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By Jun-Yan Chen, Stefan H. Boshkov

Metal mining in the People's Republic of China has shown great growth during the last three decades. Over 150 new iron ore mines and nonferrous base metal mines have been opened since 1949, althouc.11 most of them of medium and small size. Concurrently, many old mines were enlarged and reconstructed. The production of iron ore has grown from less than 1.5 million tons per year in 1949 to almost 76 million tons in 1978. A corresponding increase in the total annual output in the nonferrous metal mineral industry has also been noted. It is well known that the PRC is very rich in metal mineral resources. The reserves of tungsten, tin, antimony, molybdenum and iron ore are ranked in the top three in the world. Recently, some copper porphyry ore deposits were discovered in Jianxi and Anhui provinces. Some large nickel-copper sulfide deposits were discovered and have been developed in North- West China. Huge iron ore deposits have been found in Liaoning, Hebei and Szechwan provinces. However, the bulk of the iron ores are low grade. The growing metal mineral production has met basic domestic needs since 1949; it has also proven China's big resource potential. Mining methods have also undergone development in the past 30 years. About 80% of the annual output of iron ore comes from open pits, whereas about 58% of nonferrous metal ores come from underground mines. Blasthole open stoping, sublevel caving and induced block caving are widely used in Chinese underground metal mines (table 1). This paper summarizes in detail the planning for and application of these three bulk mining methods in the nonferrous and iron ore mines in China. CLASSIFICATION OF UNDERGROUND MINING METHODS The main principle of the classification of underground mining methods in PRC is ground support in the stoping cycles of the mining blocks or stopes. Table 2 lists this classification. It is essentially the same as that given in the SME Mining Engineering Handbook. Be- cause pillar removal is a secondary mining operation, using a variety of methods, they are not included in this classification. As is the case with most classifications in science and technology, there is no precise division between the classes of mining methods. Because of the rapid development of consolidated filling techniques in the past twenty years, some types of open stoping methods use fill in order to improve the ground conditions for the secondary recovery stage. Thus, these mining methods have features of both methods using no artificial support and those using artificial support. In this classification, this type of mining method is placed in the latter category. The shrinkage stoping method has been employed extensively to mine steeply dipping narrow veins of tungsten and tin in the Jiangxi, Hunan, Guangdong and Guangxi provinces. Shrink- age stoping is placed under the class of mining methods without artificial support be- cause this reflects the nature of the Chinese experience. The function of the broken ore serving to support the footwall and/or hanging wall is limited, because the expectation is for the host rocks to remain unsupported until the stope is drawn empty. APPLICATION OF BULK MINING METHODS Bulk mining methods consist of blasthole open stoping, sublevel caving and block caving. These stoping methods have much in common, such as: bulk ore materials blasted by long holes; higher production rates of stopes or blocks and higher production efficiencies of the whole mining systems.

Jan 1, 1981

By C. J. Bechtoldt, H. C. Vacher

Quenched alloys, prepared by powder metallurgical techniques, were examined by microscopic and X-ray diffraction methods. The compositions and heat treatments were chosen so that the chromium and nickel solvuses could be determined and a range of composition and temperature, in which a eutectoid had been reported, could be explored in small intervals. The results showed no evidence of eutectoid reactions having taken place. ALLOYS containing iron, chromium, molybdenum, and nickel are extensively used in high-temperature applications. In order to provide basic information on the solid-state reactions that occur in such alloys, the National Bureau of Standards is engaged in an extensive study of the equilibrium phases in the binary, ternary, and quaternary systems involving these four metals. Attention was directed to the chromium-nickel system because a review of the literature showed conflicting data. A recent compendium1 of the constitution of binary alloys gives two diagrams for the chromium-nickel system, one a simple eutectic and the second a diagram showing a eutectoid and a eutectic. The eutectoid was the result of an allotropic transformation in a high-temperature solid-solution form of a chromium-rich phase called 0. The approximate temperature and composition of the eutectoid was 1200°C and 30 at. pct Ni. In the preliminary study, at the Bureau, no transformation was indicated in the chromium-rich phase of ternary and quaternary alloys in which chromium and nickel were major components. Similar results have been reported from time to time in the literature,2-8 In consequence of this situation, a systematic study was made of the constitution of heat-treated chromium-nickel alloys using metallographic and X-ray diffraction methods. The compositions of the alloys were selected so as to determine the boundaries of the chromium-rich and the nickel-rich phases and to explore in small intervals the ranges in composition and temperature in which the eutectoid had been reported. The results of this study are reported and discussed in the present paper. EXPERIMENTAL PROCEDURES Materials, Alloys, and Heat Treatments—The alloys were prepared by a powder metallurgy technique similar to that used in earlier work.9 Analyses of the materials used are given in Table I. Powders were mixed using a vibrator in 30-g batches of predetermined composition; 2-g pellets were made from the mixture by compacting at room temperature in a 1/2-in. diam mold under 60,000 lb per sq in. pressure. The pellets were sintered in dry hydrogen for 10 days at 1300°C. At the end of the sintering treatment the specimens were quenched in water, which caused a pale green film to form on the chromium-rich alloys and thin black scale to form on the nickel-rich alloys. The pellets after sintering were approximately 1/2 in. diam by 3/32 in. thick. The purification train9 was modified by inserting a tube of titanium turnings, heated at 700°C to increase the efficiency of the removal of oxgen and nitrogen. It was found in the earlier work that the sintering treatment lowered the carbon, oxygen, and nitrogen contents of chromium-rich alloys to 0.01, 0.01, and 0.004 wt pct, respectively, and that there was a loss of chromium. In order to ascertain the extent of this loss, the chromium contents of certain alloys were determined chemically. They included those alloys used to determine the parameter-composition curves and those of critical composition, used to determine the chromium-solvus microscopically; these analyses were made on samples after the final heat treatments. The mixed powder values for the chromium content of those alloys that were not analyzed were adjusted to conform to a smooth curve based on the chemically analyzed values for

Jan 1, 1962

By W. M. McKewan, R. G. Olsson

In order to improve the understanding of the iron oxide reduction mechanism, the rate of equal molar diffusion of hydrogen and water vapor was measured through disks of porous iron and alumina. The measuretneizts were made at atmospheric pressure at 800°, 900- , and 1000°C. It is shown tint the reduction of dense hematite pellets with hydrogen at these temperatures and at atmospheric pressure is to a great extent limited by gaseous diffusion between the bulk-gas phase and the iron-wustile interface. THE investigation of the reduction of iron oxides with hydrogen has been the subject of numerous papers. Although the effects of temperature, pressure, and gas composition on the rate of iron oxide reduction have been studied, the actual mechanism of the reduction process has not been definitely determined. As a means of improving the understanding of the mechanism, the rate of equal molar counterdiffusion of hydrogen and water vapor was measured through porous iron and porous alumina disks at reduction temperatures. The alumina was used as a basis of compari-son because its pore structure is homogeneous and independent of temperature. The porous iron was prepared by the reduction of dense hematite disks with hydrogen at the temperature of the subsequent diffusion experiment. The hematite disks were made from pellets that were identical to those used by McKewan1,2 in his study of iron oxide reduction with hydrogen. In these investigations the weight loss and rate of movement of the various interfaces were measured as a function of the reduction temperature and gas composition. With these reduction data and the presently reported diffusion data it is possible to determine the importance of H2-H2O transport between the bulk-gas phase and the Fe/FeO interface to the reduction of dense hematite. APPARATUS AND PROCEDURE A porous iron or alumina sample was held in the base plate of a sealed canister containing porous granular wustite, as illustrated schematically in Fig. 1. The canister was suspended from an automatic recording balance in a vertical tube furnace through which flowed hydrogen and water-vapor mixtures of known composition at atmospheric pressure (0.96 atm). Hydrogen from the gas stream diffused through the porous sample, reducing the wustite in the interior of the canister. The water vapor that was formed diffused back to the gas stream. The rate of diffusion was determined from the recorded weightloss data. The furnace, automatic balance, and gas-metering equipment have been described previously.2 The main body of the canister and the tubing extension were made of stainless steel while the base plate was made of high-purity iron. The main body of the canister was % in. in diam. It held approximately 6 g of porous granular wustite that was prepared by reducing 0.1- to 0.2-cm-diam specular hematite particles at 900°C with an H2-H2O mixture of a composition near the iron-wustite equilibrium value. The upper end of the 1/8-in.-diam tubing extension was sealed with a segment of plastic tubing and a tubing clamp. The temperature at the top of the furnace was sufficiently high so that no water vapor condensed inside the extension. In the experiments with porous iron, iron oxide samples were prepared from reagent-grade hematite that was pressed and sintered in a manner previously described.' The resulting pellets had a density of 5.15 ± 0.05 g per cu cm. Each pellet was centerless-ground

Jan 1, 1967

By M. H. Harris

A solution has been obtained to the problem of calculating flow into a cased and perforated well. Equations describing the idealized system were solved by numerical analysis techniques on a high-speed digital computer. Computer experimentation indicated that the results are within 3 per cent of the exact solution. Computed results are presented as an apparent skin effect, on a series of dimensionless working curves. Productivity ratios can be rapidly calculated from these data for the wide range of wellbore and reservoir properties actually encountered in field practice. Any reasonable vertical unisotropy ratio can be included in the computation. Productivities can be calculated for wells perforated in a regular pattern, a single horizontal plane or a vertical line on one side of the casing. Solutions for asymmetrical perforation patterns can he easily obtained from the working curves. Solutions for flow into sells completed with a horizontal notch are also provided. Results show that productivity can be increased by extending perforation penetration. This is especially true for shallow penetrations. The highest productivity is obtained when perforations are arranged in horizontal planes, as opposed to a vertical line on one side of the casing. Four or five perforations in one plane will approach the maximum productivity. The effect of perforation hole diameter is small, and is rioticeable only in shallow penetrations. INTRODUCTION The perforating method of well completion has been successfully and widely used in most producing areas. In the past, the desired perforation results were achieved by simply shooting numerous large holes in the casing. A perforating scheme for an area, or particular well, was established by evaluating two types of experimental data: the well flow index and the productivity ratio.' 3 The well flow index test is a means of determining the relative flow capacity of perforations in a linear system. This test also gives information on the perforation size, shape and hole damage which can be expected under well-bore conditions. However, relative flow data from this test cannot be accurately tarnsformed into the radial wellbore system. Thus, no true indication of the productive capacity of a perforated well can be obtained from the well flow index test. A well productivity ratio is derived from electrolytic models built to simulate perforated wells. Available productivity ratio data 2,3 are limited in that all important variables are not extensively evaluated. For example, data are limited to well radii of 3 and 6 in., and to maximum perforation penetration of 1 ft. Practically no information is available on the pattern of flow into a perforation. The effect of various perforation patterns on well productivity has not yet been determined and the effect of perforation diameter has not been thoroughly studied. Also, it will be shown that this type of electrolytic model data is probably in error by as much as 10 per cent or more. Modern completion techniques such as limited-entry perforating, single-plane fracturing, steam and hot air injection and chemical consolidation of incompetent formations all rely on injection and/or production from a limited type of completion. These completions may consist of several high-capacity perforations or a horizontal notch which is equivalent to an infinite number of perforations in one plane. Proper design of these new completion techniques requires, in part, accurate estimates of a well's productive capacity. Data on perforated and notched well productivity have been determined in this investigation. Results are presented as a function of the pertinent variables. Equations describing the idealized system were solved by numerical analysis techniques on a high-speed digital computer. DESCRIPTION OF PROBLEM PRACTICAL APPLICATION The computed results can be applied to wells which meet several general specifications. An external drainage radius of the well must be known or assumed, but the well need not be drilled on a regular pattern. The well must be cased and cemented through the entire producing interval. And, the casing must be perforated with one or more horizontal planes of perforations. The perforation pattern itself must conform to three geometrical requirements. 1. The perforations in a plane must divide the plane into equal angular segments (Fig. 1). Four perforations per plane would be 90" apart. 2. Perforations in a plane must be directly above or beneath perforations in adjacent planes. For two shots per plane, perforations would lie in the BB' plane (Fig. 1). 3. Horizontal planes must have equal vertical spacing and be separated from the top and bottom of the formation by one half the spacing interval. Single planes of perforations should be in the middle of the formation. This is shown in Fig. 2 where h is the formation thickness in a single plane conlpletion or the spacnig interval in a multiple plane completion. The spacing interval at the top and bottom of the formation may vary somewhat without causing an appreciable error in the productivity calculation if the formation is reasonably thick and there are many horizontal planes of perforations. A special provision has been made to calculate the productivity ratios of wells with uneven spacing intervals, or for the case where a single plane of perfora-

Jan 1, 1967

By R. W. Guard, W. R. Hibbard

As part of a program to determine the deformation characteristics of pure metals, the tensile creep properties of high purity aluminum (99.994 pct Al) have been determined using a constant stress loading. The effects of prior annealing temperature, stress, and temperature were studied. These data have been examined on the basis of present-day theories. None of the methods was found to give an accurate representation of the data over all conditions studied. The structures of several specimens after creep were examined by optical and X-ray metallography. Marked changes in the grain size were found and it was substantiated that the magnitude of these changes was greatly influenced by the applied stress (or creep strain). The changes in fiber texture which occur on creep deformation are shown to be consistent with those observed on deformation at lower temperatures. UNDERSTANDING the properties of new mate-*-J rials under different experimental conditions must be based on considerable knowledge of the mechanisms involved in plastic flow and how to control them. Tension and creep tests have been carried out on a number of pure metals in order to document their deformation characteristics. It is hoped that a comparison of these data with theory will indicate those areas where work on mechanisms and their relation to metallurgical variables may be most fruitful. Since aluminum has often been used for studying the qualitative aspects of creep behavior, it was chosen for detailed study. The effects of annealing temperature, stress, and test temperature on the constant stress creep behavior were studied. Although most of the tests were made above one half the absolute melting temperature, a few tests were made at lower temperatures to give qualitative comparisons. Some specimens were examined metallo-graphically and by X-ray diffraction techniques after creep. Since only a limited number of specimens could be made from the available material, no effort was made to study detailed changes in sub-grain structure or other metallographic features. Servi and Grant3 nd Dushman et al.' have previously published studies of high temperature creep of high purity aluminum. In both cases, a great deal of emphasis was placed on the minimum creep rate.

Jan 1, 1957

By W. D. Forgeng, R. L. Folkman, D. C. Hilty

The solubility of oxygen in molten Fe-Cr alloys has been determined at 1550° , 1600°, and 1650°C for alloys containing up to alloyshasbeenabout 50 pct Cr and found to decrease as chromium increases to 6 pet and then to increase gradually. Phase relations in the Fe-Cr-0 system at steelmaking temperatures have been evaluated and two previously unreported oxides have been identified. OPERATIONS in the melting and refining of chromium steels are dependent to a major degree on the reactions of chromium and iron with oxygen and are primarily directed toward controlling and modifying these reactions to secure maximum advantage in the utilization of chromium. Although fairly effective practices have been developed empirically, understanding of the specific reactions is limited. Moreover, the ability of molten steel to dissolve oxygen that subsequently precipitates as oxide inclusions during solidification is well known, so that clarification of the effect of chromium on the nature and mechanism of formation of these inclusions is desirable. Study of the problem indicated that increased knowledge of the fundamental Fe-Cr-0 system is essential to further technical and economic improvement. Consequently, an investigation of the influence of chromium on the solubility of oxygen in molten iron and of phases and phase relations in the Fe-Cr-0 system was undertaken at the Metals Research Laboratories of the Electro Metallurgical Co. as part of a general program on the effective utilization of chromium in chromium steel production. Experimental Procedure All of the experimental runs made during this investigation were carried out in the rotating crucible induction furnace which has been described in detail in a previous publication.' In review, the principle underlying this furnace is that rotational forces in the crucible cause the molten metal to assume a concave shape in such a manner that the slag is contained in the molten metal cup, thereby minimizing slag/crucible contact and subsequent reaction. Practically all of the heats were melted in commercial-quality magnesia crucibles of the type usually furnished for laboratory induction furnaces. All of the runs were made under an argon atmosphere after the furnace chamber had been degassed. Bath temperatures were controlled by Pt—Pt-10 pct Rh thermocouples. The basic furnace charge consisted of a premelted 12 to 15 lb electrolytic iron slug which had been cast to a shape convenient for fitting into the rotating furnace crucible. A typical analysis of the electrolytic iron slugs is given in Table I. For certain runs, it was desirable to melt down charges containing high initial chromium contents. In these cases the chromium was added to the electrolytic iron during the premelting operations. Chromium was added to the rotating furnace bath in the form of electrolytic chromium of the analysis given in Table 11. In all of the constant temperature runs, the standard procedure was to melt down the electrolytic iron or alloy slug under vacuum, admit argon to slightly greater than atmospheric pressure, and adjust rotational speed to develop a well formed "cup" on the bath surface. The melt was then saturated with oxygen by an addition of ferric oxide and the temperature of the bath adjusted to within +5°C of the desired level. At this point the heat was permitted to come to equilibrium prior to sampling or further addition. This time interval was varied from 15 min to 2 hr but generally was about 20 min. After sampling, the desired chromium addition was made and the bath again equilibrated prior to subsequent sampling. This cycle of addition and sampling continued for the duration of the run which lasted from 4 to 8 hr. At the end of this period, power was shut off and the bath allowed to solidify in the furnace. Quenched metal samples were taken from the equilibrated melts by means of the "Taylor sampler" which has been described by Taylor and Chipman.' Before being submitted to chemical analysis, all samples were carefully examined for surface slag occlusions and cold shuts. Later in the study, each sample was radiographed and examined metal-lographically in cross-section to determine the presence of internal defects. On the basis of these examinations, sound and apparently clean specimens were selected from the Taylor samples for chemical analysis.

Jan 1, 1956

By N. A. Gokcen

THE data of Chaudron,1 Tonosaki,2 and Collins³ on the thermodynamic properties of MOO, disagree widely. These authors, by using essentially similar methods, studied the following reaction: 1/2MoO2(s) + H2(g) == i/2Mo(s) + Ph,o H2O(g),K = —----- [1] Ph2 Tonosaki used a vacuum system consisting of a furnace containing MOO, and a water saturator whose temperature was kept at 25 °C with a thermostat. After repeated evacuation, hydrogen was admitted slowly into the system. The experiments were based upon the fact that at a constant furnace temperature and constant partial pressure of water, the total pressure of gas mixture over MOO? + Mo is constant. Any attempt to vary the pressure by external forces would vary only the amounts of MoO2, and Mo, after which the pressure should return to the equilibrium value in accordance with the equilibrium constant of reaction 1. The actual value of K was determined from the total equilibrium pressure (sum of Ph2o + Ph2) at each temperature. The total pressure of gas was varied within the range of 80.2 to 125.4 mm Hg, within a temperature range of 645" to 823 °C. The results were summarized as log K = 0.9413 — 1444.6/T for reaction 1. The ratio of H2O/H2 was considered to be uniform in spite of the presence of a thermal gradient across the static gas phase. It was shown by Rosenqvist and Cox,' however, that in somewhat similar circumstances the error resulting from thermal diffusion may be large. Collins³ improved Tonosaki's method by attempting to avoid thermal diffusion errors. His equilibrium data were obtained at 700°, 800°, and 900° C, and the result for reaction 1 was expressed as log K = 1.258 — 1822/T. The purpose of this investigation was to study reaction 1, avoiding the thermal diffusion errors, and to obtain equilibrium data in a considerably wide temperature range for the reliable extrapolation of the resulting thermodynamic functions. Experimental Procedure The diagram of the apparatus is shown in Fig. 1. Tank hydrogen was passed through a tube containing platinized asbestos at 425 °C in order to convert a trace of oxygen into water vapor. The flow rate was carefully controlled with a capillary-type flow-meter B and a bubbling column D. The gas was then presaturated sufficiently at P and led into a condenser system immersed in a thermostat, controlled to within ±0.002C. The temperature of the thermostat was measured with a thermometer calibrated against a certified standard. The temperature of P was adjusted to avoid the condensation of unduly large amounts of water as judged from the rate of flow out of the capillary tube M. Argon was purified by passing it through magnesium chips kept at 630°C. After passing through the flowmeter B', it was mixed with moist hydrogen emerging from the thermostat. The resulting gas mixture was then led into the hot zone of the furnace through the heated glass tubing and the silica tube S, thus insuring the same ratio of PII2o/Ph2 from the condenser to the reaction chamber, thus avoiding thermal diffusion. The entire gas system was of all-glass construction, except at the magnesium train. The furnace comprised a glazed alumina tube over which a 15-in. platinum coil was wound. The lower end of the alumina tube was tightly closed with a brass bottom and a silicone rubber gasket, and the upper end with two glass disks, each with a hole of 1/16 in. in diameter, through which the gas mixture escaped into the atmosphere. A back-up coil of kanthal wire facilitated the temperature control of the furnace. A coil of annealed molybdenum strip of 99.99 pct purity, 0.005 in. thick and 0.050 in. wide, and weighing 17 g was hung in the furnace with a 0.010-in. platinum wire attached to one end of a sensitive analytical balance. The temperature of the furnace was measured with a Pt-Pt-10 pct Rh thermocouple checked against a standard. The experimental procedure consisted of heating the gas purification trains, adjusting the gas flow rates, attaining a constant thermostatic temperature, flushing the entire system for 2 hr while heating the furnace to well above the expected equilibrium temperature and then cooling it at a rate of 0.3°C per min during which time the change in the weight of molybdenum was observed on the balance. For a given thermostatic temperature, i.e., a constant Prr,o/Px,, molybdenum oxidized upon cooling slightly below the equilibrium temperature. The procedure was then repeated by heating the furnace and thus reaching a temperature slightly above the equilibrium value. The average of the two temperatures, differing by 2" to 3"C, was considered to be the true equilibrium temperature. In order to determine the stoichiometric composition of the oxide phase present in this investigation,

Jan 1, 1954

By G. M. Ikeda, J. G. Sibakin

An investigation was carried out to determine the variables affecting the coiling temperature of strip in the 56-in. hot strip mill. After statistical treatment, equations have been derived to determine the temperature drop between mill and coiler for both full spray (top and bottom) and top spray only practices. The individual influences of each variable in the temperature drop were derived for both practices. Limitations of the present practices were shown and adjustments in cooling for increased rolling speeds were suggested. A method of estimating the required number of sprays, their spacing, pressure, etc., to achieve a desired temperature drop is developed. MAXIMUM finishing temperature of a hot strip mill is mainly determined by the rolling speed, gage, and the temperature of the bar entering the mill. This finishing temperature may be limited by the maximum admissible coiling temperature in cases when either the cooling facilities on the runout table are not adequate or, more generally, when the cooling capacity of the runout table and the production capacity of the continuous mill are out of balance. Some time ago, the balance between these two factors was not considered detrimental to production. Recently, a new drafting schedule was introduced which increased the production rate, the entry temperature, and hence the finishing temperature. Thus, the restriction of the maximum specified coiling temperature became an important factor for many of the thicker gages. An investigation of the factors determining the coiling temperature may be, therefore, of considerable importance. A brief description of the available equipment will be a useful illustration of the techniques and methods used for this investigation. The 56 in. continuous hot strip mill is composed of six 4-high stands each containing two 221/2-in. diam work rolls and two 45-in. diam back-up rolls. Either of the last two stands can be used as the finishing stand. Which stand is used is dependent on the total percentage of reduction to be taken over the whole train, i.e., on the entry thickness and the final gage. The characteristics of these last two stands are given in Table I. Table I. Operational Characteristics of Nos. 5 and 6 Stands No. .5 NO. 6 Maximum voltage GOO 600 Power, hp 30(10 W00 I normal, kilonmp 4.35 3.73 Rpm of motor and rolls ISO 15 0 ITS to 300 Spettl ot strip, fpm 333 6 to 376T.2 103) to 2062 The speed of the finishing stand varies with the amount of reduction, strip width, and the exit gage. Finishing speeds in general use for varying gages are shown in Table 11. These speeds may change with an increase or decrease in the entry temperature of the strip. Even though the maximum speed of No. 6 stand is shown as 2062 fpm, this has so far never been attained,

Jan 1, 1957

By N. A. D. Parlee

The diffusion rate of hydrogen in liquid iron has been measured by a gas-liquid metal diffusion cell technique. The diffusion cell was formed by immersing an alumina tube containing hydrogen gas at 1 atm in a bath of stagnant liquid iron. The change in the composition of the melt in the cell was determined by measuring the rate of absorption of the gas in the cell. The appropriate solution to Fick's second law was used to examine the data and calculate diffusivi-ties. The absorption of hydrogen in stagnant pure liquid iron has been found to be diffusion-controlled. The results show that the chemical diffusion coefficient, D, of hydrogen in pure iron in the range of 1547" to 1726°C can be represented by the following Arrhenius relation: D(sq cnz per sec) = 3.2 x X exp(- 3300 i 1800/RT) where the uncertainty in the activation energy corresponds to the YO pct confidence level. Oxygen in the melt (above 0.015 pct 2) increased the apparent rate of absorption of hydrogen. The importance of diffusion data on liquid metals for predicting the rates of certain metallurgical processes has been recognized for a long time. Moreover, these data are much needed to test and develop theory for diffusion in liquid metals. Despite this practical and theoretical interest, however, relatively little reliable information about diffusion in liquid metals is available in the literature. This is particularly true for gas components such as hydrogen, oxygen, and nitrogen in liquid metals, where almost no data on chemical diffusion coefficients are to be found. This is probably due to a multitude of experimental difficulties particularly associated with high-temperature melts. In an effort to fill this gap in information, a research program was undertaken to study the diffusivities and rates of solution of gases in liquid metals. This paper presents the results of a study of the diffusion of hydrogen in liquid iron. EXPERIMENTAL METHOD Two methods for the study of the kinetics of dissolution of gases in liquid metals are being employed in this laboratory. Both involve the measurement of the volume of gas absorbed by the melt as a function of time and as such both avoid the uncertainties involved in chemical analyses of quenched samples for relatively small amounts of gas. In the first method, the gas dissolves in an inductively stirred melt and, in the absence of a slow surface reaction, the results are often interpreted in terms of mass transport across a liquid "boundary layer" between the homogeneous gas phase and well-stirred part of the melt. Other interpretations of the results of such experiments have also been described in the literature.1'5 In the second method a gas-liquid metal diffusion cell is used.' The gas dissolves in a cylindrical column of stagnant liquid metal and, in the absence of a slow surface reaction, the results are interpreted in terms of a non-steady-state diffusion solution to Fick's second law. The weakness of the first method is that while it gives information on the mechanism of absorption by stirred melts it yields an overall rate constant which even in the simplest cases depends on the nature and the thickness of the "mass transport layer" or "boundary layer". It yields no values of diffusion coefficients. The second method was used in this research because in many cases it is possible to determine the diffusion coefficient of the gas component in the liquid metal. In this research it has been utilized to measure diffusion coefficients of hydrogen in liquid iron. The apparatus used was essentially the same as that described by Mizikar, Grace, and par lee but certain modifications have been introduced to meet the elevated temperatures and special conditions of this research. Fig. 1 is a schematic drawing of the apparatus and Table I gives the identification of various parts in this figure. The diffusion cell, shown in detail in Fig. 2, was formed by immersing an impervious alumina tube (hereafter called absorption tube) in a bath of pure liquid iron contained in an alumina crucible. Two types of tubes were used, Morganite triangle RR and McDanel AP35. The crucible was contained in a vertical impervious alumina combustion tube (32 mm ID by 914 mm long) which was closed at both ends by water-cooled brass heads employing O-ring compression seals, Fig. 1. A protection tube enclosing a Pt, 5 pct Rh-Pt, 20 pct Rh thermocouple was introduced through the lower end of the combustion tube

Jan 1, 1968

By E. S. Bumps, M. Baeyert, W. F. Craig

SOME time ago during a study of impact properties of tempered martensite,1 it was postulated that the consistently good ductility of tempered martensite might be caused by its relatively small and peculiarly shaped ferrite grains. The fer-rite grains of tempered martensite have approximately the same size and shape as the martensite "needles." Thus they form an interlocking mass of needle-shaped grains quite different from equiaxed or lamellar ferrite grain structures. When the common mechanical test methods are applied to steel, variations are often observed in the ductility of specimens that have closely similar hardness and tensile strength values. The ductility so measured appears to be structure dependent. When steel from the same heat has been heat treated to produce different structures with the same hardness, the elongation and reduction of area values from the tensile test and the transition temperature determined by the notched-bar impact test vary according to whether pearlite, tempered martensite, or other structural constituents were produced by the heat treatment. It has been widely recognized that tempered martensite gives a consistently good performance, when tempered to the same hardness as many other structures with which it has been compared. In recent years the isothermal transformation of austenite to specific structural products and the quantitative evaluation of the character of these products with respect to their nature and response to deformation has received considerable attention. The objective of the present study was to pursue somewhat further the dependence of ductility upon structure; specifically, it was desired to ascertain whether ferrite grain structure, including both shape and size of the grains, can account for the consistently good performance of tempered martensite in the notched-bar impact test. It was thought that a simple experiment would indicate whether the ferrite grain structure plays any part in the good ductility exhibited by tempered martensite in contrast to other steel structures with different types of ferrite grains. By determining the impact transition temperature, it was proposed to compare spheroidites having similar carbide particle size and spacing but obtained in such a manner that their ferrite grain structures would be very different. Spheroidite obtained by tempering martensite, with its small, needle-shaped grains, was to be compared with spheroidite from pearlite. If the latter is produced by sub-critical annealing, the ferrite grains correspond to the pearlite colonies. Thus, if the pearlite was not too coarse, the ferrite grains of spheroidite from pearlite are equiaxed in contrast to the needle-shaped grains of spheroidite from martensite. It was thought that the ferrite grain structure of spheroidite from martensite might depend to some extent upon the grain size of the prior austenite. The austenite grain boundaries limit the maximum attainable size of the martensite needles and thus of the ferrite grains in the derived spheroidite. In order to evaluate any possible influence of prior austehite grain size, spheroidites were to be prepared from martensites that had been formed from fine-grain austenite and also from coarsened austenite. As the carbide particle size and distribution were to be essentially alike in the various spheroidites, the difference would be in the ferrite grain size and shape. Thus any marked difference in transition temperature could be attributable to the character of the ferrite grain structure. There are certain considerations in assuming that these spheroidites would be equivalent in all respects except ferrite grain structure, and an attempt was made to take them into account. One of the considerations was the choice of the carbon content of the steel. An approximately eutectoid steel was selected for two reasons. First, the pearlitic structure would contain no proeutectoid ferrite which might complicate the picture by producing a non-uniform ferrite grain structure in the resulting spheroidite. Then, too, the high-carbon content would inhibit ferrite grain growth during the sub-critical treatment. Another factor to be taken into account was the choice of an alloying element to assure a martensitic structure throughout on quenching the impact specimens. Nickel was chosen, because it is a common alloying element and resides in the ferrite both upon its formation from austenite and throughout tempering. The formation of alloy carbides, or even a large solubility of the alloying element in cementite, would have complicated the interpretation by changing the composition of the ferrite .during spheroid-ization. The possibility of temper brittleness was minimized insofar as possible by using a tempering temperature as high as consistent with the 1 pct of nickel in the steel, namely, 1150°F. While it certainly is not claimed that no difference other than ferrite grain structure could exist between the spheroidites, nevertheless, reasonable precaution has been exercised within the limits of steel metallurgy. It is believed that any large difference in transition temperatures would reflect the difference in ferrite grain structure and that relatively good ductility in the spheroidites from mar-

Jan 1, 1951

By E. J. Rapperport, E. D. Levine

The boundaries of the (a +ß) field in the Al-Li system were determined between 150°and 550°C utilizing quantitative metallography and lattice-parameter measurements. The solubility of lithium in aluminum decreases from 12.0at. pct Li at 550°C to 5.5 at. pct Li at 150°C. P Al-Li is saturated with aluminum at 45.8 at. pct Li and has this boundary value constant over the temperature range 150°to 550°C. THE solid solubility of lithium in aluminum has been determined by several investigators, 1-6 but, as shown in Fig. 1, there is little agreement among the various determinations. The earliest investiga-tions'-' are suspect because of the use of impure materials. Although high-purity materials were employed in more recent work,4'5 the experimental techniques may have led to contamination of the specimens. Probably the best work has been that of Costas and Marshall,6 who obtained close agreement between results obtained by two independent phase-boundary techniques: electrical resistivity and mi-crohardness. No detailed studies of the solubility of aluminum in the bcc ß phase, Al-Li, have been reported. Cursory investigations1,2,6 have indicated only that the (a+ß) -p boundary lies between 40 and 50 at. pct Li and is relatively independent of temperature. The present work was undertaken in order to provide an independent check on Costas and Marshall's determination of the solubility of lithium in aluminum, to extend knowledge of this solubility limit to temperatures below 225°C, and to make an accurate determination of the solubility of aluminum in Al-Li. EXPEFUMENTAL Alloy Preparation. In view of the difficulties encountered in previous investigations of the A1-Li system, close attention was paid to the use of methods of alloy preparation and treatment that would minimize contamination. Aluminum sheet (99.99 + pct Al) was vacuum-induction melted in a beryllia crucible to remove hydrogen. Lithium (99.9 pct Li) was charged with pre-melted aluminum into a beryllia crucible, in a helium-filled drybox. The crucible was sealed in a Vycor tube and transferred from the drybox to an induction furnace. Melting of alloys was performed by induction heating in a helium atmosphere. Solidification was accomplished by means of a suction apparatus, shown in Fig. 2, in which the alloy was forced by changes of pressure into a 3/16-in. inside diam closed-end beryllia tube. This technique produced rapid solidification of a small portion of the melt, resulting in alloys with a high degree of homogeneity. Typical lithium distributions are presented in Table I. Transverse sections 1/8 in. long were cut from the alloy rods, and each section was split in half longitudinally. One half of each section was analyzed for lithium, and the opposing halves were employed for phase-boundary determinations. Lithium contents were determined by flame photometry with an accuracy of 1 pct of the amount of lithium present. Thermal Treatments. Homogenization and equilibration heat treatments were performed in electrical-resistance furnaces with temperatures controlled to ± 2OC. Calibrated chromel-alumel thermocouples were employed to measure temperature. Homogenization was performed in helium-filled l?yrex tubes for 1 hr at 565°C. The encapsulated specimens were then transferred directly to furnaces maintained at lower temperatures for equilibration. Equilibration times were 2 hr at 550°C, 8 hr at 450°C, 27 hr at 350°c, 90 hr at 250°c, and 285 hr at 150"~. These times were chosen on the basis of conditions employed by previous investigators. Alloys were quenched from the equilibration temperatures by breaking the capsules into a silicone oil bath. By performing all possible operations either in sealed capsules or in a helium-filled drybox, the specimens were given minimum exposure to the atmosphere. Quantitative Metallography. Metallography of Al-Li alloys is difficult because of the atmospheric reactivity of the ß phase. It was found possible, however, to prepare surfaces of good metallographic quality by preventing contact with moisture during preparation. Grinding through 4/0 paper was performed in the drybox. The specimens were then transferred under kerosene to the polishing wheel. Three polishing stages were employed: 25-p alundum with kerosene lubricant on billiard cloth, 1-µ diamond paste on Microcloth, and 1/4-p diamond paste on Microcloth. Between stages the samples were cleaned by rinsing in trichloroethylene and buffing

Jan 1, 1963

By N. H. Harrison, J. K. Rodgers, S. Regier

This paper presents comparisons of data obtained from a laboratory reservoir study and from a calculated behavior prediction with the actual production history of a condensate reservoir. A small non-commercial discovery was depleted under closely controlled conditions and the well fluids were sampled at frequent intervals. Data on the reservoir and production variables were accumulated on a fixed schedule. A laboratory reservoir study war made using the initial well fluid samples as charging stock. The production procedures and operating conditions were held constant throughout the study wherever possible and in general paralleled the field work. The well fluid compositions and the cumulative recoveries ar a function of the reservoir pressure were also calculated using conventional flash vaporization procedures and equilibrium constants. Comparisons based on the composition of the well fluid show good agreement, the laboratory study agreeing within experimental accuracy with the field work and the calculated data comparing equally well. The gas-oil ratios are also in good agreement, but with somewhat greater deviations at the higher pressures. In the overall picture, it is believed that a model st,~tiy can predict within experimental accuracy the production history of a condensate reservoir. Better equilibrium constants for the heavier hydrocarbons are needed in order to attain improved composition accuracy by calculation. INTRODUCTION In Aug., 1955, a gas condensate well was completed in San Juan County, Utah, that was initially thought capable of good commercial production. These conclusions were derived principally from core data and electric logs, which indicated good permeability, porosity and gas content. However, after the usual series of potential tests it was found that the reservoir pressure had declined some 22 per cent, and it was obvious that the zone tapped was but a small pocket or trap. It became apparent that, with a controlled depletion of a small reservoir, a unique opportunity was available to compare laboratory and calculated studies with an actual field depletion and to further the present knowledge of condensate reservoirs. FIELD WORK The Coalbed Canyon Well No. 1 was conventionally completed in the Paradox limestone formation to a total depth of 5,912 ft. The producing zone from 5,762 to 5,806 ft was perforated with four jet shots per ft. The wellhead and field equipment were also conventional, the major items consisting of a two-pass indirect fired line heater, a high- and a low-pressure separator with the necessary controls and accessories, gas meters, back-pressure regulators, flare stacks and condensate stock tanks. The initial testing of this well con-sisted of a series of flow potential and pressure build-up tests during which some 30 MMcf of gas was produced. The reservoir pressure declined from an estimated 2,300 to 1,782 psig during this period, from which it was concluded that the reservoir was very small. In order to approach steady-state conditions in the reservoir and so provide optimum conditions for making comparisons, the field depletion was programmed to approach, if possible, constant production conditions. Bi-hourly readings were taken of the tubing pressure, the pressure and temperature of the separators, oil and gas rates, and other pertinent operating data. The gas rate, as indicated by the orifice meter, was held constant by the adjustment of the choke in the line heater. The temperature of the first stage separator was held constant by adjustment of the line heater jacket temperature. Practical considerations of production made the maintenance oi a constant gas rate impossible. The test started with a gas rate of 4 MMcf/D and a separator pressure of 250 psig. This rate was maintained until the choke was fully opened. The gas rate then declined with the falling tubing pressure and production was continued until the rate was about 2

By R. R. Webster, H. T. Clark

The side-blown converter has been investigated as a possible commercial process for the production of low nitrogen steel. During this work, two converters of 3-ton and 22-ton capacity were operated on a pilot plant basis for a total of 214 heats. The steel made in these converters was low in nitrogen and possessed good cold working properties. Some problems of converter operation remain to be solved. IN plants operating with a high iron capacity, sev-eral different refining methods are used in the conversion of the molten pig iron to steel. These include various ore practices in stationary and tilting open-hearths, the duplex process employing the Bessemer converter and open-hearth, and the Bessemer process. At J&L, a considerable part of the iron produced is handled by the Bessemer process, either alone or in conjunction with duplexing, and therefore an appreciable portion of the steelmaking research effort has centered about the method. This paper covers research work on the development of the side-blow converter for the commercial production of low nitrogen ingots and includes descriptions of the operation of a 3-ton and a 22-ton experimental converter at the Aliquippa Works. The refining of iron to produce steel requires the removal of a large portion of the carbon and silicon and the control of manganese, phosphorus and sulphur which are present in the iron in varying amounts. The first large-scale means of refining iron was the acid Bessemer process which was brought into use almost 100 yr ago. This method, using compressed air as the refining medium, accomplishes substantially complete removal of carbon, manganese and silicon. Phosphorus and sulphur are not affected but, by choice of an iron composition sufficiently low in these elements, a commercial product can be produced. Since the process will handle large tonnages rapidly, operates without external fuel and with a minimum of additional equipment, it quickly became the major tool in the early expansion of the steel industry. Later, the basic open-hearth process, by affording control of phosphorus and sulphur and by consuming the large quantities of steel scrap that were becoming available, forced the acid Bessemer process into a secondary position in the industry. During the past two decades the demand for steel to be used in cold forming and drawing operations has gradually increased. Bessemer steel, because of its work hardening and aging characteristics, is not as suitable for these applications as basic open-hearth steel, consequently the decline of the process was accelerated. More recently, because of changing economic conditions, this long range trend appears to have been arrested or perhaps reversed. Ingot production data for recent years furnishes only an incomplete picture of the importance of the converter in the American steel industry; open-hearth furnaces utilize large tonnages of blown metal for which no published statistics are available. Metallurgical Aspects The fundamental difference between Bessemer and open-hearth steels apparently lies not in the method of manufacture but, rather, in the differences in chemical composition of the two steels. It is further believed that the principal features distinguishing Bessemer from open-hearth steel are the higher nitrogen and phosphorus contents of the former. Evidence supporting this position is supplied by tests on laboratory induction furnace heats that were made to contain varying amounts of phosphorus and nitrogen but were otherwise similar to normal low carbon silicon-killed steels. Fig. 1, 2 and 3, summarizing the test results, are taken from G. H. Enzian's paper titled, "Some Effects of Phosphorus and Nitrogen on the Properties of Low Carbon Steels."' Fig. l indicates that phosphorus has a marked effect on the cold work embrittlement of steel as shown by the work brittleness test of Graham and Work.' In the low nitrogen steels, which as a group have the better cold working properties, the effect of phosphorus variations is the more pronounced.

Jan 1, 1951

Covering resources, production, uses, defense impact, and future outlook of nickle, Mining Engineering presents the third in a series of articles on strategic minerals. Preceding it are "Cobalt" in January and "Sulphur" in May.

Jan 8, 1951

Jan 12, 1951

By Rex B. McLellan

Studies of the eyuilibrzum between ferrite and austenite with gas mixtures (CO + CO2 and H2 + CHe) have been used as a means of deducing the energy and vibrational entropy of carbon atoms in dilute interstitial Fe-C solutions. A simple model for dilute interstitial solutions is given which enables a solubility equation for the equilibrium between the gas mixtures and the solid to be deduced. This solubility equation is used to estimate the partial In this work measurements of the equilibrium between dilute solid solutions of carbon in iron and gaseous mixtures of CO2 + CO and CH4 + Hp have been analyzed using theoretical solubility equations deduced from a knowledge of the thermodynamic parameters of the gas mixtures and an appropriate model for the solid solution. The solubility equations are deduced by equating the chemical potential of carbon atoms in the gas thermodynamic functions of dilute Fe-C solutions from the measured equilibrium between the solid and the gas mixtures. It is shown that the vibra-tional entropy of a carbon atom in a and y iron is smaller than the corresponding entropy 01. a nitrogen atom in solid solution inferrite or austenite and that there is little difference between the vibrational entropies of both nitrogen and carbon atoms in ferrite and austenite. and solid phases. The chemical potential of carbon in the gas is found from a simple statistical mechanical analysis of the gas mixtures utilizing spec-troscopic data while that for carbon in the interstitial solution is found from a model in which the carbon atoms act as bound oscillators distributed in a random fashion in the solution. The solid solution is dilute enough to enable solute-solute interactions to be ignored. Thus the configurational entropy of the solution is ideal but the mixing entropy contains additional excess terms due mainly to the vibrational changes occurring on solution formation. The partial excess entropies (and the partial energies) do

Jan 1, 1965

By C. S. Barrett, O. R. Trautz

Previous investigations have shown that lithium is body-centered cubic from near its melting point to the temperature of liquid air.1,2,3 Nevertheless there was an incentive to search again for a transformation at low temperatures: C. Zener4.5 has remarked that the low value of the elastic modulus (C11 — Cl2)/z of body-centered cubic metals and alloys implies a rapid increase in free energy with decreasing temperature, which would favor the occurrence of a transformation; also the shear movement to which this modulus applies is one that can transform a body-centered cubic structure into a slightly distorted face-centered cubic structure. It was confirmed that lithium does not transform spontaneously at liquid nitrogen temperature, but it was found that a transformation can be induced at this temperature by cold working the metal,6 and at slightly lower temperatures a different transformation occurs spontaneously. Transformations were also found in solid solutions of magnesium in lithium. The Nature of the Transformations Before presenting a detailed treatment of the technique used and the specific data obtained, it would be well to give a brief survey of the general characteristics of the transformations. A new crystal structure begins to form spontaneously in a specimen when it is cooled below a critical temperature. In lithium the structure appears to be close-packed hexagonal; in theLi-Mg alloys most of the diffraction lines (but not all) are near those for hexagonal lithium. The transformation proceeds as the temperature is lowered and soon stops if the temperature is held constant or raised. The course of the transformation on cooling is indicated by the curve at the lower left of Fig -I. This curve is drawn in stepped fashion because the transformation goes by discrete steps with audible clicks. Because of the similarity to the decomposition of austenite into martensite in steels, it seems appropriate to designate the beginning of the spontaneous transformation on cooling as the Ms point. On heating to room temperature after the low temperature treatment only the usual BCC structure is found. On heating, the low temperature modification begins to disappear at a temperature which will be designated as Ac. The transformation on heating is halted when the rise in temperature is halted. The temperature must be raised 40 to 50°C above Ac before the reversion is complete—an interval which is sensitive to the rate of heating and to the time of holding at temperatures above Ac. This behavior on heating thus has similarities also to the formation of martensite in the cooling of steels.

Jan 1, 1949

By Horace Winchell

AN EXAMINATION of the Pachuca and El Oro. districts in July, 1920, although cursory and incomplete, disclosed facts of more than passing interest to the student of ore deposits; and inasmuch as the literature on these districts is limited and some of their features are little understood, a brief account may prove valuable as reconnaissance observations to be amplified by more thorough and competent observers in the future. Where no complete monograph of important mining camps has been published a partial presentation of the data is often useful, as it sometimes leads to fuller and more accurate descriptions, by stimulating discussion. The following notes are presented with the consent of Mr. A. F. Main, managing director of the El Oro Mining and Railway Co., whose fund of information and wide acquaintance with both districts alone made it possible to cover so much ground in a short time. I have also to acknowledge gratefully the aid of Messrs. C. A. Lantz and D: S. Calland of the Santa Gertrudis and Real del Monte companies, respectively, in connection with permission to inspect geological features of interest in their mines.

Jan 6, 1921

Jan 1, 1890

By R. D. West

Miscible displacenzent recovers all oil in the area contacted by the injected .fluid, whereas water or immiscible gas drives usually leave substantial amounts of oil as residual. However, the Door mobility ratios associated with a gas-driven miscible displacement cause the sweep pattern efficiency to be much lower than that obtained with water flooding. One way in which the sweep eficiency in a miscible displacement process can be increased is by decreasing the mobility behind the flooding front. This can be achieved by injecting water along with the gas which drives the miscible slug. This water reduces the relative permeability to gas in this area and thus lowers the total mobility. The main operating conditions for the simultaneous injection -vrocess are that a zone of gas exists between the miscible slug and the leading edge of the water and that a su,@cient amount of gas be injected with the water to form the pas volume which is being left in the water zone. Laboratory model studies have shown that the ultimate sweep pattern efficiency can be as high as 90 per cent for a five-spot flooding system. If gar alone is used as the driving medium an ultimate sweep-out efficiency of about 60 per cent would be obtained in the same system. I INTRODUCTION The miscible displacement processes are a step towards total oil recovery. Conventional gas or water drives usually leave 25 to 5.0 per cent of the oil as residual in the swept portion of the reservoir. This residual can be eliminated if the oil is driven by a fluid with which it is miscible. At some reservoir conditions natural gas will become miscible with the oil. This is the "high pressure gas process".' More often, the oil does not contain enough light hydrocarbons to cause the gas to become miscible with the oil at reasonable pressures. In these cases a small band of fluid which is miscible both with the oil and gas must be kept between them2. Less than 2 per cent of the reservoir volume of the slug material is needed to keep the displacement miscible. Both processes work in the same manner, recovering all of the oil in the portion of the reservoir contacted by the injected fluids. The only difference is the manner in which the miscibility between the oil and the injected gas is obtained. Previous publications have contained detailed descriptions of these processes.1,2,3,4 However, total displacement of the oil in the swept region does not guarantee an efficient recovery process. The amount of oil to be recovered is also determined by the fraction of the reservoir contacted by the flood. This fraction is largely determined by the mobilities of the fluids. (The fluid mobility is the permeability of the rock to that fluid divided by the fluid's viscosity, k/p). This. dependence of the fraction swept on the mobility ratio has been shown in previous studies. Fig. 1 shows the ultimate fraction swept in a five-spot system as a function of the mobility ratio. The small drawings show the location of the areas left unswept for two different mobility ratios. The ultimate fraction of the reservoir swept is here considered to be attained when the producing stream contains less than 5 per cent oil at reservoir conditions. THE GAS-DRIVEN MISCIBLE DISPLACEMENT Since there is no oil left in the swept region after miscible displacement the mobility in this region is very high. It is often 50 times the mobility in the unswept regions. This means that the fraction of the reservoir contacted by the injected fluid will be less for a gas-driven miscible displacement than for a conventional water or gas drive. For a five-spot injection system, water would contact the entire reservoir volume, and the low pressure gas would contact about 90 per cent of this volume, while a gas-driven miscible displacement would only contact about 65 per cent of the reservoir. This poor sweep efficiency often offsets the benefits obtained through miscible displacement. Fig. 2 shows what the recovery curves for the three processes might look like for a five-spot system. The curves show the fraction of the in-place oil recovered as a function of reser-