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By Charles Hart

THE-report of the advisory committee to the U. S. Bureau of Mines, on the use of oxygen in metallurgy, brings to the art of steelmaking a radical change in the method of operation of the many processes of this widely diversified industry. When completed, the improvements suggested by the use of oxygen will be far-reaching and revolutionary. As to its effect upon the iron blast furnace, the use of oxygen should be as important as any of the improvements in the art of iron smelting and should take its place beside the German "Hochofen" which was the first attempt to use a shaft for preheating the stock, and beside the hot-blast stove which heated the blast before entering the furnace. The former initially produced molten iron and the latter made unbelievable economies in fuel consumption. It would seem that a discussion of this paper would be best served by following the conclusions on page 17 of the report and analyzing them seriatim. 1. (a) A decrease in costs, due to higher smelting heats is only attainable by taking full advantage of these heat units. This is affected by, adding additional ore to the burden which in turn increases production and yields a larger tonnage upon which to figure costs. These economies appear in decreased cost per ton of iron for coke and limestone consumed, and a proportionate reduction in all items entering the cost above materials. We can take no exception to these. premises. It is a well-known fact that silicon in the iron and sulfur removed" are the result of hearth temperature, other matters remaining constant. To a practical furnaceman the most satisfactory manner of controlling a furnace is by increasing the burden. It is not necessary, therefore, to consider the question of refractories, for this discussion presupposes that the temperatures in the furnaces will be kept practically where they now stand for making the various grades of iron. The same situation obtains in regard to the height of the furnace, which, as intimated, was one of the great strides forward in this art, and its abandonment at this time, is inconceivable. The shaft prepares the stock so that at each succeeding step we have exactly the proper conditions. All the stock entering the furnace is dried and preheated. The limestone is calcined by sensible heat practically at no cost, for this is sensible heat which otherwise would pass from the top with the gases. Under normal conditions, external calcination has been attempted without tangible results. Under normal average furnace operation, limestone requires about 760 B.t.u. for calcination and the loss of sensible

Jan 11, 1924

By R. O. Leach, O. W. Wagner

Because of unfavorable wetting conditions much residual oil is left when a porous material is Pushed by water. Methods suggested to change reservoir wetting to improve oil displncernrnt efficiency are generally expensitlr. The present 1aborator.y study was undertaken to gain an under.standinx of the factors which determine reservoir wettability, arid to find out if oil displacement efficiency might be improved by a wettahility change accomplished at low cost in on oil reservoir. Contact angle measurements were made on mineral surfaces using sevc.r~zl sets of reservoir oil and water samp1es. Results of the contact angle studies suggest that reservoir wetta-hility may he primarily determined by natural surface-active substances present in the reservoir fluids. The effect of changing sa1inity and pH of the water phase was studied. The re.suits suggest that gross changes in preferential wettability might be acc~o~npli.shed by injection of water containing simple chernicnls to alter pH or salinity in the reservoir. Such treatment could he much less expensive than injection of commercial surface-active agents. Waterflood tests have also been made using synthetic cores and oil and water having wening characteristics similar to those of reservoir fluids. Cores initially oil-wet were flooded in such a way that they were made prefermtial1y water-wct by the advancing flood water. This reversal in preferential wettability achieved greater oil displacement efficiency than when either oil-wet or water-wet conditions were maintained throughout the flood. For the systems studied, the higher the oil viscosity the greater the percentage improvement obtained over conventional waterflood recovery. This suggests that a flooding process making use of wettability-reversal may extend the oil viscosity range over which water flooding is attractive. Because a precise adjustment of reservoir wettability does not seem to be required, and because altering the pH or salinity in some reservoirs may be inexpensive, it appears that a waterflooding process employing wet-[ability-reversal could find .succesful field application. I NTRODUCTION The efficiency with which water will displace oil from a porous material is related to the nature of the capillary forces present. These in turn are controlled by the preferential wetting of the solid by the two fluids. Because of unfavorable wetting conditions, 30 per cent or more of the original oil in place may remain unrecovered in that portion of a reservoir flushed by water. This paper is concerned with the possibility of improving waterflood oil displacement efficiency by alterations in the wettability of the porous material. A laboratory study was made to gain a better understanding of the factors which control reservoir wettability, and to determine if the oil displacement efficiency could be improved by some inexpensive means of manipulating wettability of the porous medium. Contact angle measurements were made with several natural and synthetic oil, water and solid systems (1) to obtain a better understanding of how to duplicate reservoir wettability in the laboratory, and (2) to discover possible means for changing preferential wettability of natural reservoir systems. Flooding tests were also made in synthetic systems to determine if oil displacement efficiency could be improved by those wettability manipulations suggested by the contact angle measurements. Based on these studies a possible method for improving waterflood oil displacement efficiency is presented. This method involves causing an originally oil-wet porous material to become preferentially water-wet during the course of a water flood. The purpose of this paper is to present results of the laboratory studies. THEORY Rock surfaces in some oil reservoirs are believed to be covered with a firmly attached bituminous or other organic coating. Such surfaces would be preferentially oil-wet in the presence of both oil and water, regardless of composition of reservoir fluids. Other reservoirs are believed to contain rock surfaces not permanently coated with such materials, and which would be preferentially wet by water in the presence of water and oil free from surface-active substances. However, when the reservoir fluids do contain certain natural surface-active materials in sufficient quantity, rock surfaces acquire a degree of preferential oil wettability caused by adsorption of these natural surface-active materials on the solid. The equilibrium amount of these materials adsorbed per unit surface area is believed to depend upon their concentration in the bulk liquid phases.

The curve of Fig. 3 for pyrite requires modification. There 11% a range of pH values from 6.2 to 7.8 for which no cyanide is required to prevent contact. From 7.8 to 11.3 a small amount of cyanide is required, with a sharp maximum of 20 mg. per liter at pH=9.6. The mistake arose from considering too few solution compositions (17 were considered) in constructing the curve. Subsequent work with other collectors indicates that the corrected curve is typical for such systems; it illustrates the further development of the dip in the pyrite curve of Fig. 5.

Jan 1, 1938

By E. N. Silverman

Mixtures of' MnS, ZFeO-SiO,, ZMnO.SiO, FeO, and MnO were prepared synthetically and used to study the planes ZFeO. Si0,-ZMnO.SiO,-MnS, FeO-MnO-MnS, and Fe0-MnO.Si0,-MnS in the quaternary system. Because the oxides and silicates studied flux MnS, inclusions in this system are partly liquid during rolling. Also, oxygen can modify subsurface inclusions through the reaction MnS + FeO—FeS + MnO during the soaking of ingots and the reheating of blooms and billets. NONMETALLIC inclusions in steel have long been a subject of study and conjecture because the properties of many steels are known to be affected by the the kind and amount of inclusions present. In free-machining steels, the type of inclusion present has a direct bearing on their machinability; in other steels, cleanliness is important and metallurgists direct their efforts at reducing the amount of non-metallic inclusions. Thus, the accumulation of knowledge about the formation and behavior of inclusions during all stages of steelmaking and processing should aid in improving the quality of steels and decreasing the production costs resulting from rejections. Previous studies of inclusions have contributed greatly to our understanding. The investigators have generally examined inclusions in finished steel. Boulger, Moorehead, and Garvey1 found that in Bessemer steels, low silicon contents results in globular sulfide inclusions with attendant high machin- ability ratings. Van vlack2 also found that low silicon contents favor inclusion morphology that contributes to high machinability ratings. Boquist and Stoll* found that silicon content affected sulfide inclusions and machinability of blooms, billets and bars more than did the finishing temperature in the range between 1775° and 2075°F. Carney and Rudolphy3 studied the distribution of sulfur, manganese, silicon, and carbon in a commercial ingot of resulfur-ized steel and found that silicon was concentrated near the bottom. This helped to explain why bottom cuts had poorer machinability. Klinger and Koch4 developed techniques for extracting inclusions from steel, and the technique devised by Gurry, Chris-takos, and stricker5 for extracting carbides can also be adapted to the study of inclusions. A different approach to the study of inclusions in steel consists of synthesizing the constituents that form inclusions and determining the phase eauilibria in the system that contains the constituents. The resulting phase diagrams can then be used to determine the effect of the various constituents upon each other. In this way, it becomes possible to under-

Jan 1, 1962

By Henry Lloyd Smyth, J. Ralph Finlay

The most important area of the so-called Keewatin rocks of northern Minnesota is that which runs westerly from Lake Saganaga, near the national boundary, and finally disappears beneath the drift (or has not been farther traced), in the neighborhood of Vermilion Lake. With this belt we have a general acquaintance, extending back some four years. During the past year we have had the opportunity of studying in considerable detail a small part of it, embracing an area of about 12 square miles on the south and east shores of Vermilion Lake. In this paper we desire to record our observations and conclusions, which seem to us important. II.—Literature. Outside the Minnesota Geological Survey, the list of the investigators who have studied the geology of the Vermilion Lake area is not long. Whittlesey, in 1876,* mentioned the occurrence, in the area about Vermilion Lake, of rocks resembling the Canadian Laurentian. Chester,? in 1884, described the iron-ore at Vermilion Lake as occurring in connection with jasper and quartzite, intimately bedded with the country-rock, chiefly sericite schist, and standing in a nearly vertical attitude. The Vermilion iron-bearing rocks, and those of the Mesabi range, he says, are of the same age.

Jan 1, 1896

By R. H. Richman

Coarse-grained Fe-Ni-C martensites formed at subzero temperatures were strained in compression at room temperature and the plastic deformation modes examined as a funclion of carbon content. At very low carbon levels, defovmation occurs hy wavy slip; commencing at about 0.05 pct C, mechanical twinning accounts for an increasing proportion of the plastic flow. Beyond approximately 0.4 pct C the deformation appears to be entirely by mechanical twinning. The habit planes of the operative twin modes were determined to be (113), (0131, and "(089)" in decreasing frequency of occurrence. Some of the implicaticms of Ihe o6served deformation modes upon the structure and properties of ferrous martensites are discussed. METALLURGISTS have long sought to explain the mechanical properties of ferrous martensites, particularly the extraordinary hardness and strength of the high-carbon varieties. Until recently the lack of precise knowledge of the structure of martensite crystals was the most serious barrier to understanding; however, the advent of thin-foil techniques for transmission electron microscopy has removed much of the mystery from martensite structure. Observations by Kelly and Nutting,"' and many others since, indicate that Fe-C based martensite crystals are internally twinned to a degree dependent upon the carbon content, and that a martensite plate containing 0.8 wt pct C or more consists of a stack of twin-related lamellae with each lamella on the order of l00A thick. Such a structure would be expected to influence greatly all aspects of metallurgical behavior, and many of the properties of Fe-C based martensites have been rationalized accordingly. Recent independent experiments led Winchell and cohen3 to conclude that the strength of ferrous martensite is derived primarily from solid solution hardening of the iron lattice by interstitial carbon atoms. Strength contributions from precipitation, dislocation-atmosphere interactions, clustering, short-range order, crystallite size, and so forth, were considered to be of secondary importance. In the view of Winchell and Cohen, the twinned structure of martensite serves mainly to limit the effective length of dislocation lines in the lattice, and thereby confers an added measure of hardening. Few properties of metallic crystals are as sensitive to metallurgical structure as are deformation mechanisms. It is somewhat surprising therefore, that, except for metallographic evidence of mechanical twins in strained martensite,4 no systematic examination of plastic deformation

Jan 1, 1963

By John H. Schemel

Large Zircaloy-2 hammer or press forged bars did not exhibit the uniform excellent corrosion resistance to steam normally expected of the alloy in wrought form. Weight gains of coupons cut from forged bars were 40 to 60 mg per sq dm compared to the 28 mg per sq dm obtained on hot rolled sheet and strip. The mechanism of this corrosion and its relation to microstructure is discussed. After these observations, a solution heat treatment followed by rapid cooling was tried on coupons from eight heats of forged bars. The basket-weave structure resulting from the quench did not show agglomeration of intermetallic compounds. These coupons showed uniformly good corrosion resistance with weight gains very close to the 28 mg per sq dm expected of Zircaloy-2 after the 14-day steam test. A large forging was solution heat-treated and tested for structure, mechanical properties, and corrosion resistance. Corrosion resistance was excellent and uniform throughout the section. The normally anisotropic mechanical properties were changed to completely iso-tropic. Strength levels were raised while there was a small loss in ductility at the service temperature. Tempering of the quenched structure below the ß transus did not improve the ductility at the test temperature of 600°F. ZIRCALOY-2 end caps for nuclear fuel elements Zircaloy-2 is an alloy of 1.5 pct Sn, 0.1 pct Fe, 0.1 pct Cr, and 0.05 pct Ni, balance hafnium-free zirconium patented by Westing-house Electric Co. used in pressurized water reactors are machined from large hammer-finished forged bars. The bars forged for this application range from 3 1/2 in. to 7 1/2 in. squares. One of the tests used to evaluate Zircaloy-2 for this service is a 14-day exposure to very high-purity steam at 75oF and 1500 psi pressure. Normally wrought products will exhibit a black lustrous film of zirconium oxide after the test and show a weight gain of approximately 28 mg per sq dm. Coupons representing the forged bars exhibited a wide variety of corrosion results ranging from acceptable black coupons to some covered with white crystals of zirconium oxide that had weight gains of nearly 100 mg per sq dm. One of the most common effects was a white corrosion product that looked like a stain to some observers and the outline of massive metal grains to others. Very careful specimen preparation prior to the corrosion test did not affect the result and metallographic examination did not reveal a structural feature of a size and shape that would correlate with the corrosion product. In addition to the relatively poor corrosion resistance, the forged product was not as ductile as desired. The problem of obtaining uniform and more acceptable properties in these heavy-forged sections seemed to be a function of the microstructure of the metal and, in particular, the distribution of the intermetallic compounds. None of the four alloying elements however are appreciably soluble in a zirconium and are present as compounds which usually appear scattered randomly throughout the structure. Moudryl showed that the distribution of these intermetallic compounds in Zircaloy could be related to a ostringero corrosion failure. Grozier et al. discussed another structural defect that causes a similar corrosion effect. In this case, an elongated gas-void was determined to be the cause. M. L. Picklesimer held in his discussion of the Grozier paper that at least a part of the observed =stringersn were caused by the distribution of the intermetallic compounds. He proposed a

Jan 1, 1962

By D. J. Jr. McAdam

RESULTS of a general survey of corrosion-fatigue phenomena at the Naval Engineering Experiment Station were presented in five previous papers.1-5 In these papers references were given to the work of Haigh in 1917.6 The five papers mentioned gave a general survey of the behavior of metals when tested to failure under simultaneous corrosion and cyclic stress. As a result of this survey the fourth paper gave a tentative analysis of the corrosion-fatigue process. According to this analysis, if the initial stress is below the endurance limit but above the corrosion-fatigue limit, the corrosion-fatigue process is divided into two periods. The first period is the formation of pits. As the initial stress is below the endurance limit, the pitting is assumed to be due to corrosion, not to fatigue. The corrosion pitting, however, is not the ordinary pitting of stressless corrosion, but is an accelerated pitting due to the effect of the cyclic stress on the corrosion. As the pit progresses, both the actual stress and the effective solution pressure increase. The increase of actual stress is due to increasing stress concentration at the bottoms of the pits. The increase of effective solution pressure is due to the increase of actual stress. The mutual intensification of stress and solution pressure continues until the actual stress at the bottoms of the pits surpasses the endurance limit. The second period of corrosion-fatigue then begins. In this period the process is merely fatigue accelerated by the corrosion. The cracks advance at a continually accelerated rate until the specimen breaks.

Jan 1, 1930

By Samuel G. Vera

INTRODUCTION The Climax Mine is a property of Climax Molybdenum Company, a division of AMAX Inc. Climax is located in the central part of the Colorado Mineral Belt on the west slope of the Tenmile Range, Lake County, Colorado at 3,425' m. above sea level. Climax Mine, the largest single producer of molybdenum in the free world, has been a cornerstone of mining in the State of Colorado for many years. Before molybdenum was known, the early hunters of gold and silver laid their hands on the outcrops of the Climax deposit and left it as low quality lead or graphite without much value. Today, 44,000 TPD of ore is extracted from the heart of Bartlett Mountain. The molybdenum, separated from the ore, is vital for mankind, being used for everything from fertilizer to fine components of aerospace ships, because of its valuable physical and chemical properties. The operations at Climax have never remained static. Constant demand for the "gray gold", and technological advancements, have converted Climax into an "open book of technology", where learning the still-hidden secrets of mining is a continuing process. (All figures related to tons are metric tons) BRIEF HISTORY The mine produced its first molybdenum ore in 1918. It was shut down in 1919, resumed production in 1924, and has been in continuous production since that time. During World War 11, a peak of 20,000 tons per day was reached, then tonnage dropped from 1945 to 1950. Since 1951, production has been in- creasing, reaching a peak of 46,000 tons per day during the month of June, 1980. Early mining used shrinkage stoping. Block caving using the grizzly system was introduced in the early 1930's. Caving methods were improved through empirical studies of rock behavior and by trial and error, evolving a very efficient mining method by the late 1940's. This form of continuous retreat panel caving, with small modifications, is still used today, and has made the Climax Mine one of the biggest underground mines in the world. The Climax Mine, synonymous with molybdenum, was essentially an underground mine until 1973 when the open pit was introduced. Since then, both mining methods have operated successfully. Current production is 60% from underground, and the remaining from the open pit. Climax has been in continuous operation for 56 years, and as of December 31, 1980, more than 386 million tons of ore have been mined. The orebody is not fully defined, and at the present mining rate, the known life span of the mine will be to the year 2020. GEOLOGY The Climax deposit is a large low-grade porphyry molybdenum deposit somewhat similar to porphyry copper deposits, with a well- mineralized quartz molybdenum stock work sys- tem. It lies within the pre-Cambrian granites and schists and the Tertiary Climax porphyry. The age of mineralization is thought to be mid-Tertiary and is characterized by fracture filling and replacement through silicification. The main economic mineral is molybdenum, with pyrite, cassiterite and wolframite as by-products. Fluorite and topaz also occur, but are not recovered at this

Jan 1, 1981

By Thomas E. Garnar

Zirconium and hafnium are curious elements because they are almost always found together in nature. Zirconium was discovered by Klaproth in 1789 and isolated 35 years later by Berzelius. Because hafnium's chemical properties are so close to those of zirconium, it was not discovered until 1923 when Coster and Von-Heresey detected it using x-ray spectrographic analysis. These elements occur most commonly in nature as the mineral zircon (ZrSiO4) and less commonly as the oxide baddeleyite (ZrO2). They also are found as a variety of other silicates. Zircon was identified as a component in alluvial and beach sands in 1895, but it was not produced in any quantity until 20 years later. Zircon is always a coproduct from TiO2 mining and processing. During World War I it was produced as a coproduct of beach sand mining for titanium minerals just south of Jacksonville Beach, FL, and was patented as a refractory. It was not until the 1930s when Zircon Rutile, Ltd. began mining at Byron Bay on the east coast of Australia that zircon was first used as a foundry sand. Later in the 1940s, NL Industries, Humphreys Gold Corp., and E. I. du Pont de Nemours & Co., Inc. began production of zircon sands from fossil beaches in northeast and northcentral Florida. Baddeleyite first became available as a commercial product in 1916, but never in the quantity of zircon. Zircon holds a unique position as an industrial mineral because it is used for both its physical and chemical properties as well as an ore of zirconium and hafnium metals. Australia is the major zircon producer followed by South Africa and the US. Zircon is also produced in India, Sierra Leone, Sri Lanka, Malaysia, China, Thailand, and Brazil. Undeveloped heavy mineral beach sand reserves containing zircon are known to occur in Egypt, Malawi, Senegal, and Tanzania. Locations are shown in Fig. 1. Mineralogy Zirconium and hafnium are always present together in naturally occurring compounds. Most commonly they form as the silicate sometimes containing iron, calcium, sodium, manganese, and other elements. Less commonly they are found as oxides in combination with titanium, thorium, calcium, and iron. Zircon is the most common form. It is extremely resistant to weathering, therefore, often it is present in ancient beach sands and placer deposits. Although resistant to alteration from external sources, it is vulnerable to internal alteration as the result of thorium and uranium substituting for zirconium either in the zircon lattice or in solid solution. Alteration to the metamict state takes place as radioactive emanations from these elements disorder the crystal lattice, accompanied by hydration, reduction in specific gravity, and changes in color. The mineralogy of zircon and baddeleyite and variation of physical and chemical properties are shown in Table 1. The effects of zircon's internal alteration and darkened color can be corrected by heating to 1000°C for 30 min or so. A certain time-temperature relationship makes it possible for decolorization and reordering of the crystal lattice to take place when heating at higher temperatures for shorter periods or at lower temperatures for longer periods. After heating, x-ray diffraction patterns are sharper, the grains may be harder, and except for particles of malacon, the grains will be white or colorless in the absence of grain surface coatings. The color change is only temporary and the particles slowly darken with time. Zircon fluoresces light yellow in shortwave ultraviolet light. If exposed to ultraviolet light for extended periods of time, white (calcined) zircon turns purple. With time the induced color begins to fade and eventually disappears (e.g., calcined Florida zircon exposed to ultraviolet light for 24 hr still retains faint, but discernible, purple color after six months).

Jan 1, 1983

By W. M. Bertholf

IN 1945 tests were made in the coal washery of the Colorado Fuel and Iron Corporation, at Pueblo, Colo., to determine the value of the Humphreys spiral. So far we have demonstrated that it is of definite value to us in rewashing a portion of our table middlings; and we are fairly certain that this is not necessarily the only place in which it can be used to advantage. Because of manpower and material shortages, experimental work has been discontinued for the present. Three of the spirals are being installed for use in rewashing the middlings, and testing and experimental work will proceed when this installation is completed. All evidence secured so far points to the fact that the spiral can make an effective separation of heavy material below 8-mesh; but that it is ineffective in removing larger, heavy material. This, of course, will limit its use to fine coal or a classified feed containing no heavy material larger than 8-mesh. In considering the results of our tests, it should be noted that the feed was our table middling, and that any real separation of this material is a "moral victory," as there is little material that could be properly called coal and practically no heavy rock, the consequence being that previous attempts to clean the middlings have not been at all successful. Several articles dealing with the spiral and its use in treating heavy minerals have already been published,1 but for the benefit of those who have not seen these we include a brief description of the spiral and of the way it operates, taken from Bulletin 4 of The Humphreys Investment Co.: The Humphreys Spiral Concentrator consists of a spiral conduit of modified semicircular cross section. Ore pulp is fed to the top and, as it flows downward, the heavier particles concentrate in a band along the inner side of the pulp stream (Fig. I). Outlets for removal of products are located at the lowest points in the cross section of the conduit. Wash water, added at the inner edge of the stream, flows outwardly across the concentrate band. The width of concentrate band removed at the outlets is controlled by adjustable splitters. Concentrate is usually removed from the upper portion of the spiral and middling from the lower portion. Tailing is discharged from the lower end. Tests are usually made in closed circuit, since this provides a maximum of information with a minimum amount of sample. Fig. 2 shows the spiral set up for closed-circuit testing, and gives a good idea of the general arrangement of such an installation. The small cyclone separator is used to provide clean wash water without introducing additional water into the circuit.

Jan 1, 1946

By J. E. Papin

MORENCI ores contain as an average about 0.015 pct molybdenite, MoS2. Incidental to the concentrating operations applied for the recovery of copper minerals, approximately two-thirds of the molybdenite is floated and appears in the final copper concentrate. The economic importance of molybdenum and the success achieved in its recovery in milling operations elsewhere encouraged research directed toward its recovery in marketable form. Several procedures are utilized to effect separation of molybdenite from copper and iron sulphides, but only two have wide application. In the better known of these two methods the molybdenite in the copper concentrate is depressed in a flotation operation using soluble starch as the depressant. The tailing from this treatment thus becomes a low-grade molybdenite concentrate which after thickening, filtering, and low temperature roasting is repulped with water and subjected to additional flotation steps for recovery of the molybdenite. A thio-phos-phate collecting agent is employed in flotation of the copper minerals. Presumably the stability and lasting effects of that collector type necessitated the practice of depressing molybdenite followed by subsequent roasting to insure elimination of copper and iron sulphides from final molybdenite concentrate. The second important method of recovery is applied at various southwestern plants. In those plants xanthates are in use as copper collecting agents. It has been found that xanthates are relatively unstable and their collecting power for sulphides is destroyed by very simple procedures. The method generally applied is to subject the xanthate-acti-vated concentrate, in the form of a pulp, to prolonged heating using steam as the heating medium. A concentrate thus treated may then be subjected to a flotation operation for recovery of the molybdenite, using mineral oil collecting agents, and the copper and iron sulphides will be depressed. Neither of the above processes was applicable to Morenci concentrates. Morenci uses a thio-phos-phate collecting agent in its flotation operation. However, it was established that soluble starch was not a depressant for Morenci molybdenite; therefore the first step in that process was not applicable. AS would be expected the copper and iron sulphides in Morenci concentrates could not be depressed by the heating methods used on xanthate activated concentrates. Low-temperature roasting did eliminate the effects of the thio-phosphate but had to be rejected as uneconomic in as much as the tonnage of concentrates involved was too great. Preliminary research having established the above facts, it became obvious that new methods would have to be developed for the recovery of molybdenite from Morenci concentrates. A broad laboratory investigation was initiated along two general lines, both directed toward depression of copper and iron sulphides. One approach was through the use of water-soluble oxidizing agents with the objective of destroying the thio-phosphate in the concentrate and thus eliminating its collector effect. The other approach involved the use of soluble sulphides, which have long been recognized as sulphide depressants. These efforts resulted in laboratory processes which showed promise. Research was then extended to a pilot plant having a daily capacity of several tons of concentrate. This operation soon demonstrated that soluble sulphide—basically sodium polysulphide—when applied to a pulp made slightly acid with sulphuric acid, proved to be the most effective sulphide depressant. The rate of concentrate treatment in this plant and the low molybdenite content of the concentrate prevented carrying the process to a conclusion, namely, production of molybdenite concentrate of marketable grade. Laboratory treatment of pilot plant concentrate indicated that a marketable product could be made from it, given a tonnage suited to available cleaner flotation machine capacity. Accordingly, the molybdenite plant was enlarged to permit treatment of the total copper concentrate from the extension plant, maximum of approximately 800 tons per day. In the enlarged plant a major difficulty was encountered. No criteria could be established as a basis for control of the process. In the early stages of flotation, because of the small amount of molybdenite involved, there was no visual evidence of the relative floatability of molybdenite with respect to

Jan 1, 1956

By W. Rostoker, R. F. Domagala, R. P. Elliott

The phase equilibria of the Hg-Th system over the composition range 0-100 pct Th and temperatures up to 1000°C have been studied for a small-volume, closed system. The solubility of Th in liquid Hg is about 5 pct at 300°C and decreases sharply with decreasing temperature. Two intermediate phases occur, Hg3 Th and HgTh. The structures of these are hexagonal (nonideally close-packed) and face-centered cubic, respectively. The HgTh phase decomposes eutectoidally at 400°-500°C. The solubility of Hg in solid thorium seems to be negligible. AFULL-phase diagram for this system would have to be defined on temperature-composition-pressure co-ordinates. This paper describes the pseudo phase diagram of a closed system, that is, where the alloy enclosed in a small volume equilibrates with a vapor pressure of mercury dictated by composition and temperature. Because of the experimental difficulties in studying a system of this nature, many of the phase relations can only be sketched. Alloy Preparation Alloys over the full range of composition were made from triple distilled mercury and one of two grades of thorium. For the bulk of the work, a calcium-reduced metal in sintered pellet form of reported 99+ pct total thorium content was used. Arc-melted specimens of this thorium gave a hardness of 135 VPN. The microstructure showed small primary dendrites of ThO2. A number of alloy compositions were made with a high-purity, iodide-decomposition thorium metal. The are-melted hardness of a button of this material was 35 VPN. Although the microstructure of the arc-melted specimens showed no dendrites of ThO2, there was definite evidence of an unidentified phase enveloping the grain bound-aries. There were no distinguishable differences between the constitution of alloys made with the two grades of thorium metal. Under normal conditions thorium is not wetted by liquid mercury. The film of ThO2 on all thorium metal cannot be penetrated by either liquid or vaporous mercury. It was therefore necessary to comminute thorium in the presence of mercury under such conditions that oxide films could not reform on the newly exposed metal surfaces. This was accomplished by the use of a high-speed, carbide-tipped rotary cutter incorporated in a chamber purged with argon and connected at the bottom to a demountable Vycor bulb containing a weighed amount of mercury. This experimental device is fully described in a separate paper.1 Alloy compositions were calculated by weighing the empty bulb, the bulb containing the mercury, and the bulb containing the mercury and the thorium chips. Many alloys were analyzed chemically for thorium and/or mercury after subsequent homogenization; the agreement between analyzed and calculated compositions was invariably very close. Bulbs containing the requisite amounts of mercury and fine thorium chips were clamped off, removed to a sealing unit, evacuated and sealed. Amalgamation under these conditions proceeded rapidly even at room temperature. To insure homogeneity, the specimens were annealed to 300-400°C. Alloys containing less than 30 pct Th remained pasty after all treatments, indicating an equilibrium condition of liquid plus solid. Alloys with more than 30 pct Th were transformed into a dark powdery product. These latter specimens were annealed for times of up to 1 week to complete interdiffusion. Many of the alloy compositions are pyrophoric. On exposure to air they oxidize with considerable evolution of heat to a mixture of ThO2 and free mercury. It was mandatory that alloy specimens be handled in a "dry box" purged thoroughly with argon. All X-ray diffraction specimens were powdered, screened, and sealed in capillary tubes within the dry box. Experimental Procedures Thermal analysis experiments, useful only in the mercury-rich region of the system, were conducted with the alloys in their original containers. A reentrant thermocouple well formed an integral part of the bulb. These bulbs were heated in a silicone oil bath and cooled in a dry ice-acetone mixture. The rates of heating and cooling were slowed by immersing the specimen bulb in a larger tube containing silicone oil. This provided a suitable thermal lag. In all tests, pure mercury was run as a basic standard. While the invariant reaction at about the melting point of mercury was detected by thermal analysis, the heat effect at the liquidus was not sufficient to produce an inflection in the cooling curve. It was necessary to determine the liquidus temperatures at the mercury-rich end of the system by "breaks" in electrical reslstivity versus temperature curves for individual alloys. The apparatus for this purpose consisted of a pyrex tube about 2 in. diam and 12 in

Jan 1, 1959

By R. W. Smith, G. W. Delamore, J. A. Spittle

RECENT work by the authors1 has demonstrated that the crystals constituting the equiaxed zone in small ingots originate, on quenching, in the chilled liquid. Whether any partial remelting2 takes place of the den-drites nucleated in the chilled region was not examined. However, the claim3 that this normally occurs, leading to crystal multiplication, has been disputed.4 Thus, for an equiaxed zone to form in the central region of an otherwise columnar ingot, it is necessary to transport crystallites from the chill zone to this region. In view of the work of Uhlmann et al.,5 it was considered desirable to examine the transport process further. Experimental Technique and Results. In the earlier experiments by the authors.1 a stainless-steel crucible 17/8 in. diam, 41/2 in. high, ad containing an alloy of A1-4 wt pct Cu, was quenched from 660°C into a bath of Wood's metal maintained at 100°C. Under these conditions a central zone of equiaxed crystals was obtained. However, if a 2250-G unidirectional magnetic field was applied for 2 sec immediately following the instant of quenching, or subsequently, the equiaxed zone did not appear. Careful thermal analysis showed that the short application of the field had virtually no effect on the thermal conditions of the melt. It thus appeared that the crystallites which were ultimately to grow large enough to form the equiaxed zone existed in the liquid immediately ahead of the interface, occlusion being prevented by the convective fluid flow induced by freezing from the walls of the cylinder. When this relative movement was prevented by the Lorenz forces induced by the application of the magnetic field, the crystallites were caught up in the rapidly advancing dendrite solid-liquid interface. To test this assumption, a small ingot of super-purity aluminum was partially melted and poured into a heated stainless-steel mold which was then immediately quenched into molten Wood's alloy. The resulting structure is shown in Fig. 1, and consists of columnar grains with a central fine-grained zone. Thus the unmelted solid present at the beginning of solidification had been transported ahead of the columnar interface. Discussion. There appears to be little or no information available on the interaction of suspended particles with a metallic solid/liquid interface. However, some information is available for transparent organic sys-

Jan 1, 1969

By W. M. Bertholf

In 1945 tests were made in the coal washery of the Colorado Fuel and Iron Corporation, at Pueblo, Colo., to determine the value of the Humphreys spiral. So far we have demonstrated that it is of definite value to us in rewashing a portion of our table middlings; and we are fairly certain that this is not necessarily the only place in which it can be used to advantage. Because of manpower and material shortages, experimental work has been discontinued for the present. Three of the spirals are being installed for use in rewashing the middlings, and testing and experimental work will proceed when this installation is completed. All evidence secured so far points to the fact that the spiral call make an effective separation of heavy material below 8-mesh; but that it is ineffective in removing larger, heavy material. This, of course, will limit its use to fine coal or a classified feed containing no heavy material larger than 8-mesh. In considering the results of our tests, it should be noted that the feed was our table middling, and that any real separation of this material is a "moral victory)" as there is little material that could be properly called coal and practically no heavy rock, the consequence being that previous attempts to clean the middlings have not been at all successful. Several articles dealing with the spiral and its use in treating heavy minerals have already been published,' but for the benefit of those who have not seen these we include a brief description of the spiral and of the way it operates, taken from Bulletin 4 of The Humphreys Investment Co.: The Humphreys Spiral Concentrator consists of a spiral conduit of modified semicircular cross section. Ore pulp is fed to the top and, as it flows downward, the heavier particles concentrate in a band along the inner side of the pulp stream (Fig. I). Outlets for removal of products are located at the lowest points in the cross section of the conduit. Wash water, added at the inner edge of the stream, flows outwardly across the concentrate band. The width of concentrate band removed at the outlets is controlled by adjustable splitters. Concentrate is usually removed from the upper portion of the spiral and middling from the lower portion. Tailing is discharged from the lower end. Tests are usually made in closed circuit, since this provides a maximum of information with a minimum amount of sample. Fig. 2 shows the spiral set up for closed-circuit testing, and gives a good idea of the general arrangement of such an installation. The small cyclone separator is used to provide clean wash water without introducing additional water into the circuit.

Jan 1, 1947

By W. M. Bertholf

In 1945 tests were made in the coal washery of the Colorado Fuel and Iron Corporation, at Pueblo, Colo., to determine the value of the Humphreys spiral. So far we have demonstrated that it is of definite value to us in rewashing a portion of our table middlings; and we are fairly certain that this is not necessarily the only place in which it can be used to advantage. Because of manpower and material shortages, experimental work has been discontinued for the present. Three of the spirals are being installed for use in rewashing the middlings, and testing and experimental work will proceed when this installation is completed. All evidence secured so far points to the fact that the spiral call make an effective separation of heavy material below 8-mesh; but that it is ineffective in removing larger, heavy material. This, of course, will limit its use to fine coal or a classified feed containing no heavy material larger than 8-mesh. In considering the results of our tests, it should be noted that the feed was our table middling, and that any real separation of this material is a "moral victory)" as there is little material that could be properly called coal and practically no heavy rock, the consequence being that previous attempts to clean the middlings have not been at all successful. Several articles dealing with the spiral and its use in treating heavy minerals have already been published,' but for the benefit of those who have not seen these we include a brief description of the spiral and of the way it operates, taken from Bulletin 4 of The Humphreys Investment Co.: The Humphreys Spiral Concentrator consists of a spiral conduit of modified semicircular cross section. Ore pulp is fed to the top and, as it flows downward, the heavier particles concentrate in a band along the inner side of the pulp stream (Fig. I). Outlets for removal of products are located at the lowest points in the cross section of the conduit. Wash water, added at the inner edge of the stream, flows outwardly across the concentrate band. The width of concentrate band removed at the outlets is controlled by adjustable splitters. Concentrate is usually removed from the upper portion of the spiral and middling from the lower portion. Tailing is discharged from the lower end. Tests are usually made in closed circuit, since this provides a maximum of information with a minimum amount of sample. Fig. 2 shows the spiral set up for closed-circuit testing, and gives a good idea of the general arrangement of such an installation. The small cyclone separator is used to provide clean wash water without introducing additional water into the circuit.

Jan 1, 1947

By D. B. Carson, D. L. Katz

Natural gases under pressure form crystalline hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methanc-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbon-rich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. Introduction Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural-gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villardl and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Dcaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on tem-peraturcs and pressures of hydrate forma. tion for pure methane, ethane, propane, n-butane, methane-ethane mixtures, meth-ane-propane mixtures, methane-butane mixtures, and some Is natural gases, all- in the Presence of excess water. However, up to the Present time no method has been available for predicting the temperature at given pressures or the pressure at given at at which natural gases will form hydrates if hydrates with water. 'This Paper Presents data on the methane-propane-water, methane-pentane-water and methane-hex-""e water systems in four phases, one of which is the hydrate. he application of the phase rule to the methane-~ro~ane-water data Proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid. equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1942

By D. B. Carson, D. L. Katz

Natural gases under pressure form crystalline hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methanc-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbon-rich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. Introduction Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural-gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villardl and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Dcaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on tem-peraturcs and pressures of hydrate forma. tion for pure methane, ethane, propane, n-butane, methane-ethane mixtures, meth-ane-propane mixtures, methane-butane mixtures, and some Is natural gases, all- in the Presence of excess water. However, up to the Present time no method has been available for predicting the temperature at given pressures or the pressure at given at at which natural gases will form hydrates if hydrates with water. 'This Paper Presents data on the methane-propane-water, methane-pentane-water and methane-hex-""e water systems in four phases, one of which is the hydrate. he application of the phase rule to the methane-~ro~ane-water data Proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid. equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1942

Jan 1, 1891

By H. F. Moore

Jan 1, 1936