charge—Scrap.—The scrap consisted entirely of rail-heat butts, selected from a number of heats made the week before the test. The average analysis of the scrap was calculated from the analysis of these heats and from the weight of scrap from each heat. Pig Iron.—Two ladles of pig iron were used in the charge and two samples were taken from each ladle as it was poured into the furnace. These four samples were composited for the average pig-iron sample. Other Materials.—Weights of dolomite, ore and spar were obtained by weighing a quantity of each just before the test and weighing the amount of each left after the heat was completed. The limestone. was weighed on the charging pans. Coal for recarburizing, ferromanganese, ferro-silicon and aluminum were weighed out as used. All these materials were carefully sampled before the test was begun. Coal consumption at the producers was obtained by getting the average capacity of the hoppers that fed the producers, and then counting the number of hoppers of coal used during the course of the heat. Products Steel.—The steel made was rolled into billets, the rolling properties being very satisfactory. The weight of steel was obtained by taking a

Jan 1, 1926

By John Chipman, A. M. Samarin

It has been long known that the gas evolved during the boil in the open-hearth furnace is mainly carbon monoxide associated with smaller quantities of other gases. A number of attempts have been made to determine the precise effects of carbon and oxygen content of the bath, and of other factors, such as temperature, upon the evolution of carbon monoxide. In his investigation of the carbon-iron oxide product in liquid steel, Hertyl showed that the value of this product at equilibrium could be approximated by plotting the value of the product observed in open-hearth reactions against rate of carbon elimination, and extrapolating to zero rate. The results of this study showed a slight but definite effect of temperature upon the carbon-iron oxide reaction. Experimental studies of the evolution of gases from rimming-steel ingots have not yet attained the degree of precision necessary for an exact understanding of the effects of pouring temperature, carbon content, and iron oxide in the metal upon the composition of these gases. Klinger2 showed that the gas consists mainly of carbon monoxide, and that considerable variation in its composition occurs during the solidification of the ingot. In order that these variations may be understood in their proper relationship to the progress of solidification of the ingot and the segregation that accompanies solidification, it is essential to have a knowledge of the condition of equilibrium in the several chemical reactions by which the gases are being formed. It is also necessary to understand the effects of temperature upon the equilibria, and further, to know the manner in which the temperature of the liquid metal within the ingot changes as the skin of the ingot is being built up. The reactions in which we will be chiefly interested are those involving in the one case the oxides of carbon, and in the other case steam and

Jan 1, 1937

By Charles Pack

EXTENSIVE progress has been made in the metallurgy of alloys for die castings. Enthusiastic proponents of some alloys are inclined to make extravagant claims for their materials, which may be justified by physical tests on test bars made from the respective alloys but are seldom justified by the results obtained with commercial die castings made from those alloys. Chemical analysis of the test bars and castings fails to determine the cause of these variations, since they are due to other physical factors entering into the commercial production of die castings. In this paper, an attempt will be made to outline some of the factors in commercial die-casting practice to which these variable results may be attributed, in the hope that the manufacturer of die castings, recognizing the importance of these factors, will devote more attention to them in the design and construction of dies and equipment. In 1914,1 the author defined die castings as "metal castings made by forcing molten metal, underpressure, into metallic molds or dies." This definition was given in order to differentiate die castings from other molded metal products such as "permanent-mold" castings, "slush" castings and similar products that are sometimes erroneously termed die castings. The term "die casting" could be interpreted to include all castings made in metal molds or dies; but since this term, like most of our technical nomenclature, has been developed by commercial practice we must look to this practice for its proper definition. The Germans, with their usual devotion to descriptive names, have adopted the name of spritzguss (squirt cast) for die castings. Undoubtedly this name is more descriptive of the die-casting process, where the metal is literally squirted into the die and serves to differentiate this process from other metal mold processes, where the metal is poured into the die. In the earlier paper mentioned, the author also emphasized the fact that the definition given for die castings indicated clearly that the satisfactory operation of the process must comprise three factors, all of which must be considered of vital importance to the successful operation of the die-casting process:

Jan 1, 1930

By J. B. Davis

This paper has been prepared at the suggestion of Mr. Dunbar D. Scott, to supplement his " Evolution of Mine-Surveying Instruments."† Before entering into a detailed history of solar instruments, a few remarks will be made touching upon land-surveys in general, and on what has led to the development of these instruments.The oxidation of metals melted in contact with air takes place with dissimilar results. Tin, lead or zinc are examples of a class, the oxides of which float on the surface of the melted metal. First a film is produced, which covers the surface; then, if agitation from any cause exposes new metal to the action of the air, additional oxidation takes place, and the film is increased in volume. This change goes on until a considerable quantity of oxide (or " dross," as it is technically called) is formed; depending, of course, upon the duration of the exposure of the metal to the atmosphere. When such metals are poured, the dross may be skimmed off; and clean metal will be left underneath. The removal of such oxides is, therefore, merely a mechanical process. In the case of copper, however, the result is quite different. The sub-oxide of copper (Cu2O) is readily soluble in molten copper; and therefore, instead of the formation of a film of oxide, to be finally removed as dross, the surface of the metal remains bright and clear, because the oxide has been dissolved as soon as it was produced. It is customary in the process of copper-refining to leave a small quantity of oxide in the metal, in order to oxidize any traces of bismuth, arsenic or antimony which have not been entirely removed. As a result, these metals exist in the commercial product as oxides, and not as metals, which would form an

Jan 1, 1901

Jan 1, 1915

By Charles Wurms, Robert Steinitz

DURING an investigation to determine the compatibility of several metals with tungsten, the degree of reaction between tungsten and lead was determined. A literature survey showed considerable disagreement between the results of various earlier investigators. Information presented by M. Hansen1 states that, according to S. Inouye,2 tungsten has very poor resistance against attack by molten lead, even at the low temperature near the melting point of lead. A phase diagram in the same reference indicates a solubility of 30 wt pct W in molten lead at 1300°C. Contrary evidence was shown by Parkman and shepard3 in their investigation of materials for use in heat transfer systems containing liquid lead alloys; they performed experiments at 980°C for times up to 50 hr without noticing any appreciable attack on the tungsten. Tungsten sheet was immersed in molten lead contained in Vycor tubes evacuated to at least 10-4 mm Hg. R. Bernard4 and R. I. Jaffee5 also indicate that no reaction occurs between molten lead and tungsten. However, no experimental data were included in these reports. In order to settle the question of the solubility of tungsten in molten lead, tungsten powder with an average Fisher subsieve particle size of 6µ was pressed in a double-acting die at 6 tsi to small compacts. They were then sintered in an atmosphere of hydrogen for 2 hr at 1700°C, resulting in a sintered density of 64 pct of theoretical with final dimensions of 0.260 in. in height and 0.245 in. in diameter. For all tests, the tungsten pellets were immersed in molten lead. Table I is a summary of the experimental procedures showing atmospheres, temperatures, and times. The first experiments were performed at 650°C; at this temperature, the liquid lead should wet the porous tungsten better than at its melting point, and penetrate into the pores. The lead was heated in a graphite crucible with a graphite cover. No protective atmosphere was used, as it was expected that the formation of CO would be sufficient to prevent oxidation. This, however, proved to be wrong, and all tungsten samples showed a slight oxide film after treatment. The tungsten samples were immersed in the molten lead for times of 5 min, 10 min, 1/2 hr, 1 hr, and 2 hr. After this time, the melt was poured into a form and the

Jan 1, 1962

By Gerald Edmunds

IN a paper1 before this Institute in 1940, the writer reported that the surface orientation texture of zinc and cadmium differed from the texture existing within the casting, in that basal planes were parallel to the surface. He was unable to rationalize the origin of this surface texture. It is conceivable that the surface orientation texture is influenced by the atomic force fields, which are different at the surface and within the body of metal. It was considered that a radical change in the surface against which the metal is cast might alter the surface texture. In trial of this, zinc has been cast against a surface of molten lead, but the same result has been obtained-i.e., (001) parallel, ±20°, to the surface-as was obtained when it was cast against air, Transite or iron.1 Into the bottom of an open cast-iron tray, 7 by 14 in. by 2 in. deep, preheated to about 275°C., about ¼ in. of lead, then) ½ in. of zinc was poured, and the whole was covered with an electric heater to enforce freezing from the bottom upward. After a lapse of time sufficient for the zinc but not the lead to solidify, the zinc slab was raised free of the molten lead. The bottom surface of the zinc casting was coated with a thin layer of lead. A specimen of the slab 1 ½ in. square was metallographically polished to flatten it and remove the slight film of lead, and the orientation was determined by the method used before,1 with the result stated above. Some determinations have also been made on other metals, as follows: Surface orientation determinations were made on the 3/8-in. diameter grip section of two ¼ -in, diameter aluminum-alloy die-cast tensile bars and on a 1/8 by ½ -in. flat aluminum-alloy die-cast tensile bar. None of these three aluminum die castings exhibited any preferred orientation at-the surface. A brass die casting (nominal composition: 60 Cu, 37.75 Zn, 1.00 Sn, 1.00 Pb, 0.10 Al, 0.15 Si) furnished by C. S. Smith was also examined. The surface showed a random orientation of alpha and beta. SUMMARY A zinc casting solidified against a molten lead surface was found to have the same surface orientation texture, (001) parallel to the surface, as other zinc and cadmium castings. Aluminum and alpha-beta brass die castings were found to have random grain orientation textures at the surface. ACKNOWLEDGMENT The X-ray determinations were conduced by M. L. Fuller.

Jan 1, 1945

By Robert A. Rapp, Ronald L. Pastorek

Solid-state electrochemical measurements by three alternative experimental procedures were made with the cell FeO, Fe3O4 |Zro.85Cao.15O1.85 |Cu| Zr0.85CaO.15O1.85 | FeO, Fe304 to establish the solubility and diffusivity of oxygen in solid copper in the temperature range 800" to 1030°C. The solubility of oxygen in solid copper and the diflusivity of oxygen in solid copper Dgu = 1.7 X 10-2 exp(-16,000/RT) Cm2/sec were determined and confirmed in alternative experiments. The enthalpy of solution of oxygen in solid copper equals —10,000 cal per mole; the partial excess entropy of the oxygen atoms in the Cu-O dilute solution is approximately the same as that found for interstitial atoms in other metals. The diffusivity of oxygen in solid copper is consistent with that expected for an interstitial atom. RELIABLE values for the saturation solubility N(s) and diffusivity DO of oxygen in solid copper have not been unambiguously established in the literature. Following three early determinations by others,1"3 Rhines and Mathewson4 reported that the solubility of oxygen in solid copper increased from 0.007 at. pct 0 at 600°C to about 0.015 pct at 1050°C. Phillips and skinner,, using essentiially the same analytical procedure, reported that the solid solubility increases from 0.0018 at. pct 0 at 550°C to about 0.0075 pct at 1050OC. The only previous value for the diffusivity of oxygen in solid copper was reported by Ransley.6 Ransley deoxidized Cu-Cu2O alloys in an atmosphere of carbon monoxide gas to yield a solubility-diffusivity product. He used the solubility data of Rhines and Mathewson to calculate the diffusivity values. Another method for obtaining the solubility-diffusivity product (N(s) DO) is by measuring the widths of internal-oxidation zones in copper alloys as reported by Verfurth and Rapp.7 However, the calculated N(S)Do products depend upon the alloy content of the specimen, so that the internal oxidation of copper alloys does not follow ideal internal oxidation kinetics. As a result, unequivocal values for the N(s) DO product were not obtained by this procedure. A solid-state coulometric titration technique similar to that employed in this work was introduced by C. Wagner8 to study the dependence on silver activity of the Ag/S ratio in silver sulfide in the temperature range of 160" to 300°C. Similar experiments have been carried out by C. Wagner and co-workers9-11 to study the stoichiometry range of silver and copper tellurides, cuprous sulfide, and cuprous selenide. Numerous authors have carried out electrochemical measurements with a solid oxygen-ion-conducting electrolyte to determine the solubility and/or diffusivity of dissolved oxygen in several liquid metals.12-l6 Rickert and Steiner17,18 have used solid-state electrochemical measurements to determine the diffusivity of oxygen in solid silver from 760" to 900°C. Two different cell geometries were used. In the cell of linear geometry Fe, FeO | ZrO2 + (CaO) | Ag + [0 (dissolved)] [1] oxygen diffused from the interior of the silver electrode to the silver/electrolyte interface where the oxygen activity had been lowered from a fixed initial value to practically zero by the application of voltage to the cell. The diffusivity of oxygen in solid silver was determined from the solution of the diffusion equation and the time dependence of the cell current. However, this determination of the diffusion coefficient depended upon a knowledge of the solubility of oxygen in solid silver. A cylindrical geometry was used for the cell Pt, O2(Po2 = 0.21 atm) | ZrO2 + (CaO) | Ag + [0 (dissolved)] [II] which also allowed the diffusivity of oxygen in solid silver to be determined. These values were in agreement with other available data.l9 Recently, Raleigh20,21 used a method involving the measurement of diffusion-limited currents in a cell involving the AgBr solid electrolyte to determine the diffusion coefficient of silver in Ag-Au alloys at 400°C. Diffusivity values on the order of l0-14 sq cm per sec were measured in the alloy composition range 10 to 60 at. pct Ag in a single experiment. From numerous electrical conductivity and galvanic cell measurements,9'22"26 the solid solution Zr0.85 Ca0.15 O1.85 has been established as an electrolyte with predominant oxygen ion conduction over a wide range of intermediate and high oxygen activities. For interrelating the thermodynamics and the kinetics of the dissolution of oxygen in solid copper in this investigation, a galvanic cell was constructed with FeO-Fe3O4 as the reversible reference electrode, the Zr0.85Ca0.15 O1.85 electrolyte, and a pure copper specimen under-saturated in oxygen as the other electrode. THEORETICAL ANALYSIS Three variations of a high-temperature electrochemical technique were used in this study to provide two determinations each of the solubility and diffusivity

Jan 1, 1970

By Charles Pack

Extensive progress has been made in the metallurgy of alloys for die castings. Enthusiastic proponents of some alloys are inclined to make extravagant claims for their materials, which may be justified by physical tests on test bars made from the respective alloys but are seldom justified by the results obtained with commercial die castings made from those alloys. Chemical analysis of the test bars and castings fails to determine the cause of these variations, since they are due to other physical factors entering into the commercial production of die castings. In this paper, an attempt will be made to outline some of the factors in commercial die-casting practice to which these variable results may be attributed, in the hope that the manufacturer of die castings, recognizing the importance of these factors, will devote more attention to them in the design and construction of dies and equipment. In 1914,l the author defined die castings as "metal castings made by forcing molten metal, under pressure, into metallic molds or dies." This definition was given in order to differentiate die castings from other molded metal products such as "permanent-mold" castings, L'slush" castings and similar products that are sometimes erroneously termed die castings. The term "die casting" could be interpreted to include all castings made in metal molds or dies; but since this term, like most of our technical nomenclature, has been developed by commercial practice we must look to this practice for its proper definition. The Germans, with their usual devotion to desecriptive names, have adopted the name of sprilzguss (squirt cast) for die castings. Undoubtedly this name is more descriptive of the die-casting process, where the metal is literally squirted into the die and serves to differentiate this process from other metal mold processes, where the metal is poured into the die. In the earlier paper mentioned, the author also emphasized the fact that the definition given for die castings indicated clearly that the satisfactory operation of the process must comprise three factors, all of which must be considered of vital importance to the successful operation of the die-casting process:

Jan 1, 1931

By W. H. Bassett

THE modern smelting and refining of copper is distinctly an American development. The present demand for sound and perfect castings for rolling is due to the development of American industry. Prac-tically every article made from sheet metal or, for that matter, from any form of metal is made by mass produc-tion methods. Faulty material disturbs the orderly sequence of operations and in addition requires expen-sive inspection and unbearable rejection of finished product. This demand, therefore, is positive and will have to be met. Some mines produce ore that can be smelted and re-fined without the electrolytic process into satisfactory copper for the wrought metal industry, and some of these ores carry small amounts of impurities that are of use in hardening and toughening the copper. Most of the copper ore mined contains impurities that must be removed and, fortunately, precious metals which are separated at the same time make this re-moval profitable. The modern electrolytic refineries have their methods so well under control that the product meets all re-quirements without question if properly fire refined and cast. The "if" in this case is important, because there is evidence of carelessness or want of control at times in the material from some of the producers. It is nec-essary that the melted cathodes should be saturated with oxide to dispose of sulfur and that the copper should then be poled to the proper pitch or set. Sometimes statements leak out to the effect that it is unnecessary to oxidize completely the molten cathodes and a little less rabbling saves poles, which are expensive. The re-sult is that the rolling mill gets porous castings and produces seamy or slivered sheets or strips. The condition of the molds, their temperature, and the temperature of the metal are all important to good copper cakes, wedges, or wire bars. Cracked, and burned molds leave rough places and porous spots. Molds which are out of shape, or cracked, make shrink-age cracks which gap open when the castings are hot-rolled. Dampness means porosity. Drops of oil mean porous or honey-combed areas. Poor or irregular dress-ing means mold wash in the castings. Cold copper or slow pouring means cold sets.

Jan 4, 1928

By John Chipman

IT has been long known that the gas evolved during the boil in the open-hearth furnace is mainly carbon monoxide associated with smaller quantities of other gases. A number of attempts have been made to determine the precise effects of carbon and oxygen content of the bath, and of other factors, such as temperature, upon the evolution of carbon monoxide. In his investigation of the carbon-iron oxide product in liquid steel, Herty1 showed that the value of this product at equilibrium could be approximated by plotting the value of the product observed in open-hearth reactions against rate of carbon elimination, and extrapolating to zero rate. The results of this study showed a slight but definite effect of temperature upon the carbon-iron oxide reaction. Experimental studies of the evolution of gases from rimming-steel ingots have not yet attained the degree of precision necessary for an exact understanding of the effects of pouring temperature, carbon content, and iron oxide in the metal upon the composition of these gases. Klinger2 showed that the gas consists mainly of carbon monoxide, and that con-siderable variation in its composition occurs during the solidification of the ingot. In order that these variations may be understood in their proper relationship to the progress of solidification of the ingot and the segrega-tion that accompanies solidification, it is essential to have a knowledge of the condition of equilibrium in the several chemical reactions by which the gases are being formed. It is also necessary to understand the effects of temperature upon the equilibria, and further, to know the manner in which the temperature of the liquid metal within the ingot changes as the skin of the ingot is being built up. The reactions in which we will be chiefly interested are those involving in the one case the oxides of carbon, and in the other case steam and hydrogen, with iron oxide and carbon in the liquid metal. The reactions as they occur in unalloyed liquid iron, and their respective equilibrium constants are written as follows:

Jan 1, 1937

By H. R. Hanley, D. F. Walsh, C. Y. Clayton

Lead-refining practice at the Bunker Hill differs to some extent from that of other United States refineries using the Parkes process, in that the Bunker Hill has reverted to a custom used years ago of making two kinds of skims, or crusts, in the desilverizing kettles. Also, this was the first refinery to adopt the liquation process for silver skims as developed in Australia. Both of these ideas were brought to the attention of the operator by H. S. J. Sommerset, in the summer of 1924, while he was visiting metallurgical plants in the United States, when he was general superintendent of the Broken Hill Associated Smelters Pty., Ltd., of Port Pirie, South Australia. Since Mr. Sommerset's visit, United States patents on the liquation process have been issued to George Kenneth Williams, of Port Pirie, South Australia. At the Bunker Hill, the lead bullion is conveyed from the blast furnaces to the refinery in brick-lined cast-steel pots, each having a capacity of 5 tons, by a 20-ton electric crane, to which is suspended a Fairbanks-Morse suspension-type scale on which the gross, tare and net weights are obtained. The bullion is poured from the small bullion pots into either one of two kettles of 105 tons capacity, and when a kettle is entirely filled the heavy dross is removed by skimming it into a 5-ton pot suspended by the crane. The crane operator becomes proficient in the manipulation and a kettle is skimmed in a very short time. After the kettle is skimmed clean the bullion is pumped to a kettle of the same size alongside, where the bullion is cooled until it has almost frozen. By using two kettles for the drossing operation, one to accumulate the bullion where the heavy dross is removed, and then pumping to a clean kettle comparatively free of hangings, etc., it is possible to reduce the copper content much lower than if only one kettle is used in the operation. The average yearly analysis of bullion is given in Table 1. During July, August, September, and October, when a considerable quantity of high-grade silver ore from the Yukon Territory is smelted,

Jan 1, 1930