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By N. J. Olson, G. W. Toop

A series of equations previously derived for calculating ternary thermodynamic properties using binary data has been applied to the problem of predicting ternary phase diagrams and quaternary excess free energy. The methods are considered to be rigorous for regular ternary and quaternary systerns and empirical for nonregular systems. The equations have been used to predict ternary phase boundaries in the Pb-Sn-Zn system at 926°K and the Ag-Pd-Cu system at 1000ºK. Calculated quaternary excess free-energy values are presented for the Pb-Sn-Cd-Bi system at 773°K. A method for predicting the location of ternary phase boundaries would be a useful supplement to experimental measurements in ternary systems. This has been recognized with the considerable work that has been done to find models to predict or extend thermodynamic properties and phase diagrams in binary and ternary systems1-18 for which direct experimental measurements are limited. With the access to highspeed digital computers and mechanical plotting devices, it is currently rather easy to compare mathematical models with experimental data. The regular-solution model is consistent with systems which exhibit negative heats of mixing, positive heats of mixing, and miscibility gaps, and therefore it is applicable to simple phase diagrams. The purpose of this paper is to illustrate the use of regular-solution equations to predict, empirically, phase equilibria in some types of nonregular ternary systems. Corresponding equations for regular quaternary systems are given and used to calculate empirical quaternary excess free-energy data. METHOD FOR PREDICTING THE LOCATION OF TERNARY PHASE BOUNDARIES USING BINARY DATA Meijerin1,6 has used the regular-solution model to calculate common tangent points to ternary free energy of mixing surfaces and hence to determine phase boundaries in ternary systems involving miscibility gaps. He used the following equation to calculate ternary excess free energy of mixing values: stants characteristic of the binary solutions, and Ni is the mole fraction of component i. An alternate expression which gives for regular solutions as a function of binary values of along composition paths with constant N1/N2, N2lN3, and N1/N3 may also be derived:15 ternary r xs 1 ?c-*n.Ti*.U*. This expression for is more useful for the empirical calculation of ternary excess free-energy values for nonregular systems because actual binary AFXS data may be used in the expression rather than attempting to find suitable constants for Eq. [I]. The results of this feature of Eq. [2] are illustrated in Table I where calculated excess free-energy values for the Ni-Mn-Fe system at 1232°K are compared with experimental data of Smith, Paxton, and McCabe.19 Although regular-solution equations have been shown to give calculated thermodynamic quantities which agree quite well with experiment for single-phase nonregular ternary systems,14,15 care should be exercised in the use of the equations to predict thermo-dynamic properties of multiphase ternary systems in which strong compound formation is suspected. This precaution is consistent with the simple regular-solution model which for negative values of ai_j will indicate a tendency toward compound formation but even for very large negative values of ai-jwill not give multiphase binary or ternary systems involving a distinct stable compound. Hence, calculated ternary free-energy data using Eq. [2] might be expected to vary between being rigorous and poor, in the following order, for ternary systems which are: a) regular solutions, b) nonregular single-phase liquids in which random mixing is nearly realized, c) nonregular single-phase solids, d) nonregular multiphase systems exhibiting miscibility gaps, e) nonregular multiphase systems with binary compounds but no ternary compounds, f) nonregular multiphase systems with highly stable binary and ternary compounds. The calculated data will be expected to be least accurate for the last two cases. The general method adopted in this paper involves two-dimensional plots of ternary activity curves. The principle used is that tie lines indicating two-phase equilibria join conjugate phases a and B for example, for which a1(a) = a1(B), a2(a) = a2(B), and a3(a) = a3(B). Tie lines may be determined by plotting the ternary activities of two components along an isoactivity line for the third component and the unique points where the above equalities hold may be found graphically.

Jan 1, 1970

By Charles M. Brown, Russell Franks, W. O. Binder

Occasionally in the application of the austenitic chromium-nickel steels to corrosive conditions, failures have occurred by cracking without serious general over-all attack of the metal. As pointed out by Foyt and Scheil(1),2 and by Scheil, et al.(2) as well as by Hodge and Miller(3), the stress-corrosion failures that have occurred have been limited in number, and have taken place only when the steels were exposed to certain corrodents. These investigators have stated that while stress- corrosion cracking can be intergranular in nature and originate at the grain boundaries of the austenitic chromium-nickel steels, it can also take place in trans- granular fashion. They have shown that the cracking may be either initiated at the grain boundaries and may propagate along grain boundaries for some distance and then suddenly extend across grains, or it may begin in a transgranular fashion and suddenly proceed along grain boundaries until the cracking stops. Their data further show that when austenitic stainless steel is subject to intergranular attack, stress will concentrate and cause cracking in service. These investigators have studied the effect of the metals titanium and columbium which are added to the steels to impart immunity to intergranular attack, and molybdenum which is added to improve resistance to general corrosion.

Jan 1, 1945

By Elmer R. Kaiser

COMBUSTION of coal and transfer of heat from flames and gases to boiler surfaces continue to be of great interest to engineers here and abroad. Numerous investigations have been in progress to improve furnace and boiler performance and economy. The importance of better understanding of the processes and opportunities for improvement is apparent when it is remembered that heat from at least 500 million tons of coal a year the world over is being transferred to boiler water at efficiencies ranging mostly between 50 and 90 pct. Even slight gains in efficiency, economy, and labor saving become very significant when multiplied by the enormous quantity of fuel consumed. Also the competitive position of the large coal, oil, and gas industries in satisfying the fuel consumers is greatly affected by the achievements made through technical progress with each fuel. This paper is part of a continuing activity of Bituminous Coal Research, Inc., to extend the knowledge of coal utilization for steam generation and to seek promising directions for future research and development in cooperation with others. Particularly in the latter regard, numerous interviews were held during the last three years to seek the experience and advice of boiler and combustion-equipment manufacturers, electric-utility executives, and fuel engineers. A wealth of published information was also reviewed, which together with the interviews pointed to the advisability of further work on ash and sulphur control. For the present purpose a number of factors important to efficient heat liberation and recovery have been grouped as follows: 1—combustion, temperatures, and rates of heat liberation; 2—radiation, convection, and furnace and boiler configuration; 3—sponge ash, slag, and hard-bonded deposits; 4— low-temperature deposits and corrosion (cooling flue gas below dew point and air-pollution control); 5—the limitations of coal cleaning and boiler size and cost as related to fuel characteristics; 6—future possibilities and conclusions. The development of combustion apparatus for power boilers is progressing at a lively pace. There has been no letup in improvements in design of pulverized-coal-fired boilers, and there is a strong trend at present toward improving dry-bottom units. Spreader stokers with overfire jets and dust collectors as standard equipment are gaining favor. Less than 10 years in commercial use, cyclone burners are going into numerous installations here' and abroad.' Underfeed and traveling-grate stokers have long since been developed for heavy-duty operation, yet new developments in overfire jets and humidification of air blast have improved their performance. A water-cooled vibrating-grate stoker of German origin is being introduced into the United States and Canada." The primary objectives of an ideal coal combustion device are: capacity to burn the variety and sizes of coals likely to be economically available during the life of the unit; capacity to burn the coals automatically for a wide load range and rapid load fluctuations and to burn the coals completely to CO2, H2O, and SO2, which means without smoke and cinders, or carbon in the refuse; capacity to control and discharge all the ash in final granular form without ash adhesion to walls or tubes, and without flue dust; minimum furnace volume; minimum labor and maintenance; low initial and operating cost. Regardless of the method of burning, the gaseous products of coal combustion are N2, CO2, O2, H20, and SO?. By way of illustration, the coal analyses in Table I is assumed from an installation described by E. McCarthy.' When coal is burned with 20 pct excess air (theoretical air, 9.23 lb per lb of coal), the quantities of combustion gas shown in Table II are produced. In addition, the gases carry particles of fly ash, unconsumed cinders, soot particles, and small but significant amounts of vaporized oxides and sulphates of sodium, potassium, lithium, phosghorous, iron, and other metals. In recent years, germanium, one of the rare metals found in coal, has been shown to oxidize and vaporize at combustion temperatures and to be concentrated by reconden-sation at lower temperatures." Pulverized coal and cyclone flames" have peak temperatures of 3000' to 3500°F. Temperatures in fuel beds of large underfeed stokers reach maxima of 3000°F, sufficient to fuse almost any ash and to volatilize some of it. These peak temperatures are above the optimum necessary for rapid combustion, but they hasten heat transfer for ignition as well as boiler heat absorption. Furnace and gas temperatures increase with combustion air preheat. Low excess air has the same effect. Fine coal pulverization and highly turbulent combustion shorten the distance for fuel burnout, increase flame temperature, and speed up heat transfer. Rates of combustion of pulverized coal exceeding 200,000 Btu per cu ft per hr have been demonstrated in atmospheric gas-turbine combusters,

Jan 1, 1955

By Edmund M. Warner

Any city dweller who has walked alone along a remote mine passageway has to be impressed by the eerie silence-the total absence of noise except for one's own breathing and scuffing of boots on the bottom. An underpound mine can have tremendous contrasts, from complete silence to the ear piercing clatter of percussion drills working in the mine roof. Noise in underground mining machines is both useful and detrimental. Without characteristic noises that are recognizable to miners, operators would have a more difficult job operating their machines. Noise serves as a warning of approaching machinery, and changes in noise give indication that breakdowns may occur. But excessive noise is a health hazard. In recognition of this fact, our congress included noise exposure as a part of the "Coal Mine Health and Safety Act of 1969." As [Fig. 1] indicates, allowable noise exposure is established by specifying a time duration permitted at different noise levels. This is the well known "Walsh-Healey" criteria which govern noise exposure in many industries. In most industries noise exposure is not a constant value. Noise emitted from coal mining machinery varies widely, and therefore interpretation of compliance is not a simple matter. Time, environment, instrumentation and machine productivity, as well as the designed machine characteristics affect the results. It is the purpose of this paper to present the underground coal face machinery noise problem from a manufacturer's point of view. Manufacturers are very much aware of their responsibility to alleviate the noise problem. Not infrequently, orders are received from coal operators that a given new machine must comply with "The Coal Mine Health & Safety Act" noise regulations. Such a request is indicative of the misunderstanding which exists with machine users, while indicating their desire to comply with the law. Obviously, if all machinery could be designed and used at some arbitrary low noise level, it would be possible to simplify the regulations. However, there still remains the pervasive problem of existing machines. Extensive investigation to create practical retrofit kits for existing machines, to substantially reduce noise have been only marginally successful. Certain machine mechanisms are inherent noise makers. The only really good solution is to substitute a quieter mechanism. Such overall new designs have been undertaken, and several examples are mentioned later in this paper. Before describing machine noise problems, it is necessary to define noise values. Noise levels are measured in decibels. The designation "DBA" is decibels measured on the "A" scale, or one in which the frequency sensitivity of the instrumentation is about the same as the human ear. The numbers are often misinterpreted because it is a logarithmic, rather than an arithmetic scale. In comprehending the numbers, it should be remembered that any increase of 3 dB doubles the sound power. In practical terms this means that two noises of equal power at the same distance away increases a dB reading by three. Consider [Fig. 2] showing a simplified case of a worker on a machine subject to

Jan 1, 1980

By Charles F. Hickey, Eric B. Kula

Thermomechanical treatments applied to the maraging steels include a) cold working in the austenitic condition at 650°F, followed by transformation to martensite and aging, b) cold working in the murtensitic condition and aging, and c) cold working in the aged condition with and without subsequent reaging. The strength increases in these steels are very small compared to the increases observed in conventional carbon and alloy steels. The changes that are observed are compatible with the strengthening mechanisms operative during thermomechanical treatment of conventional steels, however. Differences are caused by the absence of a carbide precipitate and the low work-hardening rate in both the solution-treated and the aged conditions. ThE 18 pct Ni maraging steels represent a class of steels which are finding great interest for high-strength applications.1~2 They are essentially carbon-free, and contain 7 to 9 pct Co, 3 to 5 pct Mo, and 0.2 to 0.8 pct Ti. Although austenitic at elevated temperatures, they can be air-cooled to room temperature to form a martensite, which because of the absence of carbon is relatively soft. On subsequent reheating age hardening occurs and strength levels of 250 to 300 ksi yield strength can be attained. These steels appear to be particularly suitable for studying the response to various thermome-chanical treatments for additional reasons other than the obvious one of attempting to improve their already attractive properties. Thermomechanical treatments can be defined as treatments whereby plastic deformation, generally below the recrystal-lization temperature, is introduced into the heat-treatment cycle of a steel in order to improve the properties. With an absence of intermediate transformation products on air cooling the maraging steels have good hardenability and hence can readily be cold-worked in the austenitic condition prior to transformation to martensite. Further, they can be worked in the martensitic condition prior to aging, and even can be deformed in the fully aged condition. Finally, it is of interest to compare their re- sponse to that of the more conventional alloy and carbon steels, where the role of carbides is important in the strength increase by thermomechani-cal treatments. The thermomechanical treatment of conventional steels has been the subject of a recent review.' I) MATERIALS AND PROCEDURE The steel used in this investigation was a commercially produced vacuum-melt heat, which had been rolled to 0.090 in. and mill-annealed. The composition of the alloy was as follows: 0.02 C, 0.08 Mn, 0.10 Si, 0.009 P, 0.009 S, 18.96 Ni, 7.34 Co, 5.04 Mo, 0.29 Ti, 0.05 Al, 0.004 B, 0.01 Zr, and 0.05 Ca. Unless otherwise stated the heat treatments used were the standai-d solution treatment at 1500°F for 1 hr, air cool, followed by a 900°F, 3 hr age. In this condition, the material exhibited 232 ksi yield strength and 239 ksi tensile strength. Mechanical properties were determined by Vicker's hardness measurement (20 kg) and by tensile tests on standard 1/2-in.-wide, 2-in.-gage-length sheet tensile specimens. Notch tensile tests were run using the 1-in.-wide NASA type, edge-notched specimen.4 Fracture-toughness determinations were made on 3-in.-wide, center-notched, fatigue-cracked specimens, following the recommendations of the ASTM Committee on Fracture-Toughness Testing.4 An electric-potential technique was used for measuring the crack size at the onset of rapid crack propagation5 which is necessary for calculations of Kc, the critical stress-intensity factor under plane-stress conditions. The critical stress-intensity factor under plane-strain conditions KI, was also calculated, using the stress at which the first observable crack growth occurred. 11) RESULTS A) Cold-Worked in the Austenitic Condition. The reported M, temperature for the 18 pct Ni maraging steel is about 310°F.1 Therefore, a temperature of 650°F was selected as suitable for rolling in the austenitic condition. Specimens were solution-treated at 1500°F for 1 hr, air-cooled to 650°F, and rolled varying percentages from 0 to 60 pct, at 20 pct reduction per pass. Tensile and hardness properties after aging at 900°F for 3 hr are shown in Fig. 1. The tensile strength increases from 253 to 271 ksi and the yield strength from 247 to 265 ksi as a result of a reduc-

Jan 1, 1964

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 D. L. Albright, R. W. Kraft

High-purity materials have been used in producing as-cast, controlled, colony, and degenerate solidification structures in the Fe-FeS eutectic. Experiments disclosed that this eutectic can be classified as normal and has a natural morphology composed of rodlike iron particles dispersed in a matrix of iron sulfide. The metallography of the various structures was studied, and a preferred crystallography was revealed in the controlled specimens produced by unidirectional solidification. The orientation effects found in these latter specimens are an [001] fiber texture in the -mowth direction of the bcc iron bhase and a texture corresponding to bicrystalline behavior in the hexagonal iron sulfide, with the growth direction near to (2111) poles. The observed texture of the iron phase is considered as indirect evidence that the alloy un-dercooled by at least 75°C before solidification. The unidirectional solidification of binary eutectic alloys has produced materials which exhibit a structure and properties markedly dependent upon the solidification process. In many cases a controlled microstructure with pronounced metallographic and crystallographic anisotropy can be experimentally achieved by proper regulation and balance of the growth rate of the alloy, the chemical purity of the starting materials, and the thermal gradient in the liquid at the liquid-solid interface. The purposes of this investigation were to produce various micro-structures in the Fe-FeS eutectic for subsequent study of their magnetic properties and to correlate the different structures with the solidification conditions in order to obtain a better understanding of the structure of eutectics. The Fe-S equilibrium diagram exhibits a eutectic composed of nearly pure iron and stoichiometric iron sulfide (FeS1.00), with the eutectic reaction occurring at 988°C and 31.0 wt pct S.1 Calculations indicate that this eutectic should solidify with about 9.5 vol pct Fe and 90.5 vol pct FeS, which in turn suggests2 that the micros tructure will consist of a rodlike iron constituent dispersed in a matrix of FeS. This characteristic has in fact been revealed some years ago.3 Thus, controlled solidification of this alloy might yield a material whose micromorphology would consist of very small ferromagnetic iron particles, rod-like in shape and aligned parallel to one another, supported in a matrix of antiferromagnetic FeS. Such specimens, because of the magnetic characteristics of the two phases, would be interesting subjects of study as magnetic materials. Hence the magnetic properties were considered in detail and are reported elsewhere.4 EXPERIMENTAL PROCEDURE The specimens of Fe-FeS eutectic were prepared from ultrapure iron (99.99+ pct) and high-purity sulfur (99.999+ pct). The iron was estimated to contain 60 ppm impurities (99.994 pct Fe) after zone purification.5 The ingots of iron were cut into chips, and the lumps of sulfur were ground into powder. In order to redice any nometallic impurities which might have accumulated during handling, the iron chips were annealed for 5 hr at 750° ± 10°C in a dry hydrogen atmosphere. Immediately after this treatment the chips were blended with the sulfur powder in eutectic proportions; the mixture was tamped into transparent fused quartz tubing and then vacuum-encapsulated under a pressure of 40 to 60µ of Hg. Because FeS expands upon solidification it was necessary to re-encapsulate the initial capsules so that oxidation reactions would be avoided when the inner tube cracked during solidification. For purposes of homogenizing the blended mixtures before solidification, the double capsules were heated to 750° ± 20°C and held for 20 hr; after this treatment the reacted product was weakly agglomerated. Each sample was then loaded into an apparatus for very rapid melting and freezing; this was accomplished by passing a molten zone through the specimen, using induction heating and a traverse mechanism. The resulting specimens solidified in the shape of the quartz tubing. Two sizes of specimens were used in this work, 18 mm diam by 100 mm long and 5 mm diam by 30 mm long. Metallographic examination of several ingots of both sizes after the above consolidation indicated no lack of compositional homogeneity and a random "as-cast" structure, because the travel rate was so rapid that unidirectional solidification was not achieved. Unidirectionally solidified specimens were resolidified in the apparatus shown schematically in Fig. 1, This equipment consisted of a kanthal resistance furnace mounted on the carriage of a zone-melting unit so that the heating element could traverse the length of the sample at a selected rate of speed. Large specimens were solidified with the mechanism tilted at ap-

Jan 1, 1967

By E. D. Fields, R. W. Sayers, M. C. Tippett

The Duval Corp. porphyry copper deposits at Copper Canyon and Copper Basin, though widely separated, form an econornic unit requiring integrated exploitation. Contrasts in mineralization, host rocks, and mode of occurrence present unique mining and milling problems. Mixed oxide-sulfide ore is treated in extensive dump leaching facilities in both areas. Complex Cu-Au-Ag ore is treated in a 4000-tpd mill at Copper Canyon. In both areas, hypogene metallization occurs within large aureoles of metamoiphism and hydrothennal alteration related to quartz monzonite intrusions of mid-Tertiary age. Supergene processes fitrther altered the rocks and enriched the hypogene protore. At Copper Canyon, hypogene copper and iron sulfides with gold and silver occur in fractures, as partial replacement of favorable beds, and as disseminations in Paleozoic sedimentary rocks. The lower part of the Pennsylvanian Battle formation was a particularly favorable host. Metallization occurs to a lesser extent in quartz monzonite. Metal zoning is well-developed. The deposits at Copper Basin consist principally of supergene copper minerals in arenites of the Cambrian Harmony formation. Oxidation of hypogene copper and iron sulfides in tactite zones has formed at least two commercial deposits; intersections of fractures with favorable beds exerted important ore controls. Recently, the Copper Canyon and Copper Basin properties of Duval Corp. have been added to the list of porphyry copper mines in Nevada, marking the first new copper open pit in this state in 15 years. The properties are situated in the Battle Mountain

Jan 1, 1970

By R. K. Hopkins

Fox a great many years fusion welding has been used in and around petroleum refineries, but it is only within six or seven years that the more important pressure vessels have been constructed by this process, because before that time the properties of fusion welds would not withstand such rigorous service. Since the adoption of fusion welding for the construction of this equipment, the refiner has required pressure vessels suitable for operation over a very wide range of conditions. On the one hand, vessels must operate at extremely high temperatures, in the range of 950° to 1000° F., and on the other vessels must be suitable for operation at sub-zero temperatures down as low as -75° F. Also, vessels are required suitable for operation at pressures upwards of 1000 lb. per sq. in., and as low as a 29-in. vacuum. In addition, vessels are required to withstand the attack of very corrosive mediums. It has been a rather difficult task for the fabricator to meet all of these requirements, but as a result of the extensive research carried on by steel manufacturers and several fabricators of class I vessels, practically all of these demands have been met. In order to meet the refiners' requirements for this wide range of conditions, the fabricator has worked closely with the metallurgist. This has enabled him to choose the proper base metal for each service condition, but it has been the fabricator's problem to develop a welding rod and welding technique, as well as a heat-treatment, that would produce in the welded vessel characteristics in and around the weld comparable to those in the base metal. Where corrosion is not a serious problem, and where the operating temperatures are not too high, ordinary carbon steel has served very well. But when corrosion is serious, and/or when the temperatures are either very high or very low, it is necessary to use some form of alloy steel to give satisfactory service.

Jan 1, 1935

By Hollis L. Caswell

The present status of integrated circuits utilizing. superconductive switching. elements is reviewed with special attention given to fabrication techniques, methods for interconnecting completed circuits, and refrigeration requirements. Cryoelectronics has been largely an "inte- grated-circuit" technology since its conception because the switching speed of superconductive devices is attractive only when these devices are fabricated with thin-film techniques. It is true that cryotron circuits can be constructed from wires of appropriate materials (as indeed was done by Dudley Buck 1 in his early investigations) but these circuits will switch in times characteristic of milliseconds whereas similar circuits fabricated by thin-film methods have potential switching times of nanoseconds. Furthermore, cryo-electronic devices such as the cryotron lend themselves readily to fabrication by thin-film techniques since these components may be made from polycrys-talline thin films and are relatively insensitive to the presence of impurities (as measured by semiconductor standards). Therefore, during the past decade considerable effort has been devoted to developing techniques for batch fabricating circuit arrays containing superconductive switching elements. Technology had developed to the point several years ago that fabrication of cryoelectronic arrays containing up to one hundred devices was rather straightforward. However, larger arrays containing between lo4 and 106 components which are required for commercial development of cryoelectronics still pose very severe yield problems. Thus in a sense cryoelectronics found itself in 1962 at the point semiconductor technology finds itself today; namely, individual devices and small groups of integrated devices could be fabricated with acceptable yield and the outlook for building larger integrated-circuit arrays was bright. Unfortunately, problems associated largely with yield have made fabrication of these larger arrays difficult. Unlike semiconductor technology, cryoelectronics had to solve the problems of large-scale integration before it could become economically attractive. This has proven to be a sizable burden to bear. Since several reviews exist on superconductivity,2 superconductive devices,3 and cryoelectronic technology, no attempt will be made in this paper to summarize these areas. Instead a few specific topics will be dealt with in more detail. First, a brief description is given of selected superconducting switching and storage devices with special attention to several metallurgical techniques which improve the performance of these devices. Second, techniques used to fabricate cryoelectronic devices are described with emphasis on problems affecting yield. Third, techniques for interconnecting a number of cryoelectronic planes are described. And last, refrigeration of cryoelectronic components is discussed briefly since the low operating temperature of superconductive devices is an important consideration in this technology. SUPERCONDUCTING STORAGE AND SWITCHING DEVICES The basic superconductive switching device is the thin-film cryotron. The geometry of this device is attractively simple, since it involves only the intersection of two lines that are electrically insulated from each other. The switching element (gate) and control element (control) of a crossed-film cryotron are arranged as illustrated in Fig. 1. The material for the gate is selected to permit the gate to be switched from the superconducting to the normal (resistive) state by the application of a control current. Tin, which has a critical temperature (T,) of 3.7°K, is commonly used for the gate and the cryotron is operated at a temperature just below T, (for example, 3.5°K). The control material (normally lead, with T, = 7.2°K) is chosen so that the control is never driven normal during circuit operation. To improve cryotron operation, a ground plane, also of lead, is placed under all of the circuitry to act as a diamagnetic shield and improve the current-density uniformity across the width of various thin-film elements. Normally, line widths vary from 0.005 to ^ 0.020 in. and film thicknesses from 300 to 10,000A, although new fabrication techniques make narrower lines feasible. In fabricating cryotrons it is important that the edges of the gate elements be geometrically sharp to avoid undesirable switching characteristics associated with a thinner edge region, Fig. 2. One technique which has been used extensively to form patterns consists of placing a physical mask containing the film pattern between the evaporation source and the substrate and depositing through the mask. Film strips formed in this manner possess a penumbra at the film edges due to shadowing of the evapor-ant under the mask. Several techniques have been proposed for minimizing effects due to this penumbra. One of the more promising metallurgical techniques

Jan 1, 1967

By E. T. Turkdogan

This is a compilation and a critical review of the data on the Fe-Ca-0 ternary system. Using the results on the reductiorz-equilibria, an oxygen potential diagram is drawn for the greater part of the system. A number of univariant systems and invariant points, not determined experimentally, are evaluated by making use of the theorem on univariant curves intersecting at an invariant point. The formation of solid solutions and ternary compounds and the crystal structures of some of the phases in the composition-diagram are given for a feu! temperatures. DURING the past thirty years there has been a continued interest in the study of the Fe-Ca-0 system. A detailed literature survey made by white1 in 1943 indicated that further work was required to clarify the phase relationships; in fact, the work carried out in the subsequent years, reviewed by Burdese2 in 1954, made a valuable contribution to a better understanding of this subject. Most of the data were obtained by the step-wise reduction of mixtures of iron oxides and calcium ferrites. However, there is some uncertainty about the phase relationships in this system, arising mainly from insufficient use of thermodynamic concepts in the construction of phase diagrams. In this paper an attempt is made to establish the invariant points from the available data. OXYGEN POTENTIAL DIAGRAM Schenck and coworkers3,4 were the early investigators who studied part of this system by the step- wise reduction method and suggested the formation of two ternary compounds, CaO.FeO.Fe2O3 and 2Ca0.5Fe0.2Fez03, the latter being referred to as point X. They also deduced from their results that the phases Y (8.74Ca0.32.5Fe0.8.74Fe2O3 and Z (2.02CaO-97.98FeO) were formed near the w?stite corner of the system. Martin and voge15 postulated the existence of the compounds CaO.9FeO and 4Ca0.3Fe3O4; the former is very close to the composition of point Z and the latter to that of CaO.FeO-Fe2O3. The most valuable contribution to the presen knowledge on this system was made by Cirilli and Burdese6-8 who showed by X-ray and chemical anal yses that there were two ternary compounds, CaO-Fe0.Fe2O3 and CaO.3FeO-FezO3; the former is the same as that suggested by Schenck et al. and the latter is close to their point X. The results of Cirilli and Burdese show that the phases Y and Z postulated by Schenk et al. are solid solutions of calcium oxide in w?stite. In most of the above-mentioned reduction-equilibria measurements carbon monoxide-carbon dioxide mixtures were used and in a few cases hydrogen-water vapor mixtures were employed. Using the

Jan 1, 1962

By R. G. Ward, D. R. Gaskell

Using the maximum bubble pressure technique, the densities of iron silicates at 1410°C have been measured blowing helium, nitrogen, and argon. By ensuring equilibrium between the melt and the blowing gas with respect to oxygen potential and by minimizing tempcrature cycling of the furnace, iron precipitation in the melt has been prevented. Thus the previously reported effect of blowing-gas composition on the densities of the melts has been eliminated. Consideration of the oxygen densities of the melts gives an indication of the structural changes accompanying composition change. The density-composition relationship of iron oxide-silica melts in contact with solid iron has been the subject of several investigations1-7 and considerable disparities exist among the various results obtained. Of these investigations, all except one5 have employed the maximum bubble pressure method. In the most recently reported of these investigations1 the density-composition relationship obtained blowing nitrogen differed from that obtained blowing argon. The measured densities obtained under nitrogen were greater than those obtained under argon, the difference being a maximum at the pure liquid iron oxide composition and decreasing with increasing silica content. This observation rationalized the disparities existing among the results of the earlier investigations, showing that two lines, one for nitrogen and the other for argon, could be drawn to fit all the earlier results. No explanation for this phenomenon could be offered. Chemical analysis of rapidly quenched samples of melt for dissolved nitrogen, and direct weighing measurements, excluded solution of nitrogen in the melt from being the cause of the increase in density. The range of blowing gases was extended by Ward and Hendersons who measured the density of liquid iron oxide bubbling helium, nitrogen, neon, argon, and krypton. The measured density was found to decrease smoothly with increasing atomic number of the bubbling gas. The work reported here is a continuation of the program initiated by Ward and Sachdev7 to study the densities in multicomponent melts in which the iron oxide-silica system is the solvent. As such it is necessary to explain or eliminate the anomalous densities of iron silicates under different atmospheres, and the present rede termination was carried out towards this end. EXPERIMENTAL The maximum bubble pressure method of density determination was again employed and the experimen- tal apparatus used was essentially the same as that used by Ward and Sachdev.7 A molybdenum-wound resistance furnace heated an ingot iron crucible of internal diameter 1 in. containing a 2-in. depth of melt. The bubbling gas was blown through a 1/4 -in.-diam mild steel tube onto the end of which was welded a 2-in. extension of 1/4 -in.-diam ingot iron rod, drilled out to 5/32 in., and chamfered to an angle of 45 deg. The blowing tube was introduced to the furnace through a sliding seal and its position was controlled by a vertically mounted micrometer screw which allowed the depth of immersion to be determined with an accuracy of ± 0.01 cm. A Pt/Pt-10 pct Rh thermocouple was located below the crucible and temperature control was effected initially by means of an on-off controller and later by a saturable core reactor. The bubble pressure was determined by measurement of a dibutyl phthalate manometer using a cathetometer. PREPARATION OF MATERIALS Iron oxide was produced by melting ferric oxide in an inductively heated iron crucible in air. The liquid was quenched by pouring onto an iron plate. Silica was prepared by dehydrating silicic acid at 650°C for 12 hr. RESULTS Before any measurements of the density of a melt were made, the density of distilled water at room temperature was measured bubbling helium and argon. Both gases gave the density as 1.00 ± 0.01 g per cu cm which showed that the density of the manometric fluid (dibutyl phthalate) was not affected by contact with the blowing gas. With the furnace controlled by an on-off temperature controller an attempt was made to measure the density of pure liquid iron oxide by bubbling argon. The furnace atmosphere gas and bubbling gas were dried over magnesium perchlorate and deoxidized over copper turnings at 600°C. It was found that the pressure required to blow a bubble at a given depth increased slowly with time, and thus it was impossible to obtain a unique value for the density of the melt. Inspection of the blowing tube after removal from the furnace showed that rings of dendritic iron had precipitated from the melt onto the immersed part of the tube. This is shown in Fig. l(a) where the various "steps" correspond to different depths of immersion. The precipitation of iron was considered to be due to one or both of two possible causes: i) The composition of the liquid iron oxide is that of the liquidus at the temperature under consideration and can be expressed by the equilibrium

Jan 1, 1968

By S. Shapiro, J. A. Ford

The crystallo graphy of several grains of the lamellar Ni-Ni3 B eutectic solidified under conditions appvoachirt equilibriun has been examined.. A preferred interlace relationship has been observed in this system which may be described as: A detailed study of this interface by means of an atomistic model reveals the interface Plane to be puckered and more accurately describable as: Analysis of the atomic configuration on these planes reveals that this interface conforms to the orientation criteria proposed for directionally solidified lanzellar eutectics. In addition, a model is proposed to help explain the growth of a "puckered" interface. DURING the past several years an increasing number of unidirectional solidification experiments on eutectic alloys have been reported in the literature. The primary emphasis, in most cases, has been the effect of growth variables on microstructure. Some authors have, however, studied the crystallographic orientations and interfacial relationships resulting from these experiments. Four crystallographic studies have been published;'-4 in each of these there is a factor which tends to prohibit the extension of the observations beyond the particular system. In the Al-CuA12 system, the approximately equal volume fractions of the phases have resulted in sorrie controversy as to which phase constitutes the matrix. In the Mg-Mg,Sn eutectic the presence of several interconnecting lamellar systems2 complicates the analysis. The two remaining eutectics. 1nSb-b and Al-Ali, are both rodlike (the latter exhibits a plate morphology at low solidification rates): the matrix in each of these alloys is the simpler (fcc) phase. Studies of nucleation in eutectic alloys indicate that the more complex constituent is the nucleating -.phase.' For the purpose of an analysis of interface crystallography it was deemed desirable to study a lamellar system in which the matrix was the more complex and, presumably. the nucleating phase. Recently it has been shown that there is a eutectic in the Ni-B system between Ni3B and i; preliminary investigation by the authors indicated that the matrix in this eutectic is the boride phase. The structure of Ni,B is reported to be orthorhombic, the compound being isostructural with cementite. This eutectic is therefore analogous to that between austenite and cementite. Furthermore, the Ni-B system is not susceptible to a competing eutectic reaction as occurs in the Fe-C alloys; nor does it exhibit a eutectoid decomposition. For these reasons the study of the interfacial relationship in the Ni-Ni3B eutectic was undertaken. PROCEDURE Ingots of nominal composition 3.5 and 3.6 wt pct B were induction-melted in boron nitride crucibles within a graphite susceptor under a boric oxide slag; a dynamic argon atmosphere was maintained over the melt to prevent rapid oxidation of the susceptor. The raw materials used were 99.97 pct Ni from Huntington Metals Division of International Nickel Co. and 99.8+ pct B chips supplied by the United Mineral and Chemical Co. The analyses of the starting materials are listed in Table I. The melt was held at 1500cC for 2 hr to insure complete reaction and allowed to cool to room temperature. The castings were chemically analyzed for boron and were metallographically examined for uniformity. The metallographic samples were mechanically polished through 0.1 p A1,0, and etched with Carapella's reagent. Each master casting was cut up to make several specimen blanks which were remelted, in boron nitride crucibles, to form ingots of 1/2 to 3/4 in. in diarn by 7 in. long. These ingots were unidirectionally solidified using a modified vertical Bridgman technique. The rate of solidification was assumed to be equal to the uniform rate at which the crucible-susceptor assembly was withdrawn from the induction coil. This rate was varied from 1.18 to 2.21 cm per hr. In order to perform these experiments it was found necessary to redetermine the eutectic composition. This was accomplished by the zone-melting technique described by Yue and lark.' An ingot of 4.5 wt pct B was zone-melted in a horizontal boron nitride boat 7-1/2 in. long with a 112-in.-square cross section. A

Jan 1, 1967

By Michael Perch, Charles C. Russell

Nearly 75 per cent of the total coke production in the United States in 1940 was consumed in blast furnaces. In 1939 the percentage was 69.9, and in 1938 it was 61.3. To produce a net ton of pig iron 1757 lb. of coke was required in 1940 and 1760 lb. in 1939. These figures indicate how dependent the production of pig iron is upon the production of coke. The rate of iron production is in some measure influenced by the physical and chemical characteristics of the coke. Blast-furnace operators believe that the physical properties of coke profoundly influence the operation of the furnace. Although it is true that coke of a wide variety of physical properties is used in American blast furnaces, the periodic fluctuation of these properties is one of the causes of irregularity of blast-furnace operation. The purpose of this paper is to present a broad picture of the physical properties of by-product coke that are generally considered to be important by coke-oven and blast-furnace operators. Effects of the kind of coal used, the preparation of the coal, the rate of coking, and other factors will be considered. Of all these variables, the kind of coal used is by far the most important. In this discussion use will be made of the method of coal classification by rank1 standardized by the American Society for Testing Materials. Although this method of classification has been an American standard for several years, it has not been given the attention it deserves, especially in connection with the selection of coal for production of coke. Despite the fact that many producers of blast-furnace coke are limited to some particular source or sources of coal, a good understanding of the principles involved in setting up the standard method of classification may lead to a better appreciation of the causes of changes in coke characteristics. Furthermore, where it is necessary to select new coals as a substitute for the original supply, this method of classification can be of great assistance. The data presented have been gathered from many sources, but no attempt has been made to cover the vast literature. Instead, some of the more important data have been selected to show how coals and their carbonization affect some of the physical properties of coke. It must be emphasized that generalizations concerning the behavior of coking coals are presented and that individual coals may vary widely from the specific behavior depicted. Nevertheless, it is believed that the data illustrate certain typical behaviors. Neither was it possible to cover completely all the factors involved; for example, the macroscopic constituents of coal are believed to have important effects on the physical properties of coke, but since there is little information available for such study, and since vitrain, clarain, and durain are neither

Jan 1, 1942

By M. R. Geer, J. D. Davis, H. F. Yancey

ALTHOUGH the mechanical cleaning of coal is carried out at plants on the surface, preparation is actually begun at the face in the mine. Here the character of the coal and the amount, character, and distribution of the impurities within the bed may be seen. Blasting methods, dust-allaying procedures, location of mining cut with respect to bands of impurity, and the practice of discarding segregated impurities underground, all have an important bearing on the successful operation of surface cleaning units. The most important single characteristic of both coal and its asso¬ciated impurities from the standpoint of cleaning is specific gravity. Other characteristics related in one way or another to the preparation of coal are rank, petrographic composition, structure and hardness, and friability. These and still other coal properties are discussed in the first section of this chapter and impurity characteristics in the second. COAL CHARACTERISTICS RELATED TO PREPARATION Rank As a result of work done over a period of several years by committees of the American Society for Testing Materials and the American Standards Association, standard specifications are now available showing the classification of coals according to rank and quality of grade.' The term "rank" expresses the degree to which the original coal-forming material has been changed by metamorphism through successive stages from peat to anthracite. Table 1 shows the classification of coals according to rank as devised by the committees of the organizations mentioned. The basic scheme of classification for the higher-rank coals is according to

Jan 1, 1943

By Theodore Simons

Permission to present this paper at the February, 1915, meeting of the Montana Section of the American Institute of Mining Engineers was liberally granted by W. A. Clark, Jr., President-and General Manager of the Timber Butte Milling Co., and by the representative of the Minerals Separation Co. For the many courtesies shown the writer on his visits to the mill and for information supplied, he is indebted to all the officers of these companies, especially to W. N. Rossberg, W. D. Mangam, Hamilton Cooke, Jr., T. M. Owen, T. C. Wilson, R. McGillivary, L. L. Quigley, C. Bartzen and others. The writer takes this opportunity to herewith express to them his appreciation and sincere thanks. Location of Mine and Mill The concentrator of the Timber Butte Milling Co. was built to treat the ore mined at the Elm Orlu mine of the Elm Orlu Mining Co., which carries zinc and lead in sphalerite and galena; copper in bornite, chal-cocite, tennantite, and tetrahedrite; and gold and silver either free or chemically combined with the sulphides of the base metals. The gangue is chiefly quartz, barite, fluorite, rhodonite, and rhodocrosite. The iron in the ore occurs as irqn pyrites. The Elm Orlu mine is situated in Butte, Silver Bow County, Mont., near the northern border of what is locally known as the Butte sulphide-copper belt, about one mile north of the Anaconda mine, and adjoining the Black Rock zinc mine of the Butte & Superior Co. on the southwest. The mill is on the northern slope of Timber Butte, a prominent topographical landmark in the Butte district. This site permits to a large extent the gravity system of ore flow; it presents a convenient and extensive area for a tailings pond; and it is comparatively near to the source of water supply and to existing railroads.

Jan 1, 1916

The beginning of Colorado's mining industry is linked on one side with that of the Appalachian districts and on the other side with that of California, because the first discoveries were made by pioneers when on their way from Georgia to California. In the summer of 1849 a party of seven Georgians were taking a herd of thoroughbred horses across the continent to the Pacific coast. They reached Camp Lyon, on the Arkansas river, in October, and, meeting James Dempsey, a Government guide, they were persuaded by him that it was too late to cross the mountains that season. His advice was accepted, and, moving northward, they established a winter camp at the junction of Cherry creek with the Platte, close to the site of the city of Denver. Upon a sand-bar, lining the south side of the river, they built two cabins. During the closing months of 1849 they prospected the alluvial banks of Cherry creek, but they made no attempt to penetrate into the mountain canyons, near them, westward, for fear of the Indians.* They found gold in several places along Cherry creek, and particularly at a spot 16 miles up the stream from their camp. From the feathers of the wild geese that they shot they obtained quills in which they placed their gold-dust. This party of Georgians consisted of Dr. L. J. Russell and his brother, Green Russell, also A. T. Lloyd, G. W. Kiker, and P. H. Clark. Early in 1850 they crossed the main range of the Rocky Mountains by the Bridger pass and went on to California. They mined near Downieville, and were successful. Occasionally mention was made by them of the gold

Jan 1, 1932

By J. W. Faust, H. F. John

Generalized conditions for rod or ribbon growth by the twin plane re-entrant edge mechanism are given. It was shown that this mechanism can result in growth of twinned platelets from dilute metal solutions. The platelrts 01 the fee metals are faceted by (111) planes and contain two or more twin planes. Microsegregation traces were revealed in silver grown from a thallium solution. VOGEL has already set down conditions for dendritic growth;1 however, this was the normal single-crystal dendritic growth experienced during solidification. In this work it is desired to set down the crystallographic conditions that will lead to rod or ribbon growth with smooth facets. These are as follows. a) The growth must be crystallographically limited (i.e., faceted growth). b) In order to have directed growth, some mechanism must allow easier nucleation than two-dimensional nucleation. That mechanism is afforded by the re-entrant edges at twin planes.213 Thus there must be twin planes present in the rods or ribbons. c) The growth direction must lie in the twin plane. If not, the twin plane will grow to the face or side of the ribbon and the site of easy nucleation will be lost. d) The growth direction must be parallel to at least one plane of the faceting planes, and no set of the faceting planes can be perpendicular to the growth direction. A corollary to these conditions involves the number of twin planes necessary to maintain the indestructible re-entrant edge. The number depends on the crystal structure of the material. An analysis of the data available shows that a material whose faceting planes form an open figure requires at least one twin plane while materials whose faceting planes form a closed figure require at least two twin planes in order to form the indestructible re-entrant edges for extended growth. The conditions and an assessment of the possibility of rod or ribbon growth are given in Table I for several crystal systems. As can be seen the fee, diamond and zinc blende, or-thorhombic, rhombohedral, and one form of the hexagonal lattice systems can yield this type of growth, but not the bcc metals nor the hexagonal

Jan 1, 1965

By V. Balasubarmanian, Rajendra Kumar

ISOTHERMAL formation of martensite in a copper-aluminum-nickel alloy was previously reported by Hull and Garwood.' In the present work an attempt has been made to investigate some of the character- istics of the formation of isothermal martensite in binary copper-aluminum alloys containing 14.00 and 14.50 pct Al, respectively. Chill-cast alloys were prepared from OFHC copper and aluminum of greater than 99.5 pct purity. They were homogenized for 24 hr at 950° C. Polished samples were soaked at 1000°C and quenched in water to retain the p phase untransformed; martensite did not form during the quench. The surface was then repolished for isothermal microscopic studies at room temperature. The salient features of the martensitic transformation in copper-aluminum alloys observed in this investigation are: a) The transformation progresses (i) by nuclea-tion at new sites and (ii) by simultaneous slow isothermal growth of existing martensite plates. Slow isothermal growth of martensite has previously been observed by Holden2 in an uranium-chromium alloy and by Hull and Garwood in copper-aluminum-nickel alloy. b) Martensite plates nucleate preferentially at the pin holes formed during the casting of the specimen, Fig. 1. c) Some of the martensite plates pass right through other plates lying in their path, Fig. 1. d) Martensite plates cross grain boundaries without any change in the direction of growth. e) An irregular network of markings, Fig. 2, appears simultaneously with the formation of martensite. It was less prominent in the case of 14.5 pct alloy. The markings may arise due to spontaneous deformation under the lattice strains of the martensitic transformation. Crossing of martensite plates was first observed by Kulin and cohen3 when a high-nickel steel was cooled to 77°K. They suggested that the rapidly advancing plates atquire considerable kinetic energy and strike the obstructing plate with a momentum so as to nucleate the process on the other side of the plate. This, however, fails to explain the present observation where the slow isothermally growing martensite plates cross each other. Such plates would not possess large momentum to bodily displace the obstructing plate. Fig. 1 shows the martensite plates crossing each other without body displacements. This should be contrasted with Fig. 3 of Kulin and Cohen's paper where crossing of plates is accompanied by shearing or body displacements of the plates. The present observations can, how-

Jan 1, 1961

By K. K. Kohli, S. S. Peng, R. E. Thill

Introduction Since the adoption of the Surface Mining Reclamation and Control Act of 1977, which mandates that surface subsidence be an intergral part of the underground coal mine design, there has been a sudden rise of demand on guidelines for minimizing surface subsidence and its associated structural damages. Unfortunately there is no sufficient amount of systematic subsidence data to fill such a gap, although considerable research has been devoted to the subsidence induced damages of surface structures in the past. However, it was said that many surface subsidence surveys have been performed and monitored by coal companies during the past twenty years, and that it will be a great source of information for subsidence engineering design if they can be collected and assembled together. An effort was therefore initiated in the Department of Mining Engineering, West Virginia University, under contract with the U. S. Bureau of Mines in December 1978 to contact each individual coal company in the Northern Appalachian Coal Field for any surface subsidence survey data. After 10 months' survey, the data collected include: 17 longwall panels and 2 room and pillar sections. The data in each panel and section cover the complete set of subsidence survey raw data, underground mine layout maps, surface topo maps, geological loggings showing the stratigraphic sequences and thickness of the overburden, and if available, locations and types of surface structures. On-site visits were followed to study the surface terraines and structures. Interviews were conducted with the owners of the surface structures in most cases about, if any, the history and characteristics of damages. Most subsidence surveys started with the first panel and ended with the second or sometimes, but rarely, the third panel. The first panel may be located in a virgin area but frequently it was adjacent to (on the tailentry side) a mined-out room and pillar section. It must be noted that all of the subsidence data is restricted only to the amount of vertical subsidence and that the horizontal displacement measurement was completely ignored. Primarily due to the fact that vertical subsidence is the most striking feature in a subsidence trough, which is mistakenly considered to be the only critical contributor to surface structural damages, and that a horizontal displacement survey is much more complicated and time-consuming.

Jan 1, 1981