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By G. L. F. Powell, L. M. Hogan

Large degrees of undercooling have been produced in bulk samples, 400 g, of copper and Cu-O alloys by melting in a slag of commercial soda-lime glass. The maximum degrees of undercooling obtained for copper, hypoeutectic and hypereutectic Cu-O alloy samples were 208°, 218°, and 97°C, respectively. No grain refinement as a function of undercooling was observed for the pure copper samples although in Cu-O alloys there was a marked decrease in grain size at degrees of undercooling greater than 150°C. The grain size change is the result of recrystallization during or immediately following the freezing process. THE first report of a large degree of undercooling in a bulk sample of metal was that by Bardenheuer and Bleckmann1 who produced 258°C undercooling in a 150-g sample of iron by melting in a glass slag. Garbeck2 extended this technique to nickel, cobalt, and copper and reported maximum undercoolings of 220°, 230°, and 60°C, respectively, while Fehling and schei13 undercooled a large number of metals as 2 to 20-g samples slagged in glass. Subsequently, one of the authors4 applied the glass slag technique to bulk samples, -500 g, of silver and obtained a maximum undercooling of 250°C. It was concluded that impurities which normally catalyze nucleation at small degrees of undercooling could be removed by oxidation and solution in a glass slag. Large undercooling of bulk samples of iron, nickel, cobalt, and their alloys has also been reported by other authors.8'10'11 Of the five metals mentioned above, copper was the only one which had not been undercooled by at least 200°C in the form of a large bulk sample. Since copper exhibits high liquid solubility for oxygen, as do iron, nickel, cobalt, and silver, it was considered that a much larger degree of undercooling than that observed by Garbeck for copper should be possible. This was obtained by modification of the technique applied previously to silver and the results of undercooling experiments with 400-g samples of copper form part of this paper. The undercooling behavior of Cu-O alloys was also studied, and the influence of a small oxygen content on the grain structure of undercooled copper was observed metallographically. 1) EXPERIMENTAL The copper was obtained as oxygen-free high-conductivity copper, the major impurities of which were Fe 0.01 pct, Zn 0.015 pct, and Si 0.02 pct. Melting was carried out in an open-ended vertical cylindrical fur- nace wound with Kanthal wire. A schematic diagram of the experimental setup is shown in Fig. 1. The undercooling technique previously used for silver4 involved preoxidation of the samples by melting the silver in contact with the atmosphere. The oxygen content was subsequently reduced by freezing the samples under a glass slag, whereby the oxygen was evolved as gas and the continuous glass cover over the surface prevented re-solution of oxygen when the sample was remelted. Since oxygen is not released as gas when a Cu-O alloy is frozen. the technique had to be modified for use with copper. Also, copper is oxidized during fire refining so that an in situ preoxidation treatment of the samples was not considered to be a prerequisite to large undercooling. Experimentation proved that this supposition was correct. Instead, it was found that care was necessary during melting of the copper under glass to minimize oxygen pickup. Samples of copper weighing 400 g were prepared by adding 50-g pieces of copper to a vitreous silica crucible partly filled with soda lime glass at a temperature of approximately 1000°C. Each piece was quickly immersed in the glass slag and held at this temperature until the oxide coating on the surface decomposed. This change was easily observed and coincided with the formation of gas bubbles in the glass

Jan 1, 1969

By L. W. Reynolds, R. F. Campbell, K. G. Carroll, S. H. Ballard

Based on metallographic and X-ray data probable equilibrium conditions from 1340" to 2400°F are presented for the composition range investigated. These are correlated with investigations of Takei and Kuo. Provision is made for existence of Mo, C and (Fe, Mo)2,C, carbides heretofore omitted in diagrams in this composition range. These carbides and (Fe, Mo),C, in equilibrium with ferrite and austenite, restrict the austenite and austenite + ferrite fields to lower carbon contents and higher temperatures than in the Fe-C system. OK groups of steel of different molybdenum content, but with approximately the same carbon variation in each group, Table I, were studied. The alloys were melted in an acid-lined 30-lb high-frequency induction furnace, and the ingots forged to l-in. rounds, which were then ground to 0.75-in. diam. To minimize chemical segregations a short length of each bar was given a high-temperature heat treatment as listed in Table I. Specimens 0.062 to 0.125-in. thick were thereafter cut from the homogenized bars for heat treatment to determine phase changes in the alloy. Heat treatments were performed in either a lead bath or muffle-type electric furnace, depending upon the temperature required. Maximum temperature variation was * 2" F in the lead bath and * 5"F up to 1900°F and +8"F above 1900°F in the electric furnace. Adequate protection of the specimen from the oxidizing atmosphere in the electric furnace was obtained by sealing the specimen in either a pyrex or a silica capsule which was evacuated or not as circumstances required. For austenitizing followed by quenching to an isothermal temperature, the specimen was placed in a closed-end refractory tube the mouth of which, extending beyond the furnace, was connected to a vacuum pump. The specimen could be withdrawn from this tube and quenched as desired. IDENTIFICATION OF PHASES The principal method of identification of phases was metallographic examination conducted on surfaces well removed from exposure to lead or atmosphere effects during heat treatment. Hardness measurements (Dph/lOkg) were also made on these surfaces. The etching reagents used and their effects are listed in Table II. Martensite and ferrite were readily recognized by their customary appearance after etching with saturated picral or 1 pct nital. The presence of liquid at high temperature was indicated by curved interfaces characteristic of boundaries between solid and melt, by intergranular pools of dendritic areas in a carbide matrix, and by a black network coincident with austenite grain boundaries. Examples of these structures are shown in Figs. l(a) and (0). The types of carbide which were attacked by the electrolytic chromic acid etch and the alkaline KMnO, etch, Table 11, were identified by X-ray analyses of extracted carbides of five alloys. Carbide residue was obtained from a metallographic specimen by etching the specimen for 24 hr in hydrochloric-picric acid in alcohol (grain-size reagent), after which the carbides, standing in relief, were scraped from the surface of the specimen and mounted on a glass slide. Diffraction patterns were obtained with a Philips spectrometer using iron-filtered cobalt radiation. Figs. 2, 3, 4, and 5 illustrate typical etching behaviors with chromic acid and alkaline KMnO,. Chromic acid attacked Mo,C as shown in Figs. 2(a) and (b)-but not (Fe, Mo),C, Fig. 3(b). Alkaline KMnO, attacked (Fe, Mo),C, Fig. 3(c), and also attacked M0,C. In accordance with these behaviors, a typical differentiation of coexisting Mo,C and (Fe, Mo),~ is shown in Figs. 4(a) and (b). The carbide (Fe, Mo),,C, could not be obtained free of other coexisting carbides for etching experiments. The behavior. however. of coexisting carbides identified by x-ray diffraction as Mo,C ind (Fe, Mo),,C, indicate that (Fe, Mo)23C6 is not etched by chromic

Jan 1, 1961

By Paul A. Farrar, Harold Margolin

The Ti-Al-V system has been delineated from 50 to 100 wt pct Ti and front 600 to 1400°C by X-ray and ntetallographic techniques. Isothermal sections were delineated at 600, 700, 800, 900, 1000, 1100, 1200, 1300, and 1400°C. X-ray and metallographic evidence indicated the presence of two phases and in addition to those reported by previous investigators of the ternary system'-3. T HE titanium-rich region of the Ti-Al-V system as originally proposed by Rausch et UZ, and Jordan and Duwez3 was based on the binary Ti-Al diagram as proposed by Bumps et uZ. As additional phases have been shown to exist5-' in the region previously thought to be all a, the titanium-rich region of the Ti-Al-V system is open to serious question. Therefore, in order to determine the effect of the indicated changes in the Binary Ti-Al system on the ternary Ti-Al-V system the present investigation was initiated. EXPERIMENTAL PROCEDURE The experimental procedures in this investigation are the standard techniques used in the study of titanium-alloy systems which have been described in detail previously.1° Consequently, only details pertinent to the present work are discussed. The alloys employed for the delineation of this system were prepared from titanium obtained from the Bureau of Mines (73 BHN) 99.99 pct Al and 99.7 pct V, by the consumable arc-melting technique. The titanium was premelted into buttons of 25 g because spattering during the first melt caused uncontrollable loss of alloying constituents. Typical analyses of the material used have been reported elsewhere Attempts to hot roll the alloys prior to heat treatment were made on the first series of alloys prepared, but as the area of extensive hot workability was fairly restricted, see Table I, this practice was discontinued. The times of isothermal annealing are given in Table 11. A preliminary heat treatment of 96 hr at 1000°C was used prior to heat treatment at lower temperatures. The standard techniques used for polishing specimens involved belt-grinding, grinding on emery paper, polishing electrolytically, and etching with Remington "A" etch. In the low-alloy region it was found that the oRo etch, developed by Ence and Margolin,o gave better contrast between phases. Where this procedure did not differentiate between phases clearly, the method of stain etching developed by Ence and was used. It has been previously reported15 that filing of titanium alloys is not desirable for producing X-ray powders, since the powder becomes contaminated by the file material. Therefore, for those samples not brittle enough to Crush, the procedure described below was used. The specimen was wrapped in molybdenum sheet and placed in a vacuum system and evacuated to 0.03 p. Palladium-pur if ied hydrogen was then admitted to the system until a partial pressure of 5o Cm of H was reached. The specimen was heated in the system to the temperature of original heat treatment and was slowly cooled over a period of 3 hr to 400°C while the partial pressure of hydrogen was maintained. The sample was removed from the system after it had completely cooled and was crushed to a powder of 230 to 270 mesh. The powder, wrapped in molybdenum sheet, was dehydrogenated at the temperature of original heat treatment until a partial pressure of 0.03 p was maintained in the system for at least 1/2 hr. The tube containing the powders was quenched in iced brine while still connected to the vacuum system. After dehydrogenation, the powder, except for the

Jan 1, 1962

By K. Tangri, M. Chaturvedi

The addition of 0.5 wt pct Cu to Zr-2.5 Cb alloy increases the as -quenched hardness of the hexagonal martensitic a' phase, produced by water-quenching bccß-Zr phase, by about 35 pct. This strengthening has been attributed to the solid -solution hardening of the matrix. On aging ternary martensite, a' phase reverts to equilibrium a and Zr2Cu and ß-Cb precipitate out, mainly at the twin and grain boundaries, causing a secondary hardening of the matrix. COLD-worked Zircaloy-2 pressure tubes have been in use in power reactors for a considerable period of time. The search for a better material led to the development of Zr-2.5 wt pct Cb alloy which in the quench-aged condition develops 50 pct more strength than that of cold-worked Zircaloy-2, however, its corrosion resistance in water and steam in the temperature range of 316" to 400°C, in absence of neutron flux, is inferior to that of zircaloy-2.' Work carried out by Ells et al.1 and Dalgaard2 has shown that the corrosion properties of Zr-2.5 wt pct Cb alloy can be considerably improved by the ternary addition of 0.5 wt pct Cu. This paper is concerned with the effect of 0.5 wt pct Cu on the formation of martensitic a and its aging characteristics in a Zr-2.5 wt pct Cb alloy. MATERIALS AND EXPERIMENTAL TECHNIQUES Zr-2.5 Cb-0.5 Cu (referred to as the ternary alloy) and Zr-2.5 Cb (referred to as the binary alloy) alloys, supplied by the Chalk River Nuclear Laboratories of the AECL were used. The detailed chemical analysis is given in Table I. Cold rolling and swagging with frequent intermediate anneal of 1000°C were used for the initial fabrication of the alloys. All the heat treatments were carried out after the specimens were wrapped in zirconium foils and encapsulated in silica tubes under a vacuum of 5 x 10-6 mm of Hg. For optical metallography and hardness measurements specimens were mechanically and then chemically polished in a 45 pct HNOj, 45 pct HzO, and 10 pct HF solution. Hardness was measured on a Vickers hardness tester using a 10-kg load. For each specimen at least fifteen indentations were made in order to obtain a representative value. The phase identification and structural analysis were carried out using X-rays and electron diffraction techniques. Wires of 1.5 mm diam reduced to 0.12 mm diam by chemical etching were used for making Debye-Scherrer powder patterns using Cu Ka radiation in a 114.6 mm diam camera. Carbon extraction replicas were prepared by etching the specimens, after depositing a layer of carbon on the metallographic specimen, in one part HF and thirty parts ethyl alcohol. Thin films were prepared by electropolishing heat-treated 3/4 by 1/2 by 0.005 in. thick strips using a modified Bollman-Window technique. The 10 pct perchloric acid-90 pct methyl alcohol bath was kept at -50°C and polishing was done at 5 to 10 V. The thinned specimens were washed in ethyl alcohol at -30º to -40°C and dried between filter papers. Replicas and thin films were examined in a Phillips 300 G electron microscope. For resistivity measurements thin strip specimens 0.02 by 0.3 by 10.0 cm long were used. The potential leads were spot welded to the specimens in order to maintain a fixed length for the initial and the final resistivity measurements. The resistivity was measured by a Kelvin bridge in a temperature controlled room. The temperature was maintained at 72º ±1°F and the accuracy of the resistivity measurements was 0.03 µa-cm. RESULTS As-Quenched Structures. In order to produce a homogeneous matrix to study the precipitation reaction the solution-treatments of both the alloys were carried out in the -field region. From the Zr-Cb phase diagram due to Lundin and cox3 ß/a + ß phase boundary for Zr-2.5 wt pct Cb alloy is 820°C. Ells et al.1 have reported this boundary for Zr-2.5 Cb alloy containing 1100 ppm 0 to be at 920°C. Also, the addition of 0.5 wt pct Cu reduces this temperature by 50°C. Therefore, the solution-treatments were carried out at 1000°C to ensure that the alloys were in ß-phase region. The soaking time was 1 hr and the specimens were water-quenched. The as-quenched hardness of the binary alloy was 245 Vpn whereas, that of the ternary alloy was 330 Vpn. The X-ray diffraction studies indicated that the as-quenched structure of both the alloys consists of martensitic hexagonal phase a', with a c/a ratio of 1.591, and some retained ß-Zr. The presence of a' phase was further confirmed by thin film electron microscopy. Electron micrographs of typical ß-quenched structures of the ternary and the binary alloys are shown in Figs. 1 and 2, respectively. Fig. 3 shows the diffraction pattern from an area similar to that shown in Fig. 1. Although, the as-quenched hardness of the ternary alloy is about 35 pct greater than that of the binary alloy, the structure of both the alloys seems to be the same. The matrix of both alloys is heavily twinned and shows very few dislocations. Furthermore, there is no evidence of any precipitation taking place in either of the two specimens during quenching from the solution-treatment temperature. Aging Behavior of Martensitic a'. The aging kinetics of the ternary alloy were followed by resistivity and hardness measurements. The as-quenched values

Jan 1, 1970

By H. Udin

G. KUCZYNSKI* and B. H. ALEXANDER*—This paper represents a most noteworthy attempt to evaluate experimentally the surface tension of a solid metal. Because of the great importance of such measurements, any proposed method should receive the closest scrutiny before the results can be considered reliable. In regard to the experimental method, we think that the marking of the gauge length by means of tieing knots in the wire may be the cause of some of the spread in the results. Such a knot may be expected to tighten slightly, and thus increase the gauge length, when placed under stress at high temperature. Although this effect would be very small, amounting at most to only a few times the wire diameter. A fairly tight knot in a wire will decrease the wire length by about ten times the wire diameter, thus only a slight tightening of the knot would cause considerable spread in the results. Upon plotting the stress strain curves from the authors' data, the writers found that there was a fairly consistent tendency towards an S-shaped curve, instead of a straight line. Such an effect could be caused by the tightening of the knots. The writers think, however, that the experimental results are fairly reliable, but that there may be other methods of interpreting them depending upon what mechanism is assumed to be responsible for the shrinkage of the wires. The authors have assumed that the stress due to surface tension results in viscous flow. It should be made clear that it has never been demonstrated that viscous flow can occur in metal crystals even at very high temperatures. The experiments of Chalmers13 on tin, which are so frequently quoted as giving evidence of viscous flow at low stresses are by no means satisfactory. In his experiments, Chalmers found that only the initial rate of flow was approximately proportional to stress. He also found that the rate of flow varied markedly with time which, in his experiments, was less than 2 hr. Inasmuch as there is no proof of viscous flow in metals, and the authors have brought forth no conclusive evidence on this point, it may be worth while to investigate other possible mechanisms of material transport which would account for the shrinkage of the wires. The writers wish to point out that in these experiments the shrinkage of the wires can be adequately explained, according to a self diffusion mechanism. Thus, if we assume a concentration gradient for self diffusion which is a function of the radius of curvature of the wires, and assume that diffusion will occur so that the total surface area is decreased, we find the following expression for the self diffusion coefficient: where k = Boltzmann constant r0 = initial radius of the wire T = absolute temperature ? = surface energy 8 = interatomic spacing t = time e = strain at zero applied stress Eq 19 may be used to evaluate the self diffusion coefficient of copper, using the strain measurements obtained by the authors for zero stress as obtained by extrapolating their curves for 5 rail wires. By inserting a reasonable value for the surface energy (1500 ergs per cm2) we find: -66,000 D = 5 X 10e RT [20] The activation energy is of the correct order of magnitude, but the frequency coefficient is much too high, indicating that surface diffusion may be playing an important role. This discrepancy in the action constant is much smaller than the corresponding discrepancy obtained by the authors for the viscosity coefficient. The writers by no means propose that this proves that the shrinkage of the wires is due to self diffusion but we merely wish to point out that there are explanations other than that given by the authors. In this, as in any kinetic phenomena, it is necessary to study the rate of the process before anything can be said about the mechanism. The determination of surface tension given by the authors is based upon an interpretation of the data which embody the concept of viscous flow. The final proof of this concept will be obtained only after the time relationships confirming the authors' Eq 15 have been conclusively established. The rough linearity of the stress strain curves obtained by the authors for experiments run the same length of time should not be considered as proving that viscous flow is occurring. H. UDIN (authors' reply)—All of the test specimens were annealed at 1000°C for an hour or more before preliminary measurements were made. During this anneal the wires recrystallize, and the greatest part of grain growth takes place. Also, the knots sinter at the cross-over points. This does not in itself eliminate the possibility of end errors, although it greatly decreases their probable magnitude. It is still possible that some extension occurs due to creep in shear at the sintered points. If so, this effect would be quite independent of and superimposed on the normal shrinkage or extension of the wire itself. Within the precision of the experimental results, straight lines satisfy the data as well as do any other simple curves. Until data of greater precision are obtained, it is futile to discuss any possible trends away from linearity. The disagreement between Kuczynski and Alexander's Eq 19 and our Eq 18 is one of semantics and mathematics, not mechanism of flow, since Eq 18 is based on the self-diffusion concept of viscous flow. It would be interesting to learn how the mathematics leading to Eq 19 deviates from that of Eyring and of

Jan 1, 1950

By D. F. Kaufman, H. R. Spedden, A. M. Gaudin

MANY studies of comminution have been made to ascertain the size distribution of the product and to evaluate the work of comminution in the light of the size distributions of the feed and product. Up to now, these studies have been essentially statistical in character, that is, a certain lot of feed was subjected to comminution in some specified way, and the aggregate product was fractionated into sizes, thereby losing all knowledge of individual relationship of feed to product pieces. Radioactive tracers offer a means to do something in this respect which could not be done before, namely, to follow the rupturing of some particular piece in its normal environment of other pieces. That is, it permits going beyond the usual statistical limitations of size distribution studies to what may be termed a personalized or individualized study. The purpose of this paper is to present some preliminary experiments conducted with this tool. The method employed was to mark radioactively some constituent of a feed. It is possible, of course, to consider the preparation of two lots of material of which one is radioactive and the other is not, and to blend the two ahead of the comminuting step; but to do so is open to the objection that the two preparations may not be identical. Therefore a technique has been chosen that removes this objection by merely taking out a size fraction of a comminution feed, rendering that fraction radioactive by exposure to a neutron flux, and then by returning it to Table I. Size Distribution of Offspring Albite Particles Originally 28/35 Mesh and in Admixture with Other Sizes After Grinding 2 min in a Steel Ball Mill Specific Activity ' Cumu- Corrected Distrl- latlve Size for Back- butlon In Distri- Fractlon ground, Weight, Product, button, of Product, cpm/gm g Pctb Pct Mesh (A). (W) (P) (ZP) + 28 0 56.0 0 100.1 28/35 62.6 54.0 24.8 75.3 35/48 62.8 59.4 27.7 47.6 48/65 41.1 53.0 16.2 31.4 65/100 29.6 45.7 10.2 21.2 100/150 23.7 37.0 6.6 14.6 150/200 23.3 25.1 4.4 10.2 200/270 20.1 19.0 2.9 7.3 270/400 17.8 21.2 2.9 4.4 -400 22.9 25.2 4.4 — 100.1 a These activity determinations were made in rapid succession in the order given. The specific activity (Ao) of the active 28/35 mesh fraction of the feed was measured at the beginning, after the measurement on the 65/100 mesh size fraction of the product, and; The end. The decay-corrected activities at those times were 246.7, 241.0. and 236.9 cpm per gm. The weight (W0) of the active 28/35 mesh fraction in the feed was 55.0. b Example of calculation for P in the 65/100 mesh oroduct frac- A W tion; A = 29.6, W = 45.7, Ao = 242.7, Wo = 55.0: P = — x — Ao Wo = 0.102 = 10.2 pet. the remainder of the charge for the comminution experiment. A relatively simple procedure was developed by which albite, containing sodium, was activated in the M.I.T. cyclotron. The cyclotron makes highspeed deuterons which impinge on a beryllium target, thereby producing a concentrated neutron flux. The mineral was exposed to this flux for 2 hr. This treatment changed enough of the sodium to sodium 24 (14.8 hr half-life, 1.4 mev ß) as to make detection and measurement easy. The nuclear reactions taking place were: 11Na23 (n,?) 11Na24 (irradiation) 11Na24 ß,?,? 12Mg24 (decay) The detailed technique of the experimentation was as follows: 40 kg of hand-sorted, lump albite were crushed to pass 10 mesh. After careful mixing of the lot, a screen analysis was made. The whole lot of material was fractionated on standard Tyler screens from 14 down to 200 mesh. Samples for experiments were compounded from these fractions in accordance with the screen analysis. When it was desired to make an experiment in which, for example, the 28/35 mesh size fraction was to be studied, the blend of size fractions was made as indicated above, except that the 28/35 mesh size fraction was added only after irradiation in the cyclotron. The blended charge containing the activated albite was ground for 2 min in a laboratory ball mill with a steel ball charge of controlled size distribution. The ground product was carefully sized on a set of Tyler screens in a Ro-tap. Each size was analyzed for radioactivity by the use of an end-window Geiger-Mueller counter and standard scaling circuit. This analysis was carried out in detail as follows: a 20-g sample was placed in a Petri dish, packed carefully to obtain reproducible geometric distribution with reference to the Geiger-Mueller tube, and the activity was counted for a 2-min period. Several determinations of the activity of the active size fraction in the feed were made at various times to establish the decay in activity with time. Linear interpolation was used to evaluate the activity that the active size fraction in the feed would have had at any given instant. The ratio of the observed activity in a size fraction of the product to the activity that the active size fraction in the feed would have had at the same time gives the fraction in the product size that came from the irradiated size in the feed. The general formula for finding the distribution, P, of a specific individual size fraction in the feed

Jan 1, 1952

By C. L. Sollenbeger, R. B. Greenwalt

PERHAPS the most widely used dispersants or gangue depressants in nonmetallic flotation are sodium silicates, which vary in silica-to-soda ratio from 1 to 3.75. Typical manufactured silicates in order of decreasing solubility and increasing amounts of silica are Metso, silica-to-soda ratio of 1.00; D, 2.00; RU, 2.40; K, 2.90; N, 3.22; and S-35, 3.75.* References in flotation literature1,2 to the use of sodium silicates are often weak because they fail to mention the type of silicate used. Metso and silicate N have occasionally been mentioned, but when the type of silicate is not mentioned, it is usually assumed to be N, the cheapest of the soluble silicates and the one recommended by sodium silicate manufacturers as a flotation agent. In the All is-Chalmers Research Laboratories a systematic study was made of the effect of different alkali-silica ratios on the concentration by flotation of two scheelite ores. One of these was a high grade ore from the Sang Dong mine in Korea. The effect of such factors as pH; addition agents; and conditioning time, temperature, and pulp density on the flotation efficiency of this ore have been described previously. The other ore was a low grade ore from Getchell Mines Inc., Nevada. The mineralogy and techniques of concentrating this ore have been described by Kunze. Hereafter these ores will be referred to as the Korean and Nevada ores. Experiments were made with both to determine the effect of three factors—-type of silicate, concentration of silicate, and pH of the pulp—on recovery and grade of tungsten in a rougher concentrate. Average WO, content of the Korean ore was 1.50 pct and of the Nevada ore 0.27 pct. The predominant tungsten mineral in both ores was scheelite, which was accompanied by a small amount of powellite. The powellite and scheelite were finely disseminated through both ores and required a —200 mesh grind for liberation. Major gangue minerals in the Korean ore, in decreasing order of abundance, were amphi-boles, quartz, biotite, garnet, fluorite, and calcite. Bulk sulfides composed about 3 pct of the total weight. Gangue in the Nevada ore, in descending order of abundance, was garnet, alpha quartz, calcite, phlogopite, wollastonite, and amphiboles. Sulfide minerals were 3 to 4 pct of total weight. Batch flotation experiments were made with 500-g samples of ore, each sample wet-ground to 90 pct passing 200 mesh. The finely ground ore was floated in a Fagergren batch cell at 25 pct solids. The natural pH of the Nevada ore was 8.9 and of the Korean ore, 8.5. The D, RU, K, N, and S-35 sodium silicates were obtained in colloidal dispersions with varying amounts of water. The most alkaline, Metso, was in dry powdered form. For convenience in addition, 5 pct solutions by weight were prepared from each of the silicates, on the basis of dry sodium silicate dissolved in the correct amount of distilled water. Chemical analyses of the various silicates are given in Table I, together with the pH of the 5 pct solutions. A preliminary bulk sulfide float was made with secondary butyl xanthate as the collector and pine oil as the frother. The WO] analysis of the sulfide concentrate was nearly 1 pct for the Korean ore and about 0.1 pct for the Nevada ore. The tungsten contained in the sulfide concentrate constituted about 3 pct of the total tungsten in each ore. No effort was made to recover these tungsten values. The scheelite was floated with oleic acid. Adjustments in pH were made with sulfuric acid or sodium carbonate. A 1 pct solution of 85 pct Aerosol OT was sprayed on the froth and sides of the cell during the scheelite float to aid in dispersing the minerals and to decrease the entrapment of gangue particles. Six tests were planned for each of the six types of silicate in which concentrations of 1, 2, and 4 1b of silicate per ton of dry ore were investigated at both 6.5 and 10 pH. All tests were made at room temperature. The performance of each silicate was judged from the grade and recovery of WO, in the scheelite rougher concentrate. Tungsten recovery was calculated on the basis of the scheelite remaining in the ore after the preliminary sulfide float. Testing of each silicate at three levels of concentration and two levels of pH required 36 tests with each scheelite ore. Variance analyses were performed on the concentrate grades and recoveries to determine whether or not the type of sodium silicate, the concentration of sodium silicate, or the pH significantly affected recovery or grade. Results Concentrate Grade: A variance analysis of the concentrate grades for the Korean ore showed that concentration of the silicate and pH of the ore pulp were major factors in producing a high grade concentrate. Also, the silica- to-so da ratio was important as an interaction with pH. The concentrate grade vs silica-to-soda ratio is plotted in Fig. 1. The curves show that the concentrate grade improved with an increase in concentration of sodium silicate and also

Jan 1, 1959

By G. P. Conard, E. H. Rennhack

The creep behavior of hot-rolled, hypoeutectic Zn-Ti alloys was investigated in the temperature range from 0.43 to 0.53 TM. Secondary flow was found to originate primarily from strain-induced gvain growth where grain boundary )nigvation served to relieve the strain energy of distortion introduced by slip, grain boundary sliding, and subgvain formation. The extent to which this recovery mechanism operated was determined by the ratio of grain width to the spacing between planar fibers of TiZn,, compound particles generated in these alloys during rolling. When this ratio was unity, creep resistance demonstrated a marked improvement. In this condition, which was fulfilled by annealing following rolling, structural stability was enhanced with decreasing grain size below the equicohesive temperature (-0.5Tm), while the reverse was true above this temperature. TITANIUM concentrations approaching the eutectic composition of 0.23 wt pctl have been shown to promote a significant increase in the creep resistance of rolled zinc,2 The alloying effect created with titanium is somewhat unique; a structure closely resembling that of a fiber-reinforced metal composite can be developed which selectively modifies creep strength in preference to other mechanical properties. In an earlier investigation,~ the present authors found that, while the fiber network, composed of individual TiZn,, compound particles, had a distinct influence on rolled texture, the crystallographic variations produced were of minor importance with respect to creep. Rather, creep resistance seemingly increased when the grain size appeared to coincide with the in-terfiber spacing. The work described here was undertaken to explore this effect in greater detail. EXPERIMENTAL PROCEDURE Three zinc-base alloys containing 0.05, 0.12, and 0.16 wt pct Ti were prepared from CP zinc and iodide titanium in the form of 4 by 2 by f in. chill-cast ingots. The melting and casting procedures for these alloys have been detailed el~ewhere.~ Individual ingots of each alloy were hot-rolled at 200°C (392°F) to total reductions of 10, 25, 50, 75, and 90 pct in from one to five passes, respectively, employing a 10-min reheat prior to each rolling pass. With grain, tensile-type creep specimens with a 1-in.-long, -in.-wide gage section were machined from the rolled strips for test purposes. Annealing studies to explore the influence of grain size on secondary creep flow were carried out at 400°C (752°F) in argon for times extending up to 60 min. The grain-size effect was evaluated in terms of average grain width and length values statistically derived from lineal intersection measurements.4 A similar method was applied in establishing the average interfiber spacing, i.e., average perpendicular distance between adjacent planar fibers. The creep characteristics of the alloys were investigated by means of constant-load and constant-stress creep tests. The former tests were conducted at 25°C (77°F) under an initial stress of 10,000 psi, while the latter were performed in the range from 25°C (77°F) to 90°C (194°F) at stress levels varying from 8000 to 22,000 psi. Total specimen strain, as determined with Budd HE-1161-B strain gages, was in excess of 0.10. Maintenance of constant stress was achieved through periodic load reductions made at 0.01 strain intervals to compensate for the attendant incremental reduction in specimen cross-sectional area. The maximum indicated error in the applied stress at these strain intervals was less than 3.0 pct. RESULTS AND DISCUSSION Constant-Load Creep. In an effort to clarify the in-terrelation between interfiber spacing and grain size with respect to the creep resistance of the Zn-Ti alloys, their separate effects on secondary creep rate were determined as a function of titanium content and rolling reduction. These results are set forth in Figs. 1 and 2, respectively. The average grain diameter plotted in Fig. 2 was resolved from average grain width and length values. No data are presented for reductions of less than 50 pct because of the inability to obtain consistent measurements on these strips. The curves of Fig. 1 indicated that, for a given titanium content, a decrease in interfiber spacing, as produced with increasing reduction, promoted a decrease in creep rate. Depending on titanium content, however, wide variations in creep rate occurred at the same interfiber spacing suggesting that interfiber spacing, by itself, has little or no influence on creep resistance. Grain size, on the other hand, decreased progressively with both increasing rolling reduction and titanium content, the effect of which led to a pronounced decrease in creep rate, particularly when the average grain diameter became smaller than 3.0 x 10"4 in., Fig. 2. The continuity of this relationship tended to support the view that grain size rather than interfiber spacing was predominant in controlling secondary creep. Annealing Effect. The observed dependence of creep flow on grain size suggested that a further contribution to creep resistance would result when the alloys were annealed to effect a coincidence between grain width and interfiber spacing, see Fig. 3(b). ~eiides creating an immediate barrier to grain boundary movement, annealing offered the possibility of providing increased structural stability by eliminating many high-energy, mobile grain boundaries.= To test this hypothesis, specimens from the Zn-0.16 Ti strips reduced 75 and

Jan 1, 1967

By R. C. Earlougher

Based on laboratory tests conducted with the use of fresh core samples as well as a considerable amount of field data obtained from numerous water floods in northeastern Oklahoma, it appears that for any given oil saturation there is a critical maximum velocity above which the oil-recovery efficiency falls off very rapidly. In effect, when a water flood is operated above this critical velocity, the injected water-oil ratio rises extremely fast, thus shortening the economic life of the flood and reducing the ultimate oil recovery. This critical velocity apparently varies considerably with the percentage of oil saturation of the sand, so that in effect the higher the oil saturation at the beginning of a flood the higher the velocity that can be used successfully. In reviewing several of the earlier floods in the Mid-Continent area, it is concluded that most of the failures were due to two things: (I) too low an oil saturation, such as 30 per cent, and (2) too high water-injection rates, Although considerably more field data are necessary to establish definite limits, it would seem that the proper field injection rate for a 330 by 330 or 440 by 440-ft. spacing varies from approximately I bbl. per foot of sand per day where the oil saturation is as low as 30 per cent up to 5 bbl per foot of sand per day when the oil saturation is as high as 45 to 50 per cent, Introduction With secondary recovery by water-flooding receiving more and more attention throughout the industry, a greater working knowledge of multiphase flow under field conditions becomes more and more necessary A great deal of research has been carried on in highly idealized laboratory conditions, from which certain trends have been indicated, but with few exceptions no direct application to field use has been reported. widely varying conclusions have been drawn from the mass of idealized laboratory experiments and often this divergence apparently was due to the neglect of connate or interstitial water. Since interstitial water is such an important factor in water-flooding operations, it then follows that any laboratory flooding experiment must necessarily take it into account; and since it is difficult to set up laboratory models to allow for interstitial water, the next best procedure is to use fresh core samples for such tests. Even this procedure has its difficulties, inasmuch as it is possible to run only one flooding test on each sample, as each sample differs somewhat in character from all other samples. However, this disadvantage can be overcome to a large degree by the use of an extremely large number of samples. The next question that arises is: "IS it possible to get uncontaminated core samples having a true oil and water saturation like that existing in the reservoir?" If the sand under consideration is still in the primary stage of production, with a normal or relatively high amount of gas still in solution in the oil, probably it is not possible to get a nonflushed core. On the other

Jan 1, 1943

By R. C. Earlougher

Based on laboratory tests conducted with the use of fresh core samples as well as a considerable amount of field data obtained from numerous water floods in northeastern Oklahoma, it appears that for any given oil saturation there is a critical maximum velocity above which the oil-recovery efficiency falls off very rapidly. In effect, when a water flood is operated above this critical velocity, the injected water-oil ratio rises extremely fast, thus shortening the economic life of the flood and reducing the ultimate oil recovery. This critical velocity apparently varies considerably with the percentage of oil saturation of the sand, so that in effect the higher the oil saturation at the beginning of a flood the higher the velocity that can be used successfully. In reviewing several of the earlier floods in the Mid-Continent area, it is concluded that most of the failures were due to two things: (I) too low an oil saturation, such as 30 per cent, and (2) too high water-injection rates, Although considerably more field data are necessary to establish definite limits, it would seem that the proper field injection rate for a 330 by 330 or 440 by 440-ft. spacing varies from approximately I bbl. per foot of sand per day where the oil saturation is as low as 30 per cent up to 5 bbl per foot of sand per day when the oil saturation is as high as 45 to 50 per cent, Introduction With secondary recovery by water-flooding receiving more and more attention throughout the industry, a greater working knowledge of multiphase flow under field conditions becomes more and more necessary A great deal of research has been carried on in highly idealized laboratory conditions, from which certain trends have been indicated, but with few exceptions no direct application to field use has been reported. widely varying conclusions have been drawn from the mass of idealized laboratory experiments and often this divergence apparently was due to the neglect of connate or interstitial water. Since interstitial water is such an important factor in water-flooding operations, it then follows that any laboratory flooding experiment must necessarily take it into account; and since it is difficult to set up laboratory models to allow for interstitial water, the next best procedure is to use fresh core samples for such tests. Even this procedure has its difficulties, inasmuch as it is possible to run only one flooding test on each sample, as each sample differs somewhat in character from all other samples. However, this disadvantage can be overcome to a large degree by the use of an extremely large number of samples. The next question that arises is: "IS it possible to get uncontaminated core samples having a true oil and water saturation like that existing in the reservoir?" If the sand under consideration is still in the primary stage of production, with a normal or relatively high amount of gas still in solution in the oil, probably it is not possible to get a nonflushed core. On the other

Jan 1, 1943

By R. Gibson, F. S. Turneaure

The tin deposit of Monserrat, Bolivia, consists of one major vein 1600 m in length. The ore is unusual because of the notable quantity of teallite, even though cassiterite is the principal tin mineral. The deposit, formed at shallow depth under a wide range in temperature, may be classed as xenothermal. Polished sections reveal a complex history of replacement, with low-temperature minerals deposited before high-temperature minerals. THE Monserrat mine1'2 of the Compania Minera Monserrat is located 11 km east of Callipampa, a station on the Antofagasta and Bolivia Railway some 55 km south of Oruro. The mine lies in a group of low hills on the east slope of a broad valley of northerly trend. The valley is separated from the altiplano to the west by a prominent ridge that rises several hundred meters above the surrounding country (fig. 1). Callipampa is situated a short distance west of the ridge, near the east margin of the altiplano. The elevation at Callipampa is 3700 m and at the mine 4100 m. Monserrat is near the northeast limit of what may be called the Poopo-Pazna district, an area of northwesterly trend about 25 km in length and 15 km in width. The district includes the tin-silver prospects of Poopo to the north, the zinc-tin deposits of Salvador to the southwest, and the tin-tourmaline veins of Avicaya to the south. Along the prominent ridge already mentioned, which forms the western limit of the district, there are several tin and antimony prospects including the Trinacria mine, which is famous for its fine specimens of cylindrite. Although the principal ore mineral is cassiterite, the tin deposit of Monserrat contains an unusual amount of teallite. Cassiterite occurs in part as a finely granular mixture with sulphides of iron and zinc and in part as needle tin of late hypogene age. The regional structure is dominated by broad folds typical of the Andes of Central Bolivia and similar to those of the Llallagua district. The area adjacent to the Monserrat mine is underlain by thin-bedded shale somewhat variable in color but predominantly dark grey to black. The beds strike northwest and dip at low angles southwest, forming part of the northeast limb of a major syncline. A resistant sandstone formation, which underlies the black shale, crops out along a ridge east of the mine and also accounts for the high ridge to the west that was previously mentioned. No igneous rock of any kind is found at Monserrat. The nearest intrusive bodies known are the irregular dikes and masses of quartz porphyry at Avicaya about 10 km to the south. Mine Workings The Monserrat property includes one main vein, which can be followed on the surface for 1600 m, and two or three branch veins of distinctly minor importance. The principal haulage tunnel, referred to as the San Carlos adit or level III, extends northeasterly for 1700 m, following the main vein throughout most of this distance. Above the adit, there are

Jan 1, 1951

By F. S. Turneaure, R. Gibson

The tin deposit of Monserrat, Bolivia, consists of one major vein 1600 m in length. The ore is unusual because of the notable quantity of teallite, even though cassiterite is the principal tin mineral. The deposit, formed at shallow depth under a wide range in temperature, may be classed as xenothermal. Polished sections reveal a complex history of replacement, with low-temperature minerals deposited before high-temperature minerals. THE Monserrat mine1'2 of the Compania Minera Monserrat is located 11 km east of Callipampa, a station on the Antofagasta and Bolivia Railway some 55 km south of Oruro. The mine lies in a group of low hills on the east slope of a broad valley of northerly trend. The valley is separated from the altiplano to the west by a prominent ridge that rises several hundred meters above the surrounding country (fig. 1). Callipampa is situated a short distance west of the ridge, near the east margin of the altiplano. The elevation at Callipampa is 3700 m and at the mine 4100 m. Monserrat is near the northeast limit of what may be called the Poopo-Pazna district, an area of northwesterly trend about 25 km in length and 15 km in width. The district includes the tin-silver prospects of Poopo to the north, the zinc-tin deposits of Salvador to the southwest, and the tin-tourmaline veins of Avicaya to the south. Along the prominent ridge already mentioned, which forms the western limit of the district, there are several tin and antimony prospects including the Trinacria mine, which is famous for its fine specimens of cylindrite. Although the principal ore mineral is cassiterite, the tin deposit of Monserrat contains an unusual amount of teallite. Cassiterite occurs in part as a finely granular mixture with sulphides of iron and zinc and in part as needle tin of late hypogene age. The regional structure is dominated by broad folds typical of the Andes of Central Bolivia and similar to those of the Llallagua district. The area adjacent to the Monserrat mine is underlain by thin-bedded shale somewhat variable in color but predominantly dark grey to black. The beds strike northwest and dip at low angles southwest, forming part of the northeast limb of a major syncline. A resistant sandstone formation, which underlies the black shale, crops out along a ridge east of the mine and also accounts for the high ridge to the west that was previously mentioned. No igneous rock of any kind is found at Monserrat. The nearest intrusive bodies known are the irregular dikes and masses of quartz porphyry at Avicaya about 10 km to the south. Mine Workings The Monserrat property includes one main vein, which can be followed on the surface for 1600 m, and two or three branch veins of distinctly minor importance. The principal haulage tunnel, referred to as the San Carlos adit or level III, extends northeasterly for 1700 m, following the main vein throughout most of this distance. Above the adit, there are

Jan 1, 1951

By Avnulf Muan, P. V. Riboud

The effect of Cr2O3 on melting relations of iron oxide at oxygen pressures slightly above those prevailing in contact with metallic iron has been determined. Liquidus and solidus temperatures of wüstite are raised by the addition of Cr2O3, from 1385°C for pure iron oxide to 1420°C at the peri-ledie point where wüstite, iron chromite, liquid, and gas coexist in equilibrium under the atmospheric conditions used in the present investigation (CO2/H2 = 1). It has been shown in a previous investigation1 that the liquidus and solidus temperatures of iron oxide are drastically increased by the addition of Cr2O3 under the relatively oxidizing conditions prevailing in air. This is to be expected in view of the easy substitution of cr3+ for Fe3+ in crystalline oxide structures which are stable at high oxygen pressures, as demonstrated for instance by the completeness of the solid solution series Fe2O3-Cr2O3 at high temperatures (>1000°C). The stable phase of iron oxide at oxygen pressures approximating those prevailing when metallic iron is present is wüstite. This phase, although commonly represented by the simplified formula FeO for sake of convenience, in reality has a defect structure in which a part of the iron ions are present as Fe3+. It is to be expected that at least a limited amount of cr3 ions will substitute for Fe in this structure when Cr2O3 is added to wüstite. Depending on the ease of this substitution in comparison with that of cr3 substitution for Fe in iron oxide-Cr2O3 liquids under the same atmos- pheric conditions, the liquidus and solidus temperatures of wüstite may increase or decrease upon addition of Cr2O3. The methods of establishing these melting relations and the results obtained are presented in the following. I) EXPERIMENTAL METHOD 1) General Procedure. The quenching technique was used in this study. Oxide mixtures were heated at chosen constant temperatures in an atmosphere consisting of equal parts of CO2 and H2 until equilibrium was established among gas and condensed phases. The samples were then quenched in mercury to room temperature, and the phases present were determined by microscopic and X-ray investigation. 2) Preparation of the Mixtures. Starting mixtures were prepared by weighing and thoroughly mixing Fe2O3 and Cr2O3, or wüstite and Cr2O3. The Fe2O3 and Cr2O3 used were "Baker Analyzed" reagent grades, whereas wüstite of composition was synthesized by reducing Fe203 at 1325°C in an atmosphere consisting of equal parts of CG andHz. In order to avoid contact with crucibles, the equilibration runs were made with small pellets suspended from thin (-0.004-in.) platinum wires. Mixtures made from FOs and Cr203 were readily pelletized at a pressure of 500 atm in a 9.5-mm die, whereas mixtures made from wüstite and Cr203 when treated identically were too weak for handling. In order to obtain a stronger product, these pellets were sintered by heating for 2 min at -1200°C in the same atmosphere as was subsequently used for the equilibration runs (CG/H2 = 1:1). During the sintering, these pellets were wrapped in thin (0.0004-in.) platinum foil, which was stripped off before the equilibration runs. In order to reduce the time needed for equilibrium to be attained, preliminary equilibration of relatively large pellets of each mixture was carried out at -1200°C for 4 to 12 hr. Smaller pellets

Jan 1, 1964

By G. H. Kesler, J. E. Oberele, C. E. Dryden, J. H. Oxley

Heat-transfer rates were measured in a model of a multifilament vapor-deposition bulb fo the preparation of high-purzty metals. Local transfer coefficients for heat transfer frow the filaments to the circuates process stream were determined as a functiol of gas flow rates and bulb, inlet, and filament, geowzetvies. These results a-e then convertted to n mass-t7,ansfer basis to provide a method of correlating vapor-deposition rates and to predict the performance of commercial urzits. The firm1 cor?,elating equation for mass transfer was found to be- wheve k, is the mass-transfer coefficient; D, is bze gas difficsivity : P is the system pressure; R is the gas constant; T is the gas temperature; Df, DB, and Di ave tlze diameters of the filament, bulb, and inlet, respectively; k is the gas conductivity; C, is the specific heat of the gas, M is the wzolecular zleight of the gas; Npr . N,,, NRe a7'e the Prandtl, Schmidt, and Reynolds numbem of the system, respectively; LB is the height of the bulb; and SB and Sf are the total suyiace area of the bulb and filaments, respectively. ONE of the more conventional methods of preparing very high-purity metals is the vapor deposition of the metal upon heated filaments. The reactions which can be employed in such a process generally fall into two classes: 1) Pyrolysis of a volatile metal compound. Generally because of their instabilities, metal iodides are used; however, other metal halides and hydrides have been employed. These processes are frequently carried out under vacuum conditions, and the filaments are maintained at high temperatures. 2) Hydrogen reduction of a volatile metal compound. A metal chloride is normally the preferred feed for these processes, but other halides are sometimes used under special conditions. These hydro- gen-reduction processes are usually operated at atmospheric pressure. Many of the current processes for the production of semiconductor materials are actually vapor-deposition processes. However, the vapor-deposition process itself is relatively old, and almost all metals can be prepared in a state of very high purity by the use of vapor-deposition techniques. Loonam has recently given an excellent review of the iodide process for metal deposition,' and Owen has started some detailed studies with a carbonyl system.' A more general treatment of all vapor-deposition processes has been outlined by Powell, Campbell, and Gonser.3 Despite the fact that vapor-deposition techniques have been employed since 1890, there is a surprising lack of fundamental information regarding the transport characteristics of even the simplest deposition system, the heated filament. The purpose of the investigation described in this paper was to extend some of the earlier data obtained at Battelle to predict deposition rates and the uniformity of deposition in large-diameter, multifilament deposition bulbs under forced convection conditions.4'5 A number of other investigators have already presented a simplified treatment of the deposition process under non-flow conditions, i.e., pure diffusion.6"9 To obtain information on the transport characteristics of a deposition bulb, a model of a typical plant deposition unit was constructed, and local heat-transfer coefficients from the filaments to a circulating air stream were determined under various conditions of air-flow rates and bulb, inlet, and filament geometries. These results were then converted to a mass-transfer basis, and consequently provided a method to correlate experimental vapor-deposition rates and to design commercial deposition units. EXPERIMENTAL WORK Description of Model. The apparatus which was used in this work was a scaled model of one type of deposition bulb. It was constructed of Lucite and was easily altered to give several combinations of diameter of bulb liner, inlet size and location, number of filaments, and outlet geometry. The model is shown in Figs. 1 and 2. The bulb shell was made octagonal for convenience in construction and observation, and the bulb liners were cylindrical. Air, introduced through one of several different jet inlets, was used as the test fluid in these model studies. Filaments for deposition of metal were simulated by metal rods 1/4-in. in diam. Two of the rods could be heated by passing electrical current through them ¦ while the remaining rods could not be heated. This procedure minimized the amount of heat which was

Jan 1, 1962

By T. P. Chen, F. W. Bowdish

Studies made with a captive bubble apparatus on the sulfidization and collection by amyl xanthate of true chrysocolla specimens have defined the ranges of pH value and sulfide concentration which permit contact between the bubble and the mineral surface. Titanium compounds were the most effective of the materials found to activate the sulfidization of chrysocolla. With titanium activation, the contact angles and the ranges of pH value and sulfide wncentration giving bubble contact were all increased. Chrysocolla ores were concentrated by flotation. Chrysocolla ores occur at many localities in grade and quantity sufficient to make mining and millin feasible, but no satisfactory method of concentratio has been found. Although chrysocolla may be leached with acid, only those ores without acid-consuming gangue may be leached economically. Because of its potential importance, a study of the conditions nece sary for flotation of chrysocolla has been carried ou The literature contains a few references to flotation of chrysocolla. Two methods were developed by the U. S. Bureau of Mines.1,2 The first consisted of a fatty acid soap and a high xanthate as collectors of chrysocolla from a synthetic ore, while the second involved the use of hydrogen sulfide and xanthate. Ludt and DeWitt3 demonstrated the difference in adsorptive powers of chrysocolla and quartz for bas triphenyl methane dyes and suggested the use of butyl, hexyl or octyl-substituted malachite green as collector. Jackel4 emphasized the effects of combin tions of reagents such as Aerofloat 31, pine oil, and Reagents 404 and 425 with sodium sulfide and zinc hydrosulfite as conditioning agents. Although he reported recoveries of 89% from a synthetic ore and 98% from a natural ore containing azurite, malachite, chalcopyrite and chrysocolla, careful application of Jackel's method to chrysocolla from Tyrone, N.M., failed to give a high recovery. MATERIALS AND TECHNIQUE Samples from Inspiration, Ariz., and Tyrone and Magdalena, N. M., were used for experimentation and verified as true chrysocolla by leaching tests, specific gravity tests and X-ray diffraction. Chrysocolla does not dissolve at pH 4, although malachite and azurite do. Chrysocolla is about half as dense as the copper carbonates. X-ray diffraction analyses by the powder camera method confirmed the samples as true chrysocolla. A captive bubble apparatus, which cast an enlarged image of the air bubble and the mineral surface upon a screen, was used to check on the character of the surfaces. The specimens were prepared by grinding a flat surface on a glass plate using fine abrasive; then they were washed and kept in distilled water until they were to be treated with reagents. Before each reagent treatment, the specimen was carefully checked for cleanliness in the captive bubble apparatus. It was assumed that the surface was clean if, after fine grinding and washing of the specimen, the bubble would not stick. Specimens were handled with glass forceps, and precautions were taken to avoid contamination of the mineral surfaces. Contact angle measurements were carefully made several times on each treated specimen to obtain reliable average values. EFFECT OF pH VALUE AND SODIUM SULFIDE CONCENTRATION In each experiment, a specimen with a freshly ground surface was immersed for 10 min in a solution of sodium sulfide, washed and immersed for 15 min in a solution containing 30 mg per 1 of potassium amyl xanthate. The specimen was then washed again in distilled water and tested for contact angle in the captive bubble apparatus while submerged in distilled water. In this series of experiments, the pH of the sulfidizing solution was varied from 3 to 7, and the concentration of sodium sulfide, containing 60% Na2S, was varied from 50 to 650 mg per 1. Many combinations of pH value and sulfide concentration resulted in no contact between the bubble and the surface, but over a limited range of conditions, contact angles varying from 24ºto 52ºwere obtained. The data in Fig. 1 show sulfidization conditions that lead to bubble contact and those that do not. The region of contact is surprisingly small, which may indicate why flotation of chrysocolla involving sulfidization has proven so difficult in practice. Several features of the system are illustrated in Fig. 1. In the region between pH values of 4 and 6 with sodium sulfide concentrations below about 350

Jan 1, 1963

By C. E. Hottman, R. K. Johnson

Fluid pressure within the pore space of shales can be determined by using data obtained from both acoustic and resistivity logs. The method involves establishing relationships between the common logarithm of shale transit time or shale resistivity and depth for hydrostatic-pres-sure formations. On a plot of transit time vs depth, a linear relationship is generally observed, whereas on a plot of resistivity vs depth, a nonlinear trend exists. Divergence of observed transit time or resistivity values from those obtained from established normal compaction trends rinder hydrostatic pressure conditions is a measure of the pore fluid pressure in the shale and, thus, in adjacent isolated permeable formations. This relationship has been empirically established with actual pressure measurements in adjacent permeable formations. The use of these data and this method permits the interpretation of fluid pres.rure from acoustic and resistivity measurements with an accuracy of approximately 0.04 psilft, or about 400 psi at 10,000 ft. The standard deviation for the resistivity method is 0.022 psi/ft, and for the acoustic method 0.020 psi/ft. Knowledge of the first occurrence of overpressures, and of the precise pressure-depth relationship in a geologic province, enab1es improvements in drilling techniques, casing progroms, completion methods and reservoir evalzmtions. INTRODUCTION CENKRAL STATEMENT Operators engaged in the search for and production of hydrocarbon reserves in Tertiary basins are more and more frequently confronted with complications associated with over pressured (abnormally high fluid pressure) formations. This is particularly true in the Texas-Louisiana Gulf Coast area. The problems associated with these formations are of direct concern to the combined activities of all phases of operations, i.e., geophysical, drilling, geological and petroleum engineering.' - Knowledge of the pressure distribution of a given area of operations would greatly reduce the magnitude of many of these complexities and in some cases would completely eliminate specific problems. his pape; presents techniques developed for estimating formation pressures from interpretations of acoustic and electric log data. Specifically: the acoustical and electrical properties of shales, reflected by conventional acoustic and electrical surveys, can be used to infer certain reservoir properties, such as formation pressure, at any level in a well. It has been possible to develop these techniques because of a firm understanding of the basic principles that govern and apply to such overpressured provinces. NORMAL PRESSUKES Normal pressures refer to formation pressures which are approximately equal to the hydrostatic head of a column of water of equal depth. If the formations were opened to the atmosphere, a column of water from the ground surface to the subsurface formation depth would balance the formation pressure. On the Gulf Coast, the shallow, predominantly sand formations contain fluids which are under hydrostatic pressure. These formations are said to be normally pressured or to have a normal pressure gradient.* Experience has shown that the normal pressure gradient on the Gulf Coast is approximately 0.465 psi/ft of depth. OVERPRESSURES Formations with pressures higher than hydrostatic are encountered at varying depths in many areas. These formations are referred to as being abnormally pressured, abnormally high pressured, or overpressured. Formation pressures up to twice the hydrostatic pressure have been observed. These formations require extreme care and much expense to drill and to exploit. COMPACTION-FLUID PRESSURE RELATIONS THEORY The generation of overpressured formations in Tertiary sections of the Gulf Coast and several other Tertiary sedimentary basins is, in general terms, considered to be primarily the result of compaction phenomena.' This portion of the paper presents a brief review of the theory which associates compaction and fluid pressure relations, and should thus provide the necessary background for an understanding of the techniques presented. See Hubbert and Rubey' for a more comprehensive treatment of this subject. The theory of the consolidation of a water-saturated clay' has been well established by workers in soil mechanics. The concept is explained by a model with perforated metal plates separated by metal springs and water and enclosed in a cylindrical tube. Fig. 1 is a schematic representation of such a model (see Ref. 5, Fig. 27, page 74). The springs simulate communication between clay particles, and the plates simulate the clay particles. Mano-

Jan 1, 1966

By Z. F. Oszter

This paper discusses the materials handling problems encountered in cement plants in the areas of raw and finished product grinding and cement storage. It illustrates by examples taken from actual installations, how optimum feed rate is maintained in grinding circuits with properly applied bin dischargers (vibrating hoppers, Mexican feed boxes and aerated bin bottoms) for materials with high moisture content and/or difficult handling characteristics. Initial operating problems with the equipment will be discussed and maintenance requirements will be indicated for comparison purposes. In a modern cement plant, properly functioning bins and feeders are as essential as process control, for no process control system, however sophisticated, can perform efficiently if raw materials do not flow into the plant processing facilities at the required time and rate. Most materials used in the manufacture of portland cement - such as silica sand, iron ore fines, crushed limestone, gypsum, clinker or cement itself-have difficult handling characteristics under specific conditions. High moisture content or even dampness due to condensation may create bin hang-ups, arching and ratholing, all of which result in improper functioning of the feeders or proportioning equipment. The occurrence of these problems in existing cement plants spurred a search for the corrective devices discussed in this article. The equipment investigated included bin dischargers in the form of vibrating hoppers for moist raw materials, Mexican feed boxes for clinker and aerated bin bottoms for cement. Operating experience with different types of bin dischargers showed that the actual performance of some did not come up to the expected level under prevailing operating conditions. The aim of this paper is to record the results of this experience and there- by aid designers and/or operators in selecting the most suitable equipment for their requirements. BIN DISCHARGERS (GENERAL) A discharger is a device that causes stored solids to flow out of a hopper without metering the rate of flow as a feeder does. The investigation discussed here encompasses the following types of bin dischargers used in a cement plant: (1) vibrating hoppers (horizontal motion), (2) whirlpool hoppers (horizontal and vertical motion), (3) aerated bin bottoms (air fluidization), and (4) Mexican feed boxes. Most of the bins used in the cement industry are of the plug flow type. Raw materials with difficult handling characteristics such as high moisture content may cause flow problems when fed through small openings (12 x 18 in.), even if two walls of the bin are vertical.' The most appropriate solution to these flow problems would be the installation of separate mass flow bins for the different materials such as silica sand, iron ore fines, crushed limestone and gypsum, with each bin correctly designed from test data obtained by measuring the flow properties of representative samples. However, limited storage capacity and plant space usually preclude this approach. Quantitative design of bins for flow based on measured flow properties of representative samples of the bulk solid to be handled is no longer an "engineering art," thanks to the basic research done on the flow of bulk solids in bins during the last decade.2, Where space limitations exist, however, or where improvements are being sought for equipment already installed, bin dischargers offer a satisfactory solution to flow problems. They can be applied effectively under flat-bottom bins or mounted to existing plug-flow bins with very little modification to these facilities. In both the foregoing cases, plug flow will be maintained, but the flow channel will be considerably increased so that it is larger than the discharger's bin-side diameter, and material flow can be sustained if the discharger is correctly selected. The main purpose of a bin discharger is to draw the bulk solids across the whole area of the bin outlet, to make the opening fully effective. As long as the bin-side opening of the discharger is large enough

Jan 1, 1969

By P. G. Winchell, A. J. Heckler

An experimentally simple method for determining the effect of alloying elements on the activity of carbon is validated in Fe-Ni-C austenite. The technique consists of the equilibration of carbon between specimens of different nickel contents within a sealed silica capsule. The attainment of carbon equilibrium within each capsule is evidenced by: 1) in each capsule specimens of the same nickel content attained the same final carbon content regardless of their initial carbon contents, 2) in every capsule the final carbon content was reached for most nickel contents by carburizing and by decarburizing. The activity of carbon attained within each capsule was calculated from the carbon content of a binary Fe-C alloy placed within the capsule, and from the activity coefficient of carbon in the Fe-C system as found by Smith for CO/CO2/C equilibrium. The activity of carbon in Fe-Ni-C austenite determined by this method at 1000°C agrees with prior work by Smith, who used mother method. The measurements are extended to 800°and 1200°C. The activity coefficient of carbon 7c, in Fe-Ni-C austenite is given by: where xC is the ratio of carbon to metal atoms and XNi is the ratio of nickel to metal atoms and where the standard state is chosen such that yC = 1 as xc approaches zero in Fe-C alloys. This equation appears to be valid for xni < 0.3, and 1073° < T<1473°K. ThE activity of carbon in Fe-C austenite has been measured by smithL at 800°, 1000°, and 1200°C. Smith has also studied the effect of nickel on the activity A. J, HECKLER and P. G. WINCHELL are Graduate Student and Associate Professor of Metallurgical Engineering, respectively, School of Metallurgical Engineering, Purdue University, Lafayette, Ind. This paper is based on a thesis submitted ty,to Purdue University, in partial fulfillment of the requirements for the degree of M.S. in Metallurgical Engineering which A. J. HECKLER received from Purdue in January 1962. Manuscript submitted August 13, 1962. IMD of carbon in austenite at 1000°C. In both these studies the activity of carbon was fixed by a flowing CO-C02* *Gas mixtures of hydrogen and methane were also used in Ref. 1 but these results are not incorporated in Ref. 2 or in the present study. gas mixture. In the present work, Smith&apos;s results for Fe-Ni-C austenite are confirmed and extended to 800" and 1200°C by a different experimental technique. EXPERIMENTAL PROCEDURE In essence the experimental technique consisted of enclosing specimens of various nickel contents in an initially evacuated silica capsule and annealing the capsule until carbon equilibrium was attained among the enclosed specimens. The carbon activity obtained within the capsule was determined from the final carbon content of the binary Fe-C alloy included in each capsule and the results of smith.&apos; In order to evaluate this method the absence of nickel transfer between specimens must be established and the attainment of carbon equilibrium between samples must be assured. The absence of nickel transfer was demonstrated in the case of an originally pure iron sample which was annealed at 1200°C in a capsule with a 27.3 at. pct Ni alloy. The final nickel content of the iron specimen was less than 0.1 at. pct, a change which has a negligible effect on carbon activity. The attainment of carbon equilibrium was demonstrated within every capsule and in over half the results by achieving the same final carbon content in a sample which carburized during equilibration and in a sample of the same nickel content which decarburized during equilibration. The base Fe-Ni alloys were vacuum melted from Ferrovac E or electrolytic iron and Mond or electrolytic nickel. The samples were rolled and/or swaged and their carbon content adjusted to the desired pre-equilibration level either by methane-hydrogen carburization or by direct carbon transfer from a graphite source in a sealed silica capsule. As mentioned previously, high-carbon and low-carbon samples were prepared for most nickel levels in each capsule. The specimens were cleaned and

Jan 1, 1963

By J. C. Sarace, S. M. Sze, C. R. Crowell

Thin films of tungsten 077 n-type germanium, silicon, and gallium arsenide were obtained by reacting tungsten hexafluoride with the semiconductor surface in an argom atmosplrere at temperatures between 325° and 400° C. Capacity-voltage, current-iloltage, and photoelectric measurements were used to investigate the characteristics of the tungsten -semiconductor diodes thus Produced. The junctions are shown to he very close to ideal Schottky barlp/ers with barrier heights measured with respect to the Fermi energy of 0.18, 0.65, and 0.78 1.1 jar W-Ge, W-Si, and W-GaAs, respectively. The electrical properties of the W-Si interface show no deterioration when heated to 1000°C in dry forming gas for 5 min. A theoretical value of the Richardson constant, A, appropriate to the semiconductor-hand structure has been used in evaluating the current-voltage characteristics. ThE W-Si surface-barrier diode was initially proposed for investigation because the eutectic temperature with silicon (1400°C) is much higher than that in the Si-Au system 1370°C).1 This would permit more flexibility in heat treatment and possibly provide greater reliability at elevated temperatures. The lower work function of tungsten (4.54 ev)2 compared with that of gold (4.78 ev)3 also suggested that a lower barrier height would be obtained with tungsten and hence a lower forward bias and lower minority carrier injection ratio for a given current density. The investigation was extended to include the characterization of W-Ge md W-GaAs surface-barrier diodes. The tungsten films have been produced by reacting WF6 with germanium, silicon, and GaAs surfaces in an argon atmosphere at temperatures from 300° to 500°C.4 This process is a very satisfactory alternative to the relatively difficult process of evaporating tungsten films in vacuo. To ensure an adequate electrical characterization of the tungsten-semiconductor interface, three types of barrier-height measurements have been performed. The mutually consistent results obtained lead to the conclusion that the tungsten-semiconductor junctions are indeed of the Schottky type. EXPERIMENTAL PROCEDURE The apparatus used for producing tungsten films is shown schematically in Fig. 1. It consists of an argon carrier gas line to which metered amounts of tungsten hexafluoride can be rapidly added. The mixture passes through a heated reaction tube containing the semiconductor slices and is exhausted to a hood. The argon is purified by passage through a 6-in. column of titanium turnings maintained at 800°C. The tungsten hexafluoride dispensing arrangement was designed by V. C. Garbarini and W. R. Bracht.4 A measured amount of liquid tungsten hexafluoride is injected into the argon stream and vaporizes. The mixture passes through a sodium fluoride absorption cell to remove traces of hydrogen fluoride, then into the nickel reaction tube. The tube is 12 in. long with an inside diameter of 1/2 in. The center section is heated by a furnace of the self-supporting wire-filament type. It was chosen for its rapid heatup and cooling. The wall thickness is 10 mils except for a 3-in. hot zone which is 30 mils thick to reduce thermal gradients along the length. The samples to be coated are placed on a sapphire plate and centered in this section. The tungsten is deposited with the following sequential steps: the loaded reaction tube is flushed with argon at a rate of 500 cu cm per min and heated to 370°C. Then 0.45 g of liquid tungsten hexafluoride is injected into the argon stream. The samples are held at this temperature for 2 min. The tube and samples are then cooled to room temperature and the samples removed. Tungsten films were grown on (111) faces of silicon and germanium polished with Linde A abrasive and lightly etched with HF-HNO3. The GaAs surfaces were (100) faces chemically polished with a H2SO4-H2O2 solution. The films have typical sheet resistances of 0.2, 8, and 15 52/0 when grown on germanium, silicon, and GaAs, respectively. After the tungsten deposition, ohmic contacts were alloyed on the back surfaces of the wafers. Ohmic contacts to the germanium and silicon were obtained by alloying Au-Sb at 370°C, ohmic con-

Jan 1, 1965

By Y. Kondo, S. Yamazaki, Z. Asaki

Thermal deco7nposition of Pyrite particles in a fluidized bed with inert gas stream was studied. Assuming that heat transfer from the surroundings to the fluidized particles controls the overall decomposition rate, rate equations for the batch process and for the continuous process were derived. In the batch experiment, a linear rate equation satisfies the experimental results and the overall heat transfer coefficient calculated from the rate constant agrees fairly well with that obtained by Leva.l1 For the continuous process, two rate equations were derived, one on the assumption of complete mixing of particles and another on the upward piston flow of particles in a fluidized bed. The former holds for a bed containing a higher fraction of decomposed pyrite realized at lower feeding rates. The latter can be applied for a bed at higher feeding rates. Thus, segregation of particles in the fluidized bed was indicated at higher feeding rates. Bed temperatures also correspond to these conditions. ThERMAL decomposition of pyrite may be represented by Eq. [I]. The pressure of diatomic sulfur gas reaches 1 atm at about 690°C. The thermodynamics,&apos; kinetics,2&apos;3 composition, and properties3-5 of decomposed products of such a reaction have been studied. Pyrite is a very common sul-fide mineral and is often accompanied with other sul-fides. It is of basic interest in nonferrous metallurgy to clarify the behavior of pyrite in the pyrometallur-gical processes of sulfide minerals of metals such as copper, lead, zinc, nickel, and so forth. Interest in this reaction increased recently because of possible elimination of arsenic from pyrite in processing highly purified iron oxide pellets. Producing elemental sulfur from pyrite, instead of sulfuric acid, also aroused interest in this reaction. It is indicated that the thermal decomposition of solid particles, such as calcium carbonate, proceeds through three major sequential steps: heat transfer, interfacial chemical reaction, and mass transfer.637 It is known that the decomposed product of pyrite is very porous2, 3 and the diatomic sulfur gas evolved can easily escape through this layer of decomposed product. It depends upon the circumstances, therefore, whether the heat transfer to the interface within particles or the chemical reaction at the interface determines the overall decomposition rate. The enthalpy change in the decomposition of pyrite is about 33 kcal per mole FeS2 which is comparable to that of calcium carbonate. The decomposition of calcium car- bonate becomes more and more dependent on the rate of transport of heat when reaction temperature increases, such as occurs in a fluidized bed.6&apos;7 It is reasonable to presume, therefore, that the thermal decomposition of pyrite, an endothermic process, carried out in a fluidized bed may be analyzed according to the heat transfer controlling model. This work intends, first, to propose a mathematical model that determines the overall rate in a fluidized bed for the decomposition process and, second, to investigate a few characteristics of the fluidized bed based upon the experimental results obtained. KINETICS OF THERMAL DECOMPOSITION IN A FLUIDIZED BED It is intended in this section to obtain rate equations for thermal decomposition of pyrite in a fluidized bed by assuming that the overall rate is determined by heat transfer from the surroundings to the particles. Both batch and continuous processes are considered. 1) Batch Process. To obtain the rate equation in the batch process, the following two additional assumptions are made. First, the temperature of preheated inert gas, tg, blown into the fluidized bed is assumed to be the same as the temperature of the fluidized bed, tf. Thus, no heat exchange occurs between the gas and particles in the bed and only the heat transfer from the reactor wall kept at tw to the particles is to be considered. Second, the decomposition is assumed to start at the outer surface of the particles and to proceed toward the center. At any given time during decomposition, undecomposed pyrite remains in the tori at a temperature: td. The decomposed shell is composed of FeS1+x whose outer surface is at tp Diatomic sulfur gas evolving at the interface is heated to tf during its escape through the decomposed shell. This is illustrated in Fig. 1. With the above-mentioned assumptions of heat transfer, we have:

Jan 1, 1969