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By Brij M. Moudgil

Disposal of fine coal refuse is one of the major technical problems which could adversely affect growth and development of the coal industry. At present one of the most: common methods for disposal of fine coal refuse slurry involves impounding the slurry behind dams. However meeting new federal and state government regulations for building, maintaining and reclaiming these impoundments in addition to terrain and space considerations render this technique to be only marginally competitive with other disposal methods. The coal industry has been actively engaged in developing alternate disposal techniques which are economically feasible and environmentally acceptable. A review of coal refuse disposal problem and current refuse disposal practice both in the eastern and western coal fields is presented. Various promising techniques being developed for economical and safe disposal of fine coal refuse slurry are also discussed.

Jan 1, 1980

By W. David Leyshon

This paper compares the general characteristics of Florida phosphate rock for the manufacture of fertilizers and phosphoric acid. The subjects covered are relative reactivity for superphosphate manufacture and various properties of the rock for use in phosphoric acid production, including gypsum filterability, sulfuric acid consumption, foaming, relative cor-rosiveness, chemical composition, and others. Comprison will include rocks of North Africa, the western U.S., and other locations. This paper reviews some of the important properties of phosphate rock, giving particular attention to a comparison of Florida phosphate with some of the major phosphates produced in the world. It also discusses some of the techniques available for evaluatine Phosphate. rock for phosphoric. acid and fertilizer use. The use of Florida rock outside the U.S. has been increasing steadily, evidence in itself of certain desirable properties of this rock. Table I is a list of the major producers and exporters of phosphate rock as of 1965. Florida, meaning in this case Central Florida, was the largest producer of phosphate rock and the largest exporter of rock. Of a total world production estimated at 60 million tons, about 50 million tons were produced during 1965 by the areas listed in Table I. One major producing area omitted from Table I and from subsequent evaluations in this paper comprises Nauru, Ocean, and Christmas Islands, whose output totaled about three million tons in 1965. This phosphate is marketed entirely by the British Phosphate Commissioners, primarily in Australia and New Zealand, and does not get into the world market elsewhere to a significant degree at the present time. South Africa, Egypt, Israel, and North Vietnam also produce lesser quantities of rock for the international market, and these materials are also excluded from this review. The phosphate industry is now seeing the introduction of several new areas that will be significant factors in the rock market in the future. The North Carolina and North Florida areas each have capacity at present or in the near future for producing about three million tons per year. The Djebel Onk mine in Algeria has a potential of about 800,000 tons per year. In addition, announcements have been made of significant development of deposits in Peru and in the Spanish Sahara, and sizable expansions are planned in several of the existing areas that are now of minor importance. Competition for the rock market appears to be increasing so that more attention will probably be paid to evaluating phosphates available from different areas. It is not possible here to go into all the properties of even a few of the materials listed in Table I. However, it is practical to discuss some comparative properties important for making phosphoric acid and fertilizers, and to touch on the techniques used for the evaluation of various phosphate rocks. Table II gives typical analyses of the major phosphate rocks available in the world as of 1965. There is, of course, an inherent danger in labeling any analysis as typical, but it appears that variations between two samples of rock within one given area are generally less than between two samples from different areas. The analyses listed were compiled from several years of data so they may not be representative of the present output of any particular area. The range of grades represented by these analyses goes from 66 BPL for Gafsa rock to 85 BPL for Kola

Jan 1, 1968

By Fred C. Bond

SIZE of grinding media is one of the principal factors affecting efficiency and capacity of tumbling-type grinding mills. It is best determined for any particular installation by lengthy plant tests with carefully kept records. However, a method of calculating the proper sizes, based on correct theoretical principles and tested by experience, can be very helpful, both for new installations and for guiding existing operations. As a general principle, the proper size of the make-up grinding balls added to an operating mill is the size that will just break the largest feed particles. If the balls are too large the number of breaking contacts will be reduced and grinding capacity will suffer. Moreover, the amount of extreme fines produced by each contact will be increased, and size distribution of the ground product may be adversely affected.

Jan 5, 1958

By Henry Louis

IN the discussion on the paper on subsidence by R. V. Norris and H. W. Montz (Teohnical Publication No. 153), H. N. Eavenson has been good enough to quote some of my views regarding the phenomena of subsidence; he has, of course, only mentioned these briefly, and as he has not represented them quite correctly, it is evident that I have failed to make them clear. Seeing that he, and apparently some of the others who took part in the discussion, appear to hold views different from my own, I think it advisable to put my opinions down as definitely and as clearly as possible, because it appears to me at least possible that some of the differences above referred to may be differences of language and definition rather than of fact. The statements I propose to submit refer to the simplest cases, namely where an area in a practically horizontal bed has been entirely worked out. My experience has been confined to beds of bituminous coal and of ironstone, but D I do not at the moment see why there should be any difference in principle between the working of a bed of anthracite and one of bituminous coal, provided that the other conditions are the same. I wish to emphasize that I am considering the conditions of complete working out of the mineral bed with the roof allowed to come down and form goaf in accordance with the general British practice; 1 am excluding, therefore, methods of hydraulic, pneumatic, and hand stowage where extraneous material is brought in to hold up the roof. I am also excluding the case of bord and pillar working where pillars of small size are deliberately left in, apparently with the idea that these will subsequently crush and let the roof down gradually. Such a method of mining has long been discontinued in this country, indeed in Europe generally, and I venture to predict that the time will come when such a recklessly wasteful method will no longer be tolerated even in the United States. Further, I am referring entirely td static conditions after the mineral bed has been worked out and the ground has come to rest; the phenomena that occur during the course of extraction are much more complicated, and these I am not discussing here. Under these conditions, I have

Jan 1, 1929

By L. R. Duncan, O. M. Wicken

Magnesium, the eighth most abundant element in the earth's crust, is found widely distributed in a variety of minerals. Among the more commercially important ones are magnesite (MgCO3), brucite (Mg[OH]2), dolomite (CaMg[C03]2), and the salts magnesium sulfate and chloride often found in natural brines. Among other commercially important magnesium-containing minerals are olivine ([MgFe]2Si04), talc (H2Mg3[Si03]4), and serpentine (H4Mg3Si2O9). These are valuable because of desirable characteristics given them by the magnesium content and its placement in the particular crystal structure. These minerals are the raw materials for a host of products including magnesium metal and several grades of magnesia or magnesia-containing materials for refractories, fluxes, fillers, insulation, cements, decolorants, fertilizers, and chemicals. Considering only those minerals valued for their magnesia or magnesium content, over 85% of the material tonnages are processed to be used as refractories. Dolomite, which is used in enormous tonnages for its physical properties in construction, has an important use as a refractory raw material in its own right and, after calcination, as a precipitant for magnesium hydroxide, which is an intermediate for the production of magnesia or magnesium metal. Magnesia from the reaction of calcined dolomite (or limestone) with seawater or magnesium-containing brines has supplanted much of the production of magnesia from mined magnesite, particularly in the United States. The best known of the minerals directly and widely exploited for magnesia content is magnesite, one of the calcite group of rhombohedral carbonates which includes calcite (CaC03), siderite (FeCO3), and rhodochrosite (MnCO3) among others. The members of this group enter into a wide range of substitutional solid solutions when the positive ions have similar radii. The radii of magnesium and iron ions are within 6% of each other; hence, magnesite and siderite form a complete series of which breunnerite (ferroan magnesite) is a well-known end member. However, the radius of calcium ion is 36% larger than that of magnesium ion, and only limited substitution exists at each end of the MgCO3-CaCO3 series. Dolomite is not a member of the calcite group, but results when calcium and magnesium ions alternate in equal number in an ordered structure among carbonate ions. The result of these relationships is that calcite and dolomite, often found intermixed with magnesite, occur commonly as identifiable crystal entities which can often be separated to a varying degree from the magnesite by various beneficiation techniques. Magnesite, when pure, contains 47.8% MgO and 52.2% CO.. The pure mineral is sometimes, but rarely, found as transparent crystals resembling calcite, but, preponderantly, magnesite contains variable amounts of the carbonates, oxides, and silicates of iron, calcium, manganese, and aluminum. Magnesite may be either crystalline or amorphous (cryptocrystalline). The crystalline form has a hardness of 3.5 to 4.0. The color may range from white to black with shades of yellow, blue, red, or gray. The color is not a fundamentally significant indicator of purity, but in a given deposit, an experienced person can often roughly grade magnesite by assessing color and crystallinity. The crystalline form of magnesite occurs in

Jan 1, 1983

By Mary Barrett, Walter Rose

INTRODUCTION The conventional way to program reservoir problems* for solution on the electric analyzer1 is one which concentrates the block units towards the inner radius of the prototype system being represented by the analog model. This is achieved by the device of considering block units of equal value radial resistance, leading to the consequences: (1) the ratio of the external to the internal radius of each block unit is a constant (i.e. r1/ri-l = constant a); (2) the external radius of the nth block unit is equal to the innermost radius of the system times the constant a raised to the nth power: (3) the capacitance of the block units increase by a factor of a2 going out radially from the innermost to the outermost boundaries of the system; (4) given n block units in the radial direction, the capacitance ratio of the outermost to the innermost block unit is a (2n-2); and (5) the vertical resistance of the block units decrease by a factor of a going out radially from the innermost to the outermost boundaries of the system, such that the ratio of the maximum to minimum vertical resistance is also given by the factor a(2n-2) PRESENT PROGRAMMING METHOD While this conventional way of programming problems is quite adequate for routine uses of the electric analyzer, it leads to difficulties in those cases where the inner radius of the prototype system (e.g., the well-bore) is small compared to the external radius (e.g.. the external reservoir boundary). To handle such a case by the conventional method would require either that a large value be selected for the constant a or that a large number n, of radial block units be chosen. In consequence, the capacitance and vertical resistance ratios become impossibly large, as will be evident from the relations given above. In any event, the size of the smallest and largest capacitors will always be limited by the size of commercially available components, and the analyzer itself will determine how many mesh points are available for radial block units. For example, it can be shown that if the maximum capacitance ratio which can be electrically handled is a factor of l04, the maximum external radius of the system which can be considered (assuming an internal wellbore radius of 0.25 ft is: It is thus seen that in direct consequence of having the inner wellbore radius small compared to the external radius, models extending beyond 30 to 40 ft are not possible when the capacitance ratio is limited to l04. (NB. A value of 10-9 farads can perhaps be taken as the minimum electrical capacitance possible if corrections for the capacitance of the lead wires are to be avoided. Values greater than 10-5 farads would require the use of unstable and inaccurate electrolytic capacitors). On the other hand, models extending out to 500 to 5,000 ft may be desired in single-well problems, and hence the need for a revised method of problem programming. * REVISED PROGRAMMING METHOD The revised method of programming is one which attempts to retain the desirable features of the conventional method (viz. concentration of block units towards the inner boundary, simplicity in computation, etc.) without having as a consequence that impossible capacitance and vertical resistance ratios will be required. Other advantages will also be achieved by the revised

Jan 1, 1957

By B. F. Oliver, F. Garofalo

Gas-metal heterogeneous reactions and zone-lrelting were sinultarneously employed to produce several high-purity irons with low interstitial contents in a levitating- zone melter. Successive zone-tneltitzg pusses were made in carious sequences of atmospheves which included prepuvified tank hy-drogeta, water vapor hydrogen, palladiuril-purified hydrogen, and vacuunm of 2 x 10-6 Torr. Different irons ranging in purity from 99.89 to 99.996 pct with residual curbon contents of 17, 8 to 10, and 3 to 5 ppm have been Drepared. No measuvable gradient in the residual carbon content was observed along the entire zone-melted length (6-10 in.) in I-ilz.-diameter bars. The absence of a carbon-concentration gradient in the solid indicates an apparent distvihution coefficient of 1, an unusual condition. Internal friction, solid-state extraction, and hot-hardness results indicate that the level of mobile carbon in a iron depends on the gas-metal heterogeneous reactions employed. Purification under an oxidizing atmosphere resulted in the immobilization of nearly all of the carbon present at leuels of 10 ppm or less. Continuation of purification in a reducing atmosphere veturued the carbon to a state of mobility which was aguin reversed by further purification in all oxidizing atmosphere. The immobilization of curbon at "vesidual levels " is believed to be associated with a strong interaction between carbon and oxygen atoms. frons with low carbon and nitrogen contetzts which did not exhibit a hot-hardness peak were produced after zone ynelting in vacuum. CARBON, nitrogen, and oxygen have strong and well-known effects on many properties of iron. These effects persist even at concentrations of 5 to 20 ppm. The intent of the present investigation was to establish procedures for the preparation of high-purity iron with concentrations of these elements in the range of 5 to 20 ppm and lower. The results reported here deal with the procedures employed to prepare high-purity iron, and with observations on the behavior of certain elements at "residual levels": particularly carbon. The details of the (levitating) zone melter in which the final purification steps are performed and the necessary control of the pertinent solidification variables have been described previously.1,2 MATERIALS AND PROCEDURES Commercial electrolytic iron was induction vacuum-melted and cast into 30-lb ingots. Melt additions and ingot analyses for carbon, oxygen, and nitrogen are noted in Table I. All ingots were melted in stabilized zirconia crucibles conditioned with one iron wash heat. Middle sections of the ingots were forged to 1-1/4-in. rounds, machined to 1-in.-diameter bars, then cut to 36-in. lengths. The zone-melting operations were performed on six iron bars (A to F) at a freezing velocity of 2 in. per hr with the freezing interface rotating2 at 200, 300, or 400 rpm. Liquid zones were passed through the bars in various sequences of atmospheres, Table 11, including prepurified tank H2, palladium-purified Hz, wet H2, and system vacuum of 2 x 1018 Torr. Wet-Hz atmospheres were obtained by bubbling palladium-purified Hz through water exhibiting a resistance of 3 megohms. This water was heated with a platinum-immersion heater and was degassed prior to use. Zone melting in a wet-HZ atmosphere resulted in oxidation of the elements which are oxi-dizable with respect to iron. Fine oxide particles were observed on the surface of the liquid zone, and were encased in the bar surface with the passage of the molten zone. Between each zone pass, the surface of the bar was removed by filing and deep etching; this was continued until the oxide formation ceased. The filings were magnetically separated and the residues analyzed by optical spectroscopy. These were especially high in silicon and manganese. Samples were removed from the iron bars, with few exceptions, following each zone-melting operation. A 0.08-in.-thick disc was cut with an Al2O3 cut-off wheel at a point 1/2 in. above the beginning of freezing. Material from each disc was used for hot-hardness measurements, resistivity-ratio measurements, and carbon, nitrogen, and oxygen analyses. Analyses for most other elements were

Jan 1, 1965

By T. Reed Woodbridge

The object of this paper is to bring to notice a method in use at the Cedar Point laboratory of Witherbees, Sherman & Co., for determining the phosphorus in the ore mined at Mineville, N. Y. This ore is magnetite, with a gangue containing crystals of apatite. In 1886, Mr. H. F. Dawes, then head chemist at the works, suggested that as all the phosphorus seemed to be in the apatite, it could be obtained in solution by dilute nitric acid. After some experimenting the following method was adopted, and has proved invaluable for rapidity and ease; half a dozen determinations requiring very little more time or trouble than one. From + to 10 grammes of ore are weighed into a 150 c.c. beaker; 50 C.C. hot water and 10 c.c. strong nitric acid are added; the beaker is covered and the contents are boiled for 1/2 hour (10 minutes sometimes proves sufficient; but 4 hour is safer). The bumping which ensues if more than & gramme is used need cause no trouble. The hot solution is filtered into a 250 C.C. beaker. The filtration and washing (with hot water) proceed rapidly, as the magnetite itself is but slightly acted upon. After the addition of 15 C.C. ammonia and 15 c.c. nitric acid, the solution is cooled to 45' C., and from 15 to 40 C.C. of molybdic acid solution is added and stirred vigorously. In 5 minutes the precipitate will be down, and the determination can be finished by any good method. At Cedar Point the method more commonly used is weighing as yellow salt. Good washed filter-paper is used, No. 0 Swedish being preferred; and dozen 3 1/2-inch filters are numbered and dried and weighed at 110°C. These are always kept in stock. The yellow salt is filtered on one of these, washed with dilute nitric acid (2 per cent. by volume); dried for 1 hour at 110' C., and then weighed, 1.63 per cent. of weight being calculated as phosphorus. The filters vary in the two weighings from

Jan 1, 1889

By J. E. Burke, A. M. Turkalo

IN 1923 Desch¹ pointed out that the grains in a metal which is anisotropic with respect to its thermal coefficient of expansion would contract differently upon cooling, and that the stresses developed might approximate the plastic strength of the metal. More recently Boas and Honeycombe2-5 studied the behavior of several metals upon thermal cycling and observed that the stresses developed in arlisotropic metals are great enough to produce slip lines in individual grains and a roughening of the specimen surface. This phenomenon they have named "thermal fatigue." The mechanism they propose involves essentially a kneading of the grains, the deformation being alternately in compression and tension in a given grain as the temperature is changed in one direction and then the other. The present work was undertaken to investigate the possibility that an additional mechanism might operate to produce plastic deformation during thermal cycling—a "thermal ratchet" that depends upon a combination of grain boundary flow to relax the stress that develops between differently oriented grains upon raising the temperature and transcrys-talline slip to relax the oppositely directed stress which develops on lowering the temperature. Thus, thermal cycling should produce a nonreversible distortion such that certain grains will change shape differently from their neighbors with a simultaneous displacement being produced at the grain boundary. Temperature Dependence of Grain Boundary and Grain Strength The critical resolved stress for the initiation of slip in metal grains is only mildly affected by temperature." For example, in cadmium it decreases from 0.15 to about 0.05 kg per sq mm when the temperature is increased from 20° to 458°K and further temperature increase causes little further decrease. On the other hand, the work of KG1 indicates that the grain boundaries behave in a viscous fashion that can be described8 by the expression: t = BVexp(Q/RT) [1] t is the shearing stress on the boundary; B, a constant; V, the flow rate at the boundary; Q, the activation energy for grain boundary flow; R, the gas law's constant; and T, the absolute temperature. Eq 1 indicates that the stress necessary to cause a given grain boundary flow rate, V, decreases rapidly with increasing temperature. The value of the constant B is such that at sufficiently low temperature and ordinary strain rates deformation will occur preferentially by slip rather than by grain boundary flow. There is considerable evidence to indicate Consider the bicrystal shown in Fig. 1. In grain 1 the slip plane lies 45 " to the boundary while in grain 2 the slip plane is 90" to the boundary. The coefficients of expansion of the grains in a direction parallel to the length of the crystal are a1 and a, with a, > a2 for the orientations shown. The sequence of events that can occur upon heating and cooling this specimen is illustrated schematically in Fig. 2. Initially there is assumed to be no stress in the specimen (A). Upon heating, grain 1 attempts to become longer than grain 2, but is constrained by grain 2. Thus grain 1 is loaded in compression and grain 2 is loaded in tension, and a shearing stress is present across the boundary (B). As the temperature is increased, the stress will build up, and finally grain 1 will be plastically deformed by slip, since the greater stress is resolved on its slip planes. Any further heating will result in more slip and the stress will remain constant until some temperature T* is reached where the stress can be relaxed by grain boundary flow.† At this relaxation temperature (C) a step will appear between grain 1 and grain 2. Further heating above T* will cause grain 1 to become relatively longer, but no stress will appear because the grain boundary is too weak to support the stress (D). Upon cooling again, at T* (E), the grain boundary will again be able to support a shearing stress, and upon cooling further, grain 1 will be loaded in tension and grain 2 in compression (F). When the decrease in temperature below T* is sufficient to impose the critical shear stress upon the slip plane of grain 1, it will be stretched by slip.

Jan 1, 1953

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 J. E. Hanlon, S. R. Butler, R. J. Wasilewski

It is known that stoichiometric NiTi transforms to a structure of lower symmetry near room temperature. The present investigation deals primarily with the changes in the electrical and magnetic properties which occur at the transformation. The effects of composition and various heat treatments on electrical properties are also discussed. In recent investigations by Purdy and Parr,' Wang et a1.,2 Dautovich and Purdy,~ Dautovich et a1.,4 and the authors, ~,' NiTi has been observed to undergo a martensitic phase transformation from the ordered CsCl (B2) structure to one of lower symmetry. The crystal structure of the low-temperature modification is still not completely worked out. This transformation occurs near room temperature for the stoichiometric composition. The thermodynamic, elastic, crystallographic, and microstructural characteristics of this transformation for some compositions have been previously reported.'-= In the present investigation, the changes in the electrical transport properties and magnetic susceptibility of NiTi when it undergoes the martensitic phase transformation have been measured. The approximate composition range covered is 48 to 52 pct Ti.* *All compositions are given in atomic percent._____________________ EXPERIMENTAL PROCEDURES AND RESULTS 1) Sample Preparation. The NiTi alloys were prepared from iodide titanium (>99.92 pct Ti) and vacuum-premelted carbonyl nickel (>99.95 pct Ni) by repeated arc melting under gettered argon and casting in a water-cooled copper mold. After the cast buttons were hot-forged at 800" to 950°C, the oxidized surface was removed by grinding and etching. Samples were cut from the worked polycrystalline buttons. After fabrication, the samples were annealed 1 hr at 900°C and water-quenched. The composition of the alloys was assumed to be the same as in the initial feed. This assumption was supported by material balance checks on 100-g arc-melted buttons which demonstrated quantitative recovery to within k0.02 pct. The oxygen content of the alloys was '150 ppma (weight) and the carbon content was 30 to 50 ppm. 2) Electrical Resistivity and Hall Effect. The electrical resistivity was measured over the composition range 48 to 52 pct Ti for temperatures varying from 4.2"K to 900°C. The high-temperature and many of the low-temperature experiments were carried out using conventional 4-probe dc techniques.7 The Hall coefficient and ac resistivity were measured at 20 cps using the apparatus shown schematically in Fig. 1. The equipment is basically an ac potentiometer: The resistive or Hall voltage of the sample is balanced by a comparison voltage provided by a dividing network across a standard series resistance. The off-balance signal is amplified by a Tektronix 122 amplifier and detected by a Princeton Applied Research (PAR) phase-sensitive detector. The precision of the resistivity and Hall coefficient measurements is i0.1 and i3 pct, respectively. The uncertainty in the data is increased by i2 pct from the precision limits because of uncertainty in dimensions and possible end effects. The temperature dependence of the electrical resistivity and Hall effect for a stoichiometric (50.0 pct Ti) NiTi sample are illustrated in Fig. 2. Above 75"C, this sample has essentially the B2 structure, while below about 0°C it is completely in the low-tempera-

Jan 1, 1968

By S. R. B. Cooke, W. Philippoff, Donald E. Cadwell

[THE importance of contact angles in flotation has long been recognized, but little has been done to get quantitative relationships between the surface coverage of the mineral by the reagent, the length of the hydrocarbon chain, and the contact angle. It is well known that for a complete monolayer on the surface of a mineral the contact angle ? is determined only by the reagent&apos; and principally by the chain length of the hydrocarbon radical. Although for flotation the monolayer usually is regarded as being complete, early experiments of Wark and Cox2 showed that at very small concentrations of potassium ethyl xanthate the contact angle on galena changed in a continuous way from 0° to the equilibrium value of 60°. Further, Gaudin and Vincent&apos; showed a similar continuity using heptylic acid and sphalerite. This shows that with probably incomplete monolayers, ? varies with the degree of surface coverage. At the time these experiments were made it was impossible to measure the actual amount of surface coverage, especially since the decrease of the collector concentration in the liquor could be influenced by chemical side reactions. Through the use of the radioactive tracer method for the measurement of the amount of collector adsorbed on the surface of the mineral, Gaudin and Bloecher4 were able to determine accurately the actual surface coverage of dodecylamine acetate on quartz, but they did not measure any contact angles. It is believed that the relationship between the surface coverage and the contact angle is extremely important in flotation, especially as Gaudin and Bloecher showed that a 95 pct recovery is possible with a coverage of only 5 pct. Theoretical Considerations The work of adhesion W is the energy bound (in ergs per sq cm) when an interface is formed. It is determined by, the difference of the free surface energies (surface tensions) of the respective phases ?1 and ? 2 before contact and the interfacial free surface energy ?12 after contact. The definition of the contact angle permits the elimination of the unknown surface energy of the solid and hence the calculation5 of W from the surface tension of the liquid ? and the contact angle ?: [W = y (1 + cos ?)[1]] Consider a surface consisting of two components, identified as 2 and 3, 1 being the liquid. The amount of 2 in the composite surface is x, where 0 < x < 1. The respective contact angles with 1 and air are ? and ?3. The total work of adhesion of such a surface is the sum of the values of the components multiplied by their respective areas. A formal relation can be written: [W,,,=x•W2+ (1-x).WR[2] .] in which Wm is the work of adhesion of the composite surface. Eq 1 can be introduced into W2 and W3 but in the case of Wm some discussion is needed. If the two components are segregated, each component forming an integral part of the composite surface there is no physical meaning for a contact angle ?m, calculated from Wm, by using eq 1. If, on the other hand, the area of each patch of the components is small in comparison with, say, the diameter of the bubble used in measuring, it could be expected that ?m would have aphysical significance, because of the action of the surface tension of the liquid-gas interface tending to smooth out sharp corners. How small these patches would have to be is difficult to predict, but by using composite surfaces with microscopically]

Jan 1, 1952

By M. E. Learmont, R. J. Lipp, I. Iwasaki

In the selective flocculation of iron ores, the concentration of alkaline earth ions in pulp solutions plays a critical role. Sodium silicate, alone or with sodium tripolyphosphate, has been used as a dispersant. When Ca+ + concentration exceeds 15 to 20 ppm, however, only a strong complexing agent, such as ethylenediaminetetraacetate (EDTA) was found to be effective (Heerema, Lipp, and Iwasaki, 1979). Some iron ores release Ca+ + in excess of 20 ppm. With ores that contain gypsum, the Ca+ + concentration may reach several hundred ppm. The purpose of this investigation was to compare the effectiveness of EDTA with nitrilotriacetate (NTA) in countering the adverse effects of Ca+ +, particularly at high Ca+ + concentrations. Emphasis was placed on the use of NTA since it is more cost-effective than EDTA. It is also used in detergents in some countries (Malaiyandi, Williams, and O&apos;Grady, 1979). NTA, like EDTA, forms a soluble complex with Ca+ + with a 1:1 molar ratio. Its structure and the value of log Kca are given below together with EDTA (Shibata, 1963). [ ] For experimental materials, an equal weight mixture of Lac Jeannine hematite and a high-purity quartzite from Thompson, MN, both ground to - 30 µm (- 560 mesh) was used. Selective flocculation test conditions and procedures were identical to those used in previous investigations (Heerema, Lipp, and Iwasaki, 1979). The optimum level of starch addition for the above mixture was determined to be at 300 g/t (0.6 lb per st). Initially, a series of selective flocculation tests were performed on the mixture pulped with 10-3M CaC12 (40 ppm Ca + +) at pH 11. With no NTA present, flocculation of the entire suspension resulted. The selectivities achieved in tests with 90, 100, and 150% of the stoichiometric amount of NTA were virtually identical to each other and also to the selectivity of separation obtained in the absence of Ca+ + Such an observation could have been expected since Ca+ + concentrations up to a few ppm may be tolerated in selective flocculation (Krishnan and Iwasaki, 1982). A similar series of tests were performed at 10-2M CaC12 (400 ppm Ca+ +). The results are shown in Fig. 1 as grade¬recovery curves. For comparison, the results obtained in the absence of Ca++ are included. At 90% of the stoichiometric amount of NTA, a large enough concentration of uncomplexed Ca+ + was left in solution to cause indiscriminate flocculation. Note in this figure that NTA is capable of countering the adverse effect of Ca+ + even at this high concentration when it is used in excess of stoichiometric amounts. The free Ca+ + concentrations at 100 and 150% are calculated to be 2.5 and 0 ppm, respectively. [ ] The relative effectiveness of NTA and EDTA was then compared at 100% of the stoichiometric amount using 10-2M and 10-3M CaCI2 (Fig. 2). EDTA appears to be slightly more effective than NTA. The free Ca++ of 0.02 ppm in 10-2M CaC12 with EDTA compared to 2.5 ppm free Ca+ + with NTA might account for the difference. As evident, prohibitively high additions of EDTA and NTA were required to complex high concentrations of calcium ion. The use of both of these agents would result in the accumulation of complexed Ca+ + in recycle water.

Jan 1, 1985

By N. A. D. Parlee, I. D. Shah

The solubilities of oxygen in liquid Ag-Au, Ag-Pt, and Ag-Pd alloys have been determined in the range of 940° to 1200°C at 1 atm pressure of oxygen using an improved Sieverts technique. The additions of gold (0 to 57 pct), platinum (0 to 27 pct), and palladium (0 to 22 pct) to liquid silver continuously decrease the solubility of oxygen in liquid silver. Activity coefficients and interaction coefficients of oxygen in these alloys and have been calculated. The interaction coefficientscan be described by the following equations: Approximate second-order interaction coefficients (pM have been calculated. The contribution of the product, pMxNM, to In yo only becomes significant at high alloy concentrations. RECENTLY several investigators1"3 have redeter-mined the solubility of oxygen in liquid silver. In general the recent findings1" for Po, = 1 atm are in good agreement with the equation:4 log %O = 695.4/T + 1.086 [1] It is established1, 2 that the solubility of oxygen follows Sieverts&apos; law reasonably well, at least up to 1 atm partial pressure of oxygen. It should be noted that a very slight deviation from Sieverts&apos; law has been reported by Lupis and Elliott.3 Only recently has the solubility of oxygen in Ag-X binary liquid systems received much attention, and only the Ag-Cu, Ag-Au, Ag-Pt, and Ag-Pd systems have been studied. Par lee, Sacris, and zoellners reported that the solubility of oxygen in liquid silver increases progressively with the small additions of copper (0 to 0.5 pct) up to the point where the copper oxide phase appears. Lupis and ~lliott~ have reported that the solubilities of oxygen in liquid silver decrease progressively with the additions of gold, platinum, and palladium. However, their investigation was limited to 0 to 5 pct of these alloying elements, a range too limited to satisfy the requirements of the research program of this laboratory, where the solubilities of oxygen in the range of 0 to 30 pct were required for the calculation of chemical diffusion coefficients of oxygen in these alloys. The present paper deals only with the solubilities of oxygen in these alloys while another paper will deal with the diffusion of oxygen in these alloys. EXPERIMENTAL METHOD A Sieverts technique was employed which involved an improved design of the reaction tube, Fig. 1, as described briefly in a previous communication.4 Liquid melts (70 to 100 g) were held in Norton Alun-dum crucibles. The induction furnace used had a maximum output of 2.5 kw with very fine control. This induction system had excellent stability and the final equilibrium temperatures measured by calibrated Pt-Pt, 10 pct Rh thermocouples are believed to be within ±2C. These thermocouples were checked against the melting point of pure gold wire, and the results agreed with standard tables (±l°C). Each run involved a careful sequence of operations. The sample was heated to and held at about 900°C in vacuum for 3 to 4 hr with the thermocouple in a retracted position. After melting, the melts were usually exposed to a small amount of oxygen (0.5 to 2.0 cu cm) and then degassed slowly for 1 to 2 min to remove any oxidizable volatile impurities such as carbon and sulfur as CO, CO2, SO2, and SO forth. Argon gas was then allowed to enter the system. The protection tube containing the thermocouple was then

Jan 1, 1969

Jan 1, 1934

By W. O. Philbrook, C. W. McCoy

The reduction of chromous oxide from lime silica alumina slags by carbon-saturated iron behaves as a first-order process having a rate of 0.001 grams Cr min 1 cm 2 (pct Cr ) , substantially independent of slag composition and temperature over an important range for iron smelting. The equilibrium ratio (pct Cr)/[pct Crl is below 0.04 for slags having lime-silica ratios above 0.6. MANY studies have been conducted on chromium in slag-metal systems under oxidized conditions. The Purpose of these investigations has been twofold; namely, (1) to determine those conditions which lead to greater chromium recovery in electric-furnace and open-hearth practice, and (2) to determine the nature of oxide inclusions and de-

Jan 1, 1959

By D. M. S. Bhatia

The intimate association of iron formation and massive sulfide deposits has been documented by many investigators (McAllister, 1960; Hutchinson, 1972). In a classic example of such an association, four distinct facies (oxide, carbonate, silicate and sulfide) were identified in an Algoma-type iron formation occurring in Paleozoic rocks, but exhibiting physical features (banding) and chemical composition (SiO2 + A1203 + Fe2O3) typical of Precambrian iron formations. The geochemical variation of the iron formation was studied by analyzing 62 samples for Si, Al, Fe, P, S, and Cop. Following a model proposed by James (1954), the geochemical and mineralogical variation of the iron formation can be used as an excellent tool for the exploration of massive sulfide deposits.

Jan 1, 1982

By Dwight K. Smith

A new pozzolanic composition has been developed for cementing oil wells where moderate to high temperatures prevail. This material is an entirely different concept to other oil well cementing materials, such as portland cements, cements containing additives, or liquid resins. Its characteristics are such that it is not, at present, recommended for use at temperatures less than 140º F. It can he either accelerated or retarded across a wide range of well conditions. This new cement is composed of a pozzolanic material, hydrated lime, and a chemical activator to give it early initial strength. This material can be used in wells from 6,000 to 18,000 or more feet where temperature conditions are similar to those along the Gulf Coast. This cement, when set, has no soluble portion subject to leaching or any compounds that should be attacked by sulfate waters or brines. For this reason, it should be permanent when placed adjacent to formations carrying any type of fluid. The compressive strengths in 24 hours are more than adequate for wells where temperatures are 140°F and higher. These values ore in excess of many other types of cementing composition presently in use in the field. This pozzolanic composition does not retrogress in strength at high temperatures as do some other types of cementing materials. The slurry weights of this material will vary slightly according to the specific gravity and water requirements of the pozzolnn itself. The materials covered herein will mix from 13.5 to 14.3 lb/gal, and will have a waiting-on-cement time comparable to other materials used under the same conditions. Economically speaking, this composition is less expensive than either portland cements or retarded cements presently being used under deep well conditions. INTRODUCTION Pozzolans are siliceous material which, though not cementitious in themselves, contain constituents which at ordinary temperatures will combine with lime in the presence of water to form compounds which have a low solubility and possess cementing properties. The use of pozzolanic materials dates back many hundreds of years and both the ancient Greeks and Romans were aware that certain volcanic deposits, if finely ground and mixed with lime and sand, yielded a mortar which possessed special properties. Generally, the early strengths of such materials were rather weak and were considered insufficient for modern commercial usages. Pozzolanic materials have been used extensively with portland cement in mass concrete to obtain special properties. In recent years, large quantities of certain pozzolanic materials have been used successfully admixed into portland cements for oil well cementing. Pozzolans, being reactive silicates, will combine with the free lime that is an inherent component of set portland cements and thereby. becomes cementitious themselves. POZZOLANS FOR OIL WELL CEMENTING There are many types of pozzolans, some of which are more reactive than others. The quality of the pozzoIan depends on the degree of reactivity, chemical composition, fineness, and other less well understood factors. Some of the more widely accepted pozzolans are those classified as fly ashes, while others are certain materials of volcanic origin. pozzolans which require large vol-

Jan 1, 1957

By J. Laskowski, Z. Sadowski

The properties of quartz, calcite, magnezite and dolomite suspensions prepared from -30 µm size fractions of these minerals have been investigated. Selective coagulation of the quartz-calcite, quartz-magnezite and quartz-dolomite binary suspensions was possible at the pH values slightly above those for the i.e.p. of the carbonate minerals. The tests revealed that quartz suspensions were not flocculated by the anionic flocculants, whereas the same polymers were flocculants for calcite, magnezite and dolomite. Selectivity in the flocculation of the quartz-calcite, quartz-magnezite and quartz-dolomite binary suspensions was not, however, satisfactory because of the activation of quartz by ca2+ and Mg2+ ions. Dispersing reagents can be used to improve the selectivity of flocculation.

Jan 1, 1980

Draftsman and transitman for coal mine work in Middle West. Salary $125 per month. No. 277. Technical graduate wanted for metallurgical work in experimental laboratory of large New England manufacturing concern. A knowledge of metallography of steel is essential. Practical experience is desirable but not required. No. 305. High-class man to install and take charge of a coal mining property. Must be experienced in handling labor and of good sound judgment. Work will require a man to be on the grounds practically all the time. The work is drift mining and is not gaseous. No. 306. Engineer familiar with the acid treatment and melting of cyanide precipitates; also a competent assayer. Applicant must be able to furnish good references. No. 307. Wanted-practical mining man, foreman, or superintendent for work in middle or southern Atlantic States. Salary $200 per month. No. 308.

Jan 5, 1918