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By F. R. Hensel

THE demand for clean steel is increasing daily. New processes of refining steel are being developed in order to remove all nonmetallic inclusions as completely as possible, as it is the general opinion that. inclusions affect the dynamic properties of steel and iron to such an extent as to justify great expense for their removal. It is surprising to note at the same time the commercial development of a new process for making artificial wrought iron. By this process slag and steel are thoroughly mixed, the amount of nonmetallic inclusions usually exceeding 2 per cent in weight. The contradiction in these two efforts is obvious and is responsible for the investigation reported in this paper. H. W. Gillett also has recently emphasized the need for further research on wrought iron.1

Jan 1, 1932

By H. G. Moulton

H G. MOULTON should not be confused with the famous economist of the same name. Our H. G. stands for Herbert George, whereas the chief of the Brookings Institution is Harold Glenn. Like most so- called New York members of the Institute's hoard, Mr. Moulton came from the West, in this case from Idaho where he was born, and Oregon, where he was educated at the University of Oregon. His early work included such jobs as mucker, assayer, smelter, chemist, mine surveyor, draftsman, engineer on surveys and construction, and assistant on mine examinations. In 1909 he was engaged as mining engineer by the firm of Eugene Meyer, Jr. S' Co., continuing with them for the next eight years.

Jan 1, 1937

By Donald W. Gentry

In the mining industry, there are two widely accepted methods of determining the investment worth of a contemplated project. One of these is the payback method and the other is the more recent discounted cash flow (DCF) technique known as the internal rate of return. Both techniques can be useful, but it is important to know the assumptions and characteristics of each procedure and how these may affect an investment decision. The Payback Period-A Shortcut to Yes or No The payback period is simply the time it takes for the cash inflows from an investment to equal that investment. Understandably, projects with short payback periods are preferred to those with longer ones. The payback period may be measured either from the time the initial investment is made or from the time that it begins to yield positive cash flows, but the latter approach is more realistic because it permits more accurate allowance for lost interest on the invested capital.

Jan 1, 1971

By J. W. Dougherty, J. M. Douglas

THE Hollinger gold mine is in the Porcupine mining division, District of Cochrane, in the northern part of the Province of Ontario. The adjacent town of Timmins, with a population of 25,119, lies 490 miles by railway north of the city of Toronto. GEOLOGY The property is situated on the northwest limb of a major syncline, which pitches northeast at approximately 50°. The principal rocks of the Hollinger area are of pre-Cambrian age and consist of altered, schistose, Keewatin lava flows intruded by stocks of schistose, quartzfeldspar porphyry generally assigned to the Algoman period. The structure of the Keewatin series is extremely complex as a result of close folding and some faulting. The schistosity, trending north 70° east and dipping steeply to the southeast, is most highly developed along a subsidiary anticline in which the major porphyry bodies occur. The ore bodies, which exhibit three principal structures, consist of quartz veins and associated pyritized wall rock. Some lodes are composed of en echelon veins, others exhibit a main quartz body with branching stringers and a third consists of a single definite lead. Gold, in a coarse visible form, may be confined to quartz in some ore bodies but in others it is finely divided and is found not only in quartz but also associated with pyrite in the adjacent wall rock. In many veins the distribution of gold is such that there are several ore sections, separated by areas of low-grade material, in the same vein although its physical appearance remains unchanged. The veins form a very complex pattern in an ore zone which in places attains a length of 6000 ft. and a width of 4000 ft. They are most abundant in the Keewatin lavas in the neighborhood of the porphyry bodies. Few of the veins are persistent for long distances, though some

Jan 1, 1940

By W. B. McCarter

Broadly speaking, the year 1934, one of the most active in the history of the Coast, has been both disappointing and revealing. Of the 18 new oil-producing areas, only two have shown the qualities of a first class oil field. Many of the new areas are discouraging for the horizons exploited, because of close association of gas and salt water, and the absence of any appreciable oil zone. In spite of amply fulfilling the expectations of drilling and geophysical development, the year has fallen far short of the results that normally should be expected from such a campaign. In 1934, the Cockfield zone has been disappointing because its exploration down the dip from the Conroe and Tom Ball fields revealed only such distillate fields as Splendora, Eureka, and the great gas-sand thickness at Katy. The zone proved good at Raccoon Bend. Newer Oligocene and Frio fields in Texas, with the exception of Hastings, were also disappointing, as Van Vleck arid Old Ocean attest. The discovery at Dickinson is not startling. The development of Hastings, Tom Ball, Dickinson and the deep zone at Raccoon Bend will be slow. A new strip of prospective territory of minor importance lying inland from the Conroe trend was opened by the Kittrell discovery. During the year 206 unproductive wildcats were drilled on the Texas Coast, compared with 207 during 1933 and 141 during 1932. During 1934, there were 835 oil and gas wells and 229 dry holes drilled in proved fields, in contrast with 1100 in 1933 and 512 in 1932. The past year's production was actually 60,868,260 bbl., or 2,020,764 bbl. less than in 1933. The present annual rate of Texas Gulf Coast production is about 61 million barrels per year. The daily Texas Coast production decreased 5537 bbl., or 3.2 per cent, during the year. The total daily production at the end of the year was 173,598 bbl. Eighteen wildcats opened up new oil and gas pools during 1934, so that there are now 78 active pools and 3753 producing oil wells. The production of the average well is 45 bbl. per day. The price of crude oil was almost uniform in 1934,

Jan 1, 1935

By E. J. Schmitz

The mining of the Triassic coals of the Richmond basin has been carried on, upon a larger or smaller scale, for more than a hundred years. Notwithstanding the close proximity of the field to a large city and to tide-water, assuring both a good home-market and cheap transportation, and notwithstanding the good quality of the fuel and the great thickness of the principal bed developed and worked, operations in this field have been conducted with but limited success. The basin comprises about 189 square miles, being from 24 to 31½ miles in length by 5½ to 10 miles in width. Not much more than one-tenth of this area has been explored in a practical and efficient way, and not over 1200 acres have been worked near and along the outcrops or edges of the coal. The practical mistakes which have been committed undoubtedly in a number of the mine-operations of the past, do not alone explain the unsatisfactory success and progress of the industry of this field ; nor can it be ascribed to the lack of local enterprise. Other reasons have to be looked for; and, as a principal one, the irregularity and the faulted conditions of the coal deposits must be pointed out. As a second cause, the indifference of the State government, which leaves the development of the field entirely to private enterprise, instead of aiding it by systematical and practical geological investigations, deserves to be mentioned. Nothing has been done by the State since the excellent work done more than fifty years ago by Professor Rogers, who could not at that time enter into the details of such

Jan 1, 1895

By Edward Judd

CANADA'S mining industry is rapidly recovering from the depression through which it passed in 1921. Its total output of $183,029,600 in 1922 was 6.4 per cent. greater than that of 1921, and was exceeded by only three previous years, 1917, 1918, and 1920. Table 1 compares the output of a few of 'the more important items selected from preliminary data published' by the Dominion Bureau of Statistics. TABLE 1.-OUTPUT OF CERTAIN MINERAL PRODUCTS IN CANADA PER CENT. 1921 1922 CHANGE Cobalt, metal and in compounds, lb 252,000 443,800 +76.1; Copper contents of blister, matte, and exported ores, lb 47,620,820 43,321,400 - 9.0 Refined copper, lb 4,286,000 730,000 -83.0 Gold, fine oz 926,329 1,230,985 +32.8 Pig iron, sh. tons 665,676 429,024 -35.5 Lead, sh. tons 33,340 47,085 +41.2 Nickel contents of matte, etc., lb. 19,293,060 17,496,490 - 9.3 Silver, including that in base bullion, gold bullion, etc., fine, oz. 13,543,198 17,611,646 +30.0 Zinc (nearly all refined), sh. tons. 26,545 28,199 + 6.2 Asbestos shipments, sh. tons 92,761 136,657 +47.3 Coal, all grades, sh. tons 15,057,500 15,045,300 Gypsum shipments, sh. tons 386,550 441,160 +14.1 Natural gas, M. cu. ft 14,077,600 14,954,100 + 6.2 Petroleum, bbl : 187,540 178,570 - 4.8 Cement, bbl 5,752,885 6,943,968 +21.0 Brick, structural, all kinds, M. , , 109,009 127,137 +17.0 On the basis of estimated market values, the whole output of 1922 was contributed as follows: Metals, 33.4 per cent.; non-metallic minerals, 45.1 per cent.; structural materials and clay products, 21.5 percent.; this distribution indicates a return of the metal mining. industry nearly to the position of relative importance that it occupied. before 1921, in which year metals contributed only 28.7 per cent. to the total value. of output while non-metallics gave 51.1 per cent. Canadian cobalt originates entirely in the ores of the Cobalt district, which are mainly treated at smelters in southern Ontario, although some quantities of residues have been exported to England and Europe. Exports during 1922 increased even more than production, consisting of about four-fifths . cobalt oxides and salts, and one-fifth of cobalt alloys and other metal combinations.

Jan 8, 1923

By R. W. Fountain, J. Chipman

THE solubility of nitrogen in iron and steel has been of considerable interest due to the role of nitrogen in strain-aging and in quench-aging. It is generally considered that quench-aging is the result of precipitation of carbide and nitride particles from supersaturated solid solution, while strain-aging results from the segregation of carbon and nitrogen atoms to dislocations.1-9 The rate of strain-aging is controlled primarily by the amount of carbon and nitrogen in solution and the temperature. In experiments on strain-aging of pure iron with only carbon or nitrogen as impurities, Fast" has shown that even after 40 hr at 50°C carbon did not give any strain-aging while

Jan 1, 1959

By H. I. Aaronson, H. A. Domian, A. D. Brailsford

A current study of the growth kinetics of k (hcp) plates in a Cu-Si (fcc)' has generated a requirement for data 02 the chemical interdiffusion coefficient in a (termed D,) as a function of temperature at the composition of the a/a + k pJase boundary. Rhines and Mehl 2 have determined D, as a function of composition at lower silicon contents by making Matano analyses of concentration-penetration curves. However, the accelerating increase in B, which they demonstrated as the phase boundary composition is approached at constant temperature and the rapidly diminishing accuracy of this analysis as the limiting compositions of a diffusion couple are approached (the silicon-rich component of their couples contained appreciably less silicon than is permitted by the solubility limit) indicate that the required information cannot be safely obtained by extrapolation of their data. Although the quite different method employed in this study is not exact, it will be shown that the approximations made are not serious ones, particularly from the viewpoint of the prgcipal application anticipated for these data. D, was determined from the migration kinetics of the a :k boundaries formed in sandwich-type diffusion couples produced by welding a block of high-purity copper to opposite sides of a cube (* in. on edge) of homogenized high-purity Cu-5.82 wt pct Si alloy. The alloy is pure k in the temperature range employed. The surfaces of the couple components which were normal to the diffusion direction were machined accurately flat and parallel, lightly polished, and carefully cleaned. Welding was then accomplished by means of the vacuum-encapsulated pressure jig technique previously employed.3 Welding was always conducted at the intended diffusion temperature; thus the welding anneal also served as the first diffusion anneal. Subsequent diffusion anneals were performed in evacuated Vycor capsules. Following the welding anneal, one of the surfaces parallel to the diffusion direction was machined, ground, and polished flat; additional material was removed from this surface after each diffusion anneal in order to avoid any effects of composition changes. After etching,4 the average distance between a : k boundaries was measured by means of a traveling microscope with an accuracy (per measurement) of better than 1 p. Satisfactory results were obtained at four temperatures in the range 775° to 655°C; attempts to obtain data at two lower temperatures were unsuccessful, evidently as the result of the interference of surface contamination during the welding process.

Jan 1, 1969

By Charles L. Mantell, Kurt Straler

The hydrogen reduction of Cr2O3 to chromium metal was found to be feasible at very low water-vapor concentrations, corresponding to dew points of -38° to -24°C, over a temperature range of 1130" to 1490°C. Hydrogen reduction under these conditions was predicted by the calculated equilibrium curves which also indicated that CrzOs is reduced directly to chromium without forming the intermediate oxide, CrO. This reduction path was confirmed by X-ray diffraction analysis. The percent reduction of Cr2O3 at each reaction temperature was constant with time, suggesting an inhibiting effect of water vapor. A small increase in the residual water-vapor concentration of a single temperature, 1490°C, strongly retarded the rate of reduction This effect was expressed by an empim'cal equation which indicated a direct relationship between "distance from equilibrium" and the rate of reduction. me effect of temperature over the range of 1130" to 1490°C was expressed in an Arvhenius plot of log rate vs reciprocal absolute temperature. From this curve the apparent enthalpy of activation was found to be 29,600 cal. Based on the hypothesis that the rate of reductiun is contvolled at the oxide-metal interface, an over-all rate equation consistent with the experimental data and the thery of absolute reaction rates was formulated. A simplification of this expression to an Arrhenius equation was justified by the overriding effect of temperature on the rate of reaction for the minimum water-vapor concentration range. MOST of the metals in Subgroup V1 of the periodic table can be prepared commercially by direct reduction of their oxides by hydrogen or carbon monoxide, at temperatures considerably below the melting points of both the metals and their oxides. Chromium is an exception, being generally reduced from its ore, Cr2O3 . FeO, by silicon in an electric arc furnace which operates above the melting point of the Fe-Cr alloy or above the melting point of chro- mium if a chromium oxide be the starting material. In reduction of chromium oxide by hydrogen, either reduction does not occur at all or the rate of reduction is extremely slow. Theoretical considerations based on the high, exothermic, free energy of formation of Cr2O3 compared to the oxides of the other Subgroup VI metals, molybdenum, tungsten, and uranium, would also suggest a slow rate of reaction and a high activation energy. Interest in the direct gaseous reduction of fine-powdered ores in fluidized beds was considered justification for examination of this reaction. In order to develop a basis for a continuing study of the commercial feasibility of the direct gaseous reduction of chromite, a study of the kinetics of the reduction of Cr2O3 with hydrogen was undertaken. To the authors' knowledge no accurate kinetic data for this reaction have been obtained. Neither has an activation energy been determined nor has an attempt been made to establish a mechanism of reaction. LITERATURE Maier10 compared the data of I. Y. Granaat,6 H. von Wartenburg and S. Aoyama, and G. Grube and M. Flad7 with that derived from calorimetric and ther-modynamic properties for the equilibria for the reduction of Cr2O3 with hydrogen. These results, plotted as the log of the equilibrium constant vs absolute temperature for the reduction of Cr2O3 and the intermediate oxide, CrO, to chromium, show agreement between the differently derived data. In both cases the equilibrium constants were extremely low. Maier showed that, over a temperature range of 1000° to 2000°K, Cr2O3 is more readily reducible than CrO. Granat assumed that CrO was preferentially formed from Cr2o3 above 1100°C. Grube and Flad's analysis of their reaction products in the 895" to 1000°C range indicated the coexistence of only Cr2O3 and chromium. The hydrogen reduction of the other Subgroup VI metals, molybdenum, tungsten, and uranium, shows that reduction of the higher oxide proceeds through all of the intermediate oxides before being reduced to the metal. Since evidence pointed to an anomaly in the reduction behavior of Cr2O3, the authors investigated the reduction path of Cr2Os.to chromium. This was done theoretically with more recently available free-energy data and experimentally by X-ray diffraction analysis. This work reinforces Maier's conclusion.

Jan 1, 1964

A full account of the wonderful Arizona meeting will be published in the December Bulletin. For the strenuous, interesting, and altogether happy week, we express our hearty thanks to those marvels of energy and thoughtfulness, the members of the local committees in Texas, New Mexico and Arizona. In this number we publish the discussion resulting from the technical session on "Flotation." Because of the timeliness of the subject, this session's discussion was transcribed first and sent to the contributors, and, thanks to their promptness in revising, we are able to print it in this issue.

Jan 10, 1916

By Andrew R. Swanson

An experimental study of the process parameters controlling the selective agglomeration of raw coal slurries is described. Particular attention has been paid to the influence of input variables on agglomerate size and process kinetics. These factors were considered to be of paramount importance as they determine the selection and sizing of the process equipment. The variables studied include oil addition, pulp density, agitation rate and particle size of the feed. The results have been qualitatively interpreted in terms of a classical reaction kinetic model.

Jan 1, 1977

By George C. Howard, P. P. Scott

During the drilling of wells, fractures which are created or widened by drilling fluid pressure are suspected of being a frequent cause of lost circulation. A study of the variables which are believed by the authors to he related to fracturing led to the premise that the presence of an effective lost circulation material in a drilling mud stream would serve to plug small fractures at the moment they are encountered or created and thereby a a possible cause of lost Circula. tion by preventing fluid pressure from widening and extending the fractures. A large number of lost circulation materials were classified and tested in simulated fractures and in shallow wells. Granular type materials with a gradation of particle sizes were found to be the most effective for plugging. Within the limits of pumpahility, the concentration in mud of each lost circulation material tested was found to be a controlling factor in determining the maximum size fracture which could be sealed. A new type centrifugal sorter was given preliminary tests and found to be capable of concentrating cuttings for rejection and reclaiming lost circulation materials. INTRODUCTION The control and prevention of lost circulation of drilling fluids is a problem frequently encountered during the drilling of oil and gas wells. Lost circulation or lost returns may be defined as the loss to formation voids of the drilling fluids or cement slurries used in the process of rotary drilling and well completion. The loss may vary from n gradual lowering of mud level in the pits to a complete loss of returns. Not to be confused with lost circulation is the continuous reduction in mud volume caused by the loss of the fluid phase of muds as filtrate and the solid phase as filter cake during the continuous filt~ation process which occurs on permeable formation surfaces. The loss of drilling fluids and their costly constituents is only one of the detrimental effects experienced when circulation is lost. The loss of drilling time, plugging of potentially productive formations, stuck drill pipe, blow-outs, excessive inflow of water, and excessive caving of formatioils are other effects which contribute to make the control and prevention

Jan 1, 1951

By P. P. Scott, George C. Howard

During the drilling of wells, fractures which are created or widened by drilling fluid pressure are suspected of being a frequent cause of lost circulation. A study of the variables which are believed by the authors to he related to fracturing led to the premise that the presence of an effective lost circulation material in a drilling mud stream would serve to plug small fractures at the moment they are encountered or created and thereby a a possible cause of lost Circula. tion by preventing fluid pressure from widening and extending the fractures. A large number of lost circulation materials were classified and tested in simulated fractures and in shallow wells. Granular type materials with a gradation of particle sizes were found to be the most effective for plugging. Within the limits of pumpahility, the concentration in mud of each lost circulation material tested was found to be a controlling factor in determining the maximum size fracture which could be sealed. A new type centrifugal sorter was given preliminary tests and found to be capable of concentrating cuttings for rejection and reclaiming lost circulation materials. INTRODUCTION The control and prevention of lost circulation of drilling fluids is a problem frequently encountered during the drilling of oil and gas wells. Lost circulation or lost returns may be defined as the loss to formation voids of the drilling fluids or cement slurries used in the process of rotary drilling and well completion. The loss may vary from n gradual lowering of mud level in the pits to a complete loss of returns. Not to be confused with lost circulation is the continuous reduction in mud volume caused by the loss of the fluid phase of muds as filtrate and the solid phase as filter cake during the continuous filt~ation process which occurs on permeable formation surfaces. The loss of drilling fluids and their costly constituents is only one of the detrimental effects experienced when circulation is lost. The loss of drilling time, plugging of potentially productive formations, stuck drill pipe, blow-outs, excessive inflow of water, and excessive caving of formatioils are other effects which contribute to make the control and prevention

Jan 1, 1951

By D. A. Bailey, F. L. Kadey

During recent years, expanded perlite has found extensive use in a wide variety of commercial applications. Specifications for a range of uses call for aggregates having different physical properties and requiring various types of processing. The mitre scopic examination of expanded aggregates in specially prepared thin sections has yielded important information regarding internal structure and can be a useful aid in evaluation of the product. Perlite is an acid volcanic glass containing from 2 to 5 pct combined water. When crushed and rapidly raised to a temperature of 1500° to 2100°F, the volatilization of the combined water, coincident with softening of the siliceous glass, causes the particles to expand or pop. Expansion of perlite to densities as low as 1-1/2 lb per cu ft has been achieved, although the normal range is from about 2.5 to 10 lb per cu ft. Low-density materials of this nature have found application in cryogenic insula- tions, insulating tile and board, plaster and lightweight concrete, soil conditioners, filter aids after comminution, and a host of other uses. The expansion of perlite may be controlled by a number of variables. Some of these are ore milling, furnace design, expanding temperature, use of preheating techniques, screen size distribution, and feed rate of the crude. For the specific intended uses, the art of perlite expanding has developed to the point that much is known about the effect of these variables on the end product. The requirements, however, for an aggregate to be used in plaster are different from those for an expanded perlite to be used in lightweight concrete or for cryogenics. In the study of perlite, many practical questions remain unanswered. One of the most important is, "why do some perlites make hard aggregates while others cannot resist crushing or compaction?" The usual tests and methods for evaluation of nonmetallic substances have been tried and have contributed their share to our knowledge. But chemical analyses, compaction resistance tests, screen analysis, etc., will reveal only a limited amount of information. The answers to these complex questions may well be found in an examination of the intemal structure of the expanded particle. Such questions and the ex-

Jan 1, 1962

By B. G. Ricketts, A. Kelly, P. A. Beck

The isothermal kinetics (at 200" to 400°C) of subgrain growth and of softening were studied in a 99.997 pct pure Al crystal rolled to 80 pct RA, under conditions where recrystallization did not take place. It was found that the kinetics of subgrain growth and of softening were similar, and that the correlation between subgrain growth and softening was in first approximation independent of the annealing temperature. It has been shown by Heidenreich' by means of electron transmission microscopy and by Hirsch and Kellar2 by means of an X-ray microbeam technique that the crystals of heavily cold-worked polycrystalline aluminum consist of subgrains of approximately 2µ diam, which are slightly disoriented with respect to each other. This substructure is found on cold working at room temperature, without annealing. A preliminary study has been previously published3 of the softening upon annealing at 350°C of a heavily cold-rolled aluminum single crystal. Softening and X-ray line sharpening for such a rolled aluminum crystal were later studied in more detail as a function of annealing time and temperature.4 Perryman5, 6 has studied the recovery of polycrystalline aluminum after cold rolling. By means of phase contrast microscopy he found that the subgrain size increases with the annealing temperature but does not alter very much with annealing time at a given temperature. In the present work further study was made of softening as a function of annealing time and temperature and subgrain sizes were determined by two different techniques in an attempt to find any correlation that may exist between softening and subgrain growth. Subgrain size measurements were made both by the X-ray microbeam technique and by transmission electron microscopy. EXPERIMENTAL PROCEDURE For the X-ray studies specimens were cut from

Jan 1, 1960

By M. N. Brodie, John Chapman

INTRODUCTION - DEFINITION & HISTORICAL PERSPECTIVE While this symposium is concerned with comminution which, by definition, relates to all stages of size reduction of an ore body to a form suitable for mineral separation, the electrical drive aspect of the grinding section will receive most attention in contrast to the crushing, screening and materials handling elements of the process. The reason for this is that today's large mills, thirty feet diameter and upwards, present mechanical and electrical problems which require a degree of sophistication in their solution not previously required. The ability to satisfy these demands, so far as electrical technology is concerned, largely results from the development of semi-conductor devices. These can now handle typical electrical distribution power levels within remarkably s m all volumes and with high efficiency when compared with the motor-generator sets, mercury arc rectifiers, rotating amplifiers, magnetic amplifiers and vacuum tubes which were commonly used to provide speed and torque controls as recently as the early nineteen-sixties. The hardware available to the electrical engineer has changed dramatically whereby even the simplest control system formerly using hard-wired relays is now superseded by the program m able logic controller with its computer-like memory containing the sequence of operation, in other words, the software. Reverting now to the mineral process itself, it is assumed that the ore body has been mined using explosives and is delivered to the concentrating plant in its 'run of mine' form. The problem becomes one of reducing the material to a size which will permit an acceptable recovery of the mineral with the most economical use of energy. The size of 'run of mine' material will range from about minus five feet for high tonnage open pit operations to minus two feet for the smaller underground mine. The final reduction in size may range from minus ten mesh to minus two hundred mesh (exceptionally as fine as minus six hundred mesh) depending upon the concentration method and dissemination of the mineral values within the ore. There is no single circuit that satisfies all applications, but the pattern of metallurgical equipment use shown in Table 1 appears discernable from current practice, in general terms.

Jan 1, 1982

By Rex B. McLellan

A simple model for dilute interslitial solid solutions is set up which enables a solubility equation for the equilibrium between the solid solution and the gaseous solute to be deduced. This solubility equation is used to estimate the partial thermody -namic functions of Ag-O and Fe-N dilute interstitial solid solutions from the measured equilibrium between these solutions and the gas phase. It is shown that the partial excess entropy of the solute atom in solution is a vibrational entropy which is due Principally to the oscillation of the interstitial atom and does not arise from electronic or elastic interaction between the solute atoms and solvent matrix. In this work measurements of the equilibrium between dilute solid interstitial solutions and a gaseous phase are used to deduce the important thermody-namic functions of the solid solution with the aid of a theoretical solubility equation formulated from a knowledge of the thermodynamic functions of the gas and a simple model for the solid solution. The quantity of principal interest which is deduced from the equilibrium data is the change in vibrational entropy occurring when a solute atom (u) is placed in an interstial site in the solvent (u) lattice. This paper forms part of a more general study in which the properties of condensed phases are deduced from measurements of the equilibrium between the condensed phase and a gas. Previous investigations have dealt with the equilibrium between krypton and liquid metals,' a pure metal and its vapor,' and dilute substitutional alloys and the vapor,3 and the subject has been popularly reviewed by McLellan.4 In the latter investigation3 the vapor pressures of very dilute Cu-Ag and Cu-Au alloys were measured with a Knudsen cell technique over a large range of temperatures and the analysis of the vapor-pressure data showed that the relative partial excess entropies were large and positive [ds= -Sudk = 30 for Au-Ag alloys and 150 for Cu-Au alloys; these values should be compared to unity, the value assumed for these exponentials in the quasi-chemical theory of solutions]. For many interstitial solutions experimental data is available for the equilibrium between the solution and a gaseous phase, and this can be used to deduce the vibrational entropies of the solute atoms in solution. The general method employed is to calculate the chemical potential of the solute atoms in the gas and equate this to pi, the chemical potential of solute atoms in the solid, which is deduced from a simple model set up for the dilute interstitial solution (in which the solute atoms act as bound oscillators in interstitial sites). This enables a theoretical solubility equation to be set up. In the case of Ag-O and Fe-N solid solutions the solubility c, is found to vary with temperature according to a relation of the type, where PU2 is the pressure of the O2 or Np molecules. Essentially, the theoretical solubility equation enables the parameter A(T), which gives the vibration entropy, and the parameter AH, which gives the energy of solution of a solute atom, to be estimated from the measured variation of solubility with temperature. The solutions treated are dilute enough to enable solute-solute interactions to be neglected so that the partial energy and excess entropy of solution E, and GS are not functions of composition and the configurational entropy is that of a random solution. Large positive values have been found for sxSu this quantity has not been given sufficient consideration in recent work on interstitial solutions and it is felt that the partial thermodynamic quantities of very dilute solutions should be understood before the thermodynamics of concentrated solutions can be fully appreciated. EXPERIMENTAL DATA 1) The Silver-Oxygen System. The measurements of Steacie and Johnson,= using silver foils, indicate that there is a pronounced minimum in the solubility vs temperature curve for O-Ag solutions. Eichenauer and Miiller6 have recently redetermined the solubility of oxygen in silver using a method developed in the investigation of metal-hydrogen systems.7 The solubility determinations were carried out on compact specimens of differing shapes and sizes and the results indicate a much lower solubility than was obtained by Steacie and Johnson with no minimum at 400°C. Subsidiary experiments showed that the erroneous results of Steacie and

Jan 1, 1964

By L. H. Schwartz, S. K. Lahiri, M. E. Fine, D. Chandra

WHILE the yield stress of solution treated Fe-Cu alloys increases rapidly with aging, a precipitate has only been directly observed in overaged samples.'-" This precipitate is essentially pure fcc copper, the E phase. Hornbogen2 suggested that the initial hardening is due to clustering of copper atoms in a bcc iron matrix. Hornbogen was not able to obtain direct confirmation for such bcc clusters by either X-ray diffraction or electron microscopy; however, he did observe analogous clustering in Fe-Au alloys7 where the scattering factor difference between iron and gold is more favorable than that for iron and copper. Fujii, Nemoto, Suto, and Monma4 recently observed diffuse electron diffraction scattering in a 2.5 pct Cu alloy aged at 500°C: for 30 hr. They suggested that part of the diffuse SCattering was due to a modulated structure of 26 to 42 wavelength parallel to the (110) matrix plane. This disappeared with further aging. However, 30 hr at 500°C is well beyond the peak strengthening in this alloy which occurred at less than I hr at 500oc.4 By transmission electron microscopy they could not distinguish between quenched samples and samples aged to maximum strength. The purpose of the present investigation was to try to obtain further confirming evidence for a precipitation stage preceding the formation of the fcc E phase. Change in Young's modulus was selected for study be- EXPERIMENTAL PROCEDURE The Fe-1.67 at. pct Cu alloy was supplied by the U.S. Steel Corporation in the form of a hot forged rectangular bar. The carbon and nitrogen contents of this alloy were 70 ppm and less than 10 ppm, respectively. The samples for Young's modulus measurements were made by cold swaging to & in. diam and cutting to 2 in. lengths. Tensile test samples 1 in. long were prepared by cold rolling to a thickness of 0.012 in. and then machining to gage dimensions of 0.5 by 0.012 in. For Mijssbauer studies, foils 1 mil thick were prepared by cold rolling. During fabrication the alloy was given intermediate anneals at 845OC followed by quenching. The specimens after preparation were solution treated at 1000°C (y field) or 845°C (a field) for 1 to 2 and 5 to 6 hr, respectively, in a dynamic vacuum of about 2 x lom6 torr. The tensile and modulus specimens were drop-quenched into iced brine through an aluminum foil which vacuum-sealed the bottom of the furnace tube. The MOssbauer foils were drop-quenched into helium gas cooled by passing through N2 (liq) in a copper coil. The grain diameter of the modulus and tensile specimens was between 0.025 and 0.035 mm. The samples were aged from 400" to 500°C in a dynamic vacuum of 2 x 10-6 torr and cooled by pulling into a water-cooled portion of the vacuum system. The dynamic Young's modulus was measured at room temperature using electrostatic excitation and detection of longitudinal vibrations.' Neglecting any length change during the aging, (this is expected to be comparatively small), the fractional change of Young's modulus (?Et)/Eav, is equal to twice the fractional change of the resonant frequency (?ft)/fav . ?ft =ft —fo where fo and ft are the resonant frequencies of a specimen before aging and after aging to time t. The measured f's, approximately 51,000 cps, were corrected to 25°C for any variation in the ambient temperature. The tensile tests reported were carried out at room temperature in an Instron with a 1000 lb full scale load cell. The flow stress reported herein corresponds to a strain of 0.002. The Massbauer spectra were taken in a constant acceleration model AM-1 NSEC spectrometer. The

Jan 1, 1970

By D. B. Jugle, J. B. Darby

The equilibrium solubility limits of the transition elements Ti, V, Cr, Fe, and Co in liquid tin were determined in the temperature range from 827" to 1211°K. Since the equilibrium concentration of Ti, V, or Cr in liquid tin is moderately dilute in the temperature range investigated, the solubility data were employed to estimate the partial molar enthalpy and the partial molar excess entropy of solution for the three solutes in liquid tin. The reference state s for titanium or vanadium were selected relative to the solute in an intermetallic compound. The thermodynamic quantities for chromium were calculated relative to pure chromium. RECENT experiments1 have shown that the rate of solution of several transition elements in liquid aluminum can be qualitatively predicted from a knowledge of the temperature dependence of the solvent-rich liquidus. In order to extend the analysis to binary tin systems,' it was necessary to know the equilibrium solubility of several of the first-long-period transition elements in liquid tin. Since solubility data for the tin-rich portion of binary systems are meager, the present investigation was undertaken to determine the equilibrium solubility limit of Ti, V, Cr, Fe, and Co in liquid tin in the temperature range from 850" to 1200°K. EXPERIMENTAL PROCEDURE A useful technique3 to determine the equilibrium solubility of a solute in a liquid-metal solvent consists essentially of placing a pure solute in contact with a pure solvent and allowing sufficient time for equilibrium to be attained at the temperature of interest. Subsequently, the solvent is removed and the equilibrium solute concentration in the solvent is determined by an appropriate analytical procedure. The technique can be applied very successfully to relatively simple systems such as the copper-germanium system.3 However, in many binary systems of transition elements with tin, several intermediate phases are known to exist and precipitation of the phases from solution, in solubility experiments, can lead to an erroneously large solubility. The difficulty was avoided in the present work by equilibration of the most solvent-rich intermediate phase with the pure solvent over a range of temperatures. The compounds employed in this investigation, and the temperature range over which each compound is in equilibrium with liquid tin are listed in Table I. No stable intermediate phases are reported in the chromium-tin system4 and, therefore, pure chromium was utilized as the solute. The stoichiometric compounds were prepared by arc-melting on a water-cooled copper hearth in a helium-argon atmosphere. The elemental tin employed in.this investigation was 99.998 pct pure, and typical lot analyses of the transition elements were reported elsewhere.' A sample of an appropriate solute, in the form of a button and in sufficient quantity to exceed the equilibrium solubility, and the pure tin solvent were placed in a high-purity recrystallized-alumina crucible. The crucible and contents were placed in a horizontal furnace under a high vacuum (10-6 torr) and held at temperature for periods varying between 24 and 72 hr. A water-cooled quench tank, partially filled with diffusion-pump oil, was attached close to one end of the

Jan 1, 1970