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By B. M. Harra, F. G. McCutcheon, O&apos

Until about 1930, the universal practice of horizontal-retort zinc smelters in the United States, as far as the writers are aware, was to operate the retort furnaces on a 24-hr cycle; that is, the retorts were charged in the early morning of one day, and in the early morning of the following day the residues were cleaned out, the retorts recharged, and a new cycle started. During the business depression of the early thirties, zinc production fell off to the extent that zinc smelters had idle retort capacity. Rather than continue to run some of the retort furnaces on a 24-hr cycle and shut down the remainder, a few companies decided to try out a longer cycle. Although the output of zinc per retort per day is lower, the longer cycle permits a larger charge per retort and improved zinc recovery. Advantages of the longer cycle were soon evident, and the practice spread rapidly. Various lengths of cycle were used, typical examples being 28-hr, 32-hr, 36-hr, and 48-hr. The 48-hr cycle fits in best with the standard routine of smelter practice that was built up on the basis of the 24-hr cycle; that is, the retort furnace "maneuver" always comes at the same time of day, and can be performed in the cool hours of the early morning. Under some conditions, particularly in some of the older plants, where the retorts are smaller than in newer plants, a 48-hr cycle is longer than necessary, and some intermediate length of cycle may theoretically be most economical. Use of an intermediate cycle, however, means that the maneuver comes at different times on consecutive days, and that sometimes it comes during the hottest part of the day. The work on the retort furnaces is extremely hot and arduous at best, and it is much worse, of course, if it is done during the heat of a summer day. When labor was plentiful and tractable, many plants were able to operate on cycles of intermediate length, but the workmen did not like the working hours. Under present labor conditions, it is hardly practicable to operate with a cycle of intermediate length, so the choice has narrowed down to the alternatives of 24-hr or 48-hr cycles. In any discussion of economics, too comprehensive generalization is not warranted, because local conditions affecting economics vary greatly. The best economic practice at one plant at any given time may be uneconomical at another plant, or even at the same plant at another time. To determine the length of cycle that is the better practice at a given plant at a given time requires a weighing of the advantages and disadvantages of each cycle, taking into consideration all the local conditions. some of the factors that must be considered in making the comparison are discussed briefly in the following paragraphs.

Jan 1, 1949

By Robert K. Warner

Is an accurate measurement of the efficiency of a screen under a given set of operating conditions valuable? If so, what is the efficiency of a screen and how can it be measured? Sizing, especially of the finer sizes of material, has increased in importance in the development of flow sheets as a result of the perfecting of the rapid vibrating screens. More consideration should be given screens in the preparation of ball-mill feed, where they permit the admission of a dryer feed than the classifier. Where possible, the introduction of a screen ahead of the primary ball-mill, and the diverting of ore below, say, 4 mm. to a secondary mill, might result in a greater overall economy because of the thicker feed and the better adjustment of crushing media and mill operation to the reduction demanded. With the present trend back toward a combination of gravity methods and flotation, rather than flotation alone, the accurate, economical sizing possible with the new screens makes fine jigging a method to be considered. W. o. Borcherdtl and John Bland= discuss the screening problem and also the value of close sizing in the concentration of some of the rare-metal ores. If a screen is to be used, it should be selected in competition with others; other things being equal, that screen which makes the cleanest oversize should be preferred. The quality of the screening and the tons handled per dollar together determine the choice and, therefore, both of these must be accurately measured if a correct decision is to be reached. Too frequently in mill design, the capacity has been considered almost to the exclusion of the completeness with which the undersize is separated from the oversize. It is, of course, possible to increase the aperture of the screen, and thus insure the removal of a sufficiently coarse

Jan 1, 1924

By F. V. Lenel, M. V. Rose, A. B. Backensto

WHEN aluminum-flake powders are compacted and hot pressed and the resulting compacts are extruded or hot forged, a group of materials with unique properties is obtained. Not only do they exhibit high room-temperature strength of the order of some of the aluminum alloys, but they maintain this strength even after prolonged heat treatment at temperatures up to 900°F. Moreover, their strength decreases much less with increasing temperature than that of aluminum alloys of comparable room-temperature properties. Irmann,'" who discovered and first described this group of materials, which was called SAP, showed that the room-temperature mechanical properties of the extrusions are a function of the oxide content of the powders and therefore the oxide content of the extrusions. The higher the oxide content, the higher are their tensile strength, yield strength, and hardness, and the lower their ductility. Lyle" investigated the relationship between mechanical properties at elevated temperature and oxide content in the course of the development work of the Aluminum Co. of America on materials, called APMP, similar to those developed in Switzerland. He found that at 600 °F, just as at room temperatures, tensile strength and yield strength increase and elongation decreases with oxide content. A careful study of his data (Fig. 3, loc. cit.) shows, however, that the scatter is more pronounced than at room temperature. Gregory and Grant's data on the creep5 and stress-ruptureb roperties of the one commercial grade of the Swiss SAP and the various grades of APMP indicate that creep strength and stress to rupture also generally increase with increasing oxide .content. Ever since this new group of materials was discovered, attempts have been made to explain the mechanism by which they obtain their high room-temperature and particularly their elevated-temperature strength. In most of the attempts the new material was considered as a dispersion of aluminum oxide particles in a matrix of aluminum. Ir-mann, Von Zeerleder, and Rohner' applied a theory on dispersion strengthening developed by Rohners to the flake-powder extrusions. According to this theory the elastic limit S, of a dispersion would depend upon the average distance between the dispersed particles L according to the equation: 2 E ¦ a where E is the modulus of elasticity and a the distance between nearest neighbors in the lattice of the matrix material. Irmann and co-workers assumed

Jan 1, 1958

By Persifor Frazer

During the Centennial year some of our leading geologists in the United States and Canada conceived the happy thought of calling an International Congress of Geologists for the purpose of agreeing upon such important though subsidiary matters as the colors by means of which the different geological formations should be expressed ; the terms that should be applied respectively to these formations; and also upon the far more important problem of the limits and values of these different formations. The first session of this Congress was held in Paris in 1878, the second session in Bologna in 1881, and the third session in Berlin in 1884. The third session found the preliminary difficulties so far cleared away that some definite and tangible results could be attained. After a great deal of free discussion had taken place at Paris and Bologna, during which every one's views were listened to with attention; and a great deal more painstaking scientific work had been accomplished by the International Committees, having before them the objects of unifying the nomenclature of the science, and of preparing a scheme of colors between the second and third sessions of the Congress; and after the provisional results had been subjected to a searching criticism by the Congress in Berlin; it was decided to make an attempt to embody these provisional results in some work which should include as many as possible of the difficulties to

Jan 1, 1887

By R. Gatewood

The solution here offered is at once simple and important in its direct and indirect bearings. According to the principles of surface-tension, which will be found sufficiently enlarged upon for present purposes in Clerk Maxwell's excellent little treatise on The Theory of Heat, a mechanical mixture of liquids will frequently of itself divide into groups, consisting of liquids mixing among themselves but withdrawing from the other liquids. The following simple and familiar illustration will suffice: " If we mix water with alcohol, the liquids diffuse into each other. If we now attempt to mix oil with the alcohol and water, the two liquids separate from each other of themselves, and in the act of separation sufficient force is brought into play to set in motion considerable masses of the fluids." Maxwell goes on to show that this relative energy is one of arrangement, depending on the nature of the fluids and the area of the surface of contact, the act of separation tending to reduce this surface to a minimum consistent with equilibrium; that this surface-tension exists between a solid and touching fluid, either liquid or gaseous, being of one sign or the other, in the case of a liquid, according as it tends to draw itself up into a drop on its surface or to spread and wet the solid. After considering various cases, lie states that which particularly interests us, thus : " When a solid body is in contact with two fluids, then, if the

Jan 1, 1885

By William P. Blake

In the recent litigation for the possession of franklinite by one party and of zinc-ore by the other party, it was shown by the evidence of experts familiar with the original condition of the outcrops that at Mine Hill a more or less disticctly defined layer of red zincore underlay the heavier and larger body of the franklinite, so-called ; this layer or bed of zinc-ore dipping under the franklinite upon the western cropping, while at Stirling Hill, two miles south, the conditions were apparently reversed, the zinc-ore overlying the franklinite. An explanation being required, it was shown, first, that at both places, at Mine Hill on the north and at Stirling Hill on the south, the ore-bed lies in a synclinal or trough-like fold with the red zincore under the franklinite; and secondly, that at Mine Hill, we see chiefly the outcrop of the western part of the folded bed and at Stirling Hill the eastern part; the Mine Hill cropping being on the western slope, and the Stirling Hill cropping on the eastern slope of the hill. Thus the ''back vein" at Stirling (the western outcrop) corresponds with the front-vein at Mine Hill, and, like it, has the red zinc-ore on the foot-wall, while the front-vein or eastern cropping at Stirling corresponds to the back-vein or eastern cropping at Mine Hill in the part of the bed generally known as the " buckwheat-field vein." If the ore-bed were continuous in one synclinal trough between the two localities, no further explanation would be required. But it is not so ; and the synclinal folds at both places pitch steeply to the north, bringing the beds to the surface in horseshoe-like curves at their southern ends or croppings, and carrying the beds far below the surface northwards. This justifies a doubt

Jan 1, 1895

By Edwin C. Holden

In making the original estimates for a report recommending the cyanidation of Ymir stamp-mill tailings, the writer was unable to find in any of the standard works on cyanide-practice certain data applicable to the local conditions; nor has he as yet seen quite the same practice recorded in the rapidly growing literature of cyanidation. To present these figures, together with a few novel features of local practice, the present paper is offered. The ore treated is obtained from a fissure-vein of steep dip, occurring in a slate country. The ore-body is lenticular in plan, swelling from 4 ft. in width at one end to a maximum of 42 ft., and tapering irregularly to less than 18 in., where payvalues cease. In the wider portions of the fissure the ore is mixed with more or less horse-matter from the walls. The clean ore is white, massive quartz, with from 8 to 12 per cent of sulphurets; the latter being pyrite, sphalerite and galena, the predominance being in the order given. The precious metal tenor is variable, the gold more closely following the pyrite, the silver the galena. The present mill-supply is practically all from below the oxidized zone. The unavoidable admixture of horse-matter and stope-filling with the ore as mined, affects more or less the character of the mill-feed, which sometimes contains from 10 to 25 per cent of slate. During the last three months of 1902, the mill-feed carried 0.3977 oz. gold and 1.903 oz. silver per ton of 2,000 lb., 2.65 per cent lead and 2.92 per cent zinc. The iron, unfortunately, was not determined. The Ymir mill and mine have been fully described elsewhere;* suffice it to say of the milling that the crushed ore,

Jan 1, 1904

By John F. Knudsen

Following the flowsheet from the primary crushing plant of Ray mines division through the final products sample mill, there are eight exhaust systems ranging in size from 12,000 to 30,000 cfm. Where possible, hood face velocities are kept around 500 ft per min, permitting branch velocities of 2500 ft per min. Tight-fitting enclosures are provided over all ore drops, crushing operations, and vibrating screens. All enclosures are exhausted either primarily or secondarily, except those around conveyor head-pulleys where the ejector effect of the falling ore creates sufficient indraft to abate dust dissemination. IN 1947 an Industrial Hygiene Department was organized to represent and assist the four western mining divisions in industrial hygiene problems. Department headquarters are located at the Utah Copper Division, Magna Plant, Magna, Utah, with a branch office at the Chino Mines Division, Hurley, N. M. The headquarters staff includes a director, a department secretary, an industrial hygienist, a supervising ventilation engineer, and two ventilation designers. To be in closer association with work at the Southwest properties, a field engineer at the branch office conducts field studies which include ventilation problems at the New Mexico and Arizona properties;i.e., the Chino and Ray mines divisions. Functions of the department are to discover and evaluate existing hazards and to develop protective measures, either by personal protective devices or by proper ventilation, depending on the nature of the contaminant. Other than dust counting, all air samples collected at the four properties are processed at the home office. If through plant surveys or by suggestion of management some type of ventilation or air conditioning is required, the problem is usually handled by the ventilation section of the headquarters department, where general arrangement or line drawings are prepared, showing hoods, ducting, and equipment. Some hood and special parts detailing is done at headquarters; otherwise, required detailing is done by the respective plant engineering departments. Prior to the design of industrial ventilation, either new projects or the revamping of old ones, a thorough survey is made of existing conditions. In so far as possible weighted average exposures are determined and adequate ventilation provided on the basis of maximum allowable concentrations of the contaminant in question, as well as medical case histories, if these are available.

Jan 1, 1954

By S. R. Elliott

The Spies mine is located in the eastern half of the northwest quarter of section 2443-35, near the village of Iron River, Mich., and is operated by The Cleveland-Cliffs Iron Co. Speaking generally, the jasper hanging walls of most of the deposits in the Iron River district dip at a steep angle and are exceedingly strong, standing without caving, even after mining has been continued for years and after large excavations have been made. The ore is fairly hard and tough and contains no slippage faces. It occurs in large masses, which are often egg shape, with the smaller end down, and can be mined in open stopes without the use of timber. The common system employed in the district is the shrinkage stope, or some modification of it. The Spies system was developed to utilize the advantages of the open-stope method and to avoid the disadvantages of the shrinkage stope. The Spies shaft was sunk to such a depth that the bottom, or third level, was in rock at a short distance below the bottom of the orebody, the shape and extent of which had been previously determined by diamond drilling. This is shown in plan and by the ore contours at the first, second, and third levels in Fig. 1, and in section in Figs. 2 to 7. In order to provide the necessary mills and raises, three parallel crosscuts were driven on 25 ft. centers on the bottom level. Drifts on the second and first levels were driven to the orebody and followed the foot wall in a southerly direction to the end of the ore. In crosscut 3, Fig. 1, raises 30, 40, 50, and 60 were carried up on the foot wall and holed into the second level, and were ultimately carried up and holed into the first level. These foot-wall raises carry the pipes and ladders, provide a means of ventilation, and furnish safe communication to all working places in the stope. From crosscuts 1, 2, and 3, raises were completed to a height of 32 ft., or the elevation of the first sublevel. They were then connected by east and west crosscuts to the main foot-wall raises 30, 40, 50, and 60, shown in Fig. 4. The crosscuts in raises 1 to 5 were then driven west and the

Jan 1, 1923

By S. R. Elliott

The Spies mine is located in the eastern half of the northwest quarter of section 2443-35, near the village of Iron River, Mich., and is operated by The Cleveland-Cliffs Iron Co. Speaking generally, the jasper hanging walls of most of the deposits in the Iron River district dip at a steep angle and are exceedingly strong, standing without caving, even after mining has been continued for years and after large excavations have been made. The ore is fairly hard and tough and contains no slippage faces. It occurs in large masses, which are often egg shape, with the smaller end down, and can be mined in open stopes without the use of timber. The common system employed in the district is the shrinkage stope, or some modification of it. The Spies system was developed to utilize the advantages of the open-stope method and to avoid the disadvantages of the shrinkage stope. The Spies shaft was sunk to such a depth that the bottom, or third level, was in rock at a short distance below the bottom of the orebody, the shape and extent of which had been previously determined by diamond drilling. This is shown in plan and by the ore contours at the first, second, and third levels in Fig. 1, and in section in Figs. 2 to 7. In order to provide the necessary mills and raises, three parallel crosscuts were driven on 25 ft. centers on the bottom level. Drifts on the second and first levels were driven to the orebody and followed the foot wall in a southerly direction to the end of the ore. In crosscut 3, Fig. 1, raises 30, 40, 50, and 60 were carried up on the foot wall and holed into the second level, and were ultimately carried up and holed into the first level. These foot-wall raises carry the pipes and ladders, provide a means of ventilation, and furnish safe communication to all working places in the stope. From crosscuts 1, 2, and 3, raises were completed to a height of 32 ft., or the elevation of the first sublevel. They were then connected by east and west crosscuts to the main foot-wall raises 30, 40, 50, and 60, shown in Fig. 4. The crosscuts in raises 1 to 5 were then driven west and the

Jan 1, 1923

By C. H. Mathewson

BeRyllium, magnesium, zinc and cadmium, together with mercury, constitute a coherent sub-group of the periodic system and these metals, excepting mercury, have been studied in sufficient detail by the new X-ray diffraction methods to prove their common adherence to the hexagonal close-packed type of crystal structure with a progressive increase in axial ratio as we pass through the group from beryllium to cadmium. The first four columns of Table 1 summarize the data on crystal structure of these metals reported in the International Critical Tables.' The last two columns are based on results obtained in the present investigation. Twinning has often been observed in zinc and cadmium. The general aspects of this twinning are abundantly illustrated by photomicrographs, diagrams, etc., in the papers by Romig, and Mathewson and Phillips reported to this Institute in 1927.2 A determination of the composition

By R. W. Heckel

The growth and shrinkage rates of second-phase particles of various size distributions are analyzed in terms of five mathematical models. These models apply to various forms of diffusion-controlled growth (one model) and interjace-controlled growth (four models). The expression for diffusion-controlled growth assumes local equilibrium at the interface between the second Phase and the matrix and through the choice of the proper flux area perrnits the definition of minimum diffusion-controlled growth kinetics. The interface-controlled kinetics models consider the situations where the rate-controlling step occurs at either the interlace undergoing solution or the interface undergoing deposition. In addition, each of these interface-controlled kinetics models is analyzed for interface reaction rates which are independent of the thermodynamic activity gradient across the interface or proportional to the gradient. THE variation of the size distribution of second-phase particles in a solute-saturated matrix has been a stimulating topic for many years. Research has been carried out in this area for situations where the matrix was either liquid or solid. It is well-understood that the over-all process results in an increase in the average particle size, a decrease in the total number of particles per unit volume, and a net decrease in surface area. Greenwood1 has presented a mathematical model based upon the mass balance existing between growing and shrinking particles. His analysis is stated in terms of Fick's First Law using concentration gradients set up between particles of different size as a result of the effect of surface curvature on solubility. Greenwood's analysis indicates that the mean particle size should increase approximately as the cube root of time. Asimow2 has shown that several of the simplifying assumptions employed by Greenwood may be eliminated from this diffusion-controlled model with little increase in complexity. Lifshits and Slyozov3-5 have also considered the growth-shrinkage problem involving diffusion-controlled kinetics. Their analysis was extended to include the effects of interacting particles ("kinetic approximation"), particle shape, and elastic strains. These authors also show that the mean particle size varies as the cube root of the reaction time. wagner6 has formulated expressions for both diffusion-controlled kinetics and interface-controlled kinetics in the growth-shrinkage problem. Wagner's diffusion-controlled kinetics is based upon the same form of mass balance using Fick's First Law as used by others and is shown to be applicable to situations where kr >> D (k is the interface reaction constant, r is the particle radius, and D is the diffusion coefficient). This analysis also yields a mean particle size which varies as the cube root of time, in agreement with other workers. Wagner also developed interface-controlled kinetics to handle kr « D. This model was based upon the fact that the interface reaction rate is proportional to the interface area. Wagner assumed that the rate was also proportional to the thermodynamic activity difference, ?a, existing across the interface. Thus, the specific reaction rate at the surface of radius r was defined as k • 4nr2 . ?a. It is the purpose of the present paper to reconsider the processes of diffusion-controlled growth and interface-controlled growth in the variation of particle-size distributions as a function of time at constant second-phase volume. The analyses are formulated in a manner which permits data obtained

Jan 1, 1965

By W. R. Kube, W. H. Oppelt

Five low-rank coals, including two lignites, a steam-dried lignite, and two subbituminous coals, were carbonized at 940°F, in a bench-scale carbon-ize~ with a nitrogen and hydrogen atmosphere, or both, using pressures from atmospheric to 1000 psig. Coking characteristics were observed, and yields, composition, and distribution of products from thermal degradation were determined. The influence of pressure on yields from coal carbonization, as well as on modification of coke structure, has long been of interest. One of the first attempts at pressure carbonization was that of Capps and Hulett1 who in 1917 investigated the effects of pressure ranging from 1 to 20 atm on yields at 600° C for bituminous and subbituminous coals. High-pressure carbonization has not been used commercially for coke production. More recently, carbonization at relatively high pressure in the presence of catalysts and hydrogen has been proposed for the production of metallurgical-grade coke from low-rank fuels.' Another approach involves carbonization at high pressure in a hydrogen atmosphere to produce heating gas and a solid residue that is gasified with oxygen and steam to produce the hydrogen required for hydro-genation 3-4 or, alternatively, is burned to raise steam. Recently it has been proposed to carbonize coal under pressure, burn the gas in a gas turbine to produce power, and use the solid residue as fuel in a conventional steam-power plant.5 Our primary interest in pressure carbonization stems from an attempt to determine the influence of pressure on the coking characteristics of lignite to design a high-pressure slagging gasifier using oxygen and steam. At atmospheric pressure, North Dakota lignite is generally considered to be non-coking. However, lignite and subbituminous coals have been reported to show increased agglomeration properties in steam, hydrogen, or carbon-dioxide atmospheres at elevated pressures, although no strong coke was formed at pressures up to 3000 psig.6 If lignite would agglomerate seriously under gasification conditions, proper flow of charge through the gasifier could not be maintained without installing a mechanical stirring device or destroying the caking properties of the coal before gasification. Data on the caking properties of lignite or other gasification fuel, as well as on yields of products under conditions simulating the carbonization process in the pregasification zone, were required in the preliminary design stage of the gasifier. No information was available concerning the influence of pressure and type of atmosphere on North Dakota lignite. To provide this basic data, the U. S. Bureau of Mines investigated the effect of pressure and a hydrogen or nitrogen-rich atmosphere on the yield of products and on coke formation in a bench-scale pressure carbon-izer. SCOPE OF INVESTIGATION Five coals were tested at 940°F in nitrogen and hydrogen atmospheres, at pressures from atmospheric to 1000 psig. Yields and composition of solid, liquid, and gaseous products were determined as a function of the process pressure, and attention was given to the physical appearance of the solid residue. Percentage of carbon converted, sulfur retained in char, and thermal balances were calculated. In this paper, primary consideration is given to carbonization in a nitrogen atmosphere and to data concerning the solid phase. The effect of pressure in hydrogen is presented in detail for only one lignite. More complete information on the response of the other coals in a hydrogen atmosphere will be published in a USBM Report of Investigations. DESCRIPTION OF EQUIPMENT Details of the bench-scale pressure carbonizer are given in Fig. 1. The body of the carbonizer was

Jan 1, 1961

By N. S. Stoloff, R. G. Davies

The annealing behavior of a heavily cold-worked FeCo-V alloy has been studied at temperatures both above and below Tc, the critical temperature for ordering. It was found that re crystallization and grain growth can take place below Tc in the ordered state and that, in agreement with results for fcc alloys, order retards grain growth. The activation energy for pain growth is -55 kcal per mole in the disordered condition; it was not possible to assign a value to the activation energy for grain growth below Tc because the degree of order is changing rapidly over the temperature interval investigated. Precipitation of an fcc y phase was observed upon annealing the cold-worked alloy at temperatures of 675°C and below. SINCE it is known that diffusion constants are greatly affected by long-range order,' it is not unreasonable to anticipate that order will influence the diffusion-controlled phenomena of recrystallization and grain growth. In the course of a study of strain aging of ordering alloys around the composition Ni3Fe Vidoz, Lazarevic, and cahn2 noted that a disordered cold-worked alloy annealed at a temperature T1 just below Tc will order but not recrystallize; Tc is the critical temperature for order. The same alloy annealed at a temperature T2 just above Tc, or an alloy of different (nonordering) composition annealed at either T1 or T2, will recrystallize after equivalent amounts of cold work. Initially Selisskii and coworkers,3,4 who examined a series of cold-worked and annealed bcc Fe- Co alloys, reported that alloys forming the B2 FeCo super lattice could not be recrystallized below Tc. However in a later paper5 it was shown that FeCo ordered alloys could be recrystallized below Tc. Thus the first question to be answered by the present investigation was whether or not a heavily cold-worked Fe-Co-V alloy could be recrystallized below Tc. When it was found that the alloy would indeed re-crystallize below Tc, the influence of long-range order upon subsequent grain growth was studied. EXPERIMENTAL PROCEDURE The grain-growth measurements were made upon FeCo-2 pct V wire of 0.031 in. diam; the alloy was the same as that used in an earlier study of the mechanical properties of FeCO-v.6 The wire was produced by cold swageing and drawing a rod 0.125 in. diam that had been quenched into iced brine from 850°C to disorder the alloy; the initial grain size was 0.05 mm. Rates of grain browth were measured after isother-mally annealing the wire in the temperature range 675° to 825°C; T, is -720°C. Grain diameters were measured on the transverse cross section of the wires. The line-intercept method of determining the grain diameter was used; conventional light photomicrographs were taken when the grain size was greater than 10 . Carbon replicas were produced and examined in the electron microscope if the grain size was less than Dislocation configurations after recrystallization anneals were studied by electron transmission microscopy of foils produced by cold rolling a 0.125-in.-thick strip of the quenched material to 0.012 in. The foils, after heat treatments similar to the wire samples, were thinned by electropolishing in a chromic-

Jan 1, 1967

By M. C. Smith, W. V. Green, D. M. Olsen

The creep-rupture behavior of commercial powder-metallurgy molybdenum rod is reported in the temperature range 1600" to 250O°C, at stresses up to 9000 psi and times up to 1 month. The effects of temperature, stress, and grain growth are discussed. Rupture time is fitted to the Larson-Miller parameter and compared to lower-temperature and higher-stress results reported by pugh.1 BECAUSE of its high melting point, molybdenum should retain useful strength to relatively high temperatures. Combined with its ready availability in the United States, this makes it attractive for many applications in missiles, rockets, and so forth—wherever its susceptibility to oxidation can be tolerated or overcome. The mechanical properties of molybdenum rod in the temperature range —200" to 1540°C have been reported by pugh,' Bechtold,' Parke,3 and Carriker and Guard.4 Madden and chen5 have measured the tensile properties of molybdenum single crystals in vacuum up to about 2500°C. As one further step in evaluating its mechanical usefulness, the constant-load creep-rupture properties of commercial powder-metallurgy molybdenum rod have been investigated in the range 1600" to 2500°C. MATERIAL TESTED Creep specimens were machined from 1/2-in. round commercial molybdenum rod, manufactured from powder by pressing, sintering, and swaging. Spectrochemical analysis of the rod showed "traces" (less than 0.01 pct) of silicon, aluminum, chromium, iron, and zirconium, and "faint traces" (less than 0.001 pct) of manganese, magnesium, cobalt, and nickel. Carbon content was 130 to 200 ppm, nitrogen was 110 to 180 ppm, and oxygen 30 to 35 ppm. A typical microstructure of the as-received rod is shown in Fig. 1. Room temperature tensile properties for five specimens strained at about 0.015 in. per in. per min are shown in Table I. CREEP SPECIMENS USED The specimens used for creep-rupture testing are illustrated in Fig. 2. The 1/4-in.-diam gage section was 3/4 in. long, and terminated at shoulders 5 mils high. These shoulders served as fiducial marks for optical strain measurements. Surface finish on the gage section was 16pin. r.m.s. One specimen, for a "long-time" test described below, was modified by dividing the 3/4-in. gage length into three 1/4-in. long sections with individual diameters of 0.250, 0.230, and 0.210 in., each terminating in a pair of fiducial shoulders. TESTING PROCEDURE The constant-load creep-testing machine used has been described by Smith, Olson, and Brown.6 In it the specimen is held vertically on the axis of a cylindrical tantalum or tungsten heater tube by threaded molybdenum or tungsten grips. Both specimen and grips are heated by radiation from the heater-tube, which is heated by its own electrical resistance. The bottom specimen grip is held at its lower end by a clevis pin. The testing load is applied to the specimen through the upper grip by means of hanging weights, a constant force-multiplication lever system, and a pull rod sealed to the chamber lid by a bellows. The incandescent specimen is viewed by an external optical system through slots in the heater-tube and radiation shielding, and an enlarged image of it is projected on a ground-glass screen. Gage-length measurements are made on this image with a pair of cathetometers. Thorium oxide coatings were applied to the threaded ends of most specimens, to prevent diffusion-welding of specimens to grips during testing. Without such a coating welding usually occurred, and grips were often broken by subsequent efforts to remove the tested specimens.

Jan 1, 1960

By R. M. Waterstrat, B. N. Das, Paul A. Beck

The central region of the Ti-Mn system was studied by means of x-ray diffraction and metallography. The following intermediate phases were found: an MgZn2-type Laves phase having a wide range of homogeneity, the p-phase of unknozvn structure, and the + -phase with a large tetragonal unit cell, stable at 930°C and lower temperatuves. MaYKUTH, Ogden, and jaffee1 determined the soh-inh bility limits of manganese in and titanium. They also confirmed the structure of the intermediate phase TiMn2 which was previously identified as a Laves phase of the MgZn2 type.2 In the equiatomic region they found an additional intermediate phase, y, which presumably formed by a peritectic reaction at approximately 1200°C. This last observation was disputed by Rostoker, Elliott, and McPhers0n,3 who reported the formation of TiMn by a peritectoid reaction between 900" and 1000° C, but found no evidence of any intermediate phase other than the Laves phase at higher temperatures. Elliott and Rostoker4 reported furthermore that the X-ray diffraction pattern of TiMn could be identified as that of a o phase, although their data were not consistent with this inter~retation. Margolin and Ence6 presented X-ray diffraction data for the and TiMn, phases, and obtained metallographic indications for the existence of additional intermediate phases. They concluded from metallographic observations that two Laves phases are formed, separated by another phase, designated as &. A phase diagram for the Mn-Ti system has recently been published by Savitskii and Kopetskii,' which shows considerable disagreement with the work of Hellawell and Hume-Rothery,' in particular with regard to the terminal solid solutions based on the allotropes of manganese. The present investigation was undertaken primarily to clarify the phase relationships in the equiatomic region of the Ti-Mn system. The metals used in preparing the alloy specimens Were iodide titanium and electrolytic manganese, the latter having a nominal purity of approximately 99.9 pet. The electrolytic manganese was covered with a thick coating of a brown manganese oxide which was reduced by heating the manganese flakes for several hours at a temperature of 1100°C in an atmosphere of dry hydrogen. Three alloys, see Table I, were made using sponge titanium and manganese not treated in hydrogen. The alloys were prepared by arc-melting in an atmosphere of helium or argon. The composition of each alloy was calculated by assuming that the entire weight loss during melting was due to evaporation of manganese. Subsequent chemical analysis of certain alloys indicated that the compositions calculated in this manner were usually correct within 1.4 pct, as shown in Table I. All alloy specimens were wrapped in molybdenum foil before sealing them in silica tubes containing argon at a pressure of 1 atm at the annealing temperature. After quenching in cold water, the alloy specimens were bright and clean, with no evidence of any surface reaction. The alloys listed in Table I were examined metallographically, using an etchant consisting of 20 pet HNO3, 20 pet HF, and 60 pet Glycerine. powder for X-ray diffraction examination was prepared by crushing a portion of each annealed alloy

Jan 1, 1962

By F. G. Miller, T. D. Mueller, L. B. Davidson

A mathematical model of reservoir behavior during one cycle of the intermittent steam injection process is presented in this paper. A cycle of the process is considered to be composed of three stages: injection, condensation and production. The model concentrates on behavior during the production stage. The influence of several parameters on production improvement is described, using the results obtained with a numerical equivalent of the model. Reservoir system parameters considered are thickness, reservoir thermal conductivity, oil viscosity, solution gas-oil ratio and the change in oil effective permeability with temperature. Operating parameters investigated are heat injection rate, steam temperature and cumulative injection time. In the face of considerable uncertainty, the model appears to give a fair prediction of the behavior observed during an actual test. This makes the model a useful means of selecting projects. It is shown that the model may also be utilized to select an optimum set of operating conditions for a particular project. Results of this study show the extent to which production improvement depends on each of the parameters investigated and give an indication of the range of system conditions within which the process would be effective. INTRODUCTION In recent years the intermittent steam injection or steam soak process of oil recovery has become a popular method of improving recovery in reservoirs bearing high-viscosity hydrocarbons. Production improvement due to the process results from heating the reservoir near the wellbore. The process is applied on an individual well basis and is executed in a series of cycles, each consisting of three stages: injection, condensation (the soaking period) and production. During the injection stage, high-pressure steam is injected into the reservoir surrounding the well-bore. This study assumes that injection is carried out over the entire vertical section of the reservoir rock that can be exposed to fluid injection. The condition of steam entering the reservoir is considered to fall within the following limits: (1) steam pressures less than 1,000 psig, (2) steam temperatures between 300 and 700F and (3) steam quality less than 90 percent. The last restriction is due to equipment limitations. Normally, injection re maintained for less than 3 weeks. After termination of injection, the condensation stage begins. The well is shut in for several days, supposedly to make certain that the injected steam condenses. This condensation would insure the retention of injected heat. The production stage is initiated when the well is opened again. Reservoir response during this stage determines the effectiveness of the process (response is defined as the oil production rates, the water production rates and the wellbore temperatures observed during the entire production stage). The immediate response of the reservoir is sometimes quite good. Sets of case histories by Longl and by Owens and Suter2 give some typical figures for response. Duration of the production stage is equal to the time needed for the oil production rate to decline to some predetermined value. This usually requires 4 to 6 months. Termination of the production stage coincides with the start of the next cycle. The process is continued, cycle by cycle, until it becomes unprofitable to continue. One simple model2 and two more sophisticated models3,4 of the process have been presented. These are based on fundamentally different assumptions than those used in this investigation. Although the three models might be modified to fit the assumptions used in this study, it is felt that greater rigor would result by developing a

By T. D. Mueller, F. C. Miller, Jr. Earlougher R. C.

In analyzing pressure buildup tests for field wells producing both oil and gas, the common practice is to use a modification of single-phase flow theory. Validity of such an approximation has been demonstrated for single-well solution-gas-drive systems. This paper indicates that such approximations are also valid for two-well solution-gas'-drive systems. From this it is inferred that the technique can be used for multiple-well systems. A computer was used to simulate the behavior of a two-well solution-gas-drive reservoir to test the validity of the above type of analysis. Simulation results indicate that pressure buildup tests in such a system can be analyzed within engineering accuracy for formation permeability and pressure. A rule of thumb is given for estimating the length of time a well must be shut in for the pressure in a nearby producing well to increase significantly. To observe such an increase, the shut-in well would have to be left shut in much longer than normal. INTRODUCTION An important technique for obtaining data concerning a producing petroleum reservoir is the pressure buildup test. Such a test, when properly conducted and analyzed, provides information on the average reservoir pressure and the permeability in the major drainage area of a well. The theory upon which the analysis of a pressure buildup test is based assumes that the behavior of the fluid in the reservoir is adequately described by the diffusivity equation.1 Use of the diffusivity equation implies that a single fluid of small and constant compressibility is flowing. To analyze a pressure buildup test in situations which involve more than one fluid phase, the single-fluid analysis is extended. This paper verifies the extension of pressure buildup analyses to two-phase, two-well systems. Miller, Dyes and Hutchinson1 have presented a technique for analyzing pressure buildup tests in circular bounded reservoirs. Their method requires that the reservoir be producing at pseudo-steady state (constant pressure gradients) prior to shut-in. An alternate reservoir model, presented by Horner,2 assumes that the reservoir is infinite. The Homer model does not assume a Pseudo-steady state prior to shut-in, but the assumption that the reservoir is infinite implies that the average pressure can be determined only if the total production prior to shut-in is small compared to the total fluid originally present. Limitations imposed by the pseudo-steady state and infinite reservoir assumptions are avoided by the technique proposed by Matthews, Brons and Hazebroek.3 Their method can be used to calculate both the Permeability and the average pressure in bounded single-well systems which are not necessarily at steady state. They also suggested determining the average pressure of a multi-well reservoir producing from pseudo-steady state by volumetrically averaging the static pressures of the individual wells. Matthews and Lefkovits4 used numerical simulation techniques to verify that this method does produce adequate results for single-phase, multiple-well systems. Perrine5 proposed modifications to the single-phase theory so that pressure buildup tests in multiple-phase systems could be analyzed. He suggested replacing the single-phase mobility (k/µ) by the sum of the mobilities of the individual phases, and replacing the fluid compressibility by an average compressibility weighted by the saturations of the separate phases. By using numerical techniques to solve the two-phase flow problem for a single-well system, he concluded that this approximation gives results within engineering accuracy. More recently, Weller6 has shown that, for a gas-oil system with a single well at the center of a circular reservoir, pressure buildup tests can be analyzed adequately by using the modification proposed by Perrine. Feller's results also indicate that, as the gas saturation increases, this analysis becomes less accurate. To date, no evidence is available to show that the Perrine approximations can be combined with the Matthews-Brons-Hazebroek technique to calculate the average pressure of a multi-well,

By E. H. Rennhack, J. F. Libsch

Definite transition behavior was found in unalloyed titanium at 0.13 pct 0 equivalent. The addition of 0.5 Sn, 1.0 Al, 0.5 Al, and 1.0 Sn lowers the tvansition temperature of titanium at oxygen equivalents exceeding 0.22, 0.29, 0.40, and 0.51, respectively. Metallographic evidence indicates that progressive amounts of oxygen restrict deformation at low temperatures resulting eventually in brittle fracture. The presence of tin or aluminum is thought to alter the atomic distribution of oxygen within the titanium lattice in such a manner as to facilitate some degree of slip and twinning. 1 ITANIUM-like iron and zinc experiences a transition from ductile to brittle fracture with decreasing temperature. The presence of sufficient quantities of the interstitial elements, carbon, oxygen, and nitrogen in solid solution, has been shown to progressively lower the room-temperature impact resistance of titanium with increasing interstitial content.1"1 Ogden,et al,2 reported finding no transition from ductile to brittle fracture with decreasing temperature in iodide titanium. However, a definite transition was found to occur at 0.36 pct 0 equivalent in an alloy containing 0.47 pct carbon in solid solution. The oxygen equivalent in this case was obtained by assuming the effects of carbon, oxygen, and nitrogen in combination on the impact properties of titanium to be additive on the same basis as their separate effects on tensile strength, namely: Oe = 2/3 (pct C) + pet 0 + 2 (pet N) They concluded that the tendency toward transition behavior is dependent on the total interstitial content in solid solution and not on any one particular interstitial element. Rennhack,4 however, recently found transition behavior in iodide titanium at an oxygen equivalent of 0.17 pct. Ogden, etal3, reported that the strengthening effects of carbon, oxygen, and nitrogen in titanium decrease with the addition of tin. They showed that tin additions increase the tolerance of titanium for the interstitials, that is, 10 pct Sn permitted individual additions of up to 0.4 wt pct of the interstitial elements without any significant loss in ductility. Aluminum tends to decrease ductility and impact strength of titanium for a given interstitial ~ontent.3 Van Thyne and Kessler5 found that the solid solubility of carbon in titanium doubled in the presence of 10 pct Al. The precise effects of tin and aluminum in the nrespncp of rorvfen nn the impact properties of titanium had previously not been determined. The high oxygen tolerance of titanium containing tin may provide a suitable means for improving the impact properties of titanium containing the interstitial elements, particularly oxygen. Unlike tin, however, aluminum has a high affinity for oxygen and will reduce rutile titanium dioxide (TiO2)by a thermit-type reaction.6 Thus, the atomic distribution of oxygen in titanium might be different in the presence of aluminum. The present work was undertaken to: 1) Determine the effect of oxygen on the transition behavior of unalloyed iodide titanium. 2) Determine the effect of small amounts of tin and aluminum on the transition behavior of iodide titanium in the presence of oxygen and other interstitial~. EXPERIMENTAL Three different lots of iodide titanium were employed to prepare the alloys studied in the present work. Their chemical composition is presented in Table I. The compositions of the tin and aluminum used for alloying are shown in Table 11. Oxygen additions were made using calcined rutile titanium dioxide (TiO2)of 99.7 pct purity. Alloy Preparation—Four titanium-base alloys containing separate additions of 0.5 and 1.0 pct each

Jan 1, 1960

By H. R. Ogden, E. S. Bartlett, A. G. Imgram

Notched and unnotched tensile specimens of wrought and recrystallized, oxygmted and hydro-genated tantalum and columbium were tested over a range of temperatures selected to encompass the ductile-to-brittle transition. Increasing the oxygen content of tantalum and columbium increased their strength, and raised their ductility transition temperature, but did not cause a marked deterioration of notch properties below that of commercially pure material. The adverse effects of oxygen were more pronounced for recrystallized structures than for wrought material. The effects of hydrogen are complicated by strain aging or slow strain rate hydrogen embrittlement at -105°F. However, in general, hydrogen had only a minor effect an strength, but markedly increased the effective transition tem-terature and caused a deterioration of notch properties . BCC metals including the refractory metals in Groups Va and VIa (V, Cb, Ta and Cr, Mo, W) can be expected to undergo a ductile-to-brittle transition and exhibit brittle fractures at low temperatures.' Notch embrittlement is associated with this phenomenon, and can be a serious design problem. Table I compares the tensile transition behavior and notch sensitivity of commercially pure Group Va and VIa refractory metals. The Group VIa refractory metals have considerably higher transition temperatures, and become notch sensitive at higher temperatures, than do the Group Va refractory metals. In addition, the Group VIa refractory metals are sensitive to metallurgical structure. Recrystallized structures generally have higher transition temperatures than wrought material of the same composition. The relatively poor transition behavior of the recrystallized structures of these metals is generally attributed to the segregation of interstitial impurity atoms at grain boundaries. Pronounced sensitivity to structure is not evident with commercially pure Group Va refractory metals, however. Since these metals have higher solubilities for interstitial elements than do the Group VIa metals ,4 it can be expected that higher total interstitial concentrations are necessary to develop a comparable degree of grain boundary segregation and to produce a similar sensitivity of transition temperature to structure. Increasing only the concentration of interstitial atoms in solution would tend to increase the flow stress of a metal in relation to its cleavage fracture stress and thereby raise its transition temperature, but would not be expected to cause a marked sensitivity of transition temperature to structure. A research program has been conducted at the Battelle Memorial Institute to evaluate the effects of interstitial oxygen and hydrogen on the transition behavior and notch sensitivity of tantalum and columbium, and to evaluate the effects of structure on "contaminated" material. EXPERIMENTAL PROCEDURES Notched and unnotched tensile specimens of oxygenated and hydrogenated tantalum and columbium with both wrought and recrystallized structures were tested over a range of temperatures selected to encompass the ductile-to-brittle transition Oxygen levels selected for study in both tantalum and columbium were nominally 500 and 1000 ppm, whereas nominal hydrogen contents were 150 and 500 ppm in tantalum and 150 and 300 ppm in columbium. Oxygen and hydrogen additions were made directly to 6-in. lengths of 1/2-in.-diam electron beam melted wrought bar stock, in a Sieverts Apparatus. Subsequent high-temperature annealing was required for homogenization of the oxygenated material, but was not necessary in the case of hydrogenated stock. The oxygenated and hydrogenated bars were then swaged to 1/4-in.-diam rods. Tensile specimen blanks were cut from the 1/4-in.-diam rods and annealed to achieve stress-re-

Jan 1, 1963