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By I. R. Kramer

In his technical note entitled "Specimen Temperature During Electropolishing of Aluminum Crystals" Dr. Nakada 1 reported that the temperature of his aluminum specimen increased 65°C when it was polished electrolytically; he therefore concluded that the temperature of the specimens used in our work (Nakada's Refs. 4 and 5) similarly increased by this amount. From this he further concluded that the change in plastic-flow characteristics associated with the removal of the surface by electropolishing during deformation were due solely to a temperature effect. We believe that these conclusions are not justified. It is, of course, realized that the amount of the temperature increase is associated with the total heat transfer of the entire system, including the efficiency of the stirring action, heat flow through the grip on the specimen, and so forth. Of great importance is the type of electrolyte used for polishing. For example, in Dr. Nakada's experiment a methanol-perchloric acid solution was used. This solution has a relatively low conductivity and for the current densities of 0.3 amp per sq cm the electrical input appears to be 30 to 40 w. In our research a methanol-nitric acid solution was employed and for the size of specimen employed by Dr. Nakada the power never exceeded 7 w. There are major differences in his test apparatus which also appear to affect the temperature rise. In our case a steel specimen holder was used in order to provide a good heat sink and conduction path. The cathode was a coiled aluminum tube through which a coolant was passed to provide additional cooling capacity near the specimen. The stirrer was placed in a position to obtain maximum cooling efficiency. On the other hand Dr. Nakada used a teflon grip to support the specimen at one end only and a flat copper cathode, thus providing a much less efficient heat sink as compared with the metal grips used in our studies. The relationship between current density and the temperature increase for two sizes of aluminum crystals tested in our tensile apparatus is shown in Fig. 1. The temperature measurements were determined from a thermocouple spot-welded to the surface of the specimen. The thermocouple was protected from the acid by means of a thin film of stop-off lacquer which covered just the outer surface of the thermocouple junction. Whereas Dr. Nakada reported a time delay of 8 min to obtain thermal equilibrium, our temperature change occurred in less than 15 sec. This emphasizes the importance of the heat transfer in the entire system. However, readings were taken over a period in excess of 5 min to assure thermal equilibrium. The data given in Fig. 1 were also confirmed by determining the thermal expansion of the specimen in a sensitive creep apparatus. As may be seen, for the smaller specimen the increase in temperature is 8°C for a current density of 1.5 amp per sq in. The majority of our data on the effects of surface removal on the plastic behavior of aluminum were obtained at current-density values at or below this value. Above 1.5 amp per sq in. the temperature rise is uncertain; for under certain conditions, especially in the vicinity of 2 amp per sq in., the anode can become polarized and the current flow is erratic. This condition is easily recognized because wide fluctuations in the creep and stress-strain data make it virtually impossible to obtain reliable results, a condition which was always avoided in our work. The temperature increase for the larger specimen is less than that of the smaller specimens below a current density of 1.5 amp per sq in. At a current density of 2 amp per sq in. the temperature increased 13°C. The above temperature data are in accord with observations made during creep experiments. Using a transducer capable of detecting strain in the order of 10 -6, temperature changes in excess of 8°C were not detected when the current density was increased to as high a value as 1.5 amp per sq in. Finally we wish to point out that our experimental data cannot be explained solely in terms of a heat effect. For example in Fig. 1 of Ref. 2, the change in slope of Stage II as a function of the rate of re-

Jan 1, 1965

By P. A. Laxen, H. R. Spedden, A. M. Gaudin

WHEN a mineral particle is fractured, bonds between the atoms are broken. The unsatisfied forces that appear at the newly formed surface1 are considered to be responsible for the adsorption of ions at the mineral surface. A knowledge of the mechanism and extent of ion sorption from solution onto a mineral surface is of interest in the development of the theory of flotation.2,3 Study of the adsorption of sodium from an aqueous solution on quartz offers a simple approach to this complicated problem. The availability of a radioisotope as a tracer element meant that accurate data could be obtained.4,5 Three main factors which appeared likely to affect the adsorption of sodium are: 1-concentration of sodium in the solution, 2-concentration of other cations in the solution, and 3-anions present in the solution. Hydrogen and hydroxyl ions are always present in an aqueous solution. By controlling the pH, the concentration of these two ions was kept constant. The variation in the amount of sodium adsorbed with variation in sodium concentration was then determined under conditions standardized in regard to hydrogen ion. The effect of concentration of hydrogen ions and of other cations was also measured. A few experiments were made to get a preliminary idea on the effect of anions. The active isotope of sodium was available as sodium nitrate. Standard sodium nitrate solutions were used throughout these experiments except when the effects of other anions were studied. It was found that sodium adsorption increased with sodium-ion concentration, but less rapidly than in proportion to it. Increasing hydrogen-ion concentration, or conversely decreasing hydroxylion, brings about a comparatively slight decrease in sodium-ion adsorption. Increasing the concentration of cations other than hydrogen or sodium decreases somewhat the adsorption of sodium ion. It would appear as if the kind of anion is a secondary factor in guiding the amount of sodium ion that is adsorbed. Materials and Methods Quartz The quartz was prepared as in previous work in the Robert H. Richards Mineral Engineering Laboratory4 except for the refinement of using de-ionized distilled water for the final washing of the sized quartz, prior to drying5 To minimize the laborious preparation of quartz, experiments were made to determine whether the sodium-covered quartz could be washed free of sodium and re-used. The experiments were successful as indicated by lack of Na' activity on the repurified material and by its characteristic sodium adsorption. Table I gives the spectrographic analyses of the quartz used. The quartz ranged from 16 to 40 microns in size, averaging about 23 microns (microscope measurement), and had a surface of 1850 sq cm per g (lot I), 2210 (lot II) and 2000 (lot III) as determined by the Bloecher method.6 Radioactive Sodium Method of Beta Counting for Adsorbed Sodium: Na22, the radioisotope of sodium, possesses convenient properties.7 It has a half-life of 3 years, thus requiring no allowance for decay during an experiment. On decay it emits a 0.575 mev ß radiation and a 1.30 mev ? radiation. The decay scheme is illustrated in the following equation: [Y Nam S. - 'Net 3 years] The ß radiation is sufficiently strong to penetrate an end-window type of Geiger-Mueller counting tube. This, in turn, makes it possible to use external counting, a great advantage in technique. Furthermore, it permits the assaying of solids arranged in infinite thickness, while assaying evaporated liquors on standardized planchets. The equipment used was standard and similar to that employed by Chang8 The original active material was 1 ml of solution containing 1 millicurie of Na22 as nitrate. This active solution was diluted to 1000 ml. Five milliliters of this diluted active solution was found to give a quartz sample a sufficiently high activity for accurate evaluation of the sodium partition in the adsorption measurements. Also, 1 ml of final solution gave a sufficiently high count for precision on the liquor analyses. The sodium concentration of the diluted active solution was 1.2 mg per liter, so that 6 mg of sodium for 60 ml of test solution and 12 g of quartz was the minimum amount used. The active solution was stored in a Saftepak bottle. Procedure for Adsorption Tests: The method consisted of agitating 12 g of quartz with 60 ml of solution of known sodium concentration for enough time to establish equilibrium between the solution and the quartz surface. The quartz was separated as completely as possible from the solution by filtering and centrifuging. The activity on the quartz and in the equilibrium solution was measured and the partition of the sodium was calculated from the resulting data. The detailed procedure for the adsorption test is set forth in a thesis by Laxen5 In brief, it included the following steps: 1-Ascertainment of linearity between concentration of Na22 and activity measured. 2-Evaluation of factor to translate activity on solid of infinite thickness in terms of activity on an evaporated active film of minute thickness, on the various shelves of the counter shield. 3-Taking precautions to avoid evaporation of water during centrifuging.

Jan 1, 1952

By W. Mckewan, W. M. Fassell

The oxidation rates of copper have been determined at temperatures from 600" to 900°C in oxygen from 14.7 to 400 psi total oxygen pressure. The oxidation rate of copper is unchanged by oxygen pressures within the range studied. The observed data extend Feit-knecht's conclusion concerning the pressure independence of copper from atmospheric pressure to 400 psi. All samples studied in the above-mentioned temperature and pressure range have both Cu2O and CuO present in the oxide film. NUMEROUS papers have been published on the oxidation of copper, some of which have noted the effect of oxygen pressure on the oxidation rate of copper. It must be noted, however, that no data on the oxidation rates of copper at pressure in excess of 1 atm have been reported in the literature. (Le Chatelier¹ reported that a black oxide of silver was formed at 300°C and 15 atm pressure.) This is likewise true for the other metals. This investigation was initiated to obtain experimental oxidation rate constants for pure metals at elevated temperatures and high oxygen pressure. Copper was selected as the first metal since probably more reliable data are available on its oxidation rates and related physical and chemical properties than for any other metal or alloy. As a general summary, the following conclusions appear well established for the oxidation of copper: 1—The oxide coating consists of Cu2O with a superficial coating of CuO providing the ambient oxygen pressure exceeds the equilibrium pressure for the coexistence of Cu2O and CuO.² The following sequence of phases is then Cu/Cu2O/CuO/O2 (gas). The Cu2O consists of large crystals that have no relation to the orientation of the metal crystals, except for a very thin layer adjacent to the metal." The CuO consists of very fine crystals randomly oriented. If the oxygen pressure is below the equilibrium pressure for the coexistence of Cu2O and CuO, the coating consists of Cu,O only. 2—The rate-determining factor in the parabolic oxidation of copper is the diffusion of Cu+ ions through the Cu,O layer.4,6,7 The Cu+ ions are accompanied by electrons to maintain electrical neutrality. The mechanism of the reaction at the Cu2O/CuO interface and the method of growth of the CuO is in some doubt. 3—On copper, there are three reported pressure effects: (a) At pressures below 0.3 mm Hg oxygen pressure, the oxidation rate increases directly with pressure.', ' .Vxygen starvation at the surface may account for this effect. (b) At oxygen pressures from 0.3 to 63 mm, the oxidation rate increases as the 7th root of the oxygen pressure providing the temperature is such that only Cu2O is present in the film. (c) At pressures from above the equilibrium pressure for the coexistence of Cu2O and CuO (varies with temperature) to atmospheric pressure, the oxidation rate is independent of the oxygen pressure.' Equipment In order to determine the oxidation rates of metals in an oxidizing atmosphere at pressures up to 400 psi, the equipment is somewhat different than for low pressure work as is shown in Figs. 1 and 2. A Leeds and Northrup Micromax recording controller (A) is used to control the temperature of the Ni-chrome furnace winding in conjunction with a Micromax electric drive unit. The drive unit adjusts a 20 amp Variac (variable transformer) to control the power input into the Nichrome furnace winding. Due to the "self heating" of the sample by oxidation, frequently encountered in oxidation rate studies, it is essential that the sample temperature be measured independently. This is done by means of a series of six chromel-alumel calibrated thermocouples located spirally around the oxidizing metal sample. Each thermocouple is partially shielded from the direct radiation of the furnace wall by

Jan 1, 1954

By J. L. Gillson

Historically, rock deposits and sand deposits of titanium minerals came into production about the same time, although there may be some argument as to what is meant by production. Beach deposits of heavy minerals in India (Figs. 1-4) and Brazil (Figs. 5) were worked for monazite about the turn of century, but as there was then no market for titanium minerals, these were thrown away. The rock rutile deposits at Roseland, Va., Fig. 6, were worked to supply rutile for titanium chemicals and for coloring ceramics long before there was a titanium pigment business. The pigment industry started about the middle twenties, both in Europe and the U. S., and almost simultaneously the rock deposits at Ponte Vedra Beach near Jacksonville, Fla., were worked for titanium content. Since those days, production from both types of deposits has continued to grow at a rapid rate; many deposits of both types have been found, and reserves have grown to very large figures. In total tonnage of reserves, there is no doubt that the rock deposits are far ahead of the sand deposits; nevertheless there is a very large tonnage of commercial sands available. It is the quality of titanium mineral in the sand and the relatively lower costs of operating sand deposits that have kept them abreast, at least in annual tonnage produced, with the rock deposits. The principal titanium mineral used is ilmenite, but as soon as that mineral began to be sought as a titanium ore, it was obvious that there are ilmenites and ilmenites. Textbook ilmenite should have the composition FeOTiO2 and should analyze 52.6 pct TiO2 and 36.8 pct iron as Fe. The Indian ilmenite, for almost a generation the standard ore for manufacturing pigment in the U. S., was found to analyze about 60 pct TiO, and only 24 pct. Fe, and most of the iron is in the ferric condition. The whole process of pigment manufacture in the U. S. was built up on the use of a raw material of that grade, and the American chemical engineers who operate the pigment plants shuddered at the thought of using a rock ilmenite with 45 pct or so of TiO, and nearly 40 pct Fe. Intensive search was made around the world to find other deposits of rich black sand, like the Indian beaches, but although a few were found, there was some objectionable feature about each. A deposit in Senegal, south of Dakar (Fig. 7), was worked for a while, but an organic coating on the grains made attack by acid difficult. Modern practice would have included a scrubbing operation, in a caustic soda bath, to eliminate the organic coating. Brazilian deposits were numerous, but individually small, and shipping from them difficult. Deposits on the east coast of Ceylon had many attractive features, but the ilmenite analyzed only 54 pct TiO2 and could have been used only with a penalty. Sand deposits with 2 pct ilmenite, like those now worked in Florida, would not have been considered commercial ore, even if they had been known at that time. Most rock ilmenites are associated or mixed with hematite or magnetite, which accounts for the lower titanium and higher iron values than in the sand ilmenites. The Norwegians, English, and Germans, with cheap Norwegian rock ore at hand, learned to install in their pigment plants adequate capacity on the black side, as it is calltd, and counterbalanced the extra cost of plant, and larger amount of acid used, by the lower cost of ore. When World War II arrived, two of the largest pigment manufacturers in the U. S. had to learn how to use the Adirondack ilmenite, but one of them very gladly went back to sand ores when the Florida deposits came into large-scale production after the war. The other continues to use Adirondack ilmenite and finds it commercially attractive to do so. Rutile is not a raw material for titanium pigment manufacture by the sulfate process, since it is insoluble in sulfuric acid. In addition to its small consumption in chemicals and ceramics it began to be used in quantity in welding rod coatings. With the outbreak of World War 11, and the tremendous need for welding rods in shipbuilding and other structural steel construction, rutile suddenly became in heavy demand. The sand deposits on the eastern shore of Australia (Fig. 8A) which had been worked in a small way since 1934 were brought into production, and some stream placers in Brazil were worked and rutile concentrates shipped to American

Jan 1, 1960

By W. A. West

One who attempts to collect and classify equilibrium data from various iron-alloy systems is soon struck with the absence of any quantitative theory that can serve as a general background against which to compare and contrast results from different systems, at different temperatures, and with different concentrations. It is not necessary to wait for a perfect theory; investigation of divergences of theory from observation may prove of great value in acquiring understanding of the subject. For example, one has only to think of Raoult's law as applied to aqueous solutions. The equations developed by Zener1 represent an effort to provide such a quantitative theoretical background, and it is therefore desirable to subject this theory to such tests as can be applied. The present article is intended to be an application of available tests, and may thus be considered as a supplement to Zener's paper. It is assumed that this paper is available to the reader. The equations make it possible to calculate the effect on the equilibrium concentration of one alloying element due to the presence of one or more other elements. In particular. they are intended to give, for alloy steels, the carbon concentrations in alpha and gamma phases in equilibrium with each other, and in gamma in equilibrium with cementite. They may, however, be modified for use for carbon-free alloys. A summary is given later of the equations used in analyzing the data in this paper, and the symbols are there defined. About 125 papers have been examined for experimental data suitable for this investigation. An effort was made to look up all available reports of ternary systems including iron and carbon, as well as similar systems of higher order. Supplementary material was also obtained from a number of binary systems. A few noncarbon ternary systems were also found to which these methods could be applied. A comparatively small proportion oi the papers read provided usable material. In many systems the number of quantitative observations made in the iron-rich region is extremely small, and the smoothed curves to be found in most published phase diagrams are entirely useless for quantitative treatment. This opinion is confirmed by the authors of the series on Alloys of Iron Research, whose remarks show clearly that they have no illusions as to the accuracy of many diagrams that they present. A further difficulty arises from the fact that these equations apply only to rather low percentages of alloying elements. The result is that at the lowest concentrations, where the best agreement might be hoped for, the errors of observation become relatively very large. The experimental difficulties in measurements of this kind of equilibrium are, of course, an old story.

Jan 1, 1947

By W. A. West

One who attempts to collect and classify equilibrium data from various iron-alloy systems is soon struck with the absence of any quantitative theory that can serve as a general background against which to compare and contrast results from different systems, at different temperatures, and with different concentrations. It is not necessary to wait for a perfect theory; investigation of divergences of theory from observation may prove of great value in acquiring understanding of the subject. For example, one has only to think of Raoult's law as applied to aqueous solutions. The equations developed by Zener1 represent an effort to provide such a quantitative theoretical background, and it is therefore desirable to subject this theory to such tests as can be applied. The present article is intended to be an application of available tests, and may thus be considered as a supplement to Zener's paper. It is assumed that this paper is available to the reader. The equations make it possible to calculate the effect on the equilibrium concentration of one alloying element due to the presence of one or more other elements. In particular. they are intended to give, for alloy steels, the carbon concentrations in alpha and gamma phases in equilibrium with each other, and in gamma in equilibrium with cementite. They may, however, be modified for use for carbon-free alloys. A summary is given later of the equations used in analyzing the data in this paper, and the symbols are there defined. About 125 papers have been examined for experimental data suitable for this investigation. An effort was made to look up all available reports of ternary systems including iron and carbon, as well as similar systems of higher order. Supplementary material was also obtained from a number of binary systems. A few noncarbon ternary systems were also found to which these methods could be applied. A comparatively small proportion oi the papers read provided usable material. In many systems the number of quantitative observations made in the iron-rich region is extremely small, and the smoothed curves to be found in most published phase diagrams are entirely useless for quantitative treatment. This opinion is confirmed by the authors of the series on Alloys of Iron Research, whose remarks show clearly that they have no illusions as to the accuracy of many diagrams that they present. A further difficulty arises from the fact that these equations apply only to rather low percentages of alloying elements. The result is that at the lowest concentrations, where the best agreement might be hoped for, the errors of observation become relatively very large. The experimental difficulties in measurements of this kind of equilibrium are, of course, an old story.

Jan 1, 1947

By A. M. Gaudin, J. G. Morrow

FLOTATION requires the existence of a definite contact angle. This contact angle, the surface tension of the solution, and adsorption at the solid-fluid interface are quantitatively related. Adsorption of dodecylammonium acetate on hematite was measured for a wide range of concentrations of reagent in solution. Similar measurements for quartz have already been made. Contact angle measurements were then made on polished surfaces of hematite and of quartz immersed in aqueous dodecylammonium acetate solutions, and a functional relationship was sought between adsorption density at the mineral-solution interface and the contact angle. Finally, the surface tension of the aqueous amine acetate solutions was measured. These data were combined to give an evaluation of the work of adhesion for the three-phase system. Specular hematite was crushed and then ground dry in a laboratory porcelain mill, with flint pebbles, to pass a 200-mesh screen. The ground product was sized in a Haultain infrasizer, and one of the granular sizes (cone No. 3) was used in all adsorption tests. A hand magnet was used to remove magnetite and abraded iron. Quartz was removed in a Frantz isodynamic magnetic separator. The purified hematite was leached in aqua regia, washed with distilled water until the washings appeared free of electrolyte by conductance measurement, dried in a low-temperature oven, and stored in a pyrex container. The specific surface of the closely sized hematite was determined by the krypton gas adsorption method.' Three measurements gave an average value of 1350 sq cm per g. Chemical analysis showed Fe -69.37 pct, insol = 0.72 pct. The quartz used in the flotation tests had been prepared by Chang" for an earlier investigation. Demineralized distilled water was used for all test solutions. Dissolved salt content was of the order of 0.03 ppm, expressed in terms of sodium chloride, as estimated from conductance measurements. Dodecylammonium acetate was obtained from Armour & CO. in two forms, the unmarked compound and a preparation marked by carbon 14 in the hydrocarbon chain of the aminium ion. Specific activity of the active salt was 0.134 millicurie per g. The important physico-chemical constants for the primary amine salt have been reviewed by de Bruyn. The calculated effect of hydrolysis of amine salt on pH of aqueous solutions and the effect of pH on the distribution ratio of the alkylammonium ion to free amine are of particular interest. All other chemicals used in this investigation were of analytical reagent grade. A column method' was used for adsorption work. Attainment of equilibrium distribution in the adsorption column depends on the solid-solution contact time, hence upon the volume of solution passed. It was assumed that contact time required for equilibrium would be a maximum for the lowest reagent concentrations. On this premise it was demonstrated experimentally that the passage of 500 ml of solution through the mineral bed was adequate. An aliquot (1 to 5 cc) of the solution to be analyzed was transferred to a small pyrex cup and allowed to evaporate to dryness at room temperature; 4 or 5 mg of unmarked amine acetate were added to the dried sample and the cup and its contents were transferred to the combustion system for analysis. Evaporation at room temperature must be emphasized, as even slightly elevated temperatures result in loss of reagent. A laboratory model G Beckman pH meter equipped with a glass electrode was used to measure pH of amine acetate solutions. The technique of internal gas counting of radioactive carbon dioxide in a Geiger-Muller counter was used. Developed originally by Brown and Miller,- his method was adapted to the analysis of carbon-14 marked flotation reagents by Chang, de Bruyn, and Bloecher. nalytica1 method and procedures have been described in detail by Bloecher.' Contact angles were measured by the captive-bubble technique." The mineral specimens were carefully selected to avoid cracks and inclusions of other minerals. All specimens were mounted in plastic and polished to produce a smooth surface. The final polishing and contact-angle measuring

Jan 1, 1955

By Olof Löfgren

PART 1 INTRODUCTION All modern pelletizing plants are equipped with either the drum or the disc circuits. Choice of one or the other circuit is not simple and it is desirable to establish a firm basis for such a task. For a meaningful and a fair comparison it is necessary to have the two systems working in parallel in the same plant with the same concentrate under the same supervision. Furthermore, the comparison has to be based on a defined green ball quality and size distribution. BALLING CIRCUITS The LKAB straight grate plant at Malmberget, Sweden, was started up in Septenber 1973. It was designed for a 2.5 Mton annual capacity and was equipped with five balling drum circuits. During the first year of operation it was found that the induration plant had the potential for a higher capacity which required increased balling capacity. For this purpose it was decided to install a balling disc circuit complete with a roll screen. The reasons for selecting a disc were space limitations and LKAB's desire to gather experience on balling disc circuits. The disc circuit was started up in 1975 and was run in parallel with the balling drums in the same plant and with the same raw material and under the same operating personnel. The necessary conditions for a comparison were thereby fulfilled. The data for the size distribution and quality of the green balls were obtained on random sampling during one year of operation, so that all the variations which appear in a commercial plant are covered.

Jan 1, 1977

By Charles C. Rodd

Prior to 1938, proration procedure in Kansas required the physical testing of wells in order to set up a basis for allocating production. Subsequently the use of liquid-level data and bottom-hole pressure data was authorized on certain types of wells as a basis for calculating well capacities, thereby permitting wells to be tested at low rates and with small volumes of production. This paper gives some attention to the equipment used for obtaining liquid-level data but in general it is devoted to the theoretical and physical factors involved in well testing by drawdown methods. These tests are divided into two classifications: (I) liquid-level data used directly to calculate capacities, and (2) liquid-level data and liquid-level measuring equipment used in connection with other data to determine bottom-hole pressure. Equations and calculations for both types are shown. Well capacities calculated from fill-up data have not been used generally but offer a simple means of testing some wells. Theoretical factors and calculations for such tests are shown. In the state of Kansas, proration laws required that the "ability of a well to produce" be given consideration in state allocation orders and for many years this was the only factor used in prorating the allowed oil. The "ability of a well to produce", was the quantity of oil that could be obtained from a well in a prescribed period, usually 24 hr. Early in the history of State-regulated proration, Kansas operators realized that, unless some restriction were placed upon equip- ment, the competition between producers to obtain large well "potentials" might result in a race to install the largest pumping equipment. Consequently, restrictions were placed upon the size of tubing and length of pump stroke that could be used in pumping wells during potential tests. Later, restrictions were placed also upon the size of tubing and chokes that could be used in flowing walls. Despite the restriction setup, better pumping equipment was designed and installed, pumps were improved, and various devices were invoked to obtain high rates of production for short periods of time. By 1937 pumping cycles of forty to forty-five 54-in. strokes per minute were not uncommon, and numerous wells had produced at the rate of 3500 bbl. per day for short periods. Such production was far beyond any rate that could be long sustained. Equipment necessary to take "potentials" was several times larger than that needed for normal producing purposes, and repairs and replacements required by the high pumping speeds were excessive. Also, many operators suspected that the high rates of production main tained during '"potential" tests were conducivc to early water encroachment. By 1938 large-scale physical testing of wells in Kansas ended, the use of the bottom-hole pressure gauge had become common, engineers and operators were becoming familiar with the term ''productivity index," and bottom-hole pressure was being used as a factor in allocation in many areas. There were many drawbacks, however, to large-scale use of

Jan 1, 1943

By Charles C. Rodd

Prior to 1938, proration procedure in Kansas required the physical testing of wells in order to set up a basis for allocating production. Subsequently the use of liquid-level data and bottom-hole pressure data was authorized on certain types of wells as a basis for calculating well capacities, thereby permitting wells to be tested at low rates and with small volumes of production. This paper gives some attention to the equipment used for obtaining liquid-level data but in general it is devoted to the theoretical and physical factors involved in well testing by drawdown methods. These tests are divided into two classifications: (I) liquid-level data used directly to calculate capacities, and (2) liquid-level data and liquid-level measuring equipment used in connection with other data to determine bottom-hole pressure. Equations and calculations for both types are shown. Well capacities calculated from fill-up data have not been used generally but offer a simple means of testing some wells. Theoretical factors and calculations for such tests are shown. In the state of Kansas, proration laws required that the "ability of a well to produce" be given consideration in state allocation orders and for many years this was the only factor used in prorating the allowed oil. The "ability of a well to produce", was the quantity of oil that could be obtained from a well in a prescribed period, usually 24 hr. Early in the history of State-regulated proration, Kansas operators realized that, unless some restriction were placed upon equip- ment, the competition between producers to obtain large well "potentials" might result in a race to install the largest pumping equipment. Consequently, restrictions were placed upon the size of tubing and length of pump stroke that could be used in pumping wells during potential tests. Later, restrictions were placed also upon the size of tubing and chokes that could be used in flowing walls. Despite the restriction setup, better pumping equipment was designed and installed, pumps were improved, and various devices were invoked to obtain high rates of production for short periods of time. By 1937 pumping cycles of forty to forty-five 54-in. strokes per minute were not uncommon, and numerous wells had produced at the rate of 3500 bbl. per day for short periods. Such production was far beyond any rate that could be long sustained. Equipment necessary to take "potentials" was several times larger than that needed for normal producing purposes, and repairs and replacements required by the high pumping speeds were excessive. Also, many operators suspected that the high rates of production main tained during '"potential" tests were conducivc to early water encroachment. By 1938 large-scale physical testing of wells in Kansas ended, the use of the bottom-hole pressure gauge had become common, engineers and operators were becoming familiar with the term ''productivity index," and bottom-hole pressure was being used as a factor in allocation in many areas. There were many drawbacks, however, to large-scale use of

Jan 1, 1943

By O&apos, R. G. Meara, M. M. Fine

One of the principal activities of the Bureau of Mines connected with the recent war was to help to increase the supply of strategic and critical minerals. Fluorite was one of the most critical of the nonmetallic minerals because of the increased demand for it as a flux in basic open-hearth and electric steel furnaces and as a raw material for the production of artificial cryolite used in the aluminum industry. Wartime developments in the technology of hydrofluoric acid, such as the use of the anhydrous acid as a catalyst in production of high-octane gasoline and the use of organic fluorides as carriers for insecticides, also increased the demand for acid-grade fluorite. † In 1943 the consumption of acid-grade fluorite was advancing at a more rapid rate than production, and was only slightly less than production during the latter half of the year.' The outlook for the postwar market for fluorite is encouraging Steel production is expected to remain high until the domestic demand for commodities not manufactured during the war is satisfied. The uses for hydrofluoric acid are expected to increase under the impetus of war-initiated research. In consideration of these and other factors some authorities predict a postwar demand for fluorite equal to about 60 to 75 per cent of the wartime production.1,2 Others believe that the postwar fluorite industry will be permanently expanded over its prewar status3 Acknowledgment This paper is one of many reporting on various aspects of the Bureau of Mines program directed toward the more effective utilization of our mineral resources. The program has been under the general supervision of R. S. Dean, Assistant Director, since July 1942. The scope of the paper falls in the province of the Metallurgical Branch, whose activities embrace the separation of difficultly beneficiated ores, the production of pure metals from domestic deposits, the exploitation of marginal ore reserves, the recovery of secondary metals, and the improvement of present industrial metallurgical practice. The investigation was initiated at the request of Mr. J. H. Steinmesch, vice-president and general manager, Minerva Oil Co., Eldorado, Ill. His hearty cooperation and helpful suggestions, and those of Mr. 0. E. Anderson, mill superintendent,

Jan 1, 1947

By M. M. Fine, R. G. Meara, O&apos

One of the principal activities of the Bureau of Mines connected with the recent war was to help to increase the supply of strategic and critical minerals. Fluorite was one of the most critical of the nonmetallic minerals because of the increased demand for it as a flux in basic open-hearth and electric steel furnaces and as a raw material for the production of artificial cryolite used in the aluminum industry. Wartime developments in the technology of hydrofluoric acid, such as the use of the anhydrous acid as a catalyst in production of high-octane gasoline and the use of organic fluorides as carriers for insecticides, also increased the demand for acid-grade fluorite. † In 1943 the consumption of acid-grade fluorite was advancing at a more rapid rate than production, and was only slightly less than production during the latter half of the year.' The outlook for the postwar market for fluorite is encouraging Steel production is expected to remain high until the domestic demand for commodities not manufactured during the war is satisfied. The uses for hydrofluoric acid are expected to increase under the impetus of war-initiated research. In consideration of these and other factors some authorities predict a postwar demand for fluorite equal to about 60 to 75 per cent of the wartime production.1,2 Others believe that the postwar fluorite industry will be permanently expanded over its prewar status3 Acknowledgment This paper is one of many reporting on various aspects of the Bureau of Mines program directed toward the more effective utilization of our mineral resources. The program has been under the general supervision of R. S. Dean, Assistant Director, since July 1942. The scope of the paper falls in the province of the Metallurgical Branch, whose activities embrace the separation of difficultly beneficiated ores, the production of pure metals from domestic deposits, the exploitation of marginal ore reserves, the recovery of secondary metals, and the improvement of present industrial metallurgical practice. The investigation was initiated at the request of Mr. J. H. Steinmesch, vice-president and general manager, Minerva Oil Co., Eldorado, Ill. His hearty cooperation and helpful suggestions, and those of Mr. 0. E. Anderson, mill superintendent,

Jan 1, 1947

By J. H. Swisher

The rate of internal sulfidation of austenitic Fe-Ti alloys in H2S-H2 gas mixtures is controlled primarily by sulfur diffusion, with counterdiffusion of titanium playing a minor role. At temperatures below 1100°C, enhanced diffusion along grain boundaries becomes important. The rate of internal sulfidation at 1300°C is approximately equal to the rate computed from the sulfur diffusion coefficient. The diffusion coefficient of titanium in y iron has been determined from electron microprobe traces in the base alloy near the subscale interface. The solubility of sulfur in Fe-Ti alloys has been measured in the temperature range from 1150° to 1300°C. The equilibrium sulfur content is found to increase with titanium content, due to the large effect of titanium on the activity coefficient of sulfur. The Ti-S interaction becomes stronger as the temperature decreases. TITANIUM as an alloying element in stainless steels is an effective scavenger for interstitial impurities, carbon in particular. Titanium is known to form stable sulfides; however extensive thermodynamic data on the Ti-S system are not available. Schindlerova and Buzek1 have shown that the Ti-S interaction in liquid iron is moderately strong. There have been no previous studies of the Ti-S interaction in solid iron. Internal sulfidation of Fe-Mn alloys was the subject of a recent investigation by Herrnstein.2 He found the rate of internal sulfidation to be an order of magnitude greater than predicted from available solubility and diffusivity data. A satisfactory explanation for the discrepancy could not be given. In the present study, the solubility of sulfur in austenitic Fe-Ti alloys was measured using a standard gas equilibration technique. Fe-Ti alloy specimens were also internally sulfidized. The rate of internal sulfidation was measured as a function of temperature and alloy composition. Supplementary electron micro-probe measurements were made to provide additional information on the nature of the internal sulfidation process. EXPERIMENTAL The starting materials were alloys containing 0.12, 0.24, 0.38, and 0.54 wt pct Ti. The alloys were made in an induction furnace by adding titanium to electrolytic iron that previously had been vacuum-carbon-deoxidized. The major impurity in the alloys as determined by chemical analysis was carbon. The carbon content of the alloys averaged about 100 ppm; metallic impurities were presented in concentrations of 50 ppm or less. Specimens were made in the form of flat plates, 0.03 by 2 by 4 cm for the equilibrium measurements and 0.5 by 1.5 by 3 cm for the rate measurements. The experiments were performed in a vertical resistance furnace wound with molybdenum wire and containing a recrystallized alumina reaction tube. In the gas train, flow rates of the reacting gases were measured using capillary flow meters. The source of H2S was a mixture of approximately 2 pct H2S in H2, which was obtained in cylinders from the Matheson Co. A chemical analysis was provided with each cylinder. The H2-H2S mixture was diluted with additional hydrogen to obtain the desired ratio of H2S to H2, and the resulting mixture was diluted with 30 pct Ar to minimize thermal segregation of H2S in the furnace. Argon was purified by passage over copper chips at 350°C and subsequently over anhydrone. Hydrogen was purified by passage over platinized asbestos at 450°C and then over anhydrone. The H2-H2S mixture was purified by passage over platinized asbestos and then over Pas. The samples used in the solubility measurements were analyzed for sulfur by combustion and iodometric titration. The subscale thickness in the internally sulfidized samples was measured on a polished cross section, using a microscope with a micrometer stage. Electron microprobe traces for titanium in solution were made on several samples that had been internally sulfidized. A Cambridge microanalyzer was used, and the known titanium content at the center of the specimen was used as a calibration standard. The procedure for the microprobe measurements will be described further when the results are presented. RESULTS AND DISCUSSION Equilibrium Data. Fig. 1 shows the sulfur concentration as a function of gas composition for three alloys equilibrated at 1300°C. The dashed line is based on data published by Turkdogan, Ignatowicz, and pearson3 for pure iron. The breaks in the curves are the saturation points for the alloys. The fact that the initial slope decreases with increasing titanium content indicates that titanium interacts strongly with sulfur in solution. To obtain information on the composition of the precipitating sulfide phase, the measurements described in Fig. 1 were extended to higher sulfur partial pressures. These results are shown in Fig. 2. (The initial portions of the curves are reproduced from Fig. 1.) The highest PH2s /pH2 ratio used is believed to be below the ratio required for the formation of a liquid sulfide phase. Time series experiments were used to study the approach to equilibrium in the samples. It was found that equilibrium with the gas phase was reached in less than 4 hr at 1300°C.

Jan 1, 1969

By J. C. Williams

The operations described in this paper are those of the flotation plant of the Valley Forge Cement Co. at Conshohocken, Pa., and concern the use of a particular cationic reagent—namely, DP-243. The role of this reagent in this plant may be better understood by first considering the purpose of beneficiating cement rock in general and the specific problems at the Valley Forge plant. The ultimate purpose of beneficiating cement rock is to obtain a kiln feed of the desired chemical composition in a form suitable for the most efficient kiln operation. The chemical composition is governed by the type of cement to be made. Before government restrictions (the purpose of which is to simplify operations during wartime) limited the types of portland cement a manufacturer is permitted to produce, five principal types of cement were generally recognized by the industry. They are based upon chemical and physical specifications proposed by the American Society for Testing Materials, federal and other governmental agencies, state highway departments, water boards and other users of large quantities of cement. The physical as well as chemical specifications for any particular type of cement necessitate proper proportioning of the major components—that is, the silica, alumina, iron and lime—and it is necessary to establish and maintain definite limits for each in the raw mix. The manufacturer must then prepare a kiln feed of a composition that will yield a final product that will fulfill the desired specification. This step is further complicated for kilns using coal as fuel, by the amount and analysis of the ash introduced. The amount and nature of the dust lost during burning will also affect the composition of the kiln feed. The problem of preparing a kiln feed of the desired chemical composition is not a simple one, and it is the final product that governs the methods used to obtain such a feed. For example, in starting with a material deficient in lime for the mix sought, it may not be sufficient to raise it to the required lime content. The other constituents must also be present in the proper proportions. In some cases, it may be necessary to raise the lime content to a point greatly exceeding that of the final mix, then, by addition of one or more other materials lower in lime, obtain the mix. The rock used at the Valley Forge plant is a metamorphosed argillaceous limestone of the Jacksonburg formation, the same formation as that of the Lehigh Valley cement rock (which occurs approximately 50 miles north), and its oxide composition is similar to that of the latter. The only practical differences between the two are that, as a result of metamorphosis, crystallization of the Valley Forge rock is considerably coarser and it contains less carbon than the Lehigh Valley rock as well as slightly more magnesia in the form of magnesian mica. The calcium carbonate content of the various strata in the Valley Forge quarry ranges from about 65 per cent to over 85 per cent, the average for the entire quarry being somewhat under the requirement for manufacture of cement, which usually is from 75 to 76 per

Jan 1, 1947

By J. C. Williams

The operations described in this paper are those of the flotation plant of the Valley Forge Cement Co. at Conshohocken, Pa., and concern the use of a particular cationic reagent—namely, DP-243. The role of this reagent in this plant may be better understood by first considering the purpose of beneficiating cement rock in general and the specific problems at the Valley Forge plant. The ultimate purpose of beneficiating cement rock is to obtain a kiln feed of the desired chemical composition in a form suitable for the most efficient kiln operation. The chemical composition is governed by the type of cement to be made. Before government restrictions (the purpose of which is to simplify operations during wartime) limited the types of portland cement a manufacturer is permitted to produce, five principal types of cement were generally recognized by the industry. They are based upon chemical and physical specifications proposed by the American Society for Testing Materials, federal and other governmental agencies, state highway departments, water boards and other users of large quantities of cement. The physical as well as chemical specifications for any particular type of cement necessitate proper proportioning of the major components—that is, the silica, alumina, iron and lime—and it is necessary to establish and maintain definite limits for each in the raw mix. The manufacturer must then prepare a kiln feed of a composition that will yield a final product that will fulfill the desired specification. This step is further complicated for kilns using coal as fuel, by the amount and analysis of the ash introduced. The amount and nature of the dust lost during burning will also affect the composition of the kiln feed. The problem of preparing a kiln feed of the desired chemical composition is not a simple one, and it is the final product that governs the methods used to obtain such a feed. For example, in starting with a material deficient in lime for the mix sought, it may not be sufficient to raise it to the required lime content. The other constituents must also be present in the proper proportions. In some cases, it may be necessary to raise the lime content to a point greatly exceeding that of the final mix, then, by addition of one or more other materials lower in lime, obtain the mix. The rock used at the Valley Forge plant is a metamorphosed argillaceous limestone of the Jacksonburg formation, the same formation as that of the Lehigh Valley cement rock (which occurs approximately 50 miles north), and its oxide composition is similar to that of the latter. The only practical differences between the two are that, as a result of metamorphosis, crystallization of the Valley Forge rock is considerably coarser and it contains less carbon than the Lehigh Valley rock as well as slightly more magnesia in the form of magnesian mica. The calcium carbonate content of the various strata in the Valley Forge quarry ranges from about 65 per cent to over 85 per cent, the average for the entire quarry being somewhat under the requirement for manufacture of cement, which usually is from 75 to 76 per

Jan 1, 1947

By J. W. Evans

ONE possible method for the separation of hafnium from zirconium is by the vapor phase oxidation of the purified mixed chlorides. An important factor for success depends on the difference in free energies of the following reactions: ZrCl(g) + O2 = ZrO2(s) + 2C12 [1] HfCl4(g) + O2 = HfO2(s) + 2C12. [2] Prakash and Sundaram1 have calculated these values from certain data and carried out experimental work with partial success. However, their free energy values for reaction 2 diverge rather widely from other data which are presented here. The possibility of successful separation is briefly considered in the light of these alternative values. Table I shows the free energy values (?F°) for reactions 1 and 2 derived from the recent compilation of data on oxides and chlorides by Glassner.2 The corresponding values of Prakash and Sundaram for the same temperatures are also shown. The alternative values to those of Prakash and Sundaram for reaction 2 are substantially confirmed by the data of Kubaschewski and Evans" and Cough-lin' on heats of formation, entropies, and heats of vaporization. In spite of the considerable uncertainty in the hafnium data it is reasonable to suppose that the oxide-chloride free energy difference for two such chemically similar elements would not be very far apart. These figures indicate clearly that the oxidation of hafnium chloride is appreciable at all temperatures. Nevertheless, there is a significant difference between the values for reactions 1 and 2

Jan 1, 1959

By J. D. Forrester, Erich Sarapuu, T. C. Cheasley

John G. Tripp-—The concept of converting fuel deposits in-situ to useful forms of energy and chemical raw materials has important possibilities as a means of stretching out our fuel resources. The authors have worked in this field for years and in fact are among the pioneers in developing in-situ techniques based on underground electrocarbonization. Their efforts have aroused great interest in this subject and their contributions will undoubtedly gain even more significance as time goes on. The 4 to 5 billion tons of petroleum are proved reserves, that is, they are completely defined and could be produced economically with present methods of recovery. Reserves of coal, tar sands, and oil shale shown in Table I are not equivalent to proved reserves as the term is used in the oil industry. Incidentally, the 4.3 billion tons of oil shown in the tabulation is equal to about 28 billion barrels of oil and, therefore, presumably does not include reserves of natural gas liquids estimated at about 5 billion barrels. The relative comparisons would be more complete if these liquids together with the reserves of natural gas were included in the tabulation. It is stated in the report that production costs of the order of 10c per million Btu's could be expected from a large industrial electrocarbonization installation. The authors state that the operation probably could be operated successfully and at a profit. I would like to express my view that for the operation to be profitable extremely favorable conditions would have to prevail. For example, the coal seam would have to be thick and close to the surface in order to minimize drilling costs; the deposit should be dry and so situated that there would be little, if any, inflow of ground water; and the seam would have to be relatively gas tight to avoid excessive gas leakage. Notwithstanding the tremendous strides that have already been made, it is my hope that the authors plan to continue their development work. Experiments on underground electrolinking and initial carbonization at Gorgas, Ala., indicate a need for improved control over the operation. Subsequent examination of the underground system at Gorgas has shown that the gasification zone did not always follow a direct path between the electrodes. Undoubtedly the control of the in-situ thermal processes can be improved by further development work. With respect to the electrocarbonization of oil shale it may be well to point out that the cost of mining oil shale is estimated to be 50c to 60c per ton. These are low mining costs as compared to coal. Thus it would appear that there is less economic incentive for applying in-situ thermal methods to oil shale than there is for applying these methods to coal. As is the case with in-situ methods for petroleum, the product from the shale having the most economic interest would be liquid oil rather than gas. The authors point out that for distances up to several hundred miles it is cheaper to transmit energy as electricity than it is to ship energy as coal. This is a very important point, and with coal shipping rates rising periodically, it could prove increasingly important in the future. I believe that the authors deserve great credit for their outstanding work on underground electrocarbonization. The knowledge resulting from their efforts is of great value to our fuels technology. James L. Elder—The experimental work conducted by the authors on the electrolinking-carbonization of carbonaceous materials in situ is of great interest. The method is of great importance in the development

Jan 1, 1955

By Herbert H. Kellogg

RECENTLY the long-chain primary amines have been used extensively for the flotation of silicate minerals. The use of amines to float sulphide minerals has been investigated by several authors1-5,18 but most of this work has been done with the short-chain (less than six carbon atoms) primary amine compounds or the more expensive secondary, tertiary and quaternary amines. Perhaps the fact that the long-chain amines are good collectors for the common gangue minerals has led investigators to omit them from consideration as collectors for the selective flotation of metallic sulphides. The work reported in this paper was designed to investigate the use of a typical long-chain amine salt, lauryl amine hydrochloride, as a collector for the flotation of galena-sphalerite ores. The results show that lauryl amine hydrochloride (LAmHCI), when used in small amounts, is a good collector for the selective flotation of sphalerite and galena from the common gangue minerals. The differential flotation of sphalerite from galena was not accomplished but the amine flotation of sphalerite after the standard xanthate flotation of galena is possible. The experimental work reported herein is not complete enough to be able to say whether amine flotation of lead-zinc ores would prove superior to xanthate flotation, or whether the method is even applicable to a more complex ore than the one used for this work. However, the apparent reagent costs for the flotation operations described in this paper seem to be less than for xanthate flotation. This fact alone should be sufficient to encourage the millman to investigate the use of these amine reagents, especially as these reagents are available on a commercial scale at a reasonable price. This paper has as its secondary purposes to illustrate how contact-angle measurements have aided in this investigation, and to bring forward some evidence concerning the mechanism of the collecting action of primary amines. CONTACT-ANGLE TESTS The contact-angle measurements were made by the method described by del Giudice6 and used in recent work by Taggart and his collaborators.7-9 The mineral specimens for the contact-angle tests were carefully chosen, to avoid cracks and inclusions of other minerals. All specimens were mounted in "transoptic" plastic mounts and the surfaces were cleaned by polishing with levigated alumina on a cloth-covered glass polishing wheel. Distilled water was used on the lap during the polishing and at all subsequent steps in the contact-angle tests. The mounted mineral specimens were handled with glass forceps and special care was exercised to prevent exposure of the dean surface to air or any other source of contamination.

Jan 1, 1945

By M. Gensamer

THE PURPOSE OF THIS PAPER is to lay a foundation of elementary theory that might be useful in the discussions which it is hoped will be evoked during this Symposium. It is not my purpose to try to expound the details of the most complete theories as that would be impossible in the time at our disposal and, even if time were available, would probably be of less usefulness than a discussion of the principles underlying the advanced theoretical treatment. I shall try to discuss the fundamental bases for these advanced theories. There exists at the present time very much less need for a detailed description of complete theory than existed when this Symposium was being organized. The reason for this is that a series of papers by L. R. Underwood has been appearing in the magazine Sheet Metal Industries. It is understood that this series will he published soon in the form of a book. Dr. Underwood's articles are complete, critical and well written and it would be hopeless to try to do better in less space. The need, then, is for a brief treatment of basic theory. The objective of any theory of plastic forming- is to enable one to calculate the force and power requirements for the process, and where the deformation is not uniform, to calculate the distribution of strains- In the formed object. We need as the basis for the calculation the relationship between stress and strain in the metal, particularly for the combination of stresses imposed by the forming process. We need to know the stress-strain curve for some simple state of stress, and we need in addition some theory

Jan 1, 1948

By H. P. Bucker, M. Felsenthal, F. R. Conley

INTRODUCTION In the intensive analysis of core samples from oil raservoirs, there is a recognized need for pore sizc distribution data. Such data, if collected with adequate precision and in sufficient quantity, should contribute to a better interpretation of fluid flow phenomena than is now possible from a knowledge of permeability and porosity data alone. It is hoped, for instance, that pore size distribution data may eventually provide a useful aid for predicting whether a water flood, or other secondary recovery methods. will he successful in a given reservoir.' Apparatus tor measurlng pore size distribution by mercury injection at pressures ranging from 0 to 2,000 psi have been described in the literature.2,3,4 All of these apparatus are somewhat complex and fairly expensive. Furthermore, the callbration of some of the apparatus is not always easy. Great difficulty, for instance, was experienced in obtaining reproducible pressure-volume correction data for the mercury pump shown in one of the references. An apparatus was therefore developed which was less complicated and less expensive than those of previously described designs. This apparatus is, in some respects, an improved version of a previously described low pressure apparatus' (maximum pressure 150 psi) which did not cmploy a mercury pump but instead used a precision bore glass tube for measuring the injected volumes. Tests were performed with the apparatus from vacuum to 2,000 psi and it was observed that the apparatus furnished reproducible pressure-volume correction data. In addition. it was noted that the maximum correction was small. precision of measurement was high. and operation of the entirc apparatus was relatively easy. Although the apparatus was designed exclusively for samples of 1 in. diameter and 1 in, length or smaller, it could be modified without much difficulty for larger samples, if desired. APPARATUS Arrangement of the pore six distribution apparatus is shown schematically in Fig. I. The heart of the apparatus is a steel sample chamber surmounted by a precision bore capillary glass tube. A mercury reservoir is connected to the lower half of the sample chamber. The top of the glass tube is in communication with a

Jan 1, 1957