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By O. W. Simmons, L. W. Eastwood, C. M. Craighead

Binary alloys of titanium with silver, lead, tin, nickel, copper, beryllium, boron, silicon, chromium, molybdenum, manganese, vanadium, iron, and cobalt were studied. One-half-pound ingots of the alloys were prepared in an arc furnace, employing a water-cooled copper crucible, an argon atmosphere, and a water-cooled tungsten electrode. The half-pound ingots were fabricated by forging at 1700°F in air to 1/4-in. slab, followed by hot rolling at 1450°F to 0.060-in. sheet. Tensile properties, minimum bend radii, hardnesses, response to heat treatment and aging treatment, and phase relationships were determined for these alloys. EARLY in 1947, as one phase of the evaluation of materials for Air Force Project RAND, Battelle successfully arc melted Bureau of Mines titanium and obtained a few basic properties of unalloyed titanium and several titanium-base alloys. The low density, excellent resistance to corrosion, and high tensile properties of these materials stimulated a great deal of interest among metallurgists and designers seeking better materials of construction. As a result of this early work, Battelle, under contract with the Air Materiel Command, Wright-Patterson Air Force Base, has continued extensive studies of titanium alloys. The result of the first year's work is described in three papers. The present one deals with binary alloys, the second with ternary alloys, and the third paper with quaternary alloys. Melting Method The arc furnace for melting titanium and other refractory metals was developed at Battelle Institute under Air Force Project RAND. During the present work, considerable improvement has been made in the design and operation of this furnace for making small ingots of titanium and titanium alloys. The improved furnace design is illustrated by fig. 1, which shows a cross-sectional view with the dimensions of various parts and their relationship to one another. The essential features of the furnace are the inert argon atmosphere, the water-cooled copper crucible, and the water-cooled tungsten elec- trode. The melting crucible is formed by spinning 0.064-in. annealed copper sheet. A groove for an O-ring seal is spun into the flange of the crucible. A fiber gasket between the crucible flange and the water-cooled brass cover provides electrical insulation. The brass cover is fitted with a sight glass, an opening for the water-cooled electrode, and a tube through which the material is charged. Direct current is used for melting, with the positive electrical terminal connected to the water jacket and the negative terminal to the electrode. A typical heat is made in the new furnace as follows: Approximately, 0.20 lb of titanium under 2 mesh per in. and the alloy addition, if any is to be used, are placed in the bottom of the crucible. The cover is clamped on the crucible so that the O-rings make a tight seal. The remainder of the charge is placed in a glass bottle, and this is connected by a rubber hose to the charging tube of the furnace. The crucible and the charge are evacuated with a mechanical pump to a pressure below 50 mm of mercury, or less if desired, and held at this reduced pressure for 5 min. Hot water is circulated through the jacket during the evacuation period to assist in outgassing the crucible. Following the evacuation, tank argon of 99.92+ pct purity is flushed through the crucible for 5 min and then adjusted to give a positive pressure of 1 to 2 psi. During subsequent operation, an argon pressure regulator introduces only enough argon to compensate for the small leakage which occurs through a mercury trap. Re-evacuation and reflushing the melting chamber with argon produced a negligible reduction in contamination. Two 550-amp generators, connected in parallel, constitute the power source. Normally, about 800 amp are used for melting alloys which are not extremely refractory. The generators are set for 90 v open circuit and 200 amp. The arc is struck and the electrode is withdrawn to produce an arc of 23 to 26 v. This voltage is maintained while the electrode tip is moved slowly around a circle 1 in. smaller than the diameter of the ingot. The current

Jan 1, 1951

By T. B. Counselman

AN iron blast furnace of 1000 tons daily capacity will produce about 100,000 cu; ft. per minute of blast-furnace gas. This contains about 25 per cent of carbon monoxide, and has a B.t.u. value of about 95. This gas-is used primarily for heating the stoves of the blast furnace, and secondarily, under boilers, for steam production. Occasionally it is also used in gas engines. The raw gas coming out of the furnace carries about 10 grains of flue dust per cubic foot of gas, under best operating conditions. With the furnace "rolling" or slipping, this quantity may temporarily be greatly increased. This dust would, of course, deposit on the checkers of the stoves, or plug the burners under the boilers; therefore the gas must be cleaned.

Jan 1, 1936

By R. J. Colony

The failure, or disintegration, of concrete in structures, even when the cement, sand, and coarse aggregate used have passed satisfactorily all tests and inspections, is not uncommon. Such failures occur even when proper methods of mixing and placing have been used and where weather conditions were correct. In these cases, the origin of the trouble must be sought in the cement; therefore some additional mode of determining the quality of cement must be employed. The problem is to find a simple, usable, easily applied method that will supplement the standard tests. The solution of this problem involves a knowledge of the chemical composition of Portland cements, also of their constitution (or componental composition), as the behavior of a cement, when gaged, is dependent on the physical and chemical characters of the compounds of which it is composed, the proportions existing between them, and the fineness of grinding. It is likewise essential to know the character, behavior, and composition of the hydration products of Portland cement. The most promising method of attack makes use of chemical, mechanical, and petrographic methods. Chemical, by determining quantitatively not only the usual constituents, but the carbon dioxide and water. Mechanical, by determining the fineness with the air analyzer,' which separates into fractions of various grain dimensions all of that portion which in the ordinary sieve test passes the 200-mesh sieve and constitutes at least 75 per cent. of the total cement. These fractions may be further studied chemically and petrographically and micrometric measurements can be made of the grains. Petrographic, by the method of immersion, and by making thin sections from test pats of both neat cements and standard mortars. Normal Portland cement is composed of mechanical mixtures of definite chemical compounds having constant chemical and physical properties. In the order of their cementing qualities these are: Tri-

Jan 1, 1922

By Percy Gillie

THE Tralee preparation plant, owned and operated by the Semet-Solvay division of Allied Chemical and Dye Corp., is located on the Virginian railway, near Mullens, Wyoming County, W. Va., and the mine, which is in the Winding Gulf district, produces coal exclusively from Pocahontas No. 3 seam. The property, comprising 4900 acres, is leased from the Pocahontas Land Corp. Prior to 1930 four separate mines were operated in this tract, some having been started about 1916. Plans for the preparation plant were formulated soon after World War 11. Construction began in the spring of 1948, operation early in 1950. The plant was designed to be operated with minimum labor. It was equipped for production of first quality graded sizes of coal for house heating and 3/8x0-in. slack suitable for high-standard metallurgical coke. In the beginning, a thorough investigation was made of the property by means of core drilling, prospect openings, and sections from shallow mines on the property, as well as sections and analyses from mines in the immediate vicinity. After the extent of desirable coal had been established and the average seam section and nature of overlying and underlying strata had been determined, it was decided to install a system of mining which would load the full seam and would clean the product mechanically. Pocahontas No. 3 seam is characterized by draw slate and bone and rock partings. It was not known what the washing difficulties and cleaning plant requirements would be for processing the raw product of full mechanical mining. Arrangements were made, therefore, through the courtesy of the property owner, to obtain a large sample from a section of the mine along the adjoining property line. The

Jan 1, 1954

By T. M. Williams

DURING the year just ended we have had three great fires in the mines in the Wilkes-Barre district. One at the Empire Colliery, one at the Prospect shaft, and the other at the Baltimore old mine. It is proposed in this paper to give a brief history of the fire at the Empire Colliery, and the methods employed in extinguishing it. The fire was first discovered breaking out in the air-stack, alongside what is known as the " Kidder Plane," about one o'clock on the morning of December 31st, 1873. Subsequently it was ascertained that the fire originated in the return airway somewhere near the steam boiler, located inside the mine, near the head of No. 5 slope. The coal from this slope was hoisted to the shaft gangway, at a point nearly four thousand feet distant from the foot of the shaft. As there were from four to five hundred mine cars hoisted per day from this slope the steam boilers were located at this place. The mines being of considerable extent required a large volume of pure air for ventilation, and no fan having been erected at this slope at the time, the heat from the boiler was made use of to assist ventilation, by conveying the return air from No. 5 slope into the large airway made from these boilers to the surface through the old "Kidder slope" to the stack where the fire was first discovered. The length of this slope or airway was about one thousand feet, with a sectional area of about sixty feet. The quantity of air passing through it must have been over sixty thousand cubic feet per minute

Jan 1, 1875

By T. M. Williams

DURING the year just ended we have had three great fires in the mines in the Wilkes-Barre district. One at the Empire Colliery, one at the Prospect shaft, and the other at the Baltimore old mine. It is proposed in this paper to give a brief history of the fire at the Empire Colliery, and the methods employed in extinguishing it. The fire was first discovered breaking out in the air-stack, alongside what is known as the " Kidder Plane," about one o'clock on the morning of December 31st, 1873. Subsequently it was ascertained that the fire originated in the return airway somewhere near the steam boiler, located inside the mine, near the head of No. 5 slope. The coal from this slope was hoisted to the shaft gangway, at a point nearly four thousand feet distant from the foot of the shaft. As there were from four to five hundred mine cars hoisted per day from this slope the steam boilers were located at this place. The mines being of considerable extent required a large volume of pure air for ventilation, and no fan having been erected at this slope at the time, the heat from the boiler was made use of to assist ventilation, by conveying the return air from No. 5 slope into the large airway made from these boilers to the surface through the old "Kidder slope" to the stack where the fire was first discovered. The length of this slope or airway was about one thousand feet, with a sectional area of about sixty feet. The quantity of air passing through it must have been over sixty thousand cubic feet per minute

By J. H. Waxweiler, L. C. Ikenberry, R. J. Bendure

Carbon which is present as insoluble carbides in austenitic stainless steels can be measured quantitatively by dissolving the steel in iodine-methanol and analyzing the residue for carbon. Severe sen-sitization was observed in Type 302 due to precipitation of only 0.003 pet carbon. Both cold work and the presence of delta ferrite caused a marked acceleration in rate of carbide precipitation. Carbide precipitation rates in 17-7 PH were stzulied for the austenite conditioning and also the aging heat treatment. CARBON and its compounds exercise a major influence on the properties of stainless steels and their response to thermal treatment. Sensitization in 18-8 type stainless steels has been the subject of numerous investigations throughout the years. Bain, Aborn, and utherford," and Binder, Brown, Frankss all studied the effects of heating austenitic stainless steels in the temperature range of 1000° to 1500°F. The primary purpose of most of these studies was the investigation of susceptibility to in-tergranular attack in acids due to these sensitizing heat treatments. Intergranular precipitation of carbides was always associated with intergranular attack but it was recognized2 that severe attack could occur with but minute quantities of precipitated carbide. Mahla and ielsen utilized the electron microscope to make a significant contribution in illustrating the appearance and method of growth of chromium carbides during sensitizing heat treatments. However, as they stated, their studies of residues could not be used to obtain a quantitative measurement of the amount of carbon which was actually precipitated. The aim of the present investigation was to devise a relatively fast, simple method for the quantitative measurement of carbides in stainless steel. EXPERIMENTAL WORK The initial investigations were made to determine the best means of separating carbides from the matrix. A number of dissolving media were tried using both chemical and electrolytic attack. Qualitative examination of the extracted residues by X-ray diffraction indicated that solution in iodine-methanol would furnish a good means of separation. Consequently, further work was pursued along this line. The method is quite simple. The sample in the form of millings or nibblings is dissolved in iodine-methanol solution at room temperature (6-g iodine, 25-ml methanol per g of sample). The insoluble residue containing the carbides is separated by suction filtration through an ultra-fine glass filter disc. This is a very fine filter medium that will retain particles as small as 0.1 to 0.2 p in diameter. After washing with methanol and drying, the filter disc and residue are placed in a conventional combustion carbon-tube furnace and the carbon determined gravimetrically. Using this technique it was found that reproducible insoluble carbon values were obtained. However, since such small amounts of insoluble carbon were obtained on Type 302 after sensitizatipn at 1250°F and 1500°F, the values were confirmed by a second method. In the second method the sample was dissolved with copper potassium chloride and filtered through a millipore paper. This treatment dissolves the matrix but leaves undissolved practically all of the carbon irrespective of how it is present in the steel. The amount of insoluble carbon present as chromium carbide is determined by calculation from the analysis of the residue for chromium and iron. The derivation of the formula used for this calculation is discussed later. The values obtained by the indirect copper-potassium-chloride method were in agreement with those obtained by the iodine-methano1 method. See Table I. It should be pointed out that the sensitivity of the direct combustion method is not too high when the amount of carbide present is small. This is due primarily to inherent blanks and to analytical errors such as weighing. For this reason it cannot be stated with any degree of certainty that there is a significant difference between values of 0.002 and 0.005 pct. Having confirmed that the iodine-methanol extraction gave a quantitative measurement of the precipitated carbides in Type 302, exploratory tests were conducted on Armco 17-7 PH stainless steel. Samples from commercial Heat 54807 were solution annealed at 2000°F, water quenched and heated at 1250" and 1500°F, and water quenched. The analysis of Heat 54808 is as follows:

Jan 1, 1962

By T. F. Bower, M. C. Flemings, H. D. Brody

A series of experiments are reported which show thai reasonable assumptions for analysis of solute redistribution in solidification of castings and ingols illclr(de: negligible undercooling before nuclcation of solid phases, negligible increase of solute in advance of the tips of growing dendrites, complete diffusion within the Liquid oer distances the order, of dentrite arm spacings, platelike dentrite t/o?$holog?.. Qzmli/ali,e and periment is obtained JOY Al-Cu alloys front measurements of amount of nonequilibrium second phase, minimum solute content at the centers dentrites arms (after solidification), and 3) change in minimum solute content in dentrite arms during solidification. In a previous paper' analyses were given describing solute redistribution in dendritic solidification. The analyses were undertaken primarily to permit prediction of "severity of microsegregation" in a casting or ingot after solidification and cooling to room temperature, but can also be used to predict "local fraction solid' as a function of temperature in the solidifying alloy. Numerical results were given for Al-Cu alloys. The aims of this paper are to examine the validity of some of the assumptions of that analysis, and to compare predictions of the theory with experiments. All experiments reported are on Al-Cu alloys, the bulk on Al-4.5 pct Cu alloy. EXPERIMENTS Experiments conducted were on small ingots, 41/2 in. in diam by about 10 in. high. solidified in a controlled thermal environment (i.e., in a resistance-heated, re-circulating air furnace, whose temperature could be controlled to 1°C). In one series of experiments, the ingots were solidified very slowly (solidification time was varied from 8 to 1000 hr) and at constant rate of heat extraction. In a second series of experiments the ingots were solidified ( 'unidirectionally". Fig. 1 is a sketch of the method of making the two different types of ingots. The unidirectionally solidified ingots were fully columnar, and the slowly solidified ingots had equiaxed structures, Fig. 2. In making the slowly solidified ingots, the mold employed was carbon steel, coated with inert refractory. Typically the mold and its environment were heated to 700°C. The molten alloy was then poured into the mold and the temperature of the system equilibrated above the liquidus. The environment of the mold was next cooled with a controller responding to a differential thermocouple that measured the difference between the temperature of the melt and the temperature of the mold environment. The differential thermocouple consisted of one chromel-alumel junction in the melt connected in opposition with a second junction in the furnace. The potential across the differential thermocouple was input to the controller which acted to keep this potential at a set. constant value; hence the temperature difference between the two junctions was maintained nearly constant. Major resistance to heat flow in the above apparatus was between the metal surface and the furnace atmosphere, not in the metal itself. By maintaining a constant temperature difference between the metal and the furnace atmosphere, the controller maintained an essentially constant rate of heat extraction during solidification, regardless of amount of heat released by the metal per unit temperature change. When the metal temperature dropped just below the eutectic temperature. the ingot was removed from the furnace and water-quenched. The unidirectionally solidified ingots were cast in a similar mold to the foregoing except that provision was made to extract heat through the bottom face of the mold by passing air or water through the mold base, Fig. 1. For these experiments, metal and mold temperature were again equilibrated above the liquidus. Temperature of the mold environment was then held

Jan 1, 1967

By W. E. Howlett, R. L. Slobod

Jan 1, 1965

By E. W. Dewing

The nature of solid solutions of sodium in non-paphitic carbon at temperatures near 1000°C has been investigated by an electrolytic technique. The activity coefficient is found to vary strongly with the heat-treatment temperature of the carbon, and an analysis of the energy terms involved suggests that this is due to variations in the Fermi level. The diffusion coefficient for sodium is in the range implying that the sodium atoms (or ions) are not bound to specific sites on the carbon, in agreement with lack of evidence for specific compounds in the activity -composition curves. In the light of These results phenomena occurring in aluminum reduction cell linings are dis-cussed. It is concluded that sodium migrates by diffusion through the carbon lallice and not the pores, and that A14C9 is formed within the lining hy The excess of NaF invariably found in used linings is formed by this reaction and by air oxidation: There has recently been much interest in the swelling of carbon which occurs when it is made cathodic in an aluminum electrolysis cell, and there is general agreement that the phenomenon is due to the penetration of sodium atoms, derived from the reaction on the carbon lattice. (NaF and AlF3 are constituents of the fused-salt electrolyte.) The low-temperature lamellar compounds of potassium with graphite are well-known, and one compound between sodium and graphite has been reported.4 There is, however, virtually no information on the basic chemistry of the interaction of sodium with nongraphitic carbon at high temperatures, although Dell3 has made some fundamental studies of rates of penetration. At the time the present work was carried out these were not available. Rapoport and samoilenkol had measured rates of physical expansion in a dilatometer, using the fractional increase in length of a carbon specimen after electrolysis in a cryolite bath for 2 hr as an index of susceptibility to cathodic swelling. Work here with a similar apparatus showed that expansion (of a 1.5-in.-diam cylindrical specimen) ceased in less than 20 hr, and that the final expansion was much more reproducible than the value at some intermediate time. This suggested that an equilibrium was being set up, and that a thermodynamic approach was required. The results obtained are not as accurate as had been hoped, but they are the only ones of their type available and have enabled useful conclusions to be drawn. The experimental work was divided into two parts: an investigation of the activity-concentration diagram for sodium in carbon, and a rough determination of the diffusion rate. For the former, most of the experiments were made with petroleum coke even though this is not a form of carbon used in cell linings. It has the advantages, however, that it is a homogeneous material, that it is low in ash, and that its structure is reasonably well understood. Anthracites and coal cokes gave results of the same type as obtained with petroleum coke, but the reprodu-cibility from specimen to specimen was extremely poor. EXPERIMENTAL 1) The Activity-Composition Diagram for Sodium in Carbon. The petroleum coke was ground, pressed at 40,000 psi into plates 19 by 9 by 2 mm without added binder, and heat-treated. The sodium activities were established by an electrolytic technique. The carbon was made anodic in a cryolite bath with an aluminum cathode, and a controlled potential, E, applied so that the sodium activity at the anode was given by ln Na = 1n asa - EF/RT [21 where as, is the sodium activity generated by Reaction [I]. The relative activity is sufficient for many purposes and is simply given by The value of Na not at present known, but when the thermodynamics of the Na-A1 system have been worked out it can be derived from the equilibrium

Jan 1, 1963

By Colman Goldberg

IT is customary to plot crystallographic planes or axes on a Wulff stereographic net which is ruled with parallels of latitude and meridians of longitude. If a single crystal is placed at the center of a sphere, the coordinates of a crystallographic plane or axis are the coordinates of the point where the axis intersects the sphere. The standard (HKL) projection is the projection for which the sphere is rotated so that the (HKL) pole is at the center of the projection. Schiebold and Sachs' and many others have published standard projections for the more important planes of a cubic crystal. With Tables I and 11, it is possible to plot any plane (HKL) of a cubic crystal on a standard (001) projection if the absolute values of the individual H, K, and L are nine or less, which is almost always the case. Using the methods outlined by Barrett,' the standard (001) projection can be rotated so that any arbitrary plane is at the center of the projection. The tables are believed to be important for two reasons: 1—The heretofore published standard projections usually are not of the proper size to fit the stereographic nets available. With these tables a standard projection can be made which will be of exactly the proper size for the available stereographic net. 2—With the tables, planes that do not appear on the previously published standard projections can be easily plotted. For these reasons, the tables are especially useful in the study of optical reflections from etched surfaces and can also be used to make a standard projection for the axis which is normal to the macroscopic surface. (This axis can be found by X-ray or optical methods.) Then if the crystal is etched, the effect of the etchant can readily be determined by comparing the latitude and longitude of the reflecting planes (as determined with an optical goniometer) with the standard projection that has been prepared. Use of the Tables Fig. 1 shows the meridians and parallel which have been designated as zero longitude and latitude. The tables themselves are self-explanatory. The

Jan 1, 1953

By T. B. Counselman, T. B.

Continuous countercurrent decantation calculations have always been a headache to the cyanide man (and the chemical engineer) because of the simultaneous equations involved. These are tedious to solve, and there is considerable opportunity for mathematical error. This paper presents a shortcut method for making these calculations, which has been in successful use for twenty years by the author, and which is particularly valuable in selecting the best of several possible flowsheets, or evaluating the effect of various assumptions.

Jan 1, 1950

By B. F. Koch

COPPER reverberatories develop large amounts of exit gases of a temperature in the neighborhood of 2000°F. The gases are not only of a noxious nature but must usually be disposed of at considerable heights above the yard level by a stack. Handling these gases at the temperature mentioned would require rather expensive construction of conveying flues and stack. Moreover, wasting such amounts of heat is certainly most uneconomical. Numerous investigations have indicated that waste heat boilers of the water-tube type are the most practical and economical means for utilizing that heat although the gases are heavily laden with rock dust and copper-bearing slag, which upon cooling form hard deposits on the surfaces of dampers or heat absorbing elements placed in the gas stream. Avoiding Slag and Dust Deposits Based largely on the experience of the paper industry in burning black liquor, a waste heat boiler design was developed a few years ago, providing not only extensive water-wall surfaces for cooling the gases below the fusing point of the slag but also settling out, as far as possible, the solidified particles of slag by creating low gas velocity. Matter carried in a stream of gases or air has a tendency to maintain its original direction upon a change in the direction of the flow of the conveying medium. Reverberatory waste heat boilers installed at Hurley and Morenci endeavored to utilize that tendency for the elimination of slagging particles at predetermined places and before they would strike the tube banks of the boilers. Both installations were successful in minimizing the slagging of boiler tubes and thereby minimizing the need for hand lancing. However, the low draft carried at the up-take of the reverberatory furnaces resulted in a positive pressure in the upper part of the furnace of the waste heat boilers, causing the emission of gases from lancing doors and making more difficult the already unwelcome work of cleaning the boilers by handlancing. Attempting to correct this nuisance as much as possible, the overall height of the Chuquicamata waste heat boilers has been reduced to the minimum considered necessary to obtain proper water circulation in furnace walls. Moreover, it is attempted to solidify slag and dust particles by providing large amounts of water-cooled surfaces before the gas stream reaches super-heater and convection banks of the boilers. The furnaces have been made as deep as an economical and practical arrangement of headers for water

Jan 1, 1952

By A. Muan

Liquidus data are presented for mixtures in the ternary system FeO-Fe2O3-SiO2 in equilibrium with a gas phase with O2 pressures ranging from 10-10.9 to 1 atm. Data obtained are combined with previously published data to construct lines of equal 02 pressures and lines of equal CO2/H2 mixing ratios along the liquidus surface. Courses of crystallization of selected mixtures under conditions of constant total composition, constant O2 pressures, and constant CO2/H2 mixing ratios are discussed. PHASE equilibrium studies of silicate systems where iron is one component are complicated by the fact that iron readily occurs in three different states of oxidation: Fe3+, Fe2+, and Fe0. Success or failure in work with iron silicate systems is to a large extent dependent on control of the oxidation state of iron and all investigations therefore must be carried out under carefully controlled atmospheric conditions. Silicate systems containing only strongly electropositive metals (like Na+, Ca2+, Mg", etc.) can, for simplicity, be treated as condensed systems, that is, the gas phase can be neglected and the phase relationships discussed in terms of the phase rule written in the well known simplified form P + F = C + 1. In the case of iron silicate systems, however, the composition of the condensed phases varies with the gas composition, and a complete picture of phase relationships can be obtained only by varying the gas composition over a wide range. In order to understand the phase relationships in the more complicated multicomponent silicate systems with iron oxide as one of the constituents, a knowledge of the ternary system FeO-Fe2O3-SiO2 is essential, since it constitutes a bounding portion of all such systems. It was with this in mind that the present study was undertaken. Previous Work A considerable amount of work has been done on various aspects of the chemistry and metallurgy of systems containing silica and iron oxides. The two bounding binary systems FeO-Fe2O3 and FeO-SiO2" The first attempt to obtain information on phase relationships of iron oxide-SiO, mixtures at different 0, pressures was made by Greig.' Darken" determined the melting points of iron oxide on solid silica under various atmospheric conditions. Darken did not determine experimentally the composition of the melts at liquidus temperatures but discussed very ably the principles involved in applying the phase rule to the system. In a recent study Schuhmann, Powell, and Michal8 determined experimentally the liquidus surface of a portion of the ternary system and combined the new information with data in the literature to construct a phase diagram. Their method was briefly as follows: Homogeneous mixtures with various contents of SiO2, FeO, and Fe2O3 were made up by melting together stock mixtures in various proportions. Samples of the homogeneous mixtures, the compositions of which were determined by chemical analysis, were then heated in platinum crucibles in an inert atmosphere until equilibrium among the condensed phases was achieved. The samples were quenched to room temperature and the phases present determined by microscopic examination. Assuming that no change in composition takes place during the equilibration run in inert atmosphere, the liquidus surface can be determined, but no information is obtained regarding the partial pressures of 0, of the gas phase in equilibrium with the condensed phases. The author's method, to be described in the next section, permitted the location of points at the liquidus surface as well as a calculation of the corresponding partial pressures of O2. Experimental Method General Procedure: The standard quenching technique was adapted for a study under controlled variable atmospheric conditions. Premelted mixtures of silica and iron oxides in platinum envelopes were held at constant temperature under chosen atmospheric conditions until equilibrium was reached among solid, liquid, and gas phases. The sample was then quenched to room temperature, the phases present identified, and, for the most significant runs, the composition was determined by chemical analysis. The corresponding partial pressure of 0, was calculated from known equilibrium constants of the gas reactions occuring in the furnace atmosphere. Materials: Starting materials were oxides of commercially highest available purity; cp silicic acid was dehydrated by heating to 1350°C for 6 hr and cp Fe2O3 was dried at 400° C for the same length of time. Samples of 10 g were made up by mixing

Jan 1, 1956

By W. L. Martin, J. N. Dew, H. B. Steves, M. L. Powers

This paper presents and discusses the results obtained during a pilot test in the Loco field in southern Okla homa. The test was conducted in a 2%-acre pattern that was part of a 20-acre conventional waterflood pilot area. The conventional flood was well past its economic limit when the hot waterflood was initiated to obtain technical information and operating experience. Temperature data from nine observation wells showed that about 75 percent of the pattern was affected by heat, and that heat losses were severe in the pilot pattern. About 60 percent of the injected heat was lost to overburden and underburden zones during hot-water injection. Wellbore heat losses were held at tolerable levels at the shallow depth of the test by providing a low-pressure air annulus between the injection tubing and well casing. Hot water provided water injectivity increases of 200 to 400 percent. The hot water channeled across the lower portion of the oil sand in three directions through zones of relatively high water saturation. There was no conclusive evidence that natural fractures or pressure partings aflected the flow of fluids in the pilot pattern; however response undoubtedly was aflected by localized pressure gradients and by injection-production rate ratios. The results showed that hot waterflooding increased oil recovery in a reservoir containing 600 cp oil. The total tertiary oil production from the pilot pattern area was 3,896 bbl or about 156 bbl/acre-ft swept by heat. The corre.sponding WOR was about 34:I. Description of the Hot Waterflood Process To hot waterflood an oil reservoir, water is injected that has been heated to a temperature substantially higher than the original reservoir temperature, but lower than the vaporization temperature of water at the prevailing pressures. In the reservoir the hot water flows continuously into cooler sand and rapidly loses heat to the sand until it has been cooled to the original reservoir temperature. Thus, a heated zone and a region or "bank" of cooled water begins to accumulate immediately after hot water injection is started. This bank of cooled water continues to grow ahead of the heated zone, which also grows, but at a slower rate. This occurs because heat transfer is almost instantaneous, and the ratio of heat capacities of water to rock is such that two or three unit PV of hot water must be injected to heat a given unit bulk volume of the reservoir. The primary displacement mechanism is the same for both hot and conventional cold waterfloods; i.e., "piston" displacement occurs at the original reservoir temperature. The incremental benefits of hot waterflooding usually occur long after the breakthrough of cold water at producing wells, and the increased oil recovery necessarily is accomplished with high WOR's (water-oil ratios). Heat decreases the viscosity and density of oil and water. These effects result in more rapid and increased recovery of secondary or tertiary oil. If the cost of the required heat is low enough, the ultimate oil recovery of a hot waterflood should be increased substantially over what would be expected at the economic limit of a conventional cold waterflood. The economic benefits of any hot-fluid injection project depend primarily upon the cost of the heat required to produce more oil at an increased rate. This cost depends in part upon the amount of heat lost to surrounding formations. Heat loss depends upon reservoir thickness, water injection rate and temperature, the depth of the formation, well spacing, and the characteristics of the reservoir rock and surrounding formations. In general, percentage heat losses decrease as injection rate and reservoir thickness increase. Although it is an old idea, hot-water injection has not received widespread field application in the oil industry as a drive process. Much of the original field work with hot water was done in Pennsylvania fields where water permeabilities and injection rates are low. In these cases, hot-water injection was used primarily as a means of increasing in-jectivities — not as a recovery process. Ramey' recently has published an excellent review of the development of hot fluid injection processes. Recent publications"' and our own experiences now indicate that hot water or steam injection also can effectively increase the oil recovery from reservoirs containing viscous crudes. However, the economics of these methods as displacement processes have not been established. Several theoretical predictive techniques have been published (for a review see Ramey'), but simplifying assumptions make

Jan 1, 1969

By D. N. Seidrnan

In the present note we present thermal-analysis data for the liquidus curve from 0 to 76 at. pct Se and for the selenium-rich monotectic reaction in the Pb-Se system. We have previously reported that no expey-imental eviderzce was found for a lead-rich monotectic reaction, at -860°C with a monotectic composition of -20.5 at. pct Se, as found by Nozato and Igaki.&apos; Our additional data substantiated this earlier finding and extended the composition range studied. The alloys were prepared from semiconductor -grade lead and selenium purchased from the American Smelting and Refining Co. Both elements were 99.999+ wt pct pure as determined by the supplier. The impurities for lead were Fe (1 ppm) and Cu & ppm) while for selenium the impurities were Cu (< 1 ppm), As (< 1 ppm), Te (1 ppm), and C1 (<1 ppm). The general procedures used for thermal analysis were those specified by the National Bureau of Standards. A Pt/Pt-10 pct Rh thermocouple calibrated against the freezing points of zinc and copper purchased from the National Bureau of Standards and antimony (99.985 pct pure) purchased from A. D. Mackay, New York, was used for all the thermal analysis. The thermocouple electromotive force was measured with a Rubicon Type B potentiometer used in conjunction with a galvanometer with a sensitivity of 0.5 pV (mm) -&apos;. The absolute accuracy of this thermal-analysis system was *0.5"C. One-hundred-gram alloys of the desired composition were sealed in quartz crucibles, with a central thermocouple well, at a pressure of less than 10"1 Torr. The alloys were initially heated well above the liquidus curve and shaken vigorously to insure homogeneity. Cooling curves were then taken by the direct method at cooling rates ranging from -0.5" to 1.5"C (min)-&apos;. The phase diagram from 0 to 76 at. pct Se as determined by direct thermal analysis is shown in Fig. l.* An extrapolation of the selenium-rich portion of the liquidus curve to the monotectic reaction isotherm (678.3"C) gave a value of 76.1 at. pct Se for the monotectic composition. A tabulation of all the thermal-analysis data is given in Table I. As we previously reported no experimental evidence was found Fig. l—The partial Pb-Se phase diagram from 0 to 76 at. pct Se as determined by direct thermal analysis. For the sake of clarity the points for the 49.00 and 49.16 at. pct Se alloys were not drawn on this phase diagram, see Table I. for the lead-rich monotectic reaction found by Nozato and Igaki.&apos; This result was further substantiated by the fact that none of twelve lead-rich alloys, see Table I, examined for this monotectic reaction exhibited a thermal arrest in the temperature range (849" to 863°C) cited by Nozato and Igaki for the lead-rich monotectic reaction. Hence, our results tend to support the earlier qualitative work of ~elabon&apos; and Friedrich and ~eroux" in the 0 to 50 at. pct portion of the phase diagram, though the selenium-rich monotectic composition and reaction isotherm temperature were in agreement with the approximate values (75 at. pct Se and 672" to 680°C) given by Nozato and ~~aki. &apos;

Jan 1, 1967

By Herbert Dlaska

The BBU - rotary hearth treats lead concentrates and battery scrap by the roast-reaction process. It corresponds in principle to the long-known Newnam hearth, however its hearth-basin is not straight but curved to a closed ring. In operation this annular hearth is filled with liquid lead and rotates around a central blast-box. The charge, heated to a glowing-red, floats on top of the lead bath, into which air is blown from the blast-box through a horizontal slot-type tuyere. Ore pellets and brown coal are continuously charged onto the reacting mass from two storage bins. Lead is set free by the roasting reactions and trickles through the charge into the lead bath from where it is tapped from time to time. The reacting mass is continuously stirred by a mechanical agitator and backed, by a mechanical shovel, against the water-jacketed wall of the blast-box. The gangue of the charge forms lumps of scorified character, the so-called hearth slag or grey slag, which are discharged from the hearth. The waste gases are collected in a hood and conducted to a baghouse from where the fumes and dust are automatically transported to the pelletizing installation and are recycled with new material. The daily output of lead bullion depends mainly on the lead content of the charge. With lead concentrates containing 74% lead, about 24 tons of lead bullion per day are produced on the hearth at a direct lead recovery of about 89 per cent. Approximately 10 per cent of the lead content of the new material passes into the hearth slag from where it can be recovered in a blast furnace or in a rotary furnace. For small lead smelters the BBU-process represents the most economical way of melting high-grade lead concentrates. The process requires a relatively small capital investment, consumes little fuel, utilizes cheap fuel and is very flexible. Further, of great importance, is the fact that battery scrap can be treated by the BBU-process with very good results.

Jan 1, 1970

By Robert C. Weed

Leaching in place at Cananea began in the 1920&apos;s on a limited scale. The first plants were small wooden boxes located underground in the Capote and Oversight mines, and output was low. Scrap iron was used as precipitant. Later several other small plants were started up. Leaching was limited entirely to underground areas, and production remained low. The Veta precipitating plant, the first on a larger scale, was put into operation in the late 1920&apos;s. After a period of intermittent service it was rebuilt in 1946 and has since been running continuously.

Jul 1, 1956

By F. M. Lewis, J. F. Meyers

In the mining and handling of sulphide ores, some degree of oxidation takes place on the sulphide surfaces, which are exposed to the atmosphere. It is, moreover, well known that the oxidation compounds formed are a factor when such ores are subsequently treated by flotation. Modern operating technique and reagents are capable of contending with this condition to a major degree, provided that the proportions of the reagents used are varied correctly. This is particularly true at the Tennessee Copper Co., where the ore treated contains pyrrhotite in addition to other sulphides. A number of soluble salts, some of which are unstable, can be formed during the oxidation of the sulphide ores. Those unstable salts, whose oxygen requirements are unsatisfied, are constantly changing to more stable forms because oxygen reacts with them during the crushing, grinding and other operations of ore preparation. We add no chemicals of any kid to the ore pulp in its preparation for flotation feed. Consequently the only compounds that are present in the flotation feed are those produced by the natural oxidation of the ore in the presence of air and water. The Tennessee Copper Co. ore is composed of from 60 to 70 per cent sulphides and from 40 to 30 per cent non-sulphide material. It is not the purpose of this paper to discuss the nature of these various oxygen-sulphur compounds nor their effect on flotation, but to describe a method for correcting the effect. Suffice it to say that we have found that the reducing sulphur and oxygen salts have a depressing action on our bulk flotation process.&apos; From long experience we find that the best means of correcting for this variation in our work is to increase or decrease the quantity of xanthate, the promoting agent, as the quantity of the reducing salts increases or decreases. It was, therefore, very desirable to provide the operators with some quick and

Jan 1, 1947

By F. M. Lewis, J. F. Meyers

In the mining and handling of sulphide ores, some degree of oxidation takes place on the sulphide surfaces, which are exposed to the atmosphere. It is, moreover, well known that the oxidation compounds formed are a factor when such ores are subsequently treated by flotation. Modern operating technique and reagents are capable of contending with this condition to a major degree, provided that the proportions of the reagents used are varied correctly. This is particularly true at the Tennessee Copper Co., where the ore treated contains pyrrhotite in addition to other sulphides. A number of soluble salts, some of which are unstable, can be formed during the oxidation of the sulphide ores. Those unstable salts, whose oxygen requirements are unsatisfied, are constantly changing to more stable forms because oxygen reacts with them during the crushing, grinding and other operations of ore preparation. We add no chemicals of any kid to the ore pulp in its preparation for flotation feed. Consequently the only compounds that are present in the flotation feed are those produced by the natural oxidation of the ore in the presence of air and water. The Tennessee Copper Co. ore is composed of from 60 to 70 per cent sulphides and from 40 to 30 per cent non-sulphide material. It is not the purpose of this paper to discuss the nature of these various oxygen-sulphur compounds nor their effect on flotation, but to describe a method for correcting the effect. Suffice it to say that we have found that the reducing sulphur and oxygen salts have a depressing action on our bulk flotation process.&apos; From long experience we find that the best means of correcting for this variation in our work is to increase or decrease the quantity of xanthate, the promoting agent, as the quantity of the reducing salts increases or decreases. It was, therefore, very desirable to provide the operators with some quick and

Jan 1, 1947