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By P More

US 4,132,621-In the electrowinning of aluminum, the cells are aligned in a lengthwise direction so as to lessen the harmful influence of the induced magnetic fields Each cell is supplied with current from the preceding cell both via the head arid at least one side riser The output of the cathode bars is divided into two separate groups, the upstream group supplying the head of the subsequent cell arid the downstream group supplying the side risers of the subsequent cell This produces a substantial improvement in cell efficiency arid a greater regularity P Morel, J P Dugois, arid B Langon, assigned to Aluminium Pechiney. Jan 2, 1979 12 pp. (204¬243M) Filed 1-12-78 (868,861) Priority: France, 1-19-77 (77/2,213) US 4,134,806-Cells, anodes, arid methods for use in the electrowinning of nickel, cobalt, copper, zinc, or other metals from an acid ore leach solution or the like The cell is provided with vertically immersed stationary cathodes and stationary rod anodes which are noncorrodible by the electrolyte arid are electrocatalytic to the anode reaction. The spaced parallel anode rods are connected to electric current supply bars The anode rods have an electroconductive core made of a metal alloy arid a surface coating of an oxide of platinum or a platinum group metal The ratio of active cathode surface area to active anode surface area is preferably at least 3 0. De Nora arid C Traini, assigned to Diamond Shamrock Tech¬nologies, SA Jan 16, 1979 13 pp. (204-105R) Filed 9-15-77 (833,661) Priority Italy, 1-29-73 (19738 A/73). Same British 1,434,334-5, dated May 5, 1976 US 4,135,994-In the electrowinning of aluminum at a high current efficiency, the electrolytic bath is a mixed molten salt consisting of 2-15% by weight of aluminum trichloride, 15-83% of sodium chloride, 15-70% of combined calcium chloride arid magnesium chloride but riot more than 40% of calcium chloride, arid optionally up to 10% of barium chloride Preferably, plate-shaped graphite electrodes used for both cathodes and anodes are arranged in parallel inclined relation so that the axis in the lengthwise direction makes an angle of from 10° to 45° to the horizontal. T Ishikawa arid H Ichikawa, assigned to Nippon Light Metal Co Ltd Jan 23, 1979 4 pp (204-67) Filed 11-15-77(851,632) Same British 1,550,502, dated Aug 15, 1979

Jan 1, 1980

By Elmars Ence, Harold Margolin

The partial isothermal section of the Ti-Cu-Zr system at 750°C has been studied. The crystal structure of Ti2Cu has been detevnlined as tetragonal and when expressed as face-centered tetragonal, a = 4.164, c = 3.611 A, and c/a = 0.867. TITANIUM systems in which ß-titanium decomposes eutectoidally into a and a compound rather readily are known as active eutectoid systems. Recently in active eutectoid alloys based on the Ti-Cu system, and containing additionally A1 and Zr, it has been found that zirconium may produce both moderate weakening and marked strengthening at elevated temperatures.' In order to obtain some insight into the behavior of zirconium, an attempt was made to determine whether compounds of the type Tix Zr and TixZryCu exist. Only results of the Ti-Zr-Cu studies are reported here since data on Ti-Zr alloys will be presented in a separate publication. EXPERIMENTAL PROCEDURE Alloys were nonconsumably arc melted in argon atmosphere as 15-g buttons, prepared from materials of the following purities: Bureau of Mines electrolytic Ti — Bhn 63 OFHC copper Reactor Grade Zirconium Bhn .C 150 Prior to alloy preparation the electrolytic titanium was premelted to avoid excessive spattering of the charges during melting. The weight losses during melting did not exceed 1 pct of the total weight of the charge. The alloys prepared are listed in Table I together with analyzed compositions. in cases where they were determined. Specimens for heat treatment were wrapped in molybdenum sheet, annealed in argon-filled quartz capsules, and quenched by breaking the capsules under iced brine. About 1 to 2 sec are required to remove the capsule from the furnace, drop it into the iced brine and break it. Because of the insulation effect of the quartz, this delay in quenching should not produce a large drop in temperature. In many instances, no difference or little difference has been detected between the same specimen quartz capsule quenched or directly quenched in vacuum by an impinging stream of water.' Ti-Cu-Zr alloys were homogenized for 48 hr at 825°C prior to annealing at 750°C. Annealing for 5 days at 750°C produced the same results as 11 days at temperature and it was therefore assumed that 5 days was sufficient to establish equilibrium. Titanium-copper alloys were homogenized for 40 hr at 900°C prior to heat treatment for 6 days at 750°C. Specimens for metallographic examination were electropolished and etched with the following solution:

Jan 1, 1962

By J. W. Walker, G. J. Heuer, E. W. Hough

An improved apparatus is described for the deterrni-nation of interfacial tension* by the pendant drop method in the pressure range from 15 to 15000 psi and the temperature range from 100º td 280°F. The chief characteristics of this apparatus are reliability and ease of operation. Temperature control was accomplished by means of an electrically heated jacket which could he completely removed while cleaning the apptrratus. The cell was designed so that the camera could he placed about I in, from the window without overheating the carnera lens. Separate "0" rings employed to seal each window and corresponding window backup plate gave very reliable window operation at 10,000 psi. An extra pistorr-cylinder combination was added so that a high compression ratio could he attained when gas was employed as one phase in the pendant drop cell. Other essential parts of the system were similar to an apparatus already described.' The interfacial tension for carbon dioxide and water varies from about 69 dynes/cm at 15 psi to about 19 dynes/cm at 1,250 psi for 100°F. For pressure.r between t,500 and 3,500 psi, the interfacial tension is between 32 and 24 dynes/cm at this temperature. The interfacial tension at 280°F varies from about 50 dynes/cm at 200 psi to about 17 dynes /cm at 10,000 psi. The maximum surface excess for carbon dioxide, assuming the surface excess of water to be zero, occurs at about 1,500 psi jor the 100°F isotherni and Itas a value of about -79 X 1014 mol/sq cm. At 160°F this maximum IS shifted to about 2,000 psi and has a value of about 10 X 1014 111ol/.sq cm. Other maxima, us well as several minima, are present at these and other temperatures. Judging from the data on the solubility of water in carbon dioxide at elevtrted pressures2,3, it appears that the principal maxinza natned are in regions of increasing solubility of the water in the carbon dioxide rich phase. INTRODUCTION AND APPARATUS A pendant drop interfacial tension apparatus which would accommodate an opaque liquid in a gas phase was constructed several ycars ago' for industrial purposes. This apparatus was used as a starting point for the present development. The objective of the present development was to enhance reliability and convenience of operation. Other articles'" have described pendant drop apparatus which could not accommodate a gaseous phase adjacent to the windows. A schematic diagram of the apparatus is shown in Fig. 1. The water used followed the path; A, intro-

By Ralph Hultgren, Bernard York, David W. Mitchell

It is a well-known fact that magnesium-alloy castings are apt to be coarse grained if the melt is not superheated several hundred degrees above the melting point before casting. (The casting temperature varies according to the shape of the mold. A typical casting temperature is perhaps 1400°F.) British practice is to heat to 900°C. (1650°F.) for 15 min., cool rapidly to casting temperature, and cast.' In Germany superheating is carried out at 850' to 900°C. (1560° to I650°F.) depending on the amount of scrap used. It is stated that further refinement will be obtained by prolonging the period of superheating or by increasing the superheat temperature to 950°C. (I740°F.).2 In the United States superheating is carried out at 1600' to 1700°F. (871' to 927°C.), perhaps even higher in some places. It is stated that superheating effects are found as low as 1500°F. (816°C.), but several hours are required.3 These commercial treatments lead to grain sizes in sand castings that may vary from 4 to 8 grains per sq. mm.! in heavy sections and from 60 to IOO in 1/2-in. sections to perhaps 380 in thin sections. It is also generally known that the refining effect of superheating is lost if the melt is held for some time at lower temperatures before casting. Aside from these very qualitative statements, there is little to be found in the literature as to the effect of temperature and time of superheat on the final grain size. Because of the uncertainty of these factors, the Office of Production Research and Development of the War Production Board placed a research contract with the University of California, supervised by the War Metallurgy Committee. This research, which was done under the "Restricted" Project NRC-550, is the basis of this paper, which has been released for publication by the O.P.R.D. The material studied was an alloy prepared from carbothermic magnesium. The temperatures required for grain refinement proved to be widely different from those used in practice, as described in the statements in the first paragraph. This difference is attributed to the fact that the magnesium in the specimens was of carbothermic origin instead of the electrolytic magnesium in common use. Materials and Methods The magnesium alloy studied was one of the most popular sand-casting alloys, with a nominal composition of 9 Per cent aluminum, 2 per cent zinc, and 0.1 per cent (minimum) manganese and the balance magnesium. This is designated

Jan 1, 1945

By James Norman, O. C. Ralston, John Dasher

MOST mineral products are used in the finely divided state, but some are sold in larger sizes. Coal, gravel, metallurgical fluorspar, phosphate rock, hematite, chromite, and other products are sold in sizes coarser than can be treated by many mineral-dressing methods. Gravity separation of coarser sizes by log washing and jigging is probably as ancient as any process now in use. The performance of jigs on a feed with sufficient difference in density of the minerals is excellent, but many families of minerals are too similar in density to be separated effectively by this method. The use of heavy suspensions of fine solids to separate coarse coal from bone and slate has been in use for some years. This separation by sink-and-float was limited until recently to light minerals. Development of galena and ferrosilicon as suspension media, by Minerals Beneficiation, Inc., at Mascot, Tenn., Pitcher, Okla., and Crosby, Minn., under patents granted during and since 1938, has permitted excellent results to be obtained on minerals of very similar densities up to 3.3. This process has been put in the hands of American Cyanamid Co. for exploitation, and further research now in progress may increase the density of suspension obtainable so that separation, at a density of 4,0 may be practicable before this is published. The Huntington-Heberlein dense-medium process, developed in England, is also being commercialized in the United States by Sink and Float Corporation. Du Pont has developed a sink-and-float separation using halogenated hydrocarbons as parting liquids; at this writing, the method is used commercially only on coal but has been successful in the pilot plant on many other minerals using tetrabromethane at densities up to 2.95. While these processes were being developed to extend the range of separation by difference in density to the coarser sizes, the Bureau of Mines was engaged in developing a process that will extend the range of separation by difference in wettability up to 2-in, size. War work has pushed aside its further development indefinitely. The results are published here with the hope that some use may be suggested that will justify post-war development, and so that readers that may be able to make immediate use of the scheme may have the information. EARLIER WORK It has been known since the time of Herodotus (B.C. 484(?)-425) that water-repellent particles will adhere to sticky surfaces. That early historian reports the

Jan 1, 1942

By Clarence Zener

IT has long been known that the density of a metal usually decreases with cold-work. Thus O'Neill1 observed as early as 1861 that cold hammering of commercial hot-rolled copper is accompanied by a decrease of density of 0.2 per cent, and that subsequent annealing restores the original density. The origin of this density change, however, has remained obscure. In particular, experiment has not yet decided whether it is due to the presence of small cavities and an increase in intergranular surface or to an actual expansion of the lattice itself. This uncertainty in the origin of the change in density is a reflection of our uncertainty as to the changes induced in a metal by cold-working. One school regards cold-working as a breaking up of the original grains into a large number of perfect crystallites somewhat randomly orientated with respect to one another.2 According to this viewpoint, the mere introduction of a large intercrystallite surface induces a net volume expansion. Another school regards cold-working primarily as a distortion of the grains. It is not obvious that this second viewpoint will lead to a net volume expansion. The purpose of the present paper is to show that this is indeed the case, and that this expansion is of the right order of magnitude to explain existing experimental data. The physical basis for the association of an expansion with distortion lies essentially in the variation of the elastic moduli with volume. This variation is considerable. Thus from Table I we see that a I per cent increase in volume for the case of copper will decrease the bulk modulus K by 10 per cent, the shearing modulus µ by 3.8 per cent. If we thus twist a rod through a given angle, we shall do less work upon it if it increases slightly in volume, thereby reducing the torsion modulus that involves as a factor the shearing modulus. A general principle' in physics states that the rod will so adjust itself as to have a minimum potential energy consistent with the end restraints. It will therefore expand. [ ] In order to obtain a quantitative comparison with experiment, we follow Maier4 in comparing the lattice expansion with the latent energy of cold-work. This latent energy has been measured directly by Taylor and Quinney5 on copper rods subjected to torsion, and may amount to as much as 15 per cent of the total work done upon the specimens. We shall assume that this

Jan 1, 1941

By A. A. Collins

OF widespread interest to all lead metallurgists is a dross smelting process that will consistently give mattes and speiss of low lead and high copper contents. It is a problem that has intrigued operators through the years. In the past few years, with increased amounts of copper and overcrowded metallurgical furnaces, it has been almost imperative to evolve some method. Experience at El Paso has shown that high copper-to-lead ratios can be consistently attained by use of the new soda process. † Older Methods Three older methods, i.e., 1. Dross plus siliceous ore and limestone. 2. Dross plus one fourth blast-furnace speiss and siliceous ore, 3. Dross plus sulphides and siliceous ore and scrap iron, do not give consistent results and the products are higher in lead and lower in copper than those produced with the soda process. Any radical changes in the blast-furnace drosses will throw any of these older methods into a tailspin. For almost ten years, El Paso used the third method, with varying results. It was noted that as the arsenic and anti- mony contents of the dross increased, the speiss and matte steadily increased in lead and decreased in copper. A dross containing four parts of copper to one part of arsenic was considered to be ideal. At times this balance of copper to arsenic was almost impossible to obtain, especially when handling copper Cottrell dusts, which vary so greatly in copper and arsenic. Custom smelters like El Paso, handling a great variety of dusts, concentrates and ores, are apt to have anywhere from I to 15 pct copper on charge, with a variable in arsenic of from 0.5 to 2 pct. With such conditions, and drosses varying from 12 to 40 pct copper, an operator using the older dross reverberatory practices would find it just about impossible to control the reverberatory operations and to produce a good product low in lead and high in copper. These conditions prevailed at El Paso from the year 1940 to the present. In May 1942 it was decided to experiment with the soda process. The Soda Process After considerable work the soda method was finally evolved to the present state. It has never failed to produce a good product even under the most adverse conditions. It might be well to remember that many men of thought in the smelting industry have at one time or other sugge~ted the removal of all copper, arsenic and antimony from the lead blast-furnace charge as an aid to better metallurgy.

Jan 1, 1949

By Ernest G. Enck

"The Rockets' Red Glare" of the Fourth of July is produced by strontium compounds. However, strontium has a number of less spectacular uses; i.e. in, or in connection with, the manufacture of ceramics, caustic soda, glass, railway and truck signal flares, beet sugar and steel. The principal ore of strontium for use both as the mineral and for production of compounds is celestite (SrSO4). This mineral varies in color from white to pink or blue depending on presence of impurities. It has a hardness of about 3.5 and specific gravity of 3.9. It is brittle and has perfect basal and prismatic cleavages. The high grade ore is obtained from England, hence it has become the standard for all other producing areas. (See analyses, Table 1.) The most objectionable impurity in English celestite is iron, coming mostly from adhering clay. On the other hand, Mexican celestite, while no higher in strontium sulfate content, is extremely low in iron (less than 0.2 pct), hence it is more desirable for certain uses. Most of the celestite in Spain and in the United States is high in calcium and barium, and commonly high in iron, and requires some form of beneficiation in order to be equal to English ore. The natural carbonate (SrCO3), or strontianite, is less important than celestite as a source of strontium, because it is less abundant and is not so widespread in its occurrence. Furthermore, it generally occurs with calcite (CaCO3) and lead sulfide (PbS), and for most uses these impurities are detrimental. This mineral is generally white or yellowish, forming needle-like crystals. It has a hardness of about 3.7 and a specific gravity of 3.68-3.8. The mineral is brittle and has an imperfect cleavage. A typical analysis of German strontianite is shown in Table 1. [ ] Distribution of Deposits UNITED STATES Occurrences of strontium minerals are known in Arkansas, Arizona, California, Illinois, Ohio, Pennsylvania, Tennessee, Texas, and Washington. Celestite occurs in the Vulture Mountains, Maricopa County, Arizona in beds three to ten feet thick associated with sandstone, gypsum, and barite. Because of the low strontium content, approximately 86 pct SrSO4, it has no commercial value. A large deposit of celestite occurs in San Bernardino County, California, in the Cady Mountains near Argus Station, about eight miles west of Ludlow. The celestite here is interbedded with shaly and clayey tuff in a zone about 300 ft thick. Massive, finely crystalline ore has been recovered with an analysis

Jan 1, 1960

By Earl C. Herkenhoff

Publication of the article "The Flotation Behavior of Digested Asphalt Ridge Tar Sands" by R.J. Smith and J.D. Miller has confirmed and again spotlighted a most significant and important development in the field of tar sand and heavy oil mining. This is the ability to recover 95% of the bitumen in dry tar sands by a hot water process. The initial investigation by Miller and Sepulveda in early 1978. "Separation of Bitumen from Dry Tar Sands," was the first blockbuster. It is disappointing that there has been so little scientific and industry ackowledgement that the authors laid to rest the long entrenched belief that the sand grains had to be "water wetted" for a hot water process to be applicable. Dr. Miller and his researchers at the University of Utah used slightly different mineral dressing terminology in describing their process but it is essentially the old, established technique of high &lids attrition scrubbing at elevated temperatures with a conditioner or modifier, followed by dilution and froth flotation. Similar techniques were described in detail for other nonmetallic minerals in the mid-1940s by Stuart Falconer of American Cyanamid Co. The authors used a 15-minute "scrub" period (or in their terminology "digester step") at 73% solids and 95OC (203°F) in a 0.3 m solution of sodium carbonate-about 4 kg/t (8 lb per st) of tar sand. Flotation was at 10% solids. Obviously, the scrub is an expensive step with respect to energy input but the high recovery of bitumen appears to justify it. Two basic questions then arise: What are the effects of shorter scrubbing time, lower temperature, and less sodium carbonate? Would a two-stage approach be advantageous? That is, could you get the major proportion of the bitumen with a mild scrub and apply the high power and temperature only to the refractory portion? These variables should be evaluated. Apparently, all results were only for rougher flotation. What would the grade and recovery of bitumen be if multiple cleaner flotation steps were employed? We must concede that a 60.62% grade of bitumen leaves considerable room for upgrading. Finally, it should be noted by all executives who approve funds for heavy oil recovery schemes, most of which are variations of in-situ methods, that mining can yield a 95% recovery of bitumen. That is correct, 95%. Imagine what that does to the total barrels recovered from a heavy oil resource compared with the scrawny 30-35% maximum recovery we are getting now. The conclusion-let's mine heavy oil and tar sands.

Jan 1, 1983

By R. F. Stahl, W. A. Martin, R L. Huntington

A marked gravitational segregation of liquid has been observed to take place in a number of volumetric fields toward the later stages of their oil-producing periods. This phenomenon has been pronounced in thick, highly permeable sand formations such as those of the wilcox zone in Oklahoma City. This observation has prompted considerable research directed toward the semiquantitative determination of the equilibrium saturation distribution of oil vertically throughout a formation at final depletion. In this paper, data are also presented showing the transient distribution of liquid at different stages of the depletion period. Other experimental results show the effect of temperature on the drainage rates of water, Wilcox crude oil, and a close-cut heptane fraction. Intermittent drainage of liquid produced saturation gradients that might well be expected from the flow theories involved, Yields of the various liquids varied from 50 to 75 per cent of the original fluid content of the sand-packed (4 in. by 8 ft.) vertical tube. Introduction In certain volumetric Oil fields the performance of the reservoir during the latter part Of its producing life is governed to a large extent by the downward movement of liquid due to the force of gravity. This is especially true of formations having thick or tilting beds of uniformly high permeability, free of shale breaks. Laverett4 and Katz3 have presented original data and discussed the theory relating to the capillary and gravitational forces acting On liquids contained in a sand body. These investigators have pointed out the importance of such studies in the estimation of future reserves as well as the original fluid content of a reservoir. In this previous work, no data have been reported showing the history of saturation distributions during the drainage period. Since a knowledge Of these transients is helpful in obtaining crude Oil from such a reservoir, the authors have obtained these data during this investigation. Experimental Apparatus The drainage tests were carried out in two vertical tubes, 8 ft. high and consisting of 2-in. and 4-in. standard wrought-iron pipe, respectively. Each tube was equipped with a water jacket, which could be kept virtually isothermal ( ± 1.0ºF.). A diagrammatic sketch of the 4-in. tube and its auxiliaries is shown in Fig. 1. At 6 in. above the base of the tube, and at every foot above this point, core nipples were inserted through the water jacket. These nipples were closely fitted with steel-plug inserts during each drainage run. At the end of the run, these inserts were removed so that cores could be obtained from the sand-packed tube.

Jan 1, 1943

By R. F. Stahl, W. A. Martin

A marked gravitational segregation of liquid has been observed to take place in a number of volumetric fields toward the later stages of their oil-producing periods. This phenomenon has been pronounced in thick, highly permeable sand formations such as those of the wilcox zone in Oklahoma City. This observation has prompted considerable research directed toward the semiquantitative determination of the equilibrium saturation distribution of oil vertically throughout a formation at final depletion. In this paper, data are also presented showing the transient distribution of liquid at different stages of the depletion period. Other experimental results show the effect of temperature on the drainage rates of water, Wilcox crude oil, and a close-cut heptane fraction. Intermittent drainage of liquid produced saturation gradients that might well be expected from the flow theories involved, Yields of the various liquids varied from 50 to 75 per cent of the original fluid content of the sand-packed (4 in. by 8 ft.) vertical tube. Introduction In certain volumetric Oil fields the performance of the reservoir during the latter part Of its producing life is governed to a large extent by the downward movement of liquid due to the force of gravity. This is especially true of formations having thick or tilting beds of uniformly high permeability, free of shale breaks. Laverett4 and Katz3 have presented original data and discussed the theory relating to the capillary and gravitational forces acting On liquids contained in a sand body. These investigators have pointed out the importance of such studies in the estimation of future reserves as well as the original fluid content of a reservoir. In this previous work, no data have been reported showing the history of saturation distributions during the drainage period. Since a knowledge Of these transients is helpful in obtaining crude Oil from such a reservoir, the authors have obtained these data during this investigation. Experimental Apparatus The drainage tests were carried out in two vertical tubes, 8 ft. high and consisting of 2-in. and 4-in. standard wrought-iron pipe, respectively. Each tube was equipped with a water jacket, which could be kept virtually isothermal ( ± 1.0ºF.). A diagrammatic sketch of the 4-in. tube and its auxiliaries is shown in Fig. 1. At 6 in. above the base of the tube, and at every foot above this point, core nipples were inserted through the water jacket. These nipples were closely fitted with steel-plug inserts during each drainage run. At the end of the run, these inserts were removed so that cores could be obtained from the sand-packed tube.

Jan 1, 1943

By Ralph Hultgren, Bernard York, David W. Mitchell

It is a well-known fact that magnesium-alloy castings are apt to be coarse grained if the melt is not superheated several hundred degrees above the melting point before casting. (The casting temperature varies according to the shape of the mold. A typical casting temperature is perhaps 1400°F.) British practice is to heat to 900°C. (1650°°F.) for 15 min., cool rapidly to casting temperature, and cast.1 In Germany superheating is carried out at 850° to 900°C. (1560° to 1650°F.) depending on the amount of scrap used. It is stated that further refinement will be obtained by prolonging the period of superheating or by increasing the superheat temperature to 950°C. (1740°F.).2 In the United States superheating is carried out at i600° to 1700°F. (871° to 927°C.), perhaps even higher in some places. It is stated that superheating effects are found as low as 1500°F. (816°C.), but several hours are required.3 These commercial treatments lead to grain sizes in sand castings that may vary from 4 to 8 grains per sq. mm.§ in heavy sections and from 60 to l00 in 3-in sections to perhaps 380 in thin sections. It is also generally known that the refining effect of superheating is lost if the melt is held for some time at lower temperatures before casting. Aside from these very qualitative statements, there is little to be found in the literature as to the effect of temperature and time of superheat on the final grain size. Because of the uncertainty of these factors, the Office of Production Research and Development of the War Production Board placed a research contract with the University of California, supervised by the War Metallurgy Committee. This research, which was done under the "Restricted" Project NRC-550, is the basis of this paper, which has been released for publication by the O.P.R.D. The material studied was an alloy prepared from carbothermic magnesium. The temperatures required for grain refinement proved to be widely different from those used in practice, as described in the statements in the first paragraph. This difference is attributed to the fact that the magnesium in the specimens was of carbothermic origin instead of the electrolytic magnesium in common use. MATERIALS AND METHODS The magnesium alloy studied was one of the most popular sand-casting alloys, with a nominal composition of 9 per cent aluminum, 2 per cent zinc, and 0.r per cent (minimum) manganese and the balance magnesium. This is designated

Jan 1, 1945

By Harold Markus, Arthur H. Grobe, Gerhard Derge

THE high corrosion resistance possessed by tin under most circumstances, combined with its generally satisfactory appearance and useful physical properties, has led to many and varied uses for the metal. These uses have been partly limited by the fact that tin is an expensive metal, therefore many applications have been developed in which tin has been employed in combination with lead, either by coating, as in tin-lined collapsible tubes, or by the formation of alloys containing various proportions of tin-rich and lead-rich phases, as terne plate. A detailed knowledge of the corrosion characteristics of the tin-lead couple therefore is of general interest and has become specially important at the present time, when every effort is being made to conserve tin as much as possible. The present study. has been limited to carbonate solutions with a pH range from 8.4 to 11.2 so that the results may be related to earlier work on the corrosion of tin and its alloys.1-3,6 In these papers, the effects of a number of anion and cation additions to these solutions have been observed. APPARATUS AND METHOD The electrodes for the corrosion cell were cut from rolled sheet about 1/16 in. thick. The length of all specimens was held constant at 7 in., while the width was varied from 1/2 to 2 in. These electrodes were fastened to brass electrode supports, which were attached to rubber stoppers fitting into tall-type one-liter Pyrex beakers that contained the electrolyte. The lead electrodes were prepared from Omaha pig* and the tin was rolled from a slab of Chempur.? After cutting to size, the sheets were polished with No. I emery paper and cleaned with carbon tetrachloride. The edges, back and upper parts of the specimen were coated with a synthetic lacquer, which was supplemented with beeswax for the lead electrodes. The binding posts were coated with beeswax after the electrodes had been damped. The pH of the electrolyte was controlled? by adjusting the ratio of carbonate to bicarbonate. Approximately 600 ml. of electrolyte was used in each beaker. The entire assembly was placed in an oil bath thermostatically adjusted to operate at 30°C. ± 0.10. Potentials were measured against a saturated calomel electrode connected. to the cell by an agar-agar salt bridge. The carbonate solution used in the salt bridge was the same as that used in the corrosion cell. Currents were measured with a milliam-

Jan 1, 1942

By S. Suphi Yavasca, A. M. Gaudin

This paper is intended as a contribution to our knowledge of the mechanism of comminution and of the work of crushing. In a previous paper1 it was shown that with quartz comminution proceeds as follows: 1. The size distribution of broken fragments made by a single fracture is such that the new surface on each grade is the same. 2. Multiple fracturing results in a size distribution such that in the he sizes the surface per grade is the same in every grade; in coarse sizes the surface per grade decreases gradually with increasing size. In that paper it was mentioned that determinations on minerals other than quartz were in course of completion in order to establish the generality of these observations. In this paper, condensed data1 are presented for galena, pyrite and glass. Galena and pyrite are crystalline materials and glass is noncrystalline. Galena has excellent cubic cleavage. Pyrite, although cubical, does not have marked cleavage. Quartz, on which the original determinations were made, does not cleave and although crystalline (hexagonal) breaks conchoidally. Glass breaks much like quartz. It is apparent, therefore, that the minerals selected represent some range in character of the solid without covering all possible types. Glass Fifteen glass marbles were crushed individually in the pendulum crusher described in the preceding paper,' then subjected to careful screening for 30 min. Six sized fractions were selected and cleaned in a hot 0.12 N solution of hydrochloric acid, washed with distilled water and dried on a hot plate. This was followed by an examination with a binocular microscope, to remove foreign matters not eliminated in cleaning as well as to eliminate "compacts" of fine particles. These compacts are groups of he irag-ments that seem to be mechanically stuck together as a result of localized compacting during the comminution operation. The presence and the abundance of these compacts may be related to the amount and direction of the forces applied in different crushing devices. Since, properly, such compacts should be entirely eliminated in the sizing analyses, it is necessary to remove them to the last before making surface determinations on sized fractions. For example, with a — 28 + 35-mesh glass the surface areas of two samples, one cleaned with acid and under the binocular, the other only washed, were 102 and 172. cm' per gram, respectively. Examination of the samples under an Ultropak microscope showed that washing alone failed to remove the compacts and also that it fails to remove certain fine dusts attached to the particles. Cleaning with acid loosens the fine dusts and

Jan 1, 1947

By S. Suphi Yavasca, A. M. Gaudin

This paper is intended as a contribution to our knowledge of the mechanism of comminution and of the work of crushing. In a previous paper1 it was shown that with quartz comminution proceeds as follows: 1. The size distribution of broken fragments made by a single fracture is such that the new surface on each grade is the same. 2. Multiple fracturing results in a size distribution such that in the he sizes the surface per grade is the same in every grade; in coarse sizes the surface per grade decreases gradually with increasing size. In that paper it was mentioned that determinations on minerals other than quartz were in course of completion in order to establish the generality of these observations. In this paper, condensed data1 are presented for galena, pyrite and glass. Galena and pyrite are crystalline materials and glass is noncrystalline. Galena has excellent cubic cleavage. Pyrite, although cubical, does not have marked cleavage. Quartz, on which the original determinations were made, does not cleave and although crystalline (hexagonal) breaks conchoidally. Glass breaks much like quartz. It is apparent, therefore, that the minerals selected represent some range in character of the solid without covering all possible types. Glass Fifteen glass marbles were crushed individually in the pendulum crusher described in the preceding paper,' then subjected to careful screening for 30 min. Six sized fractions were selected and cleaned in a hot 0.12 N solution of hydrochloric acid, washed with distilled water and dried on a hot plate. This was followed by an examination with a binocular microscope, to remove foreign matters not eliminated in cleaning as well as to eliminate "compacts" of fine particles. These compacts are groups of he irag-ments that seem to be mechanically stuck together as a result of localized compacting during the comminution operation. The presence and the abundance of these compacts may be related to the amount and direction of the forces applied in different crushing devices. Since, properly, such compacts should be entirely eliminated in the sizing analyses, it is necessary to remove them to the last before making surface determinations on sized fractions. For example, with a — 28 + 35-mesh glass the surface areas of two samples, one cleaned with acid and under the binocular, the other only washed, were 102 and 172. cm' per gram, respectively. Examination of the samples under an Ultropak microscope showed that washing alone failed to remove the compacts and also that it fails to remove certain fine dusts attached to the particles. Cleaning with acid loosens the fine dusts and

Jan 1, 1947

By Clarence Zener

IT has long been known that the density of a metal usually decreases with cold-work. Thus O'Neilll observed as early as 1861 that cold hammering of commercial hot-rolled copper is accompanied by a decrease of density of 0.2 per cent, and that subsequent annealing restores the original density. The origin of this density change, however, has remained obscure. In particular, experiment has not yet decided whether it is due to the presence of small cavities and an increase in inter-granular surface or to an actual expansion of the lattice itself. This uncertainty in the origin of the change in density is a reflection of our uncertainty as to the changes induced in a metal by cold-working. One school regards cold-working as a breaking up of the original grains into a large number of perfect crystallites somewhat randomly orientated with respect to one another.2 According to this viewpoint, the mere introduction of a large intercrystallite surface induces a net volume expansion. Another school regards cold-working primarily as a distortion of the grains. It is not obvious that this second viewpoint will lead to a net volume expansion. The purpose of the present paper is to show that this is indeed the case, and that this expansion is of the right order of magnitude to explain existing experimental data. The physical basis for the association of an expansion with distortion lies essentially in the variation of the elastic moduli with volume. This variation is considerable. Thus from Table I we see that a I per cent increase in volume for the case of copper will decrease the bulk modulus K by 10 per cent, the shearing modulus µ by 3.8 per cent. If we thus twist a rod through a given angle, we shall do less work upon it if it increases slightly in volume, thereby reducing the torsion modulus that involves as a factor the shearing modulus. A general principle3 in physics states that the rod will so adjust itself as to have a minimum potential energy consistent with the end restraints. It will therefore expand. In order to obtain a quantitative comparison with experiment, we follow Maier4 in comparing the lattice expansion with the latent energy of cold-work. This latent energy has been measured directly by Taylor and Quinney5 on copper rods subjected to torsion, and may amount to as much as 15 per cent of the total work done upon the specimens. We shall assume that this

Jan 1, 1942

By C. W. Phillips, R. S. Busk

WITH most cast metals the grain size may vary within wide limits, depending upon the conditions at the moment of freezing. These conditions are subject to control in magnesium-base alloys, by proper melting and superheating techniques, enabling production of quite uniform and fine-grained castings, almost independent of section thickness. However, such variations of grain size as do exist, in common with all metals, are reflected in corresponding changes in mechanical properties. It is the intent of this paper to present data giving the relationship between grain size and mechanical properties. Data are also included on the combined effects of grain size and microporosity. In addition, a short discussion of factors influencing the grain size of sand castings is included. MEASUREMENT OF GRAIN SIZE By grain size is meant the statistical distribution of volumes occupied by the individual crystallites in a metal section. Since this is almost always impossible of direct measurement, several methods of estimating and expressing the size have been evolved. Most exact methods make use of the microscope. This involves study of a single plane cut at random through the metal. What is seen in the microscope are polygons, each the cross section of a grain. The diameters or areas of these polygons are then measured and the grain size is expressed as an average diameter, number of grains per unit area, average area per grain, or, rarely, average volume per grain. Rutherford, Aborn, and Bain3 have discussed extensively the errors involved when using a plane section to estimate volume. They clearly point out that the tendency is to underestimate the true grain size because of the nature of the measurement. The A.S.T.M.. recommends that measurement be made by comparison with a standard chart, by means of Jeffries' planimetric method' or Heyn's intercept method. The Society recommends that the notation be in terms of the number of grains per unit area (as is the grain-size number used for steel) or as an average diameter, expressed in inches or millimeters (as for copper and brass). The method of measurement used for this study was comparison with a standard chart, which has been described by P. F. George.', The chart was constructed by photographing at i00 diameters a uniform specimen with an average grain diameter of 0.003 in. The average diameter of this specimen was determined by numerous measurements, using both the Jeffries and Heyn methods. The other grain sizes were then obtained by appropriate enlargement of the master sample. Careful comparison of the chart method with other methods on identical samples indicates that though the differences be-

Jan 1, 1945

By Clarence Zener

IT has long been known that the density of a metal usually decreases with cold-work. Thus O'Neilll observed as early as 1861 that cold hammering of commercial hot-rolled copper is accompanied by a decrease of density of 0.2 per cent, and that subsequent annealing restores the original density. The origin of this density change, however, has remained obscure. In particular, experiment has not yet decided whether it is due to the presence of small cavities and an increase in inter-granular surface or to an actual expansion of the lattice itself. This uncertainty in the origin of the change in density is a reflection of our uncertainty as to the changes induced in a metal by cold-working. One school regards cold-working as a breaking up of the original grains into a large number of perfect crystallites somewhat randomly orientated with respect to one another.2 According to this viewpoint, the mere introduction of a large intercrystallite surface induces a net volume expansion. Another school regards cold-working primarily as a distortion of the grains. It is not obvious that this second viewpoint will lead to a net volume expansion. The purpose of the present paper is to show that this is indeed the case, and that this expansion is of the right order of magnitude to explain existing experimental data. The physical basis for the association of an expansion with distortion lies essentially in the variation of the elastic moduli with volume. This variation is considerable. Thus from Table I we see that a I per cent increase in volume for the case of copper will decrease the bulk modulus K by 10 per cent, the shearing modulus µ by 3.8 per cent. If we thus twist a rod through a given angle, we shall do less work upon it if it increases slightly in volume, thereby reducing the torsion modulus that involves as a factor the shearing modulus. A general principle3 in physics states that the rod will so adjust itself as to have a minimum potential energy consistent with the end restraints. It will therefore expand. In order to obtain a quantitative comparison with experiment, we follow Maier4 in comparing the lattice expansion with the latent energy of cold-work. This latent energy has been measured directly by Taylor and Quinney5 on copper rods subjected to torsion, and may amount to as much as 15 per cent of the total work done upon the specimens. We shall assume that this

Jan 1, 1942

By C. E. Birchenall

DaVIES and Richardson1 have measured composition changes for Mn1-Owith variation in the equilibrium partial pressure of oxygen at 1500°, 1575°, and 1650°C, where 6 is the deviation from the simple stoichiometric ratio. No trend in this relationship with temperature was observed, so these remarks apply to the whole temperature range. The experimental values and their spread are shown by the bounded straight-line segments in the figure. Davies and Richardson assume that the stoichiometric oxide shows Frenkel disorder, given by the equation Mn2+Mn2+ + Mn" [1] where Mn2+ is a normal lattice ion which moves into an interstitial site (Mni2+) leaving a vacancy (Mn,"). The superscript dashes indicate that there is an excess charge on the anions surrounding the vacancy. Schottky disorder, in which a perfect crystal acquires equal numbers of cation and anion (Ov") vacancies according to leads to equations of exactly the same form in the analysis below. In view of the neutron diffraction results of Roth,2 which shows extensive Frenkel disorder in Fe1-o, Eq. [I] seems more appropriate. The deviations from stoichiometric composition, MnO, result from the addition of oxygen according to In effect Davies and Richardson ignore the variation of Mn3+in constructing equilibrium constants. This approximation might not appear to be very serious if the excess positive charges are really free posi- tive holes (P+) and if the intrinsic conductivity is high as a result of the reaction where e- is a conducting electron. However, the calculations of Buessem and Butler3 indicate that the partition functions of the free charges make a large contribution to the equilibrium constant, and this approximation would not be a desirable one. Furthermore, Morin4 shows that the positive holes are probably localized in MnO and therefore are described better by the mass action principle than by a degenerate gas model. Davies and Richardson's considerations require that activity corrections be applied beyond a 6 value of about 0.005. It is proposed to show here that the dissociation pressure curve can be calculated reasonably well over the whole composition range studied without activity corrections by choosing appropriate equilibrium constants for reactions 1 and 2. As stoichiometric composition The mass action constant, Ks, for reaction [I.] and the equilibrium constant, K,, for reaction [2] are given by where the concentrations which do not change significantly have been absorbed into the constants. The brackets denote concentrations. The deviation from stoichometric composition is given by gardless of [Mni2 ]. Substituting Eq. [7] in [6]

Jan 1, 1961

By J. H. Frye, R. M. Treco

One of the chief hindrances to an understanding of the hardness of solid solutions is the sparsity of suitable hardness data. There is great need of a large body of hardness data obtained from many different alloys of high purity by identical testing methods and corrected to correspond to a single grain size. A considerable amount of such data has been obtained by means of the Meyer analysis on copper-rich and silver-rich solid solutions. There are enough of these data to permit comparison of numerous alloys at equal solute concentration in these two solvents, but only in a few cases is it possible to construct hardness-concentration curves for any given alloy. Therefore additional hardness work on most of these alloys is desirable. The primary solid solutions of silver with cadmium, indium, tin, or antimony as solute are of special interest, since all elements are from the same period of the periodic table and since, as shown previously,l the hardening effect of equal percentages of these solutes is proportional to the lattice expansion produced by them. This paper presents the relation between hardness and concentration in the silver-antimony system from very dilute to nearly saturated solutions of antimony in silver. Experimental Procedure Alloys were made from silver, 99.99 per cent pure, and antimony, 99.975 per cent pure. Silver and antimony were placed in graphite crucibles that had an ash content of less than 0.7 5 per cent. These metals were melted and allowed to solidify in a vacuum, which, after melting was corn- . plete, was usually equivalent to 3 mm. of mercury. A high-frequency furnace was used. The ingots so obtained were worked and annealed to lessen segregation and to control grain size. Annealing was done in evacuated and sealed glass tubes. Hardness measuremeuts on specimens from these ingots were by means of the Meyer analysis.394 Using a 4-mm. ball, impressions were made under seven loads from 25 to 400 kg. The diameter of impression made under each load was measured. This enabled calculation of the constants in the well-known formula of Meyer. L = adn where L = load, d = diameter of impression, a = a constant, n = a constant The Meyer hardness is defined as P = L/i(1/4pd2) or P = 4adn-2/p Meyer hardnesses corresponding to d = I and to d = 4 are of especial interest, since the first corresponds to comparatively slight 'plastic deformation and the second to the maximum plastic deformation producible by penetration of the ball. These

Jan 1, 1945