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By Oliver C. Ralston, James E. Norman

Separation of minerals by froth flotation is rightly called an art. It can truthfully be said that no two ores separate in the same way. The difference in results obtained when natural and synthetic mixtures of minerals are separated is so great that such tests frequently have been worthless in attempting to select conditions in which a natural mixture will separate. With a few rare exceptions, the natural mixture is much more difficult to treat than a synthetic mixture, and a much poorer separation is obtained. Perhaps several experimenters have wondered why 10 or 20 per cent of a mineral being floated from an ore does not float and is different from the 90 or 80 per cent that is recovered. In experimental tests on pure sphalerite, observers' have noted that varying amounts of sphalerite may be froth-floated with pine oil alone, the amount recovered in the froth depending apparently upon the source of the sulphide. The only explanation of results such as these, barring insufficiency of frother or time of flotation, is that the surface of the mineral floated is different from that of the mineral depressed. This difference often has been found to be caused by natural contamination of mineral surfaces, apparently brought about by weathering and exposure to natural solutions. There is virtually no rock that is absolutely unweathered. One of the writers had an exceedingly instructive experience in 1931 while working with United Verde copper-zinc iron sulphide ore in Arizona. Nonselective flotation of chalcopyrite and sphalerite away from some of the pyrite was all that could be accomplished. All known depressants produced only slight effect. Sodium cyanide showed some effect, but so much had to be used that only a small amount of chalcopyrite could be

Jan 1, 1939

By Oliver C. Ralston, James E. Norman

Separation of minerals by froth flotation is rightly called an art. It can truthfully be said that no two ores separate in the same way. The difference in results obtained when natural and synthetic mixtures of minerals are separated is so great that such tests frequently have been worthless in attempting to select conditions in which a natural mixture will separate. With a few rare exceptions, the natural mixture is much more difficult to treat than a synthetic mixture, and a much poorer separation is obtained. Perhaps several experimenters have wondered why 10 or 20 per cent of a mineral being floated from an ore does not float and is different from the 90 or 80 per cent that is recovered. In experimental tests on pure sphalerite, observers' have noted that varying amounts of sphalerite may be froth-floated with pine oil alone, the amount recovered in the froth depending apparently upon the source of the sulphide. The only explanation of results such as these, barring insufficiency of frother or time of flotation, is that the surface of the mineral floated is different from that of the mineral depressed. This difference often has been found to be caused by natural contamination of mineral surfaces, apparently brought about by weathering and exposure to natural solutions. There is virtually no rock that is absolutely unweathered. One of the writers had an exceedingly instructive experience in 1931 while working with United Verde copper-zinc iron sulphide ore in Arizona. Nonselective flotation of chalcopyrite and sphalerite away from some of the pyrite was all that could be accomplished. All known depressants produced only slight effect. Sodium cyanide showed some effect, but so much had to be used that only a small amount of chalcopyrite could be

Jan 1, 1939

By A. L. Field

This general subject has been so thoroughly discussed by Dr. Herty and his associates, especially with regard to the degree of oxidation of the metal at the time that the silicon pig or spiegel is added, that I am not going to spend much time on that today. I should like to propound a question, which is based on my own observations made some years ago while with a large alloy-steel company which had two open-hearth furnace plants. It is true that one of these plants was not engaged particularly in making alloy steels, but there were certain relations between slag and metal composition which appeared to me to be entirely different in the two plants. I have an explanation for it that is more or less incomplete, but possibly Dr. Herty or Mr. Reinartz or some of the others may be able to complete it. Suppose we take our three layers; the metal on the bottom, on top of that the slag, and on top of the slag, the gas. We cannot overlook the gaseous phase. Regardless of the effect of the iron oxide in the slag on the rate of carbon elimination—and that, of course, is rather important in alloy practice since it is not desirable to have the carbon dropping too rapidly at the time the deoxidizing is had in the furnace—it will probably be admitted that it depends on the iron oxide in the metal for a given carbon oxide. I have seen cases where with approximately identical metal and slag compositions one furnace would work twice as rapidly as another in removing carbon. Of course, there is some explanation of this in what others have already said, that the question of the exact lime and silica content of the slag determines the activity and viscosity of the slag; but I am convinced, without having reviewed the actual records since I was asked to make this talk, because they were not available at the time, that the slags in these two furnaces were not materially different. Putting it another way, one furnace would have

Jan 1, 1935

By A. L. Field

This general subject has been so thoroughly discussed by Dr. Herty and his associates, especially with regard to the degree of oxidation of the metal at the time that the silicon pig or spiegel is added, that I am not going to spend much time on that today. I should like to propound a question, which is based on my own observations made some years ago while with a large alloy-steel company which had two open-hearth furnace plants. It is true that one of these plants was not engaged particularly in making alloy steels, but there were certain relations between slag and metal composition which appeared to me to be entirely different in the two plants. I have an explanation for it that is more or less incomplete, but possibly Dr. Herty or Mr. Reinartz or some of the others may be able to complete it. Suppose we take our three layers; the metal on the bottom, on top of that the slag, and on top of the slag, the gas. We cannot overlook the gaseous phase. Regardless of the effect of the iron oxide in the slag on the rate of carbon elimination—and that, of course, is rather important in alloy practice since it is not desirable to have the carbon dropping too rapidly at the time the deoxidizing is had in the furnace—it will probably be admitted that it depends on the iron oxide in the metal for a given carbon oxide. I have seen cases where with approximately identical metal and slag compositions one furnace would work twice as rapidly as another in removing carbon. Of course, there is some explanation of this in what others have already said, that the question of the exact lime and silica content of the slag determines the activity and viscosity of the slag; but I am convinced, without having reviewed the actual records since I was asked to make this talk, because they were not available at the time, that the slags in these two furnaces were not materially different. Putting it another way, one furnace would have

Jan 1, 1935

H. RIES, Ithaca, N. Y.-The part of Mr. Fiske's paper that interests me especially is that portion dealing with the raw materials, and the tests that were applied to the raw materials in order to determine their value in advance, if possible, because that, I believe, is a step in the right direction. For a number of years I have done my best to persuade different consumers of clay to develop standard methods for testing raw materials. We have in this country a large variety of clays which can be used for a great many different purposes, but in many cases the consumers either have no standard methods for determining the value of those clays in. advance, or if they have they do not publish them; consequently it often puts the clay miner at a disadvantage. If, for example, manufacturers of different types of refractory materials would state publicly just what physical tests their raw materials have to meet, it would, I believe, help them to find more easily the materials that they are looking for, and the clay producer would also be benefited. It would also encourage him to have his clays tested in advance, so that samples could be accompanied by certificates of physical tests that would be of convenience to the manufacturer. At the present time, in this country there are certain types of clay which seem to be rather scarce. There apparently are not many deposits of clay that are exactly suited for the manufacture of zinc refractories. So, too, there are not many deposits of clay that are suited for the manufacture of glass-pots, or the blocks for glass tank furnaces, or clays that can be used for graphite crucibles. Now, in many cases, no standard series of tests has been developed. I am also gratified to see that Mr. Fiske considers the tensile strength. tests of value. Some years ago the American Ceramic Society appointed a committee to draw up a series of recommendations covering standard tests. These recommendations were especially for the use of State geologists and the U., .S. Geological, Survey. Among the tests that were considered was the tensile-strength test, which Mr. Fiske has mentioned in his paper. Unfortunately, a majority of the committee turned it down, and the test was therefore not officially approved, but two of us, who formed the minority, believed in it. Since then the other members of the Committee have come to see that that is an important test to make and Mr. Fiske has emphasized it in his paper.

Jan 1, 1918

By John Garcia

IN some districts of the bituminous coal field the problem of construct-ing bulkheads to seal off water under pressure is becoming increasingly important. Recently this matter has been brought very much to the front by the loss of a large Illinois mine due to failure of a bulkhead that separated it from several old, flooded mines. As this great misfortune has provoked much inquiry about proper bulkhead design, it-is felt that a description, of the successful and extensive water-sealing practice at three mines that have different natural conditions will be of considerable interest to those connected with properties having a present or future water problem and to engineers that may have to design safe bulkheads of economical construction. These three mines are the Saxton and Dresser, near Terre Haute, Ind., and the Hegeler, near Danville, Ill. All three have water conditions that make it necessary to regularly seal off all worked-out sections of the mine, and there are considerably over a hundred bulkheads in each. As far as the writers know, these three mines are the only ones in the bitu-minous coal fields of the United States with anything like so large number of water seals and experience, although a number of other mines are known to have a few bulkheads. More detail will be included herein on the Saxton mine than on the others, as the writers are more familiar with it.

Jan 1, 1937

By E. De Golyer

The only known direct method of discovering oil deposits is by the drilling of test wells. Such exploration is always hazardous and generally very costly. The problem of the prospector, therefore, is one of selecting test sites that are favorably located and so to reduce the odds against his venture. Early in the history of the oil industry, it was realized that oil and gas deposits, other conditions being favor- able, were usually found in anticlinal types of structure. This very understandable and rational habit of occurrence furnished the first substantial clue to the prospector. Oil occurs in sedimentary rocks, and beds of such rocks are deposited originally in parallel planes. An anticline at the surface, therefore, could be accepted as an indication of an anticline in lower beds. Structural geology became the tool of the prospector, and by its use in the past two decades, the majority of the known important oil deposits of the world have been discovered. This is but an incomplete, and the simplest, statement of the problem. Nine-tenths and more of the important oil pools of the world belong to the great class of accumulations controlled by structural traps- anticlines, faulted structures, salt domes, etc.-but by

Jan 1, 1932

Although the Suggestions to Institute Authors, as revised and amplified over the years to meet changing conditions and experience, have had as their primary objective the guidance of the author who is preparing a paper for record in the TRANSACTIONS, there are in this current version many excellent suggestions for the preparation of any material for publication by the Institute In this connection it should be emphasized that in a sense, and to a degree determined by the editors, the Institute has in its journals "a place for everything," especially a place for the article of practical nature that is of immediate but not necessarily permanent interest Such articles may be referred by the Institute Technical Publications Committee to the editors or submitted directly to them , [Papers (TECHNICAL PUBLICATIONS and TECHNICAL NOTES) authorized for the TRANSACTIONS are, with the discussion, gathered together at the end of the calendar year and with a table of contents and index, bound, according to Branch classification, as volumes of the TRANSACTIONS

Jan 1, 1952

By Samuel E. Doak

The utilization of rotary kilns, of the well-known cement type, for the preparation of iron ores for the blast furnace, has become of considerable economic importance within the past 10 years in certain localities, notably those where the native ores are lean. Such kilns may be used simply for the agglomeration of ores too fine to be charged into the blast furnace (i.e., ores whose, loss in the dust catchers is excessive, and whose fineness is detrimental to the working of the furnace), or for the desulphurization of lump and fine ores the sulphur content of which does not exceed 6 or 7 per cent. The desulphurizing action can be combined with that of agglomeration provided the kiln is sufficiently large. Other processes have been developed for the same purpose, but while I am not able to draw a comparison between them by reason of lack of sufficient data, it is safe to say that the kiln, if properly dimensioned for the character of ore to be treated, will compare favorably in its results, both as to economy and quality of product, with any other process. It is not, however, as well adapted for the treatment of flue dust as is a sintering operation, on account of the large percentage of fine coke contained therein. Any combustible entering the kiln at its feed end renders the process very much more expensive and unsatisfactory on account of the difficulty of controlling the temperature, also because of the rapidity with which long "rings" form, due to the increased heat at the cooler end of the kiln. The greatest value of the kiln at present is in the treatment of pyrites cinder; that is, the residue from pyrites ore after the extraction of the greater part of the sulphur. This cinder, while high in iron content, has too much sulphur remaining in it to be allowed to form a large part of the blast-furnace burden, without further treatment. It will range in metallic iron from 42 per cent., representing a very low-grade cinder from a domestic pyrites, to 64 per cent. of the residue from the best Spanish ore, and the corresponding silica content will vary from the maximum of about 25 per cent. to 11/2 per cent. The residual sulphur depends largely on the type of burner used in the original desulphurization. In general, the leanest original ores retain the greatest amounts of sulphur. In modern practice the percentage of sulphur in the cinder is rarely as great as six, and seldom lower than one and one-half. Average analyses for iron, silica, and sulphur of the cinders that have come under my personal observation are as follows:

Jan 1, 1916

By Karl J. Benecke

Though the first patent on a bucket wheel excavator (BWE) was granted in 1881 in the US, this technology was developed in Germany to the high standards of today. However, this development was only possible in parallel with development of shiftable belt conveyors and boom stackers. The combination of these three types of equipment in the open pits of the Federal Republic of Germany has made lignite the cheapest energy source for power generation, despite the low heating value of German lignite on the order of 8500 kJ/kg (3600 Btu/lb) only. Comparing the costs for fuels used in power generating on the basis of their heating value, the relation between lignite, high quality black coal, and imported crude oil is on the order of 1 to 1.5 to 2.5, hence highly in favour of lignite. These cost advantages for lignite in Germany are due mainly to the concentration of lignite mining in a few high-output mines. The largest one, Fortuna mine in the Cologne district, produced a total of 45 million tons of lignite in 1976. That equals the annual fuel need of a 5750 MW power plant running 7000 hours per year at full capacity. Altogether 95.2 million bank m3 equal to 200 million tons of overburden had to be removed to accomplish this lignite output. The largest BWE ever built is working in the Fortuna mine [(Fig. 1)]. At a digging height of 51 m above crawler level, the total vertical reach in relation to the face conveyor level is 98 m by means of its conveying bridge and loading unit. The hourly output is 10 400 bank m3. Its weight in operation is 13 000 tons and its wheel diameter 21.6 m, as high as a seven-story building. Major reasons for the development of BWE technology in Germany were: ? Lignite deposits with moderately consolidated, alluvial-type overburden (gravel, sand, loam, marl, clay, etc.) ? Great overall depth of the deposits, ranging far beyond 100 m, requiring a wide opening of the mine, hence not permitting direct overcasting of overburden. ? Multiple-seam deposits of poor-quality coal divided by reject partings, which demand a perfectly selective digging tool for clean separation. In general, these conditions are almost identical to those prevailing in the lignite deposits of Texas and neighbouring states: The type of overburden suitable for BWE digging, the overall deposit depth ranges down to around 100 m, and finally, the multi-seam occurrence with partings between seams, the latter ranging from just 1 m to a few meters in thickness. Technique As the Texas-type lignite deposits come into focus more and more as a possible fuel source in power plants to replace natural gas and crude oil, the following will deal with the BWE technology for mining a typical Texas lignite deposit under the aspect of producing enough fuel for a 500-MW power plant located at the mine mouth.

Jan 1, 1980

By A. C. Dorenfeld

ORES of the Mammoth mining district, some 45 miles northeast of Tucson, Arizona, are treated by Mammoth-St. Anthony, Ltd. The ores now treated come from a complex system of veins and faults, comprising three mines, in close proximity: The Mohawk, Mammoth and Collins. The ore treated in the past was oxide ore, which contains economic amounts of gold, silver, lead, molybdenum, and vanadium (as wulfenite and vanadanite). The lead-zinc sulphide ore has never been treated before. THE ORE The sulphide ore contains galena, sphalerite, marmatite, pyrite and some chalcopyrite, covellite, chalcocite and bornite, as well as small amounts of gold and silver. The value of the ore is principally in the lead and zinc content. The lead-zinc sulphides are substantially liberated at a minus 65-mesh grind. However, a large part of the chalcopyrite and other copper minerals is not freed, but remains as pin points on the sphalerite. Economically, the copper is unimportant. The gangue is a rhyolite granite, with very little limestone. There is no molybdenum or vanadium in the sulphide ore. HISTORY OF SULPHIDE TREATMENT Test work on samples of the sulphide ore was conducted by several equipment companies, the Arizona Bureau of Mines and the company's laboratory. Results of this test work indicated that for some reason, which at the time could not be explained, recoveries would be only about 65 per cent lead and 50 per cent zinc. Not-withstanding this, because of the nation's need for metals, the management built a 150-ton treatment plant. The mill was started in June 1942. During December 1942, using the standard method of treating lead-zinc ore, the monthly results were as shown in Table 1. These results were poor. Too much lead was in the zinc concentrate, and too much zinc in the lead concentrate. [ ] It should be noted here that prior to December attempts were made to depress the sphalerite with large and varied amounts of cyanide, zinc sulphate, and sodium sulphite with poor results.

Jan 1, 1944

By Dorsey Hager

NORTH -CENTRAL Texas has recently become a center of interest for the oil men of America. The bringing in of the McClosky well at Ranger, Eastland County, and the shallow pool at Brownwood, Brown County, in 1917, has stimulated interest in this area to fever pitch. Oil men from all over the United States are now investing there. The area of present interest is shown by the accompanying map (Fig. 1). The money spent in leases runs into millions of dollars. It is no exaggeration to say that a strip of country 200 miles (321 km.) long and 125 miles (201 km.) wide, comprising some 15,000,000 acres (6,070,310 ha.)., has been leased practically solid at a cost for rentals and bonuses of at least $1 per acre. The test holes contracted for will certainly number 400, at a cost of at, east $5,000,000. From what has been done in the past six months, $20,000,000 at least will be spent. To pay, returns on this amount of money, new production to the extent of at least 12,000,000 bbl. must be obtained. At present, the production from new fields will not average over 5000 bbl. per (lay; three wells at Ranger are producing 3000 bbl.; 250 wells at Brownwood produce 1000 bbl.; and the Gray well, Coleman County, is as yet an unknown factor. However, at Ranger there is every indication of developing a good pool covering from 1500 to 2000 acres (607 to 809 ha;), more or less, but the wells are deep, 3400 to 3800 ft. (1036 to 1158 m.), and cost $35,000 to $40,000 to drill. Large wells are necessary to pay for such expensive holes. As new wells are drilled, the gas pressure will be lowered rapidly, and large production need not be expected. For those oil men who expect a second Cushing or an Eldorado, Ranger holds little of promise. At Brownwood, Brown County, there are some 250 shallow wells (depths from. 200 to 350 ft.) averaging 4 to 7 bbl. per day. There is a chance of an extensive producing area, for these shallow sands to the southwest, and the opening of several thousand acres of shallow oil territory, and also some promise of deeper oil horizons in the Ranger horizon, but probably all under 2500 ft.

Jan 6, 1918

By Vernon Read, John K. Hayes

Generally speaking, drilling equipment and techniques presently in use are not capable of meeting the complex technical-and economic-requirements of deep core drilling. Drilling to great depths involves increasing risk, time, and money. And it is especially true that costs increase with depth when conventional core drilling methods are used. Introduction of wire-line drilling techniques has been a great boon to deep core drilling, and is rapidly gaining general acceptance. But, in spite of recent progress, there remains a great need to improve productive drilling time and penetration rates, and still maintain high core recoveries.

Jan 1, 1959

By J. Parke Channing

THE production and use of copper in the world, like that of other metals, has been of slow growth. In 1880, production in the United States, was only about 60,000,000 lb. and the world's production 325,000,000 lb. Up to 1913 there was a gradual and regular increase in production; in 1912 the production was 1,250,000,000 lb. for the United States and 2,200,-000,000 lb. for the world. At the outbreak of the war there was a slight falling off, both in the United States and elsewhere, but when it was realized that the war was not to be a short one and that copper was one of the most important things for carrying it on, there was a tremendous increase in production every-where. Roughly speaking, the average production for the years 1916, 1917 and 1918 was very close to two billion pounds in the United States and three billion pounds in the world. WAR DEMANDS STIMULATED PRODUCTION Not only did the production of copper in the United States increase, but the same may be said of .all the base metals, particularly of zinc. Much of the zinc used by the Allies came from Australia, but had been smelted in Belgium and Germany, now closed to them. We were called upon to make good this lost supply and in feverish haste built new zinc smelteries and opened new mines. The armistice found the United States with a large surplus of copper on hand, variously estimated at from 800,000,000 to 1,000,000,000 lb. In addition to this surplus in the United States, there were considerable stocks in the hands of the Allies and also immense quantities of unused brass. To. complicate the situa-tion still further, the reclamation of old brass shell cases and other used material was instituted, still further curtailing the demand for new material. This situation was- not appreciated at the time and it was assumed, that the Central Powers would immediately come into the market ? replenish their exhausted stock of copper. During the war Germany had torn down copper trolley wires and roofs, and melted up bronze bells, doors, statues and other copper-bearing material to reclaim this metal for military purposes. But Germany-was unable or at least unwilling immediately to replace her copper substitutes.

Jan 1, 1923

By E. V. Howard

During the recent expansion of precipitate copper production at the Chino Mines Division of Kennecott Copper Corp., Santa Rita, N. Mex., local studies of the dump leaching process were intensified. As these studies progressed, it became apparent that a reliable method for locating leach solutions within the dump was required, since the contact between the leach solutions and the copper-bearing ma.teria1 determines recovery. In the past, the problem of determining leach solution contact has been attacked by various methods, including destructive testing (dump dissection), indirect observation (such as chloride or dye tracers) and mathematical or laboratory model studies, but they have not proved completely satisfactory. The investigation of methods for in situ observation of leach solutions led to consideration of radiation logging in drillholes, which are subsurface techniques used in petroleum exploration and development for locating fluids and measuring porosity. A significant advantage of radiation logging is that, unlike other types of logging, measurements may be made in cased holes, since gamma rays and neutrons will penetrate steel and cement. Three techniques are currently used at Chino: Natural gamma ray logging; neutron-neutron, or moisture logging; and gamma-gamma, or bulk density logging.

Jan 4, 1968

By C. M. Marquardt

Tramp iron and steel moving on a conveyor belt cause small currents to be generated in a coil situated in a strong magnetic field, which are converted to an alternating current and are amplified. The output voltage from the amplifier fires a thyratron with a relay in its anode circuit, which actuates a howler and simultaneously drops a spot of marker material on the belt.

Jan 6, 1950

By Mason K. Banks

A process has been developed which produces spodumene concentrates assaying 6.0 pct Li20 and 0.45 pct Fe203, with 70 to 75 pct recovery of spodumene. Two flotation separations are required: the simultaneous removal of mica, feldspar, and quartz as a froth product using a cationic collector, and the subsequent removal of iron-bearing minerals as a froth product while spodumene is depressed as a tailing.

Jan 2, 1953

By Gregg A. Scott

Upper Stillwater Dam is to be a roller-compacted concrete gravity structure, founded on nearly horizontally bedded sandstone and argillite rock. An overview of the testing and analyses used to evaluate the adequacy of the foundation relative to deformation, seepage, and stability is presented.

Jan 1, 1984

By A. W. Schlechten

The proposition is advanced that edutcation specifically for exlractive metallurgy is desirable not because the course content is cmique but rather as a means of indoctrinating the student with a backgrocmd that will give him an interest and pride in the profession. Factors that have caused the decline in enrollment in metallurgical engineering courses emphasizing extractive processes are being overcome. There is a need to distinguish between the sciences of metallurgy and the engineering applications to avoid confusion both in and out of the profession. AS a first step in preparing the 1967 EMD Lecture I searched the literature to determine what my predecessors had done hoping thereby to gain some clues for my own performance. The Transactions of the Metallurgical Society show that the first EMD Lec- turer in 1959 was Dr. W. J. Kroll, known chiefly today for his pioneering work on the production of titanium and zirconium, but equally respected by an earlier generation for his contributions to lead refining. He has been followed by a series of well-known and competent metallurgists all possessing specialized knowledge that has served as a basis for their lectures. The EMD Lectures have in general been a review of the development of a certain aspect of the extractive metallurgical industry or a preview of a particular area of science or technology that has applications in extractive metallurgy. The usual format is to describe developments of the past, summarize the present state of knowledge, and make predictions for the future. There has been great variation in the relative amount of time devoted to these three subdivisions, the past, the present, and the future. For example, Professor Gaudin, the 1961 EMD Lecturer, in speaking of Separation Engineering on the Moon, did not have too many examples of past practice and so had to emphasize the future. It is cheering to observe that all of these authorities were optimistic in their predictions. Despite the fact that four of the previous EMD Lecturers have been educators, Professors Gaudin, Pidgeon, Schuhmann, and Kellogg, none of them discussed the subject of education for extractive metallurgists. I might say parenthetically that lecturers in other divisions, such as B. M. Larsen, J. B. Austin, F. D. Richardson, John Chipman, and R. F. Mehl, have commented with concern on the present state of training for extractive metallurgy. What can you say that is new about extractive metallurgy education? Certainly nothing new can be said about the educational process itself. Professional educators do have new approaches to teaching and learn-

Jan 1, 1968

By E. J. Rapperport, J. P. Pemsler

The thermodynamic activities of zinc in six solid solution Cu-Zn alloys ranging from 5 to 35 at. pct Zn were determined experimentally in the temperature range 400° to 600°C. This low temperature investigation was canducted in order to evaluate techniques developed to utilize the inherently high sensitivity of atomic absorption flocesses in the measurement of thermodynamic activities. Analytical expressions ,for the activity and actizlity coeflcient are given for the six alloys in the temperature ranges investigated. RELATIVELY few experimental methods are available for investigation of thermodynamic activities of alloys, especially in the solid state. The techniques most frequently used have been the electrochemical potential and the effusion methods, both of which have severe limitations in many instances. It is therefore desirable to expand the ability to perform such measurements in order to obtain new information as well as to provide an additional independent verification capability. In this work, we present a significant improvement in the spectrophotometric method for sensing small vapor pressures in static absorption cells. Similar techniques have been used previously;1"5 however, applications had been limited to relatively high pressures, often greater than 1 torr. Prior investigators have, for the most part, used broad spectral sources such as xenon or mercury lamps, and high intensity arcs. Hollow cathode sources were first suggested in 1956 6 and were used soon afterwards.4'5 These sources offer significant improvements in sensitivity and freedom from interfering spectral lines.'-' EXPERIMENTAL High purity zinc was obtained from Cominco Products, Inc., and copper from American Smelting and Refining Co. Both elements were of 99.999 pct purity. Copper-zinc alloys were vacuum melted in a high fired carbon crucible with each alloy pulled from the melt as a 4 -in. diam bar. The bars were swaged to -1/4 in. rods and vacuum annealed for 160 hr at 800° + 1°C. Samples for gross chemical analysis were taken at intervals along the length of the rods to ascertain the axial zinc gradient. Electron microprobe analysis of homogenized specimens indicated that the alloys had uniform compositions over their cross sections on a macro (200 p) and micro (1 u) scale to better than *1 pct (20) of the gross composition. This tolerance was determined by counting statistics, rather than assured composition fluctuations. All SiO 2 windows were high-ultraviolet-transmission grade to minimize intensity losses. Silica absorption cells were scrupulously cleaned consecutively in organic solvents, dilute HF, and distilled water before use. The empty cells were then flamed while under a dynamic vacuum, cooled, and removed to an argon-filled glove bag. Alloy pieces were cut and filed in the glove bag to produce fresh surfaces, and then loaded into the cells. The loaded cells were temporarily sealed, removed from the glove bag, reevacuated to 10-5 torr or better, and permanently sealed. The instrument used is schematically shown in Fig. 1. The spectral emission from a commercially made hollow cathode lamp (A) of a selected element is focused through an absorption cell (B) inside a well-controlled furnace (C). The intensity of the transmitted beam is measured using the spectrometer* (D) 'Techtron model AA4 atomic absorption spectrometer. which contains a grating (E) that disperses the light prior to impingement on the photomultiplier (F). The monochromator grating is adjusted so that only the wavelength of interest is measured. The power supply delivered an interrupted voltage to the lamp, causing a chopped radiation output to be transmitted. The detector read only the intermittent component of radiation incident upon it, so that all continuous noise signals (furnace radiation, and so forth) were eliminated. Three recording thermocouples contained in the muffle furnace were positioned along the length of the absorption cell: one at each end and one at the center. An effort was made to keep the ends of the cell several degrees hotter than the center to avoid window condensate. Appropriate thermal corrections were then necessary to relate cell pressure to radiation attenuation. Water-cooled heat shields, as shown in Fig. 1, were found to aid signal stability by protecting the hollow cathode and the photomultiplier from furnace radiation. The furnace had a 2-in. diam muffle, Kan-thal wound, with SiO 2 windows at its ends to minimize convective effects. The hollow cathode radiation was masked and focused to form a conic beam that was a maximum of { in. diam within the furnace. Thus, the 1.5 in. diam absorption cell easily contained the entire beam. The furnace was mounted on ball-bearing slides with positive positioning detents. This arrangement allowed the removal of the entire furnace assembly from the radiation path, position [I], Fig. 1, so that frequent sampling of the unattenuated beam intensity could be obtained. In all cases the beam intensity was kept constant to 0.1 pct as judged by readings taken immediately before and immediately after data collection. Only data for absorptions of less than 80 pct were utilized, as systematic deviations from linearity were found for greater absorptions.

Jan 1, 1970