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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 R. H. Gautschi, F. C. Langenberg

Rare-earth additions were made to laboratory heats of Type 310 stainless to observe their effect on as-cast ingot structure, nitrogen and sulfur contents, and nonmetallic inclusions. Lanthanum had a grain-refining effect in 30-lb ingots, but results with 200-lb ingots were inconsistent. Cerium, lanthanum, and misch metal lowered the sulfur content when the sulfur exceeded 0.015 pct and the rare-earth addition was greater than 0.1 pct. The rare-eardh content in the metal dropped very rapidly within the first few minutes after the addition. The size, shape, and distribution of nonmetallic inclusions was not changed in 30-lb ingots, but changes were noticed in larger ingots. RARE-earth* additions have been made to austenitic Cr-Ni and Cr-Mn steels to improve their hot workability. The high alloy content of these steels often results in a considerable resistance to deformation and inherent hot shortness at rolling temperatures, particularly in larger ingots. Rare earths in the metallic, oxide, or halide form are usually added to the steel in the ladle after deoxidation although they can be added in the furnace prior to tap or in the molds during teeming. The literature- indicates that the effects of rare-earth treatments on these stainless steels are not consistent, and sometimes even contradictory. Since no mechanism has been presented which satisfactorily accounts for the claimed improvements, the effects of rare earths are a qualitative matter. The work described in this paper was initiated to expand the knowledge of the effects of rare-earth additions on melting variables such as ingot structure, chemical analysis, and nonmetallic inclusions. REVIEW OF LITERATURE Ingot Structure—Rare-earth additions to stainless steels have been reported to cause a change in primary ingot structure in that there are fewer coarse columnar grains. However, the results are inconsistent. While one investigation1 has shown a large reduction in coarse columnar crystals, another2 has been unable to observe this effect, particularly when small ingots were poured. Post and coworkers3 observed ingot structures for a number of years and found that the columnar type of structure is not definitely a cause of any particular trouble in rolling or hammering, provided the alloy is ductile. Knapp and Bolkcom4 found rare-earth additions to be quite effective in preventing grain coarsening in Type 310 stainless steel. Chemical Analysis—Many effects of rare-earth treatment on chemical analysis have been claimed in the literature. Russell5 observed that some sulfur is removed by rare-earth metals, and that a high initial sulfur content improved the efficiency of sulfur removal. Lillieqvist and Mickelson6 report that rare-earth treatment causes sulfur removal in basic open-hearth furnaces, but not in basic lined induction furnaces. Knapp and Bolkcom found no sulfur removal in acid open-hearth and acid electric furnaces, probably because the acid slag can not retain sul-fides. snellmann7 showed that sulfur could be lowered apprecfably with rare-earth additions; however, a sulfur reversion occurred with time. Langenberg and chipman8 studied the reaction CeS(s) = Ce(in Fe) + S(in Fe), and found the solubilit product [%Ce] [%S] equal to (1.5 + 0.5) X 10-3'at 1600°C. Results in 17 Cr-9 Ni stainless were about the same as those in iron. Beaver2 treated chromium-nickel steels with 0.3 pct misch metal and observed some reduction in the oxygen content. He also noted an inconsistent but beneficial effect of rare earths when tramp elements were present in amounts sufficient to cause difficulty in hot working. It is not known whether rare earths reduce the content of the tramp elements or change the form in which these elements appear in the final structure. No quantitative data are available concerning a possible effect of rare-earth treatment on hydrogen and nitrogen contents. However, Schwartzbart and sheehan9 stated that additions of rare earths had no effect on impact properties when the nitrogen content was low (0.006 pct), but served to counteract the adverse effects of high nitrogen content (0.030 pct) on these properties. Knapp and Bolkcom4 analyzed open-hearth heats in the treated and untreated conditions and found the nitrogen content (0.006 pct) to be unaffected. These two results lead to the speculation that rare-earth additions can reduce the nitrogen content to a certain level. Decker and coworkers10 have observed that small amounts of boron or zirconium, picked up from magnesia or zirconia crucibles, increased high-tem-

Jan 1, 1961

By F. E. Pawlek, J. K. Gerlach

The chloridizing roasting of ores is applied when metal sulfides and oxides are to be converted into soluble or volatile compounds. The chlorine required is either obtained from the admixed chlorides of sodium or calcium or added in the gaseous state. In the first part of the investigations the reaction rate of the chlorides of sodium or calcium with gas mixtures of SO,-0, or SO ,-O2 ,-SO , was measured. The rate for reactions with gas mixtures SO2-O2 is ThE chloridizing roasting of ores is applied when metal sulfides and oxides are to be converted into soluble or volatile compounds. At present the process is mainly applied to produce nonferrous metals which occur in pyrite cinders in small concentrations. Thereby the nonferrous metals are converted into water-soluble, acid-soluble, or volatile compounds whereas all the iron remains as insoluble oxide. The chlorine required is either obtained from the admixed chlorides of sodium or calcium or added in the gaseous state. The reactions occurring during the roasting process can be divided into two groups: solid-solid reaction and gas-solid reaction. The reactions between solids proceed by means of solid-state diffusion and are therefore of low velocity. The heterogeneous reactions between solids and gases of the roasting atmosphere5 are high-velocity processes and determine the velocity of the chloridizing roasting. These gas-solid reactions shall be the subject of the paper presented. In order to investigate the still little-known processes which occur during the chloridizing roasting 6-' the complex reaction is split into several partial steps. First the reactions of NaCl and CaCl, with gas mixtures of SO2 and 0, have been investigated at temperatures between 500" and 600°C by measuring the weight increase of the samples. The gas mixtures used in this series of experiments had first variable compositions, then the amount of SO 2 had been increased. Furthermore the influence of Fe 2 O3 admixtures upon these reactions, the behavior of pure Fe 2 O3 with the gaseous reactants, and the chlorination of the sulfides of lead, copper, nickel, and zinc have been investigated. FORMATION OF GASEOUS CHLORINE Pyrite cinders are never completely roasted and therefore contain still a small amount of sulfide sulfur. When heated again in air, this sulfur is converted into SO,. Accordingly the formation of chlorine can first be described by the reactions: dependent on the composition of the gas phase. If more than 1 pct SO 3 is added to the roasting gas, the reaction rate is determined only by the concentrations of the SO,. In the second part the reactions between chlorine and metal sulfides are discussed. The rate of formation of gaseous chlorine is higher by me order of magnitude than is the reaction rate between ZnS and chlorine. The reaction rate of NiS and PbS lies considerably below that of ZnS. The conversion rate of both pure Fe 2 O 3 and Fe 2 O 3 containing NaCl or CaCl2 when reacting with SO2-O2, mixtures with and without SO3 portions was measured at temperatures of 500", 550°, and 600°C. The weight increase of pressings was determined by means of a spiral balanceg and the reaction rate calculated therefrom according to Eqs. [ll to [31 and [5] to [7]. The prepared samples were suspended on a platinum filament in a vertically mounted tube of mullite (ID 4 cm, length 110 cm) which could be heated by a resistance tube furnace. The platinum filament was tied to the lower end of the spiral balance. A supremax glass tube (length 70 cm) was mounted gas-tight on top of the reaction tube. The unit was sealed up at its top by a ground-in stopper which was holding the spiral balance with the sample. The spiral balance therefore hung outside the high-temperature region of the furnace. Fig. 2 shows the experimental arrangement schematically. While lowering the sample into the reaction tube pure nitrogen was flowing through the reaction zone providing a protective atmosphere. After the sample had reached the reaction temperature within approximately 1 min, the protective gas was replaced by the sulfur dioxide-oxygen reaction mixture. It took about 30 sec until the mixture filled the tube homogeneously. A Ni/NiCr thermocouple placed in the center of the furnace where the sample hung during the measure-

Jan 1, 1968

By Theodore W. Robinson

WHEREVER the amount of work renders it practicable the plan of using permanent standard solutions, in connection with the colorimetric carbon test, affords such manifold advantages that it is to be strongly recommended. That it has not attained a wider and more general application, is mainly due to the fact that, as the method is generally employed, the difficulty attending the production of the colors, and their doubtful stability when produced, have been only too evident to those who have undertaken their composition. The old method of using standard solutions made from sugar, coffee, etc., has always been hampered by the tendency of the colors to change upon exposure to the light, and the consequent liability to serious error, unless they are closely watched. Appreciating these difficulties, while recognizing the desirability of permanent colors, Mr. Magnus Troilius, at the suggestion of Prof. F. L. Erkmann, investigated the properties of cobalt, copper and ferric chlorides, with the view of determining their efficacy in the production of standard solutions. His results, as obtained, seem to have been satisfactory, but his treatment failed to eliminate many of the objections that have rendered the use of organic colors undesirable. The

Jan 1, 1888

Jan 1, 1955

By R. A. Garling

INTRODUCTION Since the infancy of in situ uranium mining, a growing number of hydrometallurgical processes have been incorporated into pilot and commercial scale flowsheets. Although initial design efforts were geared toward maximizing uranium recovery and minimizing plant and wellfield flow circuit maintenance, recent emphasis has shifted to improved means of water conservation and aquifer restoration. As mining units approached depletion, evaporation ponds reached minimum freeboard, and state and federal agencies demanded proof of groundwater restoration, processes including mixed bed and conventional ion exchange, reverse osmosis and electrodialysis were adopted by the industry. These units served the additional function of reducing process bleed flows during mining in states where the deep disposal well permitting ice remains unbroken. This report concerns the use of electrodialysis as an alternative to the more conventional processes used in in situ mining. In addition to a brief history and description of the process, a comparison to reverse osmosis and operational data derived from testing an Ionics, Inc. 1.31 x 10-3 m /s (30,000 gallon/day) unit at the Teton-Nedco Leuenberger Research and Development pilot will be presented. HISTORY Commercially practicable electrodialysis was contingent upon the development of synthetic ion exchange membranes in 1940's. In 1952, Ionics Inc. demonstrated that the process was amenable to the treatment of salt and brackish water and, in 1954, made their first commercial sale. The following decade saw several major electrodialysis unit sales which were generally targeted for use on private or municipal potable water treatment. Major increases in membrane desalting unit capacities, facilitated by technological advances in the reserve osmosis industry, were noted during the 1970's. The development of polarity reversing electrodialysis equipment which reduced feed pretreatment requirements, increased water recovery rates, and simplified unit operation, kept Ionics Inc. competetive in the water treatment industry. Engineering advances which incorporated automated equipment, non-corrosive construction materials, and improved ion exchange membranes allowed the electrodialysis process to compete in industrial waste treatment among other commercial markets. PROCESS AND APPARATUS DESCRIPTION The electrodialysis process utilizes direct electrical current passed across a stack of alternating cation and anion selective membranes in order to achieve an electrochemical separation of ionized materials in an aqueous solution. The membrane stack has the appearance of a plate and frame filter press and auxilliary equipment includes solution pumps, electrically actuated valves, filters, piping and a direct current power source. The ion separation membranes are thin sheets of synthetic cation or anion selective resins. Attaching sulfonate or quaternary ammonium groups to the cross linked copolymer structure determines the ion selectivity of the membrane. The membranes are separated from each other in the stack by non-conductive spacers that house flow channels which route the flow tortuously and parallel to the membranes. Direct electrical current passing perpendicularly to the membranes and solution passages attracts cations toward the cathode and anions toward the anode (Figure 1). As the ions from the feed stream pass through the ion selective membranes, they become concentrated in the adjacent brine channel and are retained there by the combined attractive force of the electrode and the repelling force of the next membrane toward the electrode. Limiting factors on the degree of demineralization possible include chemical solubilities in the brine flow and the current density that will produce an unacceptable degree of polarization (Figure 1). Feed or brine solution treatment with complexing agents or acids has been successfully applied to prevent membrane scaling. Polarization can occur when sufficient current density is applied to dissociate water in the ion depleted region of the diluting compartments near the membrane surfaces. Significant polarization is evidenced by large electrical resistances across cell pairs and notable pH differences between diluting and concentrating streams. Limiting current densities have been increased in U.S. manufactured equipment by utilizing tortuous flow paths of relatively high linear velocities thereby promoting continous solution mixing. Energy consumption is due to separating electrolytes and solutions, oxidation and reduction reactions occurring in electrode compartments, overcoming electrical resistance, conversion from AC to DC power, solution pumping and auxiliary equipment actuation. A major improvement to the basic electrodialysis process was applied in 1970 which resulted in frequent, automatic cleaning and descaling of membrane surfaces. The process, polarity reversal, incorporates alternating the cathode and anode on a periodic basis while exchanging product and brine flow channels via electrically actuated values. The reversal reduces the potential of stack plugging with CaCO3 (calcite), CaSO4 (gypsum), and colloidal materials and, in most waters, eliminates feed pre-treatment requirements. For approximately two minutes during and following the reversal, off spec. water is flushed to waste or reintroduced to the feed supply. The usual feed treatment on polarity reversing electro-

Jan 1, 1982

By C. B. Alcock, L. I. Cheng

By the use of radiochemical methods for the study of the gas-liquid equilibria at low temperature, and for the determination of the sulfur contents of metal beads which had been equilibrated with H2S/H2 mixtures of known sulfur potential, it has been possible to obtain the liquid solubility and the free energy of solution of sulfur in liquid tin and lead at temperatures between 500°and 680°C. THE gas-liquid equilibrium method has proved in the past to be most successful in the determination of the thermodynamic behavior of dilute solutions of sulfur in liquid metals.1,2 One of the basic requirements for success with this method is that the volatility of both the metal and its lowest sulfide should be small, otherwise sulfide will be deposited at the cool end of the furnace, where it may react with the outgoing gases to form either sulfur-rich lowest sulfide or higher sulfides. The resultant value of the apparent equilibrium constant will then be lower than the correct one. This argument applies even at sulfur potentials below that in equilibrium with a separate condensed phase of the lowest sulfide at the reaction temperature, T. The mass of sulfide which is deposited at the cold end of the furnace, and hence the extent to which further reaction occurs with the outgoing gases, depends on the time taken for equilibrium to be reached between metal and gas. Since this will depend principally on the bulk of the metal phase which is used, one should clearly attempt to uie as small metal samples as possible. These considerations are important in the study of dilute solutions of sulfur dissolved in liquid tin and lead which both have moderately high vapor pressures as metals and form volatile sulfides. The limit on the size of the metal samples which may be used is set chiefly by the difficulties of analysis for very small amounts of sulfur. The oxygen or carbon dioxide combustion method, followed by iodimetric determination of the sulfur dioxide which is formed,has been found to be successful for the determination of small amounts of sulfur in copper, iron, cobalt and nickel.4 This method was unsatisfactory for sulfur dissolved in tin and lead, mainly because the sulfur dioxide was to some extent absorbed by the copious tin or lead oxide deposits which were formed on the walls of the combustion tube. Furthermore some of the sulfur was found to segregate on the surface of the beads as flaky sulfide crystals which would easily be lost in the transfer of a bead from a boat in the gas equilibration apparatus to one in the combustion apparatus. Oxidation in aqueous media to sulfate ion followed by precipitation as barium sulfate was, therefore, adopted as the analytical procedure. The gas-metal equilibrium experiments were all carried out with radioactive sulfur and thus the analysis involved the counting of barium radiosulfate. Furthermore the use of the radioisotope meant that the approach to the gas-metal equilibrium could be followed continuously by gas counting.' The metal beads were held separately in glass crucibles during equilibration and were transferred from the furnace to the beaker for dissolution in nitric acid still in the crucibles, and thus the possibility of sulfur loss by detachment of the sulfide segregates was eliminated. The temperature range of this investigation was 500° to 680°C. EXPERIMENTAL APPARATUS AND METHOD The apparatus consisted of two furnaces placed in series in a gas recirculation system, Fig. 1. One furnace F1, which was vertical was used to heat the alumina crucible, A, holding six metal beads in separate glass crucibles. The beads weighed between 300 and 700 mg each. The crucible assembly was introduced and removed from the furnace mechanically under a stream of oxygen-free argon. The other furnace, F2, was horizontal and was used to heat a cobalt Co9S8 mixture, held in an alumina boat, and made with radiosulfur containing about 1/2 millicurie per g of sulphur. This mixture, which was finely powdered, was used as a source of known H2S/H2 mixtures6 for a given furnace temperature. The recirculation system also contained a gas re-circulation pump (P), an end window Geiger-Miiller counter (N)—placed downstream of F1 so as to monitor the H2S pressure in the gas leaving this furnace— a sample volume for chemical analysis of the gas phase (G), gas drying tubes (D), filling taps and other standard ancillary equipment. The gas sampling volume was principally used in the cali-

Jan 1, 1962

By D. R. Irving

Prior to this time, ample supplies of high grade mineral fillers, such as clay, have been available close to consuming centers. Now depletion of these accessible deposits, coupled with other factors such as increasing demand due to population expansion and standard of living rise, has made development of upgrading techniques attractive to producers. Various investigations being carried out by the U.S. Bureau of Mines are described. Factors making the development of improved methods for upgrading clays attractive to producers include: depletion of accessible deposits of high-grade clays, rising transportation and labor costs, more exacting specifications, and increased demand resulting from an expanding population and a constantly rising standard of living. Industry recognizes the need for upgrading presently unusable materials and has cooperated with the U.S. Bureau of Mines by providing samples from submarginal deposits and by evaluating the products that USBM upgrades. Following are some examples of recent clay beneficiation work by the Bureau. FIRE CLAY BENEFICIATION At the Rolla Metallurgical Center, Rolla, Mo., the Bureau is conducting research to develop technically and economically feasible mineral-dressing methods to remove quartz, pyrite, and other impurities from submarginal fire clays. The research has been spurred by the growing shortage of high-grade bur-ley, flint, and plastic clays in the Missouri fire-clay district resulting from increased consumption and the low rate of discovery of new deposits of adequate quality. There apparently is ample tonnage of submarginal flint and plastic clays to maintain the industry for many years if such material can be upgraded to commercial quality. Samples have been submitted to USBM by several major producers of refractories, including A. P. Green Fire Brick Co.; Harbison-Walker Refractories Co.; Mexico Refractories Div., Kaiser Aluminum and Chemical Corp.; and Wellsville Fire Brick Co. Research on some samples has been completed and still is in progress on others. The Bureau has found that specimens containing quartz or pyrite in grains coarser than the accompanying clay generally can be upgraded either with a gravity table or hydraulic cyclone. The improvement in quality is notable not only in chemical analysis but in an increase in pyrometric cone equivalent (PCE) of one or more cones. As an example, consider the results attained on a sandy flint—a fine-grained mixture of kaolin and halloysite with quartz and minor quantities of iron and manganese oxides. Chemical analysis was: 35.4 pct alumina (A12O3) and 47.8 pct silica (SiO2). The sample contained 9.2 pct free silica as quartz. The PCE was 33. The sample was crushed to -10-mesh, blunged with water, and then stage-ground to -48-mesh. The ground sample was tabled to yield a clay fraction containing 37.6 pct A12O3, and 45.3 pct SiO2 of which 2.4 pct was free silica. The PCE was 34. Recovery of alumina by this process was 73.6 pct. Concentration of the same clay in the hydraulic cyclone was even more effective in respect to quartz removal. The clay fraction analyzed 38.6 pct A12O3, 45.0 pct SiO2 of which 0.5 pct was free silica as quartz, and had a PCE of 34. Recovery of alumina was 71.9 pct. The hydraulic cyclone was also effective in reducing the pyrite content of a plastic clay which likewise was a mixture of kaolin and halloysite, plus some pyrite, quartz, and carbonaceous material. It analyzed 30.6 pct Al2O3, 52.3 pct SiO2, 2.3 pct Fe2O3, and 0.76 pct S. The sample was blunged and screened through 10-mesh to remove some coarse pyrite, then ground to -65-mesh and cycloned to remove most of the remainder. The final product recovered 81.8 pct of the alumina at a grade of 32.3 pct A12O3, 50.9 pct SiO2, 1.4 pct Fe2O3, and 0.1 pct S. The PCE was 32-1/2, compared with a PCE of 31-1/2 for the crude clay. The fine beneficiated clays, of course, must be pelletized and dried or fired to meet commercial acceptance. This operation has already been solved by industry. Little progress has been made on two remaining problems. One is that of fine-grained impurities, not separable by table or cyclone. Flotation is being investigated to solve this. Although fine pyrite is readily rejected, a satisfactory quartz-clay separation has not been attained. The second problem, a stubborn one, is that of alkali. Samples containing as much as 5 pct potas-

Jan 1, 1961

By H. P. Rassbach, E. R. Saunders

MUCH progress has been made in recent years in the theory and practice of making stainless steel. By effective utilization of oxygen for decar-burization and more suitable alloying agents, it has been possible to attain consistent production of very low-carbon stainless steel. In order to facilitate economical production of stainless steels, the Electro Metallurgical Co. has carried out an extended experimental program that has clarified some of the complex interrelations of temperature and composition under decarburizing and reducing conditions. These results'-:' have been founded in large part on small experimental heats, and in order to confirm their validity and significance under commercial conditions, a survey of stainless steel melting practice has been made with the cooperation of stainless steel producers. Conditions required for decarburization and associated oxidation of chromium, manganese, and iron have been fairly well established in relation to the beneficial effect of the highest practicable temperature. The recovery of chromium and manganese from highly oxidized slags by reduction with silicon has been indicated with somewhat less precision and this study has shown significant deviation in large commercial heats from the small experimental heats. In spite of an unsatisfactory degree of accuracy in estimating the conditions affecting reduction of metallic values, it has been possible to calculate a slag weight in reasonably good agreement with the results observed in large heats. While there still is much to be learned about both the qualitative and quantitative aspects of stainless steel melting, this survey has indicated the manner by which the efficiency of the production process may be measured. Oxidation Period In order to establish practices for the recovery of chromium and manganese from the slag the amounts of these metals oxidized should be known. Moreover, since reduction of oxidized chromium and manganese must necessarily be accompanied by similar reduction of iron, knowledge of the total quantity of metallics oxidized is essential. The relations between carbon, chromium, and temperature under oxidizing conditions were developed by Hilty in 1948.' While it had been realized previously that retention of chromium in the metal during carbon oxidation is favored by high temperatures, the Hilty relation provided quantitative information useful for evaluating melting procedures. For example, it was shown that decarburization to moderate carbon levels can be achieved while retaining substantial amounts of chromium. However, in decarburizing to the low-carbon level necessary for producing 0.03 pct maximum carbon stainless steel, very little chromium remains in the bath at the temperatures generally employed. For this reason, Hilty, Healy, and Crafts' later projected an extension of the chromium-carbon relation to the low-chromium region. Although this chromium-carbon-temperature relation defined the composition of a chromium steel bath at the end of the oxidizing period, it did not provide a direct means for estimating the total amount of metallic oxidation occurring during decarburization of a stainless steel heat. This subject was investigated by Crafts and Rassbach³ and, later, by Hilty, Healy, and Crafts" who demonstrated that metallic oxidation is a function of the chromium content of the initial furnace charge, the minimum carbon content attained, and the temperature. It was further demonstrated from data on 1-ton heats that an empirical relationship exists between the ratio of chromium plus manganese to iron in the slag (S) to the corresponding ratio of these components present in the metal bath. The following expression was derived to permit the calculation of the amount of metallics oxidized during decarburization of a given charge: W-2000 (Cr1 + Mn1)-(Cr2 + Mn2) 1 100s/s+1-(Cr3 + Mn2) where W is the pounds of chromium, manganese, and iron oxidized per ton of charge; Cr1, the percentage of chromium in the charge; Mn1, the percentage of manganese in the charge; Cr2, the percentage of chromium in the bath after oxidation; Mn2, the percentage of manganese in the bath after % Cr + % Mn oxidation; and S =%cr+ % Mn/%Fe in the slag after %Fe oxidation. In order to establish whether the slag ratios of commercial heats are consistent with those found in the experimental heats, the slag and metal analyses shown in Table I were evaluated. These data represent samples taken after the oxidation of two 1-ton and seven 15 to 25-ton heats of types 303, 304, and 304L stainless steel made in chromite, acid, and basic hearths. Fig. 1 illustrates that the results for the commercial heats correlate reasonably well with the relationship originally established for experimental 1-ton heats. It will be noted that in the range of metal composition of these heats, the slag values generally lie above the line. As was suggested by

Jan 1, 1954

By D. A. Kraai, S. Floreen

The effect of 1 to 50 ppm S on the ductility of nickel at 800° to 1400°F was studied. Results at each temperature showed a decrease in the reduction of area from approximately 95 to 5 pet over the sulfur range studied. Ductility varied with grain size, but only to a minor extent relative to the sulfiw effect. The effects of sulfur were completely offset by the addition of small amounts of magnesium. The results indicate that the "hot-short" loss in ductility is not an inherent property of nickel. Some possible mechanisms which cause the loss in ductility are described. MANY metals or alloys that normally possess high ductility exhibit a ductility loss at intermediate temperatures. This loss in ductility is often called "hot-shortness". Numerous examples of this phenomenon have been reported in the literature. Much of this work has been reviewed by McLean1 and by Rhines and Wray.2 To date there is no fully satisfactory explanation of the cause of this intermediate-temperature hot-shortness. It is generally recognized that impurities, and particularly impurities that form low-melting phases, can cause embrittlement. Examples of hot-shortness have been reported, however, where there were no obvious impurities present which would lower the ductility. Thus there has been some basis for believing that hot-shortness is an inherent property, and that even the purest metal would display a hot-short loss in ductility. This latter hypothesis was recently put forward by Rhines and wray2 based on studies of nickel and nickel alloys. In the discussion of this paper, however, Guard noted that high-purity nickel showed no hot-shortness.3 Thus there is reason to doubt whether pure nickel, or by inference any other pure metal, will inherently exhibit hot-shortness. The present work was initiated to determine the extent to which hot ductility was sensitive to very small amounts of an impurity element. If it could be demonstrated that hot-shortness could be induced by only minor amounts of an impurity, then it might be argued that hot-shortness in general is an impurity effect, and not a fundamental property of pure metals. The particular impurity studied was sulfur in nickel. The deleterious effects of sulfur are well- known. It is also well-known, and will be shown below, that additions of magnesium will render sulfur innocuous. When no such refining agents are added, however, the Ni-S system is a very useful one for studying the influence of small amounts of impurities. EXPERIMENTAL PROCEDURE Two heats containing -24 ppm S were vacuum-melted and small amounts of magnesium were then added under an argon atmosphere. These alloys were used to show the effectiveness of the normal magnesium treatment in overcoming the influence of sulfur. A second series of alloys with a sulfur range of 1 to 50 ppm was then prepared by vacuum melting nickel in alumina crucibles. No elements, such as magnesium, which tend to combine with sulfur were added. The higher sulfur contents were attained by adding nickel sulfide. Lower sulfur contents were prepared using a method in which the melt was oxidized under vacuum to produce the reaction S + 2O = SO2 These heats were subsequently deoxidized with carbon. Ten- to twenty-pound ingots were cast of all of the alloys studied. The compositions are given in Table I. The ingots were forged and hot-rolled to 3/4-in. bar. They were then annealed at either 2000" or 1600°F to produce different grain sizes. One-quarter-in.-diam tensile specimens were machined from the bars. These were tested at 800°, 1000o, 1200°, and 1400°F. The specimens were held at temperature approximately 45 min before testing. The strain rates were 0.005 min-1 to yielding, and 0.05 min-' after yielding. No extensometers or gage marks were placed on the specimens because the higher sulfur heats tended to fracture at the knife-edge indentations or gage marks. The properties measured were ultimate tensile strength and reduction of area. The analytical technique for determining sulfur at low levels was that developed by Burke and Davis.4 They reported a standard deviation of 1 ppm at an average sulfur level of 4 ppm in NBS standards. A standard deviation of 3 ppm is probably more realistic for the alloys used in this investigation considering the possibility of some segregation in the ingots. RESULTS A summary of the tensile results is given in Table I. As shown in the table, both heats to which

Jan 1, 1964

Jan 1, 1931

By Jacques B. Wertz

Among the parameters to be considered in the continuous search for new base-metal deposits, there often is a stratigraphic controlling factor that seems instrumental in the localization of ore. In British Columbia, for instance, the Upper Triassic as well as Lower Jurassic volcanics mixed with sediments are a useful indication in the search for copper while, in some parts of Australia, rhyolite bodies seem to be the favorable indicator, and this always within the geosynclinal environment. In Arizona, this stratigraphic factor becomes highly significant and it will be shown here that a large number of ore deposits are to be located around the flanks of ancient calcareous basins or depressions, preferentially corresponding to a certain optimum thickness as revealed by isopachs. The Martin limestone, of Devonian age, is already known for its basal O'Carroll bed which coincides with mineralization at places, and this is a relatively minor control. However, several limestone basins outlined by isopachs are in reality of greater importance as they localize mining districts. Indeed, most mines are found to coincide with a specific thickness of limestone while occurring simultaneously close to major, regional fracture intersections. The regional fractures in question were interpolated and extrapolated from known, important fault expressions, integrating quite well with the existing geology and further confirmed by minor criteria such as contacts, igneous plugs, axes of elongation of batholiths, dikes, etc. Although elements of subjectivity remain, this grid of fractures can be used quite successfully as a working hypothesis in the search for ore. Results of the present study which superposes major structural

Jan 1, 1971

I HIT the ceiling when I opened my November MINING ENGINEERING and after waiting a week to cool off I' still find it necessary to express my resentment of the gross libel embodied in the editorial introduction to Norman Stines' legitimate criticism of my paper on "Russia's Mineral Potential" (p. 949). The underlying thesis of my article, and a point that I tried to make even more clearly in my oral presentation at the St. Louis meeting last February, is that we should not over estimate the present and near-future mineral production of the USSR. The words that I resent in your boxed introduction are: "Opinions range from those presented by Paul Tyler ... to those of Norman C. Stines . . ." This is not merely an understatement that can be defended by admitting that the range goes much farther to the left, beyond me. It represents the appraisal that 90 pct of your members will carry away, namely that I am not only an incompetent observer-which may be true-but always that my bias is to applaud the efficiency of the beasts in the Kremlin-which is not true. Notwithstanding my efforts to clarify the record I now find myself branded as being at the opposite pole from 'Mr. Stines among the red-eyed worshipers of Communism or at least among the timid souls that shake in their boots in the belief that the Soviet system has created an invincible as well as an evil menace to the decent peoples of the world. My ideas are somewhere in the middle ground between Mr. Stines' complaisance or contempt and the exaggerated fears of several other observers whose views have received wide acceptance. PAUL M. TYLER MINERAL TECHNOLOGIST & ECONOMIST 5005 EDGEMOOR LANE, BETHESDA, MD. The introductory paragraph to Mr. Stines' criticism of Mr. Tyler's article (Russia's Mineral Potential, June issue MINING ENGINEERING, page 494) is erroneous as pointed out in author Tyler's letter above. In his article he objectively presented an estimate of the mineral position of the Soviet based on the statistics available to him which sources are credited in the first paragraph of his article. We happen to know that, Mr. Tyler was reluctant to prepare the article for the Mineral Economics Division sessions at the 1951 Annual Meeting and did so only because of his loyalty to AIME. It was thought that this article would be a basis for discussion of this important subject at the Annual Meeting. We apologize to Mr. Tyler for any embarrassment our introduction, may have caused him. Editor

Jan 1, 1952

By J. McLaren Forbes

Geologists and engineers in charge of diamond drilling often have no practical experience in the work, yet they must direct the drillers. In discussing some of the problems that arise, the author of this paper has tried to remember the things he did not know about diamond drilling when he first came in contact with that work. The basic reason for most diamond-drill holes is to obtain information. The more thorough the understanding of the geological and engineering problems involved, the greater will be the benefit derived from a drilling program. One of the best methods to ensure some thinking before drilling is to record on the permanent drill log, before the hole is collared, the reasons for the work and the information desired from that particular hole. When the hole is finished, the information obtained should be recorded. Driller The choice of a diamond driller is very important. If no experienced driller is available, a competent miner who has a sense of responsibility and better than average mechanical ingenuity can do the work. The best answer to most practical drilling problems, from the standpoint of the person in charge of the drilling program, is the service of experienced diamond drillers or drilling firms. Equipment Drilling equipment should be adequate to put down the longest hole desired and handle the toughest ground encountered. The type of bit used depends upon the ground drilled. Experimenting with various bits and careful study of footage records are the best means of determining which to use. Under ordinary circumstances it is best to drill using an EX barrel when possible. The length of rod and core barrels that can be used depends on the size of the drill station. Also, the length of core barrel depends on the way the ground cores. In good ground as much core will be recovered with a 10-ft. barrel as with a shorter one, and with considerable saving of drilling time. A water pump is needed if the hole is so deep that the water pressure is not strong enough to wash out the cuttings, or if it is drilled at an angle that prevents full force of the water pressure. Instructions For an Inexperienced Driller 1. Never run a bit too long a time. When a bit seems to be "good for one more run," discard it. 2. Always let the rods down on bottom easily. Protect the bit from sudden shock. 3. Start the drilling slowly and easily. Do not put pressure on the bit too fast. Diamonds can break. 4. Be sure the water pressure is strong enough to clear the bit, but do not use more water than is needed, as it may wash away the core. Usually, if no core is recovered the hole is a total loss. 5. When dry-blocking, do not run without water longer than necessary as the bit may burn. 6. Be sure the rods are well caulked and tightly screwed together. If not well caulked they will lose water, and if not

Jan 1, 1946

By A. Eilers

A number of the copper refineries in this country have lately separated some of the rarer metals from the slimes in the refinery tanks. One of these has furnished me the following table of recoveries from given amounts of blister. I publish this to show the proportions, to gold and silver and to each other, in which these rarer metals may be expected to occur in copper from certain localities. GarFIeld, Utah :—The blister copper comes principally from the Bingham porphyry copper mines. Steptoe, Nev. :—All the blister copper is produced from the Nevada Consolidated mines. (Also porphyry deposits.) Omaha, Neb. :—Blister copper comes principally from concentrated copper-lead mattes shipped from the different lead-silver plants of the Rocky Mountain region to the converters at the Omaha lead refinery. Mountain, Cal. :—Ores occur in connection with diorite (?).

Jan 1, 1914

Jan 1, 1954

By George H. K. Schenck, Peter G. Donald

There is an accelerating acceptance of change by management of cement companies. Diversity of response is noticeable in efforts across the country to reverse the downward trend in profits that brought margins in 1966 to the lowest point in 20 years. New concepts are emerging among managers as they seek to increase the efficiency in use of the basic corporate resources of men, capital and technology. The shift towards computerized control of cement manufacturing is making new gains as is diversification of cement companies into allied fields such as production and sale of natural and light- weight aggregates, crushed stone and concrete products. Increased interest in special products such as white cement and further moves overseas are also significant. Perhaps the most dramatic event of recent years occurred in Washington at hearings before the Federal Trade Commission where cement producers split on whether there should be FTC guidelines that would prevent ownership of ready-mixed concrete producers by cement companies.

Jan 4, 1967

By AIME

Compiled by Mary Ann Gross, Department of Energy. Bruceton. PA. Supplemental data from Coal Age indicated by (*). Reprinted by permission from CoalAge magazine.

Jan 1, 1981

By AIME

WE produce Charles Van Ormer "Charlie" Millikan as living proof that man need not make a loud noise to be heard. His quietly affable, analytical, and soft-spoken manner in the face of all problems belies his ability to "get tough" when the situation demands it. As a chief engineer with many responsibilities for the success of a large producing company there must have been many occasions to tempt Charlie to excitement, but there are few, if any, who can say they saw him yield. He has an abiding faith in the benefits of hard and persistent work and will not admit the existence of a problem that cannot be reduced by it.

Jan 1, 1948

By R. A. Morse, P. M. Bridges, L. E. Wilsey, Howard N. Hall, P. L. Terwilliger

Theoretical and experimental investigations of a constant pressure gravity drainage system are reported. Experimental data are presented to show that recovery to gas breakthrough by gravity drainage is inversely proportional to rate. The gravity drainage reference rate, which is numerically equal to the so-called "maximum theoretical rate of gravity drainage" is shown to have no particular significance from a recovery standpoint. Before this rate can be used as a basis of comparison for recoveries, it is necessary that the relative permeability and capillary pressure characteristics and displacing fluid viscosities be identical for the systems compared. A method is presented by which accurate prediction of the performance of a gravity drainage system can be made. Close agreement between experimental and calculated drainage performance shows that steady state relative permeability and static capillary pressure data can be used to describe fluid displacement behavior. The very wide range of liquid recoveries before gas breakthrough which result from production rate variation alone demonstrates the importance of this factor in planning depletion of a gravity drainage reservoir. Calculated results are presented which show that little additional recovery can be expected from a high pressure gravity drainage system between the times of gas breakthrough and attainment of such high gas/liquid ratios as to make further pressure maintenance impractical. INTRODUCTION It bas been recognized for some time that gravity forces play an important part in the recovery of oil from some types of reservoirs. Field experience has shown that under certain conditions, gravity drainage can result in very high oil recov- eries. Qualitative reasoning has led most engineers to the general conclusions that: (1) Where gravity drainage is important, the reservoir pressure should be maintained by gas injection at the crest of the structure to prevent shrinkage of the oil in place and to keep a low viscosity so the oil can drain at the fastest possible rate. (2) Recovery by gravity drainage is rate sensitive. A survey of the literature indicates that while considerable work has been done on the effects of gravity in oil production problems, no satisfactory method of calculating the performance of gravity drainage reservoirs has been reported.1,2,3,4,5 In the absence of any proven method of calculating reservoir performance, the level at which pressure should be maintained and the rate of production for most efficient operation has been open to debate. The limits and general character of the recovery us rate relationships are apparent from the following: As rates of production approach zero, oil will drain by virtue of its own weight fast enough that the saturation distribution is always approximately the same as the original static capillary distribution. That is, at the gas-oil contact the liquid saturation goes from 100 per cent to a value of perhaps 10 to 30 per cent in a very short distance, so that as production continues. a relatively sharp gas-oil contact moves down-structure, leaving a very low residual oil saturation in the originally oil saturated zone. At very high rates of production, the oil that drains by virtue of its own weight is negligible and recovery will approach that of a horizontal gas drive, leaving a much higher residual oil saturation. At intermediate rates of production. recovery should be between these extreme*. Despite the lack of quantitative methods, tentative agreement had been reached on the question of optimum producing rate. It has been generally concluded that rather sharp decrease in recovery would occur at rates of production above the "maximum rate of gravity drainage" and hence this rate should not be exceeded. The "maximum rate of gravity drainage" is defined as the rate of production from a 100 per cent

Jan 1, 1951