Search Documents

By CYRIL W., William Campbell, Henry M. Howe

THIS paper gives the results of an investigation of the behavior of the argentiferous cobalt-nickel arsenides of Temiskaming, Ontario, in roasting, made in the metallurgical laboratories of the School of Mines, of Columbia University in the City of New York. The ore was kindly given by the owners of the La Rose and Trethewey properties at Cobalt, Ontario, and Mr. E. J. Hall, Tutor in Assaying in Columbia University, has helped us much. I. OBJECT OF THE INVESTIGATION. The object of the investigation was to learn:- 1. The temperature at which the arsenic is most rapidly expelled; 2. The thoroughness with which it is expelled by prolonged roasting at this temperature; 3. The effect of adding charcoal (a) near the end of the roast and (b) at the beginning of the roast. II. NATURE OF THE ORE. The important ores mined in the Temiskaming deposits are native silver-with small amounts of dyscrasite (Ag6 Sb), argentite (Ag2S), pyrargyrite (Ag3SbS3)-smaltite (CoAs2), chloanthite (NiAs2) and niccolite (NiAs). Mispickel (FeAsS) and cobaltite (CoAsS) also occur in smaller quantities. The average composition of the ore shipped from this district for the first six months of 1905 -was: silver, from 4.1 to 4.8 per cent.; cobalt, from 6.9 to 8.2 per cent ; nickel, from 3 to 4.7 per cent ; and arsenic, from 30.9 to 34.6 per cent. The ore which we treated consists chiefly of smaltite ; In our laboratory-work

Jan 1, 1907

By A. Faber du Faur

At the request of some of the members to whom I have shown a collection of specimens of sulphur from southern Utah, I herewith present some notes relating to the mines and the method of extracting the sulphur from the ore. In preparing these notes I have borrowed from a paper by Prof. G. vom Rath, published in the Neue Jahrbuch fur Mineralogie, vol. i., 1884, dated Salt Lake City, December, 1883. The Cove Creek sulphur-bed, now worked by the Dickert & Myers Sulphur Co., is in Beaver county, near the line of Millard county. It was first discovered by Mr. Ferdinand Dickert in 1869 ; other beds in the same neighborhood mere found by him from 1872 to 1875, making altogether 22 mining claims. The want of railroad communication prevented the early development of these claims; but in 1883 Mr. F. Dickert put up a plant for extracting sulphur from the ore, which proved a perfect success; and in 1885 the property was transferred to a stock company organized under the laws of Utah. The railroad station nearest to the Cove Creek mines is Black Rock, on the Utah Central Railroad, 204 miles south from Salt Lake City, and about 26 miles west of the mines. The road from Black Rock to the mines passes through desert and lava-bed, to the road leading from Kanosh to Beaver, which latter road it joins near Cove Creek fort, a square stone enclosure, erected by the Mormons for protection against the Indians. Cove Creek fort is situated near the eastern limit of a plain bounded on the west at a distance of about 12 miles by the Mineral range, and on the east by the Sulphur mountains, forming part of the Tushar mountains. To the northwest the plain runs into the Sandy desert. About 3 miles from the fort rises a solitary hill about 1000 feet above the

Jan 1, 1888

By F. F. Hintze

Petroleum production in the Rocky Mountain district during 1929 registered a small decline from that of the previous year, conforming with a gradual decrease in the amount of oil produced during the last few years. A number of causes may be mentioned to account for this result, chiefly overproduction in other regions and the apparent desire of operators in this territory to conform to the policy of proration and retrenchment adopted by special agreement among operators in many of the fields. Unit operation has been adopted to control oil production from the Sundance sands in the Salt Creek field, Wyoming, in line with the general effort to stabilize this phase of the industry and prevent excessive drilling of new wells. Another factor which greatly retarded development in the Rocky Mountain region was the executive order of President Hoover issued in March refusing the award of new prospecting permits to future applicants and threatening cancellation of all existing permits upon which actual drilling had not been done as specified by law. Only four states in the Rocky Mountain region are important oil producers. In 1929 Wyoming led with an average daily output of 52,600 bbl., followed by Montana, with 10,730 bbl.; Colorado, with 6500 bbl., and New Mexico with 2700 bbl. daily average. These states bear the following percentage relation to total production in the Rocky Mountain district: Wyoming, 72; Montana, 15; Colorado, 9; New Mexico, 4., (Table 1.) The total average daily production was approximately 73,000 bbl. and the total production of all four states during the year was 26,534,606 bbl. This is 2.7 per cent. of the total oil production of the United States during this period. Colorado Although Colorado is not a large producer of oil and natural gas, its oil operations are widely distributed over the state. The Florence field is one of the oldest oil fields in the country, and there are good reasons for believing that the state will retain its place for many years to

Jan 1, 1930

By A. L. Sweetser

Experience has shown how difficult it is to obtain information regarding laboratory-tests in connection with the chlorina-tion-process for the extraction of gold from its ores, and I therefore present the following method, somewhat in detail, for the benefit of those who may desire to pursue research work in this field. The ore chosen was a partly-decomposed porphyry, extremely siliceous and comparatively soft, and of an average value per ton of from $25 to $26 in gold and $0.68 in silver. The chemical analysis gave: Fe,O,, 3.35; FeS, 1.5; MnO,, 0.75; ZuCO,, 4; A1,0,, 3.20; H,O, 0.7 ; SiO, and insol., 83.50 per cent. The ore, first crushed to pass a 5-mesh screen, was coned and quartered until a 45-lb. sample was obtained. Samples for assay and analysis, taken from this lot by means of riffles, were crushed to pass a 100-mesh screen. The original sample was divided into 10-lb. lots, of which one was crushed to pass a 10-mesh screen; another through a 12-; the third through a 20-, and the last through a 30-mesh screen. Because of the production of an excessive quantity of fine material it was deemed inexpedient to crush finer than 30-mesh size—a decision the wisdom of which is proved by the data in Table I., showing the increasing ratio of slimes, in proportion as the ore is crushed finer. In order to determine the percentage of fines in the sizes of mesh selected, a weighed sample of ore was taken from each mesh, and a sample from the 10-mesh lot was passed successively through 20-, 40- and 100-mesh screens, and the percentage remaining on each screen determined. This process was repeated with the 12-, 20- and 30-mesh lots, with the results given in Table I.

Jan 1, 1908

By John D. Price

R. W. Campbell (Jones and Laughlin Steel Carp., Pittsburgh)—As usual John Price has presented an excellent paper. I know of no one who has devoted more time and conscientious thought to this subject than he has, and his efforts have produced scientific data and conclusions of real value. Results of similar studies made by the Jones and Laughlin Steel Corp. on the blending of Pennsylvania coals may be of interest. During 1935 the late F. W. Wagner and the present writer developed an empirical physical fuel value formula for evaluating the combined physical tests of metallurgical coke, see Table IV. In the development of the formula, the tumbler test, shatter test, screen test, and porosity of coke have been taken into consideration. Each of these tests brings out some physical property not expressed by the others, and in estimation of the importance of these tests as a medium for evaluating coke for the blast furnace, their worth has been graded as follows: It was thought that some additional penalty should be applied to cokes that do not show a uniform screen size, assuming that coke larger than 4 in. was not desirable and that this size was an indication of irregular size. Therefore the screen test factor is further corrected by applying a penalty of 1 pct for each 1 pct material greater than 4-in. size as shown by the screen test. The physical fitness of coke for blast furnace use depends upon four fundamental characteristics: l—gen-era1 strength, as indicated by the shatter test; 2— abradability, or the resistance of cell walls to reduction in size by attrition, as indicated by the tumbler test; 3—porosity; and 4—size and uniformity. Each of these characteristics is not of equal importance, but surely, in an attempt to determine an accurate physical value, the individual value of each should be taken into consideration. The formula is used as a yardstick, so to speak, in determining variations in the normal production of metallurgical coke and in making comparisons between normal coke and experimental blends with other coals. Table IV gives results of coking tests on raw and washed high volatile coals and these same coals with blends of coke breeze, anthracite coal, char and low volatile coals, all from Pennsylvania. The table also gives the source of the coals and coke breeze, as well as their proximate analyses. It will be noted that the washing of the raw high volatile coal increased the physical fuel value from 26.17 to 39.16, showing the effect of removing shale and slate which produces a detrimental fracturing and weakening of the coke. It is a well known fact that many Pennsylvania high volatile coals contain an excess of resinous material or binder which has a tendency to weaken the coke, owing to its high evolution of gases during carbonization. Tests were therefore made with coke breeze, an inert material, in an attempt to alleviate this condition. Blends of washed coal with 5 pct and 7.5 pct coke breeze collected from the coke plant quenching sump (82.9 pct through 1/8-in. screen) resulted in cokes with a physical fuel value of 20.75 and 16.73 respectively, lower than results obtained from 100 pct raw high volatile coal. It will be noted that the percentage of + 4-in. coke increased but that the tumbler test was very low. Undoubtedly better results could have been obtained if the coke breeze could have been crushed extremely fine. During World War II the government asked the coking industry to consider the use of anthracite coal as a substitute for high quality low volatile coal, which was extremely scarce at the time. The next series of tests was made with blends of raw and washed high volatile coals and 5, 10, and 15 pct Pennsylvania No. 5 buckwheat anthracite (100 pct through l/8-in. screen). It was necessary to use some raw high volatile coal in these blends because of insufficient washer capacity at the time. It will be noted that the physical fuel values

Jan 1, 1954

By William L. Batt

FROM the time the Japs overran the Far East, the United Nations faced a serious military problem in the critical shortage of many raw materials desperately needed to prose¬cute the war on two fronts. For many months this critical shortage threatened substantially to limit the gigantic effort to get shooting equipment into the hands of the fighting men on the far-flung battle lines. Now this crisis has been met. Solvency in raw materials has been achieved. Simply stated, this job of producing solvency has been done by "cutting cloth to fit the garment." This does not mean that we have all the raw materials we need. Unfortunately, a few raw materials are still short, thereby limiting the total production of certain war goods, or making these goods less effective. Where the supply of raw materials is known to be limited, however, substitutions have been made or production schedules have been geared to the amounts available, and an over-all balance has been achieved between various parts of the war-production program.

Jan 1, 1943

By Edgar C. Bain, William E. Griffiths

The results of an inquiry into the structural nature of some 70 iron alloys containing both nickel and chromium over a considerable range of concentration are briefly described in this paper. This study is a part of a comprehensive program of investigation into alloys involving chromium in progress at the Union Carbide and Carbon Research 1aboratories. All the compositions studied contained carbon in amount comparable to commercial alloys. The B Constituent In addition to locating the limits of composition for the three principal types of structure (polyhedral ferrite, martensite and austenite) and their combinations, certain other features of the system were observed. A hitherto undescribed brittle constituent (designated here as the "B constituent") was discovered. It is very hard, non-magnetic and forms in two modes from chrome-ferrite by recrystallization. It is the stable low-temperature condition for the equal-proportion chromium-iron materials containing less than 10 per cent. nickel. Although it partakes of the nature of an inter-metallic compound, yet it may exist over a considerable range of composition. It is non-existent above a temperalure zone, varying with composition, from 800° C. to 950° C., and heating above this critical temperature develops chrome ferrite persistent after average cooling rate; a few hours just below this temperature will develop the complicated brittle crystalline type. The B constituent, when found in the grain boundaries of alloys of lower chromium content, contributes a serious brittleness removable, however, by heating and cooling rapid enough to prevent its re-format'ion. By suitable means of precipitution, the hard B constituent can be made to strengthen the already stiff alloy matrix in the manner of submicro-scopic particles, as exemplified in duralumin or the Sykes iron-tungsten and iron-molybdenum alloys. A possible explanation is offered for the familiar brittleness developed in chrome iron at temperatures above about 475" C. and removable by

Jan 1, 1927

By AIME AIME

AWRDED jointly by the four AW Founder Engineering Societies the John Fritz Medal is generally regarded as the most signal honor that American engineers can confer on a fellow engineer. The roll of 34 recipients contains the names of Lord Kelvin, George Westinghouse, Alexander Graham Bell, Thomas. A. Edison, George W. Goethals, Guglielmo Marconi, and Michael I. Pupin; and among members of the A.I.M.E. now living, Sir Robert A. Hadfield, Herbert Hoover, and Daniel C. Jackling. On the evening of March 1 7 the name of Paul Dyer Merica was formally added to this list of illustrious engineers when the medal was presented to him at a dinner at the Metropolitan Club in New York. The citation read. For important contributions to the development of alloys for industrial uses. Arrangements for the dinner were made by the following committee representing the four Founder Societies: R. C. Allen, George S. Davison, A. A. Potter, and J. B. Whitehead.

Jan 1, 1938

By Donald M. Liddell, G. C. RIDDELL

THE cosmic ray continues to engage the attention of the physicists, and according to Millikan and Compton, experiments of the past summer indicate that these rays must come from interstellar space, but not from the stars themselves. According to press reports of the International Congress of Physicists at Rome, the view was given there that these rays have an initiating potential of over 750,000.000 volts. In the field of spectrographic investigation great strides have been made. The U. S. Naval Research Laboratories (R. F. Mehl and G. E. Doan of Lehigh) have just finished a year's work with a "radium torch" or "shadowgraphic apparatus" in the field of the X-ray, that bids fair to displace the latter to a great extent. The torch is more powerful., easier to operate and cheaper. Penetration of 10 in. of steel has been accomplished, which. is much -beyond the- -scope-, of the X-ray..

Jan 1, 1932

By Charles G. Maier

SCIENCE beginning in rational observation came of age, when its devotees first began to measure and count. It has been said that the most striking aspect, of science today is its growing abstraction, and its preoccupation with mathematical symbolism. Technology with specific and concrete objectives in the satisfaction of human wants, cannot conceivably achieve the abstract unification that science seeks, but .the utility of the' scientist's method has been too well proved to require bolstering. Metallurgy is in its scientific infancy.

Jan 1, 1931

By PALMER H. TYLER

WHEN the Mid-Continent Section of the A. I. M. E. met at the roof garden dining room of the Tulsa Club on Monday evening, May 13, most of the members present came prepared with a credulity-stretching yarn of some sort or other, gathered from actual experience. Perhaps it was not realized at the time that such anecdotes would eventually burst into print, but while the excellent dinner was appeasing the inner man the word was passed around that informality and spontaneity of expression would characterize the meeting, with the result that the shackles of convention were eventually cast aside and the meeting waxed better and better until the hour grew ,late, and the chairman, L. G. E. Bignell, originator of the idea, brought to a close what was agreed to be a profitable and entertaining evening. The ball was started rolling by Paul Ruedemann of the program committee, who offered the following:

Jan 1, 1929

By AIME AIME

THE Board of Directors of the Institute has authorized the appointment of a committee to draw up rules of procedure under which awards can be made from time to time to petroleum engineers for outstanding contributions to the art of finding and producing oil and gas. These awards will 11e sponsored by the Petroleum Division and are the first recognition by any professional society of outstanding achievement in "oil mining." They will be in the form of either a gold medal, scholar- ship, or other suitable prize. The awards will be financed from the income of the Anthony F. Lucas Memorial Fund, which was started about fifteen years ago, shortly after' his death, by admirers of Captain Lucas.

Jan 1, 1936

By Clark A. Sumner, D. Arthur Burnham

A process for recovery of greater than 99% of the copper contained in acid leach solutions by sulfide precipitation using hydrogen sulfide as a hydrometallurgical reagent has been developed. The process incorporates the concept of hydrogen sulfide addition to recycled copper sulfide solids in a turbulent flow area where further precipitation or agglomeration occurs to increase the effective particle size of the copper sulfide precipitate. Because the recycled solids provide a larger number of particles upon which momentary excesses of hydrogen sulfide are absorbed, oversulfidization of the product is prevented. Copper sulfide precipitates produced in this manner in a laboratory test reactor showed greatly improved physical characteristics compared to copper sulfide precipitates obtained by conventional direct precipitation in which H2S is bubbled directly into acid leach liquor. Copper sulfide precipitates were evaluated and compared by use of filtration tests and settling rate studies. Electron microscopic examination of the solids confirmed the presence of larger particles in reactor-precipitated copper sulfide. Flotation was examined as an alternative to filtration for recovery of CuS precipitates and was found to achieve complete CuS removal without addition of collector or frothing reagents in a period of 2 min. In the same test reactor, a rapidly floatable CuS precipitate was also formed by mixing H2S with acid liquors used to leach crushed copper oxide-copper sulfide ore (LPF process). In the presence of gangue from the crushed ore, flotation of both natural and reactor-produced copper sulfides resulted in recovery of better than 90% of the copper contained in the crushed ore.

Jan 1, 1974

By C. A. Fisher

THE discovery of petroleum in Pennsylvania in 1859 marked the birth of an industry of paramount importance. Spreading from - Oil Creek, this remarkable industry may be said to have embraced the earth in a little more than half a century. Those who made the discovery little realized its deep significance or far reaching influence on our national life. For over sixty years, during which time this nation has created and developed the oil industry to a high state of efficiency and' carried its activities to all parts of the world, we have' at all times been the leaders in the production of crude oil and in the development of its technology. During the unprecedented growth and expanse of the oil industry there has been an increasing dependency of our basic industries on, petroleum, until at present it has become essential to our national existence. To meet the ever increasing demand for petroleum and its products, we have explored, at one time or another, for their oil possibilities, practically all parts of the sedimentary rock area in the United States. Furthermore, detailed surface and, in many places, subsurface studies have been made of all the promising regions; over 640,000 jewells have 'been drilled for. oil since the beginning of the industry; $12,000,000,000 have been spent in this work; seventeen major fields exceeding 100,000 bbl. daily production and more than a thousand minor pools have been opened up, and 8,000,000,000 bbl. 'of oil have been produced, or an amount nearly equal to the estimated future reserves of the United States made in 1921.

Jan 1, 1925

J. E. Stead, Middlesborough, England (communication to the author): Prof. Howe's valuable paper on cast-iron brings forward most prominently the correct explanation of the part played by combined carbon in pearlite and cementite, in determining the strength and hardness of cast-iron. On a previous occasioil I have shown that castings made by melting a white Cleveland iron and glazed iron, one containing 1.5 and the other from 4 to 5 per cent. of silicon, and each about 3 per cent. of carbon, were stronger than those made of ordinary foundry-iron; the difference in the final castings being a differ-

Jan 1, 1902

By Edwin B. Wilson, Joseph W. Leonard, Richard W. Borio

preparation of specification coals for the utility industry is approached from the standpoint of a cooperative effort with the power company to assure that the shipped product will be a noncorrosive coal. Selective mining, coal preparation, the use of additives, and coal blending are mine-site techniques proposed as means for upgrading corrosion-retarding constituents of utility coals (CaO and MgO) while, at the same time, reducing the concentration of those constituents of coal (Na20 and K,O) which cause corrosion. Data obtained from large-scale boiler testing in combination with bench-scale physical and chemical tests are used as a basis for the formulation of mine-site procedures to improve coal combustion utilization. Electric power generation remains the greatest market for coal in the United States. A major reason for this strong market has been the ability of the coal industry to supply a superior product for combustion while maintaining competitive prices. Now that the coal industry is engaged in intensive competition with nuclear power for future energy demand, it becomes ever more imperative that superior coal products are produced. One important problem when burning some coals is a liquid phase corrosive attack on boiler tube metal in the superheater and reheater areas of the furnace where steam temperatures may exceed 1050°F. In addition to causing power outages and high maintenance costs, corrosion is a continuing barrier to the future development of more efficient steam cycles which permit lower generation costs when using coal. Research methods of the past which have been directed at finding solutions which could be applied at the power plant site have been only partially successful and are generally costly. This paper contains a suggested --method of corrosion control through investigation of the problem at the source of the trouble—the coal supplier facility. It is proposed that mine-site pre-ventative procedures be considered as an effective means of cooperative corrosion control between the power company and the coal supplier. Economic justification must be applied to the individual situation. This paper is based on recent work by Combustion Engineering, Inc. and the Coal Research Bureau of West Virginia University under a contract from the Department of the Interior Office of Coal Research.',' Results which are of importance to this discussion may be summarized as follows: 1) The alkali minerals of coal (Na2O and K2O), as measured by an acid leaching process, can be related to corrosion rate in utility boilers. As these constituents increase in a coal product, its corrosiveness can be expected to worsen. 2) The alkaline-earth minerals contained in coal, reported as total CaO and MgO reduce corrosiveness 2s their concentration increases. 3) Naturally occuring, alkaline-earth-bearing materials, such as limestone and dolomite, may be added to a coal to reduce its corrosiveness. 4) Coals with very low iron contents tend to be less corrosive. These results provide the groundwork for examination of the system of operations which occur at the supplier facility from the seam face where mining is begun to the point of loading for shipment. The Mining System Fig. 1 is a cross section of one of the typical coal seams (designated coal A) that was boiler tested during this research program. This seam is overlain by material which consists primarily of a gray-black shale. In the lower third of this seam, there exists a thin rock parting of less than 4 in. in thickness which is consistent throughout the seam. The floor material is fireclay. In order to examine mineral distribution throughout this particular seam, the Coal Research Bureau collected a

Jan 1, 1971

By AIME AIME

This volume, an octavo of 626 pages, is now ready for delivery. By its aid, any subject treated or alluded to in the Transactions can be instantly tracked. The names of persons, mines, works, towns, etc., have been included; and abundant cross-references and classified sub-headings have been added to facilitate rapid consultation. Thus, the student remembering the name but not the locality, or the locality but not the name, or neither the name nor the precise locality of a gold-mine, can find it under ?Gold-mines," or under either of the other heads. For a more extended statement of the nature and use of this Index, which is intended specially for the benefit of those who do not possess complete sets of the Transactions, and who consult the Library by correspondence, see the Bi-Monthly Bulletin for September, 1907. The price of the Index bound in cloth is $5, delivery charges prepaid. Half-morocco binding costs $1 extra. Buy at once a copy of this Index, and also as many back-volumes of the Transactions as you can afford. Every such purchase from the stock on hand is so much added to the income of the Institute. As far as possible, the money thus received will be devoted to maintaining and perfecting the Library, and making it useful to members in all parts of the world.

Jan 11, 1907

By J. A. Roberson, Robert A. Rapp

From the observation of platinum wire marker movement in the oxidation of columbium at high lemperatures and low oxygen pressures, predonzinant cation diffusion in CbO, has been demonstrated. The Cu,0 molecule was used as an oxidizing species to study the nature of the porous scale and the location of the reduction site in the oxidation of colum-bium. The Cb205 scale contains microporosity and forms by alternate ionic diffusional growth and fracture. The oxidation of columbium at high temperatures and very low po, results in a relatively compact and protective Cb205 layer. THE observation of marker movements during oxidation is one means for the identification of the mobile ionic species in an oxide lattice. Previous marker experiments in the oxidation of columbium have all resulted in the markers being found on the outside surface of the Cbz05 scale. The Cr203 powder markers of Klopp et a1.,' the gold film marker of Kofstad and ~jijllesdal,' and the platinum wire marker of Cathcart et a1 .3 were found at the oxide/gas interface for oxidation temperatures ranging from 450" to 120O0C. However, in all experiments relatively high oxygen pressures were used. As discussed by Mrowec, even the interpretation of marker experiments in simple scales containing only one compound is not without ambiguities. In brief, it can be said that a marker may be found almost anywhere in the scale layer if the metal oxidizes by cation diffusion through the scale; the position of the marker depends upon morphological happenings in the scale. When considering marker movement in a polyphase scale one must proceed with extreme caution. For example, in the past (and present) work markers have never been found at the columbium-scale interface, and one might infer that the oxygen ion is mobile in CbO and CbO,. However, only trace quantities of CbO and CbOz have been present on any of the specimens, so no firm statement is justified on this basis. Despite previous experimental work, considerable doubt still exists concerning the role of the oxides CbO and CbOz in the oxidation of columbium. The identification of the mobile ionic species in CbO and CbOz from the observation of platinum wire markers was one goal of the present investigation . The linear kinetics of columbium oxidation at high temperatures (T - 1000°C) suggests that the Cbz05 scales which form on columbium are porous. From mercury absorption measurements on a Cbz05 scale formed at 500"C, Aylmore et al.' reported a minimum volume fraction of connected voids equal to 0.15. While these scales often appear to be quite porous when viewed in metallographic cross section, they are so brittle that metallographic preparation is likely to exaggerate any porosity originally present. In this investigation, porosity developed during the oxidation of pure columbium and present at the high temperature was detected by oxidizing specimens in sealed evacuated capsules containing large compacts of mixed copper and CuzO powders. wooda has demonstrated that the CuzO, or (CuzO),, molecule is volatile and that oxygen is transferred by the CuzO molecule from a Cu/CuzO mixture to materials having a greater affinity for oxygen. For each molecule of CuzO that is reduced at a sink for oxygen, two atoms of copper are deposited. Quantitatively, essentially all of the oxidation carried out by a Cu-Cu20 compact results from a displacement reaction involving the CuzO molecule. When a metal which oxidizes to form a porous scale is exposed to the CuzO vapor, the CUZO molecules are reduced in the pores leaving a deposit of metallic copper to mark the site of the reduction. This technique has the rather unique advantage that any copper-coated pores found in the scale are unambiguously related to the reduction site in the growth of the scale under consideration. Pores or cracks which form in a msition*- external to the reduction site or which occur as a result of cooling or handling of the specimen will not exhibit the copper deposit. EXPERIMENTAL PROCEDURE Marker experiments were made on columbium metal, and on pellets of CbO which had been pressed and sintered. Platinum wire markers (0.001 and

Jan 1, 1968

By M. C. Flemings, F. R. Mollard

Two-phase Pb-Sn alloys, ranging in compositiotz from 12 to 26 at. pct Pb, were unidirectionally solidified in a convection-fvee system, with thermal gradients in the liquid of up to 480°C per cm. Plane front solidification Loas achieved in all alloys at sufficiently steep gradient and slow growth rate. Conditions causing breakdown of the interface to a cellular or dendritic structure were roughly as predicted by a sinlple constitutional supercooling criterion. Structures of alloys of near-eutectic composition, solidified with plane front, exhibited a lamellar structure; the alloys furthest from the eutectic exhibited a rod-like morphology. Assumptions used in a previous paper for calculations of solute redistribution in two-phase plane front growth are shown to be reasonable for Pb-Sn alloys. Results of calculations are in good agveement with experiment. These show that variations in growth rate during solidification of the composite produce marked changes in average composition of the solid. IN a previous paper, Part I,' conditions necessary for plane front solidification of two-phase alloys were discussed and calculations given on solute redistribution in this type of solidification. This paper, Part 11, describes experiments on Pb-Sn alloys, designed to check the assumptions of the analyses presented, and to demonstrate their applicability to a given alloy system (Pb-Sn). APPARATUS AND PROCEDURE General. A vertical crystal growing unit was built for the study as described below, and "normal solidification" employed throughout (i.e., the ingot was completely melted except for a portion near the bottom end and then solidification initiated). The furnace was designed to permit achieving very low interface velocities, and steep gradients, in essential absence of convection; it is sketched in Figs. 1 and 2. Simple heat flow considerations indicated choice of a small-diameter specimen (ingot) to achieve high thermal gradients; ingot size chosen was 0.3 cm in diam. The ingots were held inside silica tubes 0.06 cm wall thickness. The requirement for an essentially convection-free system was met by use of the vertical furnace with the heat source over the heat sink, as well as by use of the small diameter ingots. In addition, by selection of tin-rich Pb-Sn alloys, the diffusion boundary layer (lead-rich) was denser than the bulk liquid and would not cause convection. The only apparent driving force for convection in this system was the small transverse temperature gradient resulting from heat flow into the samples from the furnace. Such convection must have been small, however, since 1) no temperature fluctuations in the melt were noted in the recordings, which would have indicated turbulent convection, and 2) experimental results obtained and described below could not have been achieved in presence of significant convection. Ingot Preparation. Pb-Sn alloys ranging from 12 to 26 at. pct Pb were prepared from high-purity lead and tin (99.9999 pct pure metal). Each alloy was prepared by first melting the pure metals in the proper ratio in air, in a Pyrex container. The melt was then stirred thoroughly with a graphite rod and cast into a preheated graphite mold. Ingots were then prepared from these castings for use in the actual experiments; each ingot consisted of a rod of alloy, 15 cm long in a 25-cm-long transparent fused-silica tube, 0.3 cm ID and 0.06 cm wall thickness. One chromel-alumel thermocouple, made with 0.004-in.-diam wire and protected by a two-hole alumina tube, was inserted into each ingot. The 1.5 cm of the thermocouple nearest the bead were protruding from the alumina tube and were coated with a very thin layer of boron nitride paste which provided electrical insulation while allowing good heat conduction. The electrically welded junction size was about that of each wire and the cross section of the two wires represented about 0.3 pct of the sample cross section. Including the coating, the thermocouple cross section still represented less than 0.5 pct of the ingot cross

Jan 1, 1968

By J. M. Steininger

The mechanism of flotation of sphalerite with sulthydryl compounds of different acidities has been interpreted in terms of chemisorption of unionized collector molecules on hydroxylated zinc surface sites. At a constant collector concentration of 1.5 x 10 -4 M, the upper pH limit of flotation has been found to be directly and closely related to the negative logarithm of the collector acidity constant, pKa The experimental results indicate that flotation is prevented when about 95% of the collector is ionized. At low pH, collector adsorption decreases because of the reduction in number of hydroxylated zinc surface sites. These two effects explain why sphalerite does not float with the more acidic sulfhydryl compounds. Typical anionic collectors for sulfide minerals are short chain xanthates or dithiophosphates which are nearly completely ionized in the generally alka- line flotation circuits.1,2 Flotation mechanisms have therefore been usually interpreted in terms of ionic collector adsorption and competition with ionic depressants of the same sign as the collector. A few attempts have been made, however, to consider adsorption of neutral collector molecules. Contact angle measurements obtained by Wark and cox3 have been interpreted by Cook and Nixon4 as representing adsorption of the free acid molecules on sulfide minerals such as pyrite, galena, chalcopyrite, and sphalerite. Cook and Nixon tried to show that the free acid concentration of the collector was substantially constant along the curves relating collector addition and minimum pH for bubble adherence. However, in a review of the subject,5 Sutherland presented new data on the flotation of pyrite with mercaptobenzothiazole which did not support the hypothesis of constant concentration of either collector ions or collector free molecules. He further showed that, with the assumption of constant occupation of surface sites, both theories lead to relations between pH and collector addition having similar mathematical expressions. In fact, with the more likely assumption of variable occupation of surface sites which results in more complex relationships, it appears impossible to

Jan 1, 1968