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By C. S. Samis, D. P. Seraphim

In the presence of oxygen, galena is oxidized in an aqueous medium containing ammonium acetate in accordance with the following reaction: PbS + 1/2 0, + 2 NH~Ac -» PbAc, + So + 2 NH: + H2O. This reaction was studied in an autoclave under oxygen pressure by polarographic measurement of the concentration of lead ion in solution. Oxidation rate is parabolic. The reaction products are lead acetote and elemental sulfur, the latter forming a film on the galena crystal. Reaction kinetics appear to be determined by the diffusion of lead from the galena phase to the solution interface through the film of sulfur. RECENT applications of pressure leaching on a commercial scale have emphasized the metallurgical importance of the oxidation of sulfide minerals in aqueous media by oxygen under pressure. Research experience has shown that sulfates, thio-nates, and metal oxides are the products of humid oxidation of sulfide minerals in basic solutions. The metal oxides may be solubilized in the presence of a complexing ion.' Certain oxide minerals are also amenable to treatment by this type of oxidation.' Several kinetic studies have been made of reactions of this type. Stenhouse' found that pyrite (FeS?) oxidized in a sodium hydroxide solution to produce a soluble sulfate and an insoluble layer of iron oxide and that the kinetics of the reaction were controlled by oxygen diffusion through the oxide layer. Andersen' studied the oxidation of galena (PbS) in a sodium hydroxide solution under oxygen pressure. He found the lead and sulfur to be simultaneously oxidized to produce plum bite ions and sulfate ions, and that the reaction rate was proportional to the surface area of the galena. The kinetics appeared to be determined by the reaction of oxygen and water with the galena surface. In each of the above reactions the metal and sulfur components of the mineral were oxidized simultaneously and at equal rates. In the present study the alkaline medium has been replaced by an approximately neutral solution of ammonium acetate in which lead sulfate is soluble. Under the conditions no sulfate was produced and no sulfur could be detected in the solution. The metal component of the mineral was solubilized and the liberated sulfur remained as a film of elemental sulfur on the surface of the galena crystal. A kinetic study of this reaction was undertaken to establish the kinetic mechanism and to determine the rate controlling step. Specific reaction rates were determined by oxidizing crystals of galena of measured surface areas in an autoclave maintained at the desired temperature and oxygen pressure. The rate of reaction was followed by measuring the concentration of lead in the ammonium acetate solution with a cathode ray polarograph, employing stationary platinum electrodes incorporated in the autoclave. Experimental Materials and Equipment Crystals of galena obtained from Violamac Mines, Retallack, B. C., were selected for oxidation because

Jan 1, 1957

By R. V. Lundquist

Aeration in water slurries and controlled drying of manganous hydroxide produced from dithionate leaching of Artillery Peak manganese ores from Arizona were investigated by the Bureau of Mines at its Electrometallurgical Experiment Station, Boulder City, Nev., to determine whether a simple process could be developed for converting this product into a battery-grade manganese dioxide. The properties of manganese dioxide prepared by the thermal decomposition of manganous nitrate were investigated also. Manganese dioxide suitable for use in batteries was not obtained from the dithionate leach product, but some of the factors controlling its oxidation were isolated. Aging of manganous hydroxide was of major importance in retarding its oxidation by aeration. Sodium hydroxide and sodium silicate promoted oxidation by drying. Optimum quantities were about 0.85 mol of sodium hydroxide and 0.2 mol of sodium silicate per mol of manganese, and drying temperatures of 200° C. produced yields of manganese dioxide up to 90 percent of the manganese present. Higher temperatures and concentrations of reagents carried oxidation of manganese beyond its tetravalent state.

Jan 1, 1957

By I. Fatt

This paper proposes the network of tubes as a model more closely representing real porous media than does the bundle of tubes. Capillary pressure curves are derived from network models and pore size distributions are calculated from these curves. In this way is shown the difference between the true and calculated pore size distributions when the capillary pressure curve is used to obtain pore size distribution for porous media. INTRODUCTION Despite the technological importance of the laws governing flow through porous media, many of these laws have not yet been clearly formulated. This is especially true of the laws governing multiphase flow. The static properties, such as the capillary pressure curve, are also not at present interpretable correctly in terms of the pore size distribution and other structural properties of porous media. In the absence of any well founded theoretical description of fluid flow through porous media, many empirical descriptions have been proposed. In addition to the strictly empirical flow equa- tions, some equations have been developed rigorously from simple geometrical models of the pore spaces. These equations are only as valid as is the model used in their development. The two models used in the past, the sphere pack and the bundle of tubes, have been too simple, and as a result, the equations derived from them have failed to predict the observed properties. Agreement between theory and observation has been achieved for these models by inserting parameters of doubtful physical significance. The work to be reported here was undertaken in the belief that the study of a model more closely resembling most real porous media than does the sphere pack or bundle of tubes would yield useful information concerning the structure of real porous media and the relation between structure and flow properties. There was no intention of developing any calculational procedures, as for example calculating relative permeability from capillary pressure data. The objective of the study was instead to develop a better qualitative understanding of the relation between the various measurable properties of porous media. The model chosen for study is the network of tubes in which each tube represents a pore space in the porous medium. Microscopic observations leave no doubt that sandstones and clastic carbonates are three-dimensional irregular networks of irregularly shaped pores. The irregularity of these structures makes any accurate theoretical study of their properties impossible. Results from an oversimplified model such as the bundle of tubes are worthless when applied to real systerns. The sphere pack model, on the other hand, not

Jan 1, 1957

By L. Bombardieri, H. F. Mills

IRON KING mine, producing gold-silver-lead-zinc ore, is 10 miles east of Prescott, Ariz. At present the 1806 level is being developed. The echelon pattern of ore deposit continues at depth but is less pronounced, and the orebody is now more or less continuous over 2600 ft of strike length. with widths 5 ft to as high as 26 ft where overlapping of lenses occurs in one section of the mine. Better continuity of ore at depth has encouraged systematic mining and improved plant facilities to offset higher operating costs. With favorable persistence of ore at depth. the three-compartment No. 6 hoisting shaft appeared inadequate to handle increased tonnage from greater depths, and in 1952, a four-compartment steel and concrete shaft was started. This is now at a depth of 1906 ft, and shaft pockets and loading cartridges are being installed on the 1806 level. Ore from the new shaft, hoisted in 51/2 -ton Jeto bottom dump skips, is dumped into a 500-ton shaft bin, from which it is fed to a 16x30-in. gyratory crusher and conveyed 415 ft through an undersurface concrete gallery to the secondary crusher and conveying system supplying the 900-ton mill. Lead, zinc, and pyrite concentrates are floated, and the flotation tailings are cyanided after desliming. Waste from the new shaft is dumped into a 250-ton surge bin, fed from this bin to a 24-in. conveyor, and discharged into the glory hole above the block cave. The new shaft is served by a double-drum 400-hp hoist used for ore and waste; the No. 6 shaft conveys men and material To secure a cheap source of waste fill for stoping operations, a block cave area was undercut In the hanging wall near the north end of the mine above the 600 level. Waste from the block cave is drawn from any of three large drawpoints on the 600 level, and a series of hanging wall transfer raises with controls and bypasses on each level provide a fast low-cost material for fill. The block cave is worked vertically through to surface in the form of a steep-sided hole 350x250 ft and several hundred feet deep, the sides of which cave and provide fill material without any blasting. Fill is a mixture of caliche-cemented surface gravel and small particles of hanging wall schist. Level Development: An orebody 300 times as long as it is wide requires a lot of development work. Former practice consisted of driving a haulage drift about 30 ft from the ore in an andesitic footwall, a drift on the ore, and crosscuts from the haulage drift at 100-ft intervals. Crosscuts are about 90 ft long. At present, only the odd numbered levels are so developed, and on the even numbered levels only the haulage drift and crosscuts are driven. Little or no timber is used for this development. This change resulted in 20 pct reduction of development costs and 50 pet reduction of square set stoping required for removal of floor pillars. Elimination of ore drifts on alternate levels leaves

Jan 1, 1957

By R. E. Boni, G. Derge

Application of surface tension measurements has been made to molten silicates in order to determine the effect of sulphur upon the surface tensions of synthetic blast furnace slags. In melts with the same molar ratios of AI2O3 + SiO2 to the basic oxides BaO, CaO, and MgO, the surface tensions increase in the order of oxides listed. Sulphur lowers the surface tensions of the basic BaO, basic CaO, acid BaO, acid CaO, and acid MgO slags in that order; and the concentration of excess sulphur at the slag surface increases in this same order of slags. The rate and amount of desulphurization of iron by these slags is favored by a low excess surface sulphur in the slag. IN a previous paper,1 the authors discussed the applications of surface tension measurements of molten silicates to problems of metallurgical interest. Of major importance is the aid that such studies lend to forming a working concept of slag structure. Since the ability of a slag to desulphurize metal depends strongly upon its composition,2"4 fundamental information about the structural differences between various slags which contain sulphur should aid the development of better desulphurizing media. For that reason, the present investigation concerns the effect of sulphur upon the surface tensions of synthetic blast furnace slags. Experimental Procedure , The maximum bubble-pressure method was used to measure the surface tensions of synthetic blast furnace slags in the temperature range 1300° to 1600°C. The method is based upon the equation which was developed by Schrödinger5 from a consideration of the forces of hydrostatic pressure and surface tension of a liquid which oppose bubble formation when a gas is forced through a tube immersed in the liquid. where y is the surface tension between argon and slag in dynes per centimeter; g is the gravitational constant, centimeters per second2; H is the manometer reading in centimeters; s2 is the density of manometer fluid in grams per cubic centimeter; S1 is the density of the medium in grams per cubic

Jan 1, 1957

YEARS ago, when metal mining was more an adventure than a well-organized business, it was often said (with some color of truth) that unless a mine could stand bad management or mismanagement, it was not much good. Today, the natural excellencies of an ore deposit are merely a challenge to the engineers to exploit it as skillfully, as efficiently, and as profit- ably as possible. A vast amount of competent and imaginative engineering management (which includes economic analysis no less than the technologic arts of mining ore and treating it) has been required to make New Cornelia the smooth-running and successful operation that can be seen at Ajo today. New Cornelia was acquired by the Phelps Dodge Corporation when it absorbed the Calumet and Arizona Mining Company in 1931. Next to Morenci, it doubtless is the corporation's biggest asset. It in no way detracts from the achievement of Phelps Dodge engineers to say that they had an admirable ore deposit to work on. New Cornelia ore, as mined, is relatively low in grade and the deposit is by no means the largest of the Porphyries; but it has these attractive features : (1) It is peculiarly suitable for opencut mining because: (a) The overburden of waste rock lying above the ore deposit was (it has long since disappeared) almost negligible. (b) The deposit is roughly circular in horizontal section, with the horizontal dimensions four to five times as great as the maximum thickness. (Nevertheless, eventually some underground mining may be desirable.)

Jan 1, 1957

By G. K. Manning, A. R. Elsea, C. R. Simcoe

It was found that a critical boron content exists which yields the maximum boron-hardenability effect in hypoeutectoid steels, as was predicted from the mechanism proposed in a previous paper. The hardenability of boron steels with boron contents between 0.00005 and 0.0017 pct was dependent on the boron content, austenitizing temperature, quenching temperature, and austenite grain size. The effects of these variables on hardenability can be explained by the mechanism previously proposed for the boron effect. A MECHANISM has been proposed to explain the effect of boron on the hardenability of steel.' The proposed mechanism assumes that transformation particles nucleate at concentrations of lattice imperfections where the energy level is high, and

Jan 1, 1957

By H. C. Theuerer

GeC14 may be purified by extraction with HCI and chlorine. The process is as effective for the removal of AsCI:, as the more cumbersome distillation methods usually used for this purpose. GERMANIUM for semiconductor use contains impurities at levels no higher than a few parts in ten million. Material of this quality is obtained from highly purified GeC1, by hydrolysis to the oxide and reduction of the oxide in hydrogen. When purifying GeCl,, AsC1, is the most difficult impurity to remove. This is usually accomplished by multiple distillation procedures.1-3 AsC1, may also be removed from GeC1, by extraction with HC1.1-4 Reducing the arsenic to low concentrations is not practicable, however, because of the large number of extractions needed. This paper discusses a new method for the removal of arsenic from GeC1, by extraction with HC1 and chlorine. The method is rapid, leads to little loss of germanium and is at least as efficient as the distillation procedures currently being used. Theory of Extraction Procedures In the simple extraction of GeC1, with HC1, the following reaction occurs ASCl8G8C1 D AsCl3rc1 at equilibrium CA/Cn= K, where K is the distribution coefficient, and C, and C,, are the molar concentrations of AsC13 in HC1 and GeCl,, respectively. The materials balance equation for this reaction is VACA + vncn = VnC,, where V, and Vn are the volumes of HC1 and GeCl4, respectively, and C, is the initial concentration of AsC13 in GeC1,. From this it can be shown that for multiple extractions where C,, is the concentration of AsC13 in GeC14 after n extractions, and r is the ratio of V, to V,,. It is assumed that r is maintained constant, that equilibrium is established during each extraction, and that K is independent of the AsCl3 concentration. By saturating the system with chlorine, the following reaction occurs in the aqueous phase AsCl3 + 4H2O + Cl2 D H5AsO4 + 5HC1 at equilibrium K' = ------------ ai - a4 h2u - aet2 where a is the activity of the various components. The effect of this reaction is to reduce the concentration of the AsC1, in the aqueous layer and, therefore, to promote further extraction of this component from the GeC1, layer. If the arsenic acid remains entirely in the aqueous phase, the net effect of this reaction is to promote the removal of arsenic from the GeC11. The materials balance equation for extraction with HC1 and chlorine with the foregoing reaction is, then, VaCC + VACA + VACn = VnCo where C,. is the molar concentration of H3AsO, in the HC1. With the added assumptions that the activities of AsC13 and H8ASO4 in the aqueous phase are equal to their molar concentrations, it can be shown that for n extractions Cn/Cu = (1/rkK + rK + 1) n where k - K1 a4h2o - acl2/aoncl. It can be seen by comparing Eqs. 1 and 2 that if k is large, the removal of AsC1, by HC1 extraction will be greatly improved by the addition of chlorine. Dilution of the HCI used in the extraction with chlorine would also favor the separation. This, however, would increase the loss of GeCl,, which is undesirable. Experimental Procedure Germanium prepared from oxide of semiconductor purity is n-type with resistivities greater than one ohm-cm. The resistivity is controlled by the donor concentration, which is —lo-: mol pct. Germanium prepared from material with added arsenic will have lower resistivity commensurate with the arsenic concentration. With such material, at arsenic concentrations above 10-1 mol pct the resistivity is controlled by the added arsenic, and effects due to other impurities initially in the oxide are negligible. In this investigation GeO, of semiconductor purity was converted to GeCl,, and -0.01 mol pct As was added. This material was used for the extraction experiments and the purification attained determined by a comparison of the resistivity data for samples of germanium prepared from the initial and purified GeC1,. A method for calculating the arsenic concentration from the resistivity data is discussed later. The details of the experimental procedures used are as follows: Two hundred and thirty cu cm GeC1, were prepared by the solution of GeO, in HC1, followed by

Jan 1, 1957

By Milton E. Wadsworth, John N. Ong, W. Martin Fassell

The temperature and oxygen concentration dependence on the reaction of sphalerite in oxygen at pressures from 6 to 640 mm Hg have been investigated in the temperature range 700° to 870°C. Sphalerite has been found to oxidize linearly over this entire temperature and pressure range. At higher rates, considerable self-heating was observed. The dependence of the oxidation rate on the oxygen concentration may be expressed by: Rate = k' where k' is the specific rate constant and 0 = K1[O2]/(1 + KI[O2]), where K1 is the equilibrium rate constant for the adsorption of oxygen on sphalerite. Values of the activation energy and the enthalpy of adsorption were found to be 60.3 and —59.6 kcal per mol, respectively. Data have been presented that indicate conditions under which either a sulphatizing or an oxidizing roast may be obtained. ROASTING processes have been employed in the metallurgy of a great number of basic metals in use today. Until recently, however, little attempt has been made to deduce the fundamental mechanism by which oxidation takes place. Structural changes upon oxidation have been investigated1 = and thorough work has been performed with regard to the reaction products and the thermodynamics of the oxidation reactions. The objective of this investigation was to determine the rate of oxidation of sphalerite and to apply the absolute reaction rate theory in the theoretilcal interpretation of the experimental results." "O Description of Apparatus The apparatus contains the following features: 1—a furnace with gas system, 2—an autographic weighing system, and 3—a temperature control system. Furnace With Gas System—The furnace was mounted by a yoke on each end and was free to travel up and down on steel guide rods, permitting the introduction and removal of samples from the apparatus with minimum difficulty. The furnace was heated by three sections of Kanthal wire wound externally on a zirconia tube and insulated with Fiber-frax. Pure gases or mixtures of gases were introduced into the lower end of the furnace through two flowmeters, a mixing chamber, and a gas-tight sparger, Fig. 1. The gaseous products of the reaction and the unused gases were prevented from escaping to the atmosphere by maintaining a small negative pressure on the system. This procedure permitted air from the outside to enter through the small an-nulus around the quartz suspension fiber and prevented the escape of the internal gases. Autographic Weighing System—The autographic weighing system consisted of an adapted gold balance, a photoelectric circuit, and a weight recorder, Fig. 2. The sample was suspended from one end of the balance beam by means of a platinum chain outside the furnace and a long thin quartz fiber on the inside of the furnace. On the other end of the balance beam, the necessary weights were added to counterbalance the sample. In addition, a calibrated chain was added to the balance which was linked directly to the weight recording unit. Control was effected by means of a photoelectric circuit." A parallel beam of light from a strong source was directed onto a small front-surfaced aluminum mirror mounted in the middle of the balance beam and then to a front-surfaced mirror mounted on the ceiling of the room. The beam was then reflected onto a front-surfaced right prism at a distance of 9 ft from the balance

Jan 1, 1957

When the new No. 3 Shaft is in full operation, the main hoisting duties will be in connection with the raising of: (a) ore from the various mining operations, and (b) mullock, or broken country rock, from development work in extending access to existing levels, opening up new levels, exploratory work, or sinking the shaft to greater depths.

Jan 1, 1957

By R. J. Charles

SEARCH for a consistent theory to explain the relationship between energy input and size reduction in a comminution process has accumulated, over the years, an enormous amount of plant and laboratory data. Although some correlation of these data has been possible for purposes of engineering design and for the advancement of research in fracture, there is still great need of a means of predicting behaviour of a solid when it is reduced in size by mechanical forces. The best known hypotheses proposed to describe the energy-size reduction relationships in crushing and grinding stem from a common origin. The present article analyzes problems of comminution in the light of the precepts of this origin. Its object is to reconcile points of difference between these well known hypotheses and to present relationships more widely applicable to comminution studies.

Jan 1, 1957

By G. M. Ikeda, J. G. Sibakin

An investigation was carried out to determine the variables affecting the coiling temperature of strip in the 56-in. hot strip mill. After statistical treatment, equations have been derived to determine the temperature drop between mill and coiler for both full spray (top and bottom) and top spray only practices. The individual influences of each variable in the temperature drop were derived for both practices. Limitations of the present practices were shown and adjustments in cooling for increased rolling speeds were suggested. A method of estimating the required number of sprays, their spacing, pressure, etc., to achieve a desired temperature drop is developed. MAXIMUM finishing temperature of a hot strip mill is mainly determined by the rolling speed, gage, and the temperature of the bar entering the mill. This finishing temperature may be limited by the maximum admissible coiling temperature in cases when either the cooling facilities on the runout table are not adequate or, more generally, when the cooling capacity of the runout table and the production capacity of the continuous mill are out of balance. Some time ago, the balance between these two factors was not considered detrimental to production. Recently, a new drafting schedule was introduced which increased the production rate, the entry temperature, and hence the finishing temperature. Thus, the restriction of the maximum specified coiling temperature became an important factor for many of the thicker gages. An investigation of the factors determining the coiling temperature may be, therefore, of considerable importance. A brief description of the available equipment will be a useful illustration of the techniques and methods used for this investigation. The 56 in. continuous hot strip mill is composed of six 4-high stands each containing two 221/2-in. diam work rolls and two 45-in. diam back-up rolls. Either of the last two stands can be used as the finishing stand. Which stand is used is dependent on the total percentage of reduction to be taken over the whole train, i.e., on the entry thickness and the final gage. The characteristics of these last two stands are given in Table I. Table I. Operational Characteristics of Nos. 5 and 6 Stands No. .5 NO. 6 Maximum voltage GOO 600 Power, hp 30(10 W00 I normal, kilonmp 4.35 3.73 Rpm of motor and rolls ISO 15 0 ITS to 300 Spettl ot strip, fpm 333 6 to 376T.2 103) to 2062 The speed of the finishing stand varies with the amount of reduction, strip width, and the exit gage. Finishing speeds in general use for varying gages are shown in Table 11. These speeds may change with an increase or decrease in the entry temperature of the strip. Even though the maximum speed of No. 6 stand is shown as 2062 fpm, this has so far never been attained,

Jan 1, 1957

By Edward I. Salkovitz

RECENTLY a set of crystallographic angles for bismuth was calculated and a standard (111) projection was constructed. Since these calculations

Jan 1, 1957

By Clarence Karr

In 1955 the Federal Bureau of Mines established a low-temperature tar laboratory at its new Appalachian Experiment Station in Morgantown, W. Va. The objective of the laboratory is to investigate the yields and chemical and physical properties of tars from low-temperature carbonization of coal, to investigate means of economically upgrading these tars, and to make available to industry and the public essential data for increasing coal utilization through the establishment of a new coal-chemical industry, based on the utilization of low-temperature tars. Because of the obvious economic significance of phenols, as well as the relative ease with which they can be separated and analyzed, initial research has centered mainly around this class of tar constituents. It was realized early that no listing of phenols and their physical properties existed that included enough compounds to be practicable. The purpose of this paper is to make such a compilation available.

Jan 1, 1957

By Herty, C. H.

One of the numerous requirements of many grades of present- day steel is that the steel shall be free from non-metallic inclusions. These inclusions may be composed of oxides, sulphides, complex oxy- sulphides, and nitrides, which enter the steel with the furnace charge, result from sulphur absorption from the furnace gases, or are formed in the steel during the deoxidation process. Although few' data are available which indicate in any quantitative manner the specific effects of inclusions in steel, there is a large mass of circumstantial evidence which points to the advisability of producing steel free from these impurities for many purposes. At the present time there is a growing feeling among metallurgists that non-metallic inclusions should be divided into two distinct types: (I) those readily visible under the microscope at ordinary magnifications; and (2) those in colloidal suspension or in solid solution. Both types are profoundly influenced by the character of the charge, the manipulation of the furnace slag, and the method of deoxidation. The work described in this bulletin deals primarily with inclusions visible under the microscope at ordinary magnifications, but the steels made by the various methods of deoxidation are being used LO study certain effects which may be ascribed to the second classification, named above. This latter work will be the subject of further bulletins on the effect of deoxidation practice on the physical properties of the steels involved.

Jan 1, 1957

By D. D. Pollock, D. I. Finch

Relationships between the compositions of specially prepared manganin-type alloys and some of their electrical properties have been established. Empirical equations, based upon the electronic configurations of the alloying elements, are given which describe the resistivity, temperature coefficient, peak temperature, and thermoelectric power of Cu-Mn-Ni-Fe alloys at approximately room temperature. Calculations based upon these relationships are correlated with experimental data. SECURING suitable alloys for the construction of stable resistors, for use in precise electrical measuring devices, has been important ever since the art of electrical measurement was begun. German silver, Pt-Ag, and Platinoid are examples of some of the alloys in early use. These early alloys were un- satisfactory for one or more of the following reasons: l—insufficient stability of electrical properties with time, 2—poor reproducibility of electrical characteristics from melt to melt, 3—excessive temperature coefficients of resistance, and 4—excessive cost. Weston introduced the Cu-Mn-Fe and Cu-Mn-Ni-Fe alloys of the type now generally known as manganins. His patents are believed to represent the first disclosure of any alloy with a negative temperature coefficient of resistance. After this work, the German company, Isabellenhutte, in conjunction with Feussner and St. Lindeck, produced alloys of

Jan 1, 1957

By Glenn R. Zellars, J. P. Morris

The carrier gas method was used to measure the vapor pressure of copper over liquid copper and Fe-Cu alloys. From these results, the activity of copper in the alloys was determined at 146°, 1550°, and 1600°C. Calculations of the activity of iron were made from the results for copper. The activities of copper and iron show strong positive deviations from Raoult's law. KNOWLEDGE of vapor pressures of liquid metals has both practical and theoretical value. Fuming of metal baths is directly related to vapor pressure, and the data should bc particularly important to the technology of vacuum metallurgy. Theoretical applications include determinations of heats of vaporization, heats of solution, and activity coefficients in alloys. Methods for measuring vapor pressures of metals have been reviewed by Speiser and Spretnak.' High-vacuum procedures, such as the Langmuir and Knudsen methods, have been used most widely in recent years. However, these methods are not applicable to vapor pressures greater than lo-' mm Hg and often cannot be used in the temperature range of greatest interest. The purpose of this investigation was to develop a procedure for measuring vapor pressures of pure metals and alloys that would be applicable to pressures greater than lo-' mm Hg. The transportation or carrier gas method has been used. Copper was chosen for the initial work because its vapor pressure has been established fairly well and the reliability of the technique could be ascertained. Applicability to alloys was studied by determining the vapor pressure of copper over liquid Fe-Cu alloys. Experimental Procedure The tests were carried out in a graphite-spiral resistance furnace. The charge consisted of 50 g of metal contajned in a covered sintered-alumina crucible 1/2 in. deep and 13/8 in. ID. Two sintered-alumina tubes led from outside the furnace to within the crucible, passing through close-fitting holes in the crucible cover and radiation shield. The arrangement of the crucible and the two alumina tubes is shown in Fig. 1. The small-bore tube (1/16 in. ID by 5/16 in. OD) served as the inlet for the carrier gas. The tip of this tube touched the metal surface and the flow of gas imparted a rippling motion to the metal. In this manner the gas was brought into close contact with the metal and became saturated with metal vapor. In most of the tests the flow rate of the carrier gas was 560 ml per min, measured at room temperature. Approximately half of this saturated gas was allowed to escape from the crucible through the second alumina tube (3/16 in. ID by 5/16 in. OD) and was discharged to the atmosphere through a

Jan 1, 1957

By B. S. Butler

AN understanding of mineralizing solutions and how they carry and deposit metals is of prime importance to students of ore deposits. Lindgren states: "The whole problem surely is very complicated. One difficulty is that we know so little about the stability field of ore minerals."1 Lindgren further states: It is believed that they [the solutions] were in small part oxidized to sulphates, for instance, but in large part they were composed of hydrogen sulphide, alkaline sulphides and various halogen compounds. Doubtless, however, free carbon dioxide was present. Becker's view of the double sulphides as important constituents of the solutions probably holds good. In the fourth edition of Mineral Deposits2 Lindgren had changed his views somewhat: From the work of Day, Allen, Shepard, and others, it would seem probable that many of the volcanic gases are acid when given off but are in unstable equilibrium, and could not have preserved this acid character after having been long in contact with the surrounding rocks. It is believed that they were in small part oxidized to sulphates, for instance, but in larger part they were composed of hydrogen sulphides, alkaline sulphide, and various halogen compounds. Doubtless, however, free carbon dioxide was present. Becker's view of double alkaline sulphides as important constituents of the solution probably holds good. The writer wonders if progress would not result from an attack on the problem in steps, the steps to contribute to the attack on the whole. The initial step would deal with the simpler bodies of supposed magmatic (hydrothermal) origin, that is, those composed essentially of silicates, oxides, sulfates, and sulfides. The following discussion attempts to develop one step of a method that was proposed on a more comprehensive scale in 1929 by the writer and W. S. Burbank.3 The accompanying partial table (Table I) of the electromotive series is from a table distributed by Merck & Co. Inc., manufacturing chemists, prepared in turn from Fundamental Chemistry.& The electromotive arrangement brings together elements that in hypogene ore deposits occur: 1) in oxygen combination only; 2) in combination with sulfur as well as with oxygen; and 3) as sulfides, arsenides etc., and as native metals, see Table 11. The writer clearly recognizes that he is not qualified to discuss the formation of ore deposits as a chemical problem, but he feel that some of the relations that are met by the geologist can well be stated with the hope that the chemical explanation will be forthcoming. By consideration of a group including mainly the elements oxygen, hydrogen, sulfur and iron, complications are avoided, especially with elements of the lower electromotive group. The results can only contribute to the solution of the problem, not to the completion of it. The pH and Eh of the solutions and also temperature probably determine what minerals form. The mineral groups that contain elements high in the electromotive series are alumino-silicates, titanites, simple silicates, spinels, oxides, carbonates and sulfates, in all of which the elements are combined with oxygen. These groups are also recognized as the general order of temperature at which the minerals start to form, see Table 11. At low temperature are sulfides, arsenides, antimonides, sulfo-salts, and native metals, in all of which the elements are characteristically not combined with oxygen. The intermediate temperature group contains elements that form both oxygen compounds and sulfur compounds.

Jan 1, 1957

By Jack C. Bokros, Philip C. Rosenthal

DEVELOPMENT of the autoradiographic method in metallurgical research has been directed mainly toward gaining higher resolution, i.e., toward being able to locate segregation of a radioactive isotope on a finer scale. In the investigation reported, the liquid emulsion autoradiographic technique' used in the biological science was adapted to the autoradiography of metals. The distribution of carbon-14 in pure iron after various treatments was studied using this technique. Amorphous carbon uniformly labelled with carbon-14 at a specific activity of 6.95 microcuries per millimole was obtained from Tracerlab Inc. Carbon-14 emits P particles having a maximum energy of 157 kev and an average energy of about 50 kev. These ßs have a maximum range of about 30 mg per cm' and a half-thickness of about 3 mg per cm2. The iron used was spectroscopically pure electrolytic iron prepared by the Oak Ridge National Laboratory. Unhardened nuclear track emulsion, type NTB, was kindly supplied by the Eastman Kodak Co. This emulsion contains approximately 80 pct Ag halide,

Jan 1, 1957

By Pol Duwez, Ellis P. Frink, Paul Pietrokowsky

Ti-Au alloys in the composition interval 0 to 66 213 atomic pct Au have been studied over a temperature range from 400° to 1500°C. A partial phase diagram has been established from micrographic and macroscopic observations. All intermediate phases, Ti3Au, TiAu, and TiAu., exhibit open melting maxima. It has been observed that small additions of gold lower the allotropic transformation temperature of titanium. The P solid solution decomposes eutectoidally to a solid solution plus Ti3Au. The solubility of gold in a solid solution decreases with temperature. THERE have been several papers in the literature pertaining to the alloy system Ti-Au. However, a comprehensive study of this interesting constitu- tion diagram has not been conducted. Previous investigations have been concerned with the crystal structure of intermediate phases or partial phase diagrams. This paper represents a partial constitution diagram, Ti-TiAu,, the first portion of an investigation of the entire binary system. Laves and Wallbaum' reported the intermediate phase Ti,Au to be isomorphous with CuAu, L12 type. In a more recent paper, Duwez and Jordan' have concluded that TiAu has an atomic arrangement which is related to Cr,Si. The intermediate phase

Jan 1, 1957