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By A. S. Nowick, C. Y. Li

It is deMonstrated that quenching from an elevated temperataupe accelerates the grain boundary relaxation in two solid solutions (aAg-Zn and a Cu-Al). This result is consistent with the proposal that, in solid solutions, grain boundary relaxation occurs by a mechanism of' self diffusion. Nevertheless, an alternative possibilitg, that quenching introduces vacancies into the boundary itself, must also be considered. THE phcnomenon of grain boundary relaxation has been well known for many years,1,2 yet the mechanism of this process is very poorly understood. One of the most interesting suggestions which relates to the mechanism of grain boundary relaxation was that of Ke,3 who claimed that the activation energy for grain boundary relaxation and for lattice self diffusion were essentially the same. The implication is therefore that the elementary step in the two processes is the same. This suggestion is particularly startling in view of the fact that activation energy for self diffusion along a grain boundary is very significantly lower than that for volume self-diffusion. Later evidence5-7 showed that there really are two grain boundary peaks, one which appears in high-purity metals, and the other (which develops at a higher temperature than the first) which appears in solid solutions beginning at solute concentrations in the range of 0.1 pct. Data for silver6 show that Kg's hypothesis is surely incorrect for the grain boundary peak in the high-purity metal, since it has an activation energy of only 22 kcal per mole, but that the hypothesis may still be correct for the grain boundary peak in various silver solid solutions, for which activation energies in the range 40 to 50 kcal per mole are observed. If the elementary step in the grain boundary relaxation process were the same as that for self-diffusion, it would be expected that the relaxation process could be hastened by quenching, 2.c. by introducing a non-equilibrium excess of lattice vacancies. Such a quenching effect has already been demonstrated in the case of another anelastic relaxation process, viz., the Zener relaxation effect. The Zener effect, which occurs in essentially all solid solutions, may be attributed to the reorientation of pairs of solute atoms in the presence of an applied shear stress,' and therefore must take place by means of a volume diffusion mechanism. The hastening of this process through quenching9 has been one way of demonstrating that atom movements in the lattice take place through a defect mechanism, presumably single vacancies. In order to see if the grain boundary relaxation is affected by quenching, it is particularly convenient to compare the grain boundary relaxation with the Zener effect, by choosing a specimen for which both relaxation effects appear. Specifically, a fine-grained sample of a solid solution shows in the curve of internal friction vs temperature, first a peak due to the Zener effect, then a second rise (and eventually a peak at substantially higher temperatures) due to the grain boundary relaxation. The same phenomena are also observable in static anelastic measurements, such as creep at very low stress levels. Thus, for the same fine-grained solid solution, the creepstrain, when plotted against log time, falls on a sigmodial curve with a sharp inflection point, due to the Zener effect, which is followed by a second rise and inflection resulting from the grain boundary relaxation. To look for a quenching effect, static measurements are preferable to the dynamic internal friction measurements, due to the fact that quenching effects tend to anneal out too rapidly at the temperatures at which the internal friction is measured.9 RESULTS AND DISCUSSION Creep experiments in torsion were carried out in an apparatus similar to that described by Ke1, whereby a wire is held under constant torque and its angular displacement is observed as a function of time. The alloy Ag-30 at. pct Znwas selected because of the large Zener relaxation that it displays. The two samples used were a "coarse grained" wire with a mean grain size about twice the diameter of the wire (diam = 0.032 in.), and a "fine-grained" wire which had several grains across the diameter. In Fig. 1 a comparison is made of the creep curves at 160°C of these two samples after they had been cooled slowly from 400°C. Curve A, which represents the coarsegrained sample, shows a unique relaxation process due to the Zener relaxation, with a relaxation time, T , in the vicinity of 100 sec. Curve B, which represents the behavior of the fine-grained sample, on the other hand, shows first the same relaxation process as that in A, followed by a turning up of the curve which corresponds to the onset of a second overlap-

Jan 1, 1962

By Samuel G. Lasky

What the evidence prevails upon the mind to believe, depends upon the mind as well as upon the evidence. M. L. IN a recent discussion of the mineral resource position of the United States, published in the September 1946 issue of MINING AND METALLURGY, I expressed my conviction that ore deposits of major magnitude remain to be found in this country and that they can be found without undue cost or risk. I stated with equally strong conviction, however, that if the search for such deposits is to be notably successful there must be, among other things, a reorientation of philosophy and mental habits on the part of many who would be connected with the search. I would now like to enlarge upon that statement. For such a purpose, we may consider that the search for concealed deposits involves four steps: (I) the selection of areas for further study; (2) the geologic study of those areas in order to verify their general favorableness and in order to choose specific patches worthy of being tested; (3) the decision whether exploration of the patches chosen should actually be undertaken; and (4) the exploration itself. The first two steps and the last rest upon the judgment and skill of geologists. The third step-the decision whether exploration should be undertaken-rests upon management. In my opinion, the philosophies or principles that have guided these steps in the past are now inadequate. PHILOSOPHY OF APPRAISAL If concealed deposits are to be looked for, how are the places of their possible concealment to be recognized? Every known mineralized area still in the prospect stage has already been repeatedly examined and condemned. As for those deposits concealed under later rocks, there may be not even the clue of a near-by outcrop for engineer or geologist to consider. How then, are we to know where to look? Geologic Probability In the early days of our mining industry, ore deposits were found mainly by "following the ore." Later, as such opportunities decreased, and as geologic concepts became accepted, deposits were found more and more through use of the notion of geologic probability. Many instances can be cited wherein a courageous operator ignored the implications of the unsuccessful efforts of predecessors and, solely by "following the ore," converted a discredited prospect into a good mine. Similar experience doubtless will occur in the future, but "following the ore" will no longer in itself find new deposits in the amount needed. Nor can enough new ore be expected from further use of the notion of geologic probability, for, as mentioned above, our known prospects `have already been ex-

Jan 1, 1947

CHARGING of an open-hearth heat is begun as soon as possible after the previous heat has been tapped. Ordinarily, about 40 min is required to drain and dress the furnace hearth, make up the taphole, and perform routine repairs of the banks. Repairs to the upper back wall and to the front wall and jambs can ordinarily be done while the first scrap charge is being heated and are therefore allowed to wait in order to save furnace time. Any major repairs required on the hearth or other parts of the furnace necessitate longer delays because such repairs must be made while the furnace is empty. Although charging practice varies considerably in detail with the type and proportions of scrap and iron used, many factors are common to all varieties of charge. Such general considerations are dealt with first. CHARGING EQUIPMENT AND STOCK HANDLING The physical equipment available for loading and weighing the stock, transporting it to the furnace, and charging it, may have a major effect on charging practice. Limestone, scrap, and all other solid melting stock are charged mechanically by means of equipment illustrated in Fig 2-1. The charging of hot metal is shown in- the background of this figure. Mechanical equipment and plant layout for stock handling are described in Chapter 1. It is generally desirable to charge the scrap about as fast as the physical volume can be put into the furnace. Charging scrap that is too heavy or adding the charge too rapidly (less than 45 min) may be detrimental to melting rate because of excessive chilling of the entire furnace system and also because of poor conduction of heat to the lower layers in the furnace; but the more common problem is the reverse one of charging light scrap fast enough to maintain a normal heat time. A limiting factor may be the height to which the scrap may he piled in the fur-

Jan 1, 1964

By M. Friedman

Applications of rock mechanics to the design of engineering structures in rock involve the assumption that the stresses are due entirely to the present applied loads. For instance, it is assumed that the vertical normal stress in undisturbed rock free of topographic effects is equal to the weight per unit area of the overburden. In fact, vertical dilatational strains associated with stresses of more than 100 times the present overburden pressure have been measured by strain-relief methods on outcrops. 1,2 The notion of residual strain (stress) or latent stress3 seems unassailable; and indeed this has long been recognized by metallurgists. It is difficult, however, to assess the residual component of the in-situ state of elastic strain with conventional strain relief methods employed in mines or down boreholes. That is, in principle, the in-situ state results from the superposition of present applied loads (natural or man- induced) and potentially recoverable elastic strains (stresses) that exist in a given volume of material even though there are no external forces across the boundaries of the body (Voight,4 and Fig, 1). Accordingly, only in unloaded blocks can the true residual strains be measured by strain relief methods. Using X-rays, the elastic strains locked within the quartz grains or crystals of a rock can be measured. These strains are known to persist even when the rock is reduced to small chips but to vanish when the rock is disaggregated and the grains are powdered. Although we have just begun to investigate the mechanisms by which the strains are stored (see Preliminary Results), we believe that "pressure solution'' at grain boundaries, secondary cementation under load, permanent ("plastic") deformation, and temperature changes are possible processes. In any event, in our study of naturally deformed rocks, it is significant that we are work-

Jan 1, 1972

CHARGING of an open-hearth heat is begun as soon as possible after the previous heat has been tapped. Ordinarily, about 40 min is required to drain and dress the furnace hearth, make up the taphole, and perform routine repairs of the banks. Repairs to the upper back wall and to the front wall and jambs can ordinarily be done while the first scrap charge is being heated and are therefore allowed to wait in order to save furnace time. Any major repairs required on the hearth or other parts of the furnace necessitate longer delays because such repairs must be made while the furnace is empty. Although charging practice varies considerably in detail with the type and proportions of scrap and iron used, many factors are common to all varieties of charge. Such general considerations are dealt with first. CHARGING EQUIPMENT AND STOCK HANDLING The physical equipment available for loading and weighing the stock, transporting it to the furnace, and charging it, may have a major effect on charging practice. Limestone, scrap, and all other solid melting stock are charged mechanically by means of equipment illustrated in Fig 2-1. The charging of hot metal is shown in the background of this figure. Mechanical equipment and plant layout for stock handling are described in Chapter 1. It is generally desirable to charge the scrap about as fast as the physical volume can be put into the furnace. Charging scrap that is too heavy or adding the charge too rapidly (less than 45 min) may be detrimental to melting rate because of excessive chilling of the entire furnace system and also because of poor conduction of heat to the lower layers in the furnace; but the more common problem is the reverse one of charging light 'scrap fast enough to maintain a normal heat time. A limiting factor may be the height to which the scrap may he piled in the fur-

Jan 1, 1951

By P. C. J. Gallagher

A number of recmt determinations for the ratio of extrinsic to intrinsic stacking fault energy in fcc solid solutions are examined. Some of these arise from incomplete analyses which can yield only approxi?nate values for the ratio. Reliable results, on the other hand, obtained using extrinsic-intrinsic fault pairs, show that the extrinsic and intrinsic fault energies are essentially equal in several materials. There is some reason to believe that this finding is of general applicability to fcc elements and alloys. A wide range of values has been obtained for the relative magnitudes of the extrinsic and intrinsic stacking fault energies (yext and yint, respectively) in recently published studies in a variety of materials. In contrast, Hirth and Lothe' using a central force model have shown that out to tenth nearest-neighbor interactions the perturbation in energy caused by both types of fault is the same. Although the model used is not completely valid in metals, there is nevertheless some indication that marked variations of yext/nnt should not be observed from one material to another. In early work in Cu-A1, Cu-Ge, Ni-Co, and stainless steel all the deformation faults observed in the electron microscope were found to be intrinsic in nature, which led to an attitude that the extrinsic fault energy must be considerably greater than the intrinsic. Extrinsic faulting arising from deformation has, however, more recently been directly observed in Au-4.8 at. pct n;~ Ag-6 at. pct Sn and Ag-8 at. pct sn; Ag-7.5 at. pct In and Ag-11.8 at. pct 1n;"' pure silwer and Ag-0.5 at. pct ~n;' and Cu-22 at. pct Zn, Cu-30 at. pct Zn, and Cu-7.5 at. pct ~1.l' Multilayer loops containing extrinsic faulting have also been observed in quenched aluminum." While peak asymmetries in X-ray faulting probability studies were generally attributed to the presence of twins,Lelel2 has recently reinterpreted earlier X-ray data in Ag-Sb alloysU in terms of the presence of extrinsic faulting. The determinations of yeXt/yint made from the above studies are shown in Table I, with a brief description of the techniques employed. A number of the methods utilized are deficient in one or more respects, and the reliability of the values listed will be discussed. ~ele'~ recognizes that his approximate determinations of yext/yint assumes equal numbers of extrin-sically and intrinsically faulted dislocations. It is well-known, however, that such an assumption is not at all justified since extrinsic faulting has but rarely been observed in samples studied in the electron microscope. The only conclusion that should be drawn from the X-ray results at present is that the total intrinsic scattering cross section (i.e., the product of the width of the intrinsically faulted dislocations with their density) is approximately ten times greater than for extrinsic faulting in these particular samples. An important point is that the relative magnitudes of the energies cannot be inferred from results of this type, unless the intrinsic and extrinsic faults form with equal ease. One must recognize that, although a formation barrier may restrict the amount of extrinsic faulting which occurs, this in no way implies that the extrinsic and intrinsic energies should be different. It is unlikely that a worthwhile estimate of the relative densities of extrinsically and intrinsically faulted dislocations can be made at the high deformations present in X-ray samples. ~oretto,'~ from a statistical argument applied to the nonobservation of extrinsically faulted tetrahedra out of a large sample, concluded that yeXt/yint could not be less than -4.5. However, the present author feels that a high-energy formation barrier as just supposed also explains this finding satisfactorily and that no conclusion can possibly be drawn concerning the actual extrinsic stacking fault energy. The same argument also serves to explain the fact that extrinsic faulting has been relatively little observed in the electron microscope. Extrinsic-intrinsic node pairs and isolated extrinsic nodes were first reported by Loretto~ and subsequently by Ives and Ruff,' Gallaher,' and Gallagher and Wash-burn.' Ives and Ruff' found a wide spread in the ratio of extrinsically to intrinsically faulted area in the node pairs they observed, and drew the very tentative conclusion that yeXt/yint 2 2. They recognized that a straightforward comparison of the size of the faulted areas could provide no more than a qualitative result without a theoretical analysis of the dislocation geometry associated with extrinsic faulting. A theoretical

Jan 1, 1969

By B. F. Tillson

ALTHOUGH most accidents occur through the A carelessness or misfortune of the workmen; that is no reason why we should not take all physical precautions practicable. The best way to approach the problem of mine safety is to acquire a personal feeling of responsibility for the accident and then plan how it might have been prevented had we known that it was to occur. A statistical analysis of the physical conditions contributory to accidents will give an indication of some of the methods or mechanisms that should be revised or safeguarded. The handling of rock or ore is a common source of minor injuries. Freedom from accident when mucking largely depends on the skill and care of the workman; this also is true, to a certain degree, to loading cars from chutes, but much can be done in the layout of chutes and their equipment to provide equal safety with less skill. Permanent stagings, or rigid units that may be easily assembled, should be provided so that the men handling the chute boards or gates and barring the jammed chunks will have a convenient safe footing for their operations. A stance to the side of the chute mouth is to one in front, because a man will not be liable to be struck by flying lumps or his bar, should it he caught in the mass, yet in many mines the workmen face the chute when loading a car. Fig. 1 shows the operation of a plank chute having special latches which support the chute boards in such manner that they may be conveniently dropped into place to stop the flow of ore.

Jan 1, 1926

By A. U. Seybol

Eight binary iron alloys were examined after ion nitriding experiments to determine the behavior of the following elements: Al, Mo, Mn, Si, Ti, V,Cr, and C. Only Al, Cr, Ti, and V additions caused hardening in binary iron alloys. A few steels were examined to see the effect of Cr, Cr + Al, Cr + Ti, and Cr + V. It is suggested that a useful new class of ni-triding grade steels might be those containing about I pct V. The nitriding of steel, first described by Fry1 about 45 years ago, rapidly attained commercial application with very little knowledge of the fundamentals involved. While Fry,' in describing the status of nitriding in 1932, apparently correctly postulated hardening by precipitated nitrides, the details of the nitriding process were not understood, nor has the situation changed much since that time. It is also interesting to note that the compositions of some typical nitriding steels given by Fry at that time have changed little in the intervening years. Currently used nitriding steels owe their surface hardening to either chromium (as in 4340 steel) or aluminum plus chromium as in the Nitralloy grades, where both CrN and AlN appear to contribute to harden ing. Titanium additions have been studied experimentally, but thus far titanium steels have not won wide commercial acceptance. This subject will be expanded later. The orthodox ammonia nitriding process has been reviewed very adequately many times as in Jenkins3 and Case and VanHorn,4 and their is no need to outline the process here. Ion nitriding is not as well-known, although there have been several descriptions5-9 of the process given, sometimes with comparisons with the ammonia process. Most of these papers are primarily concerned with a description of the equipment, or of the physics or electrical engineering aspects of ion nitriding, but Noren and Kindbom9 gave the results of a metallurgical investigation using both processes. In brief, ion nitriding is carried out in a vacuum chamber from which the air is exhausted and replaced by a N2-H2 mixture, typically containing 10 to 20 pct N2, at about 5 to 10 torr pressure. While ammonia gas has also been used in ion nitriding, there is no evidence that ammonia makes any improvement in the ion nitriding process. A few hundred volts dc is applied between the grounded container wall (positive) and an insulated center post supporting the work (negative) to be nitrided. A glow discharge is created in the ionized gas, accelerating positive nitrogen ions to the work. These ions contain enough energy to form the normally unstable Fe4N "white layer", thus establish- ing surface nitrogen solubility characteristic of the a Fe/Fe4N equilibrium. This creates a substantial concentration gradient, driving dissolved nitrogen into the steel. The temperature employed is in the same range (around 500" to 550°C) as in ammonia nitriding, but because of factors which are not understood at present the nitriding time is ordinarily considerably reduced in ion nitriding. Other advantages have been cited,9 but it is not the purpose of the present work to contrast the two processes. The present objective was to examine the behavior of binary iron alloys during ion nitriding with respect to the microstructure, hardness level, and depth, and to examine some of these factors in steels as well. In this way it was hoped to be able to find out something about the individual role of these elements in steels. While all the work was done by ion nitriding, there seems to be no reason why any conclusions reached would not equally apply to ammonia nitriding, excepting only the kinetic aspects of the process. Another objective was an exploration of the critical-ity of the ion nitriding variables: gas composition, pressure, temperature, and time. EQUIPMENT AND MATERIALS The equipment used was substantially as described by Jones and Martin.8 The vacuum tank was about 12 in. in diam by about 18 in. high, and consisted of water-cooled stainless steel, with a single small window at the top for viewing inside. This sat on a heavy mild steel base equipped with the main pumping port, pressure control port, and vacuum gaging. A series of variable resistances was interposed between the glow discharge and a large-capacity -40 amp variable primary transformer feeding a 1000-v transformer, but 600 v were about the maximum ordinarily used. With the small l-in.-round, 4-in.-thick discs used for nitriding, the electrical load was usually about 500 v at 0.8 amp. The specimen temperature was controlled by a stainless-steel sheathed chromel-alumel couple, whose junction was in the steel stool upon which the flat discs were placed. These were ground through 400 Sic paper. Cycling of the temperature controller caused -0.2 amp variation in ion current, providing an ample control band. The binary iron alloys were made from vacuum-melted hydrogen-deoxidized electrolytic iron and alloys of 99.9 pct purity. Cast ll-lb-square tapered ingots were forged and hot-rolled to about 11/4-in.-diam rounds. Discs of 1/4 in. thickness by about 1 in. diam were machined from the rods for nitriding specimens. The following alloys were prepared: 1 pct each of Mn, Mo, Cr, Ti, Al, V, Si, and an Fe-0.8 pct C alloy. EXPERIMENTAL VARIABLES Of the variables total gas pressure, nitrogen partial pressure, temperature, and time, only nitrogen partial pressure was found to be critical to the operation. A critical nitrogen partial pressure was found corre-

Jan 1, 1970

By A. T. Peters

DURING an investigation concerning the use of large nozzles for pouring of low-carbon rimming steels, the practical details of which were reported elsewhere, it was noticed that increases of nozzle sizes were generally followed by improvements of slab surface quality. It is the purpose of this note to present the data available and some tentative opinions about this phenomenon. The problem of correlating pouring rates with the metallurgical performance of steels is complicated by several factors. The two most important are; 1) Variations of the steel pouring rate throughout a pour, these being due to the nozzle erosion, which enlarges the bore area, and the dropping ferrostatic pressure in the ladle. The pouring rate is lowest towards the end of a heat when the ladle is nearly empty. 2) Variations in the ingot pouring time due to the different ingot weights poured. Consequently, the use of the average pouring rate of a heat may not be exact, but in large-scale production it is not practical to treat ingots separately according to their pouring rates. The variations of ingot weights and sizes may be overcome by considering the rate of rise of steel in the mold. Hence, the average rate of filling of molds throughout the pour of a heat, inches per second, will be used in this note. Every ingot rolled at Inland is rated at the blooming mills prior to hot machine scarfing as being good, fair, or poor for cracks, scabs, and checking. The latter term refers to the network of breaks or lines associated with overheating or burning in the soaking pits. It is also known that thin-skinned steel is prone to show this defect if the subsurface blowholes are exposed during reheating or rolling. The experiences with the surface quality of slabs rolled from ingots poured at different rates are presented in Fig. 1. The data represent nearly 11,000 ingots. It appears that all three types of defects are in-

Jan 1, 1960

THE discussion at the annual meeting of the paper on "Devices for Detecting Dangerous Gases in Mine Air" (published in. MINING AND METAL-LURGY, February 1, 1927, p. 69) was prefaced by the following description of a new portable methane indi-cator, presented by D. C. Ashmead: Two comparatively recent disasters in Utah are directly responsible for the perfection of the new methane detector. The first of these occurred on May 1, 1900, when 200 work-men lost their lives. The second disaster did not occur for more than two decades, when, on March 8, 1924, at the Castle Gate Mine No. 2, 172 workmen were killed. A dis-sembled safety lamp was later found at the seat of the ex-plosion. This indicated, as a possible cause, that the safety lamp had gone out and the fire boss had tried to relight it. These two disasters brought, the mine operators of the State of Utah to the concentrated attempt to end the loss of life through mine explosions. The Governor of the State appointed a committee, known as the Utah Mine Op-erators Committee, to study the phases of the problem, and this Committee in turn enlisted scientists all over the country in cooperative research. One group, under the direction of E. K. Judd, of the Union Carbide and Carbon Research Laboratories, of Long Island City, New York, concentrated its efforts on develop-ing a methane detector which would be completely ade-quate. This is now successful, since in laboratory as well as actual coal-mine tests the apparatus has instantaneously and accurately detected the presence of extremely small amounts of methane.

Jan 3, 1927

By Marvin Lee

Kansas retained, for the eighth consecutive year, the fourth position in the list of oil-producing states. The total crude-oil production during 1934, as reported by purchasers to the State Corporation Commission, was 45,538,564 bbl. on 97 per cent tank table calculations of the purchasers, or 46,946,973 bbl. as carried on 100 per cent measurement in U.S. Government reports. The corresponding figures for 1933 are 40,008,940 and 41,236,021, respectively. The increase of production over 1933 was due to the rising demand for oil from Kansas, caused principally by three factors: the continued regulation of the producing branch of the industry by Federal and State authorities, which had the effect of reducing illegal production that has been so destructively competitive with Kansas crude and refined products; the normal decline of production in other areas; and, last and best, general increased demand of the public for petroleum products. The price level remained unchanged for the first time in oil history for so long a period. Kansas 36" gravity crude remained at $1 per barrel from September, 1933, and throughout 1934. Price stability and the confidence in the regulation of production to meet the consumer demand, which is increasing, brought greatly renewed interest in Kansas fields. Drilling activity has been largely in the western part of the state where expiration of leases, on large blocks of acreage, assembled before the depression, is forcing either action or loss of the lease investment carried for a long period. The drilling of these many blocks of acreage, previously assembled on geologic information, has caused the opening of more fields than during any previous year of Kansas oil history and is proceeding faster than anticipated a year ago. Interest grows within a successful enterprise, and the momentum caused by the successes of 1934 will continue in 1935 unless unusual conditions arise and end the apparently good opportunity for financial return. Geological exploration methods used in new field discoveries are shown in the tabulation of new discoveries (Table 3).

Jan 1, 1935

By John Wulff, J. H. Hollomon

THE opinion has been widely held that the corrosion of alpha brass occurs by the selective solution of zinc. As late as 1939, Fink1 and Evans2 suggested that in the initial stage of the corrosion the selective solution of zinc produces copper-rich areas, which subsequently act as cathodes that facilitate the deposition of copper. Previously Abrams3 had shown that most of the copper found on corroded brass was redeposited and not residual, although he did not consider the nature of the initiation of the corrosion process. Enough data exist to indicate that any metal surface is sufliciently heterogeneous to provide the anodes and cathodes necessary for the initiation of corrosion .4,5 Thus, for alpha brass we need postulate not an initial selective solution of zinc, but only the existence of local differences in electrochemical potential. The heterogeneity responsible for potential differences may arise from oxide and other films as well as from alloy concentration gradients. Even though selective corrosion may be possible in some alloy systems, previous data on alpha brass as well as the experimental work reported in this paper do not require this supposition. Bengough and May,6 in a discussion of Abrams' paper, first suggested the addition of small amounts of arsenic (0.03 per cent) to alpha brass to prevent the redeposition of copper (dezincification). This suggestion was later substantiated by Nixon.7 In their studies of the inhibiting influence of arsenic, Evans and Fink were led to the selective-solution hypothesis in order to explain the initial corrosion of such alloys. "I hey believed that an arsenic film covered anode areas and prevented the formation of copper-rich spots capable of acting as cathodes for the deposition of copper. They (lid not consider, however, the mechanism by which the arsenical film was formed. Bengough and May,8 in another publication, suggested that the commonly found gray or black arsenical film may act to: (1) carry oxygen to the brass surface, (2) increase the discharge potential of copper on brass, (3) precipitate cuprous chloride from colloidal suspension in chloride solutions. Masing9 assumed that the film found upon arsenical brass was metallic arsenic. His measurements of hydrogen overvoltage of bulk arsenic led hint to believe that the inhibition of dezincification occurs because the overvoltage of a brass surface is lowered by the arsenic film. He reasoned that this film would permit the more rapid reduction of hydrogen at the cathode, which would prevent the redeposition of copper. In a recent paper,10 we have pointed out that the film formed (luring the corrosion of arsenical brass and copper in stagnant solutions is essentially arsenious oxide (AS208)

Jan 1, 1942

By H. M. Roche

MAGNETITE mining and milling in the Eastern States was sharply curtailed in 1938, production showing a decrease of 36 per cent from 1936 and 57 per cent from 1937. Six mines, one in Pennsylvania, two in New York, and three in New Jersey were in operation, either part or full time, during the year. In recent years ten Eastern magnetite mines have been more or less active but since the World War the market for Eastern ores- has been spotty. The scrapping of Eastern merchant pig iron furnaces, imports of cheaply mined duty-free foreign ore, and high freight cost have been contributing factors.

Jan 1, 1939

By D. T. Van Zandt

IN the late 1920's rotary drills began to replace the churn drills in the petroleum industry, but until the middle 1940's the churn drill was the only widely accepted means of drilling large-diameter blastholes for quarry operations. The Calcite plant of the Michigan Limestone Div., U. S. Steel Corp., was one of the first to experiment with rotary drills for quarry blasthole drilling, and the first to employ compressed air on a fully rotary rig to cool the bit and raise the cuttings to the collar of the blasthole.

Jan 8, 1954

By L. D. Mullins, E. B. Elfrink, W. L. Wahl

In the past few years several articles and papers presenting results of solution gas-drive depletion calculations have appeared in the lit-erature. Such calculations are of interest to the oil industry, for investment decisions must often be made before much is known about a reservoir. At other times, an estimate of the possible benefits to be realized from alternate production methods is desirable, and theoretical depletion calculations can serve as a floor or reference level from which to work. In any case, an estimate of ultimate oil recovery based upon engineering data is commonly required. An engineer confronted with the problem of obtaining, for a specific reservoir system, an estimate of ultimate oil recovery by solution gas-drive depletion usually will be forced to perform the calculations himself. This is despite the quantity of data in the literature. Rarely will either experience or the literature provide results from a reservoir system similar in all important respects to the one under consideration, and calculated results are not so plentiful that satisfactory interpolation procedures can be devised. Performing the calculations, however, is a tedious, time-consuming task unless an electronic computer is available, and, in practice, time and manpower are not always available for this purpose. A quick, simple, consistent method was needed for reducing the uncer- tainty in estimated oil recovery from solution gas-drive reservoirs when only minimum information about the reservoir system is available. PROCEDURE Method of Calculation The usual requisite assumptions were made so that the material balance equation could be used to calculate data for the charts. The following assumptions were made: (1) the reservoir is homogeneous and isotropic; (2) oil recovery is due entirely to solution gas drive and neither a gas cap nor a water drive nor gravity drainage is present; (3) the initial reservoir pressure is the bubble-point pressure of the reservoir fluid; (4) initial total liquid saturation is 100 per cent of pore space; (5) interstitial water saturation remains at the initial value as the reservoir pressure declines from the bubble-point pressure to atmospheric pressure; (6) equilibrium gas saturation is 5 per cent of pore space; and (7) oil and gas saturations are uniformly distributed throughout the reservoir at all times. There are no saturation gradients due to a wellbore, nor is the geometry of the reservoir system considered. The material balance equation was written in the form of a differential equation' which was integrated to determine the change in oil saturation for an assigned pressure drop. Formal integration was not possible, so recourse was made to the Runge-Kutta method' of numerical integration. All computations were performed on IBM equipment. Numerical integration yielded the change in oil saturation within the reservoir as the pressure. declined from the bubble-point pressure to atmospheric pressure. The initial oil saturation minus the change in oil saturation yielded the oil saturation at atmospheric pressure. The oil originally in place was obtained by dividing the initial oil saturation by the initial formation volume factor (differential liberation) while the oil in place at atmospheric pressure was obtained by dividing the final oil saturation by the formation volume factor at atmospheric pressure. U1timate oil recovery, expressed as a percentage of the initial oil in place, was obtained by dividing the difference between the oil initially in place and the oil in place at atmospheric pressure by the oil initially in place and multiplying by 100. PVT Data Charts were based upon 135 solutions to the material balance equation. PVT properties of the reservoir fluids were variables in this equation and had to be known as functions of pressure. The required PVT data might have been obtained from either actual reservoir fluid systems or correlated data. However, correlated PVT data were developed and employed in the calculations for the following reasons: (1) it is doubtful that 135 sets of PVT data could have been obtained for the values of variables investigated in this study, and (2) results of recovery calculations from randomly obtained PVT data could not be correlated as well as rssults from selected PVT data. The PVT data used to develop the

By Robert D. Pehlke, Robert G. Blossey

The solubility of nitrogen in liquid cobalt and a number of dilute cobalt alloys Was measured in the temperature range 1550" to 1700°C at nitrogen pressures to 1 atm. At 1600°C and 1 atm nitrogen pressure, the solubility in pure cobalt is 0.0047 wt pct [3.8 cu cm (stp) per 100 g Co]. The standard free- energy change for the solution reaction 1/2 N,(g) = gout pct in Co) is iF - 10,000 + 5.24 T cal per g atom N. The alloying elements Cv, Cu, Mo, Nb, Tu, W, and V increase the nitrogen solubility, while Al, Fe, Ni, and Si decrease the nitrogen solubility. THE solubility of nitrogen in cobalt was studied previously by Sieverts, Busch and Dodd,2 and Schenck, Frohberg, and Graf.3 Sieverts investigated the solution below the melting point of cobalt, and Busch and Dodd worked with the liquid metal; however, neither study found any solubility for nitrogen in cobalt. Schenck et al, reported a solubility of 0.005 wt pct N in cobalt at 1600°C. Seagle et al. 4 reported residual nitrogen in cobalt after electron-beam melting, although no reasons were ventured for the presence of this interstitial impurity. This investigation was undertaken to clarify these inconsistencies, and to provide additional data on atomic interactions in dilute metallic solution. EXPERIMENTAL PROCEDURE This study was well-suited to the Sieverts' method, which has not changed significantly since its introduction by Sieverts. 5 The apparatus was of the same design as that described by Humbert and Elliott, 6 with a reaction bulb similar to that reported by Weinstein and Elliott. 7 The buret was not water-jacketed, but the measured gas volumes were corrected for small changes in room temperature. The melt temperature was measured by a disappear ing-filament optical pyrometer sighted through a prism onto the melt surface. Temperature calibration was made based on a measurement of the melting point of pure cobalt taken as 1495°C. The difference between the reciprocal of the observed and the true temperatures was assumed to be a constant, neglecting the changes in emissivity with small additions of alloying elements. The total error in gas-volume measurement caused by accuracy limitations in reading the mercury level in the buret, variation in ambient temperature, and variation in melt temperature was about 0.5 cu cm. This represents approximately 10 pct of the total solubility, and is a larger relative error than in previous studies6-' because of the small nitrogen solubilities encountered in the present investigation. The source and purity of the materials used are listed in Table IA. Recrystallized alumina crucibles were used throughout the investigation. Examination of the crucibles after solidification of the melts showed no reaction or penetration. Alloying of the cobalt melt was accomplished with the dropping technique described by Humbert. 6 The investigation was started using cobalt from African Metals Corp. in shot form, but this material was not of sufficient purity and did not yield consistent solubility results. Sherritt Gordon Mines Ltd. cobalt was then used throughout the investigation. In experiments involving alloying elements which could react with oxygen dissolved in the melt, the cobalt was further refined by annealing at 1400°C in a dry-hydrogen atmosphere. This treatment, described by Woolley and Pehlke, 8 markedly reduced the oxygen content. The oxygen and nitrogen analyses of the cobalt used in this study are presented in Table IB. RESULTS Hot Volume. The hot volume was measured prior to each run and was 50 to 55 cu cm (stp) at 1600°C. It increased linearly with increasing pressure and decreasing melt temperature. Pure Cobalt. Measurements of the solubility of nitrogen in pure cobalt and the temperature coefficient of solubility are summarized in Table 11. At 1600°C and 1 atm nitrogen pressure, the solubility was found

Jan 1, 1967

By N. J. Grant, B. C. Giessen, U. Wolff

With the aid of the splat-cooling technique of rapid quenching, metastable alloy phases based on antimony ad bismuth have been prepared. At room temperature, simple cubic phases were found in the Sb + Au, 56 + Yd, and Sb + Ni systems. Another phase was retained in the Au-Bi system at -190°C; in this systent, a microcrystalline phase and a rhombohedrally distorted phase were also observed. The crystal chemistry of these phases is discussed in terms of their valence electron concentration range. A remarkable five-step Phase sequence was found upon heating and equilibration of certain metastable Au-Bi alloys. USING the splat- cooling technique of rapid quenching from the liquid,' a large number of metastable intermediate alloy phases have been prepared in recent years. Thus, Hume-Rothery phases of the hexagonal type based on the valence electron concentration have been produced in systems where they are missing in equilibrium, e.g., Ag-Ge 1 or AU-Sb. 3 In a comprehensive study of metastable alloys based on tin, simple hexagonal metastable y phases were found, raising the total of stable and metastable y phases from 3 to 13. 4 In the In-Bi system, five new metastable intermediate phases were retained.' In most cases, the new metastable phases have some crystal chemical characteristics in common: a) They have rather simple, elementlike structures with few atoms per unit cell, e.g., y phase,4'5 or the metastable primitive cubic phases in the Ag-Te and and Au-Te systems.= b) Their structures are often related to those of the terminal phases, or to elements that are straddled in their position in the periodic table by the constituent elements; this is the case for metastable ß (In-Bi) with the structure of white ß Sn,' or metastable a (Cd-sn). 4 c) They seem to represent the crystal structures appropriate to certain average group number (AGN) ranges in which no or few single-phase structures exist in equilibrium. These average group number ranges can probably be equated in the case of many elements of the Ba(Zn)-Bs(As) groups with the averaged valence electron concentration. In the present work, the splat-cooling technique has been applied to the alloys of antimony and bismuth. In equilibrium, neither element forms intermediate alloy phases with other B elements from groups Bl(Cu) to B4(Si) that contain more than 66.7 at. pct of Sb or Bi, respectively, e.g., AUSb 2. 7 Thus, antimony- or bismuth-rich phases, which might be closely related to antimony or bismuth, and which would reflect struc- tural changes occurring on alloying with small amounts of addition elements, do not exist. Also, the terminal solubility of antimony and bismuth for all B metals is very small. It was therefore of interest to investigate the influence of enforced, nonequilibrium solid solution of addition elements in antimony and bismuth on their crystal structures. It was found that additions of group B 2-B4 metals act distinctly differently than additions of group T 10 and B1 metals. The latter set of additives will be treated here. EXPERIMENTAL TECHNIQUES Alloy preparation and splat-quenching followed closely the procedures described in Refs. 1, 4, and 5; they consisted of the preparation of master alloys from high-purity starting materials (99.99+ pct) and blast-atomizing of 20-mg quantities onto copper sheets. The resulting approximately 1 to 5 u thick foils were investigated by X-ray diffraction. The cooling rates obtained are of the order of 107 to 10 8 C per set,'" causing solidification to proceed at a rat; of approximately 100 cm per sec.' Powder patterns of the resulting fine-crystalline materials were taken with filtered CuK, radiation. For antimony alloys the substrates were held at room temperature and for bismuth alloys at -190°C both during splat foil deposition and X-ray investigation. Annealing treatments at several

Jan 1, 1969

By Clemens Jones

The peculiar property of the lode-stone has been known for many centuries. It was very early observed that, by contact with it, iron is magnetized; and it is needless to dwell here upon the history allied to this discovery, now constituting the wonderful science of magnetism. Deposits of magnetic ore are distributed all over the world. The ore is sometimes very rich and comparatively free from gangue, sometimes sparsely disseminated in the native rock. These bodies of lean ore often cover large areas. Modern ingenuity has utilized the principle of the magrtet, originally derived from the ore itself, and really belonging to the time of Plato and Theophrastus, to separate the magnetic ore-particles from the rock which has previously been crushed. This process recovers the ore in the state of a concentrate very rich in iron and, in some cases, desirable for Bessemer purposes. The magnetic separator is no longer a novelty. It was only at the last meeting of the Institute in New York, that Messrs. Birkinbine and Edison (Trans., xvii., 728) and Mr. Robert Cook (Ib., 599) described some of' the principal designs of apparatus in use. E. S. Dana classifies the natural magnetic minerals in the following order: magnetite, pyrrhotite, franklinite, almandite and minerals " containing considerable FeO." Of these, ferroso-ferric oxide, or magnetite, is the type. The proportionate amount of ferrous oxide essential to magnetize the compound, is not established. Ferrous oxide appears to be the only magnetic oxide of iron. Tissandier (Compt. Rend., lxxiv., 531) produced ferrous oxide in the anhydrous state, by the action of carbon dioxide on pure iron at a red heat, according to the equation : Fe + CO2 = FeO + CO. This is black, crystalline and magnetic. Heated to redness in the air, it is converted into Fe3O4. Sidot (Compt. Rend., lxvii., 175) has also produced an oxide exhibiting magnetic polarity, by heating ferric oxide to a temperature

Jan 1, 1891

By C. H. Wayman, D. W. Fuerstenau

THE gas phase is one of the indispensible ingredients in flotation operations. Flotation depends on the collision of an air bubble and a mineral particle in a pulp and their ability to remain in contact long enough for adherence to take place. Before it is possible to understand the mechanics of air bubble-mineral particle encounter, it is necessary to learn more about the nature of bubbles themselves before collision with a mineral particle has taken place. To date, little work has been done on air bubbles in flotation systems. In 1945 Fahrenwald1 presented a study of the role of frothers on air bubbles and on aeration in flotation, and recently Wark and Sutherland2 discussed the work of Rosenberg3 in relation to flotation. The research reported in this present article was undertaken to investigate systematically the effect of bubble size and the concentration of certain reagents on the terminal velocity, shape, path, and drag coefficient of single bubbles in distilled water. Most of the work is concerned with the effect of a-terpineol on bubble motion in water, but studies were made with potassium chloride, potassium hydroxide, potassium ethyl xanthate, and potassium amyl xanthate.

Jan 6, 1958

By C. S. Smith, E. W. Palmer

IN 1934, when Gregg and Daniloffl wrote their excellent monograph on the alloys of iron and copper, the most recent literature on the constitution of the alloys indicated a narrow single-liquid area for 20" above the liquidus with a closed liquid mis-cibility gap above this. Since that time, however, a number of investigators have confirmed the much earlier studies of Mushet2 and Stead3 who, among others in the nineteenth century, had described the true state of affairs. Liquid copper and iron are completely miscible in the absence of carbon, but small amounts of carbon cause liquid segregation. In 1934, one of the writers' mentioned evidence for the absence of liquid separation in carbon-free alloys at temperatures up to 1700°C. Two years later, Mad-docks and Claussen5 unequivocally established the absence of liquid segregation and published a revised diagram, reproduced in fig. 1. They also studied the limits of the two-liquid area in ternary alloys of iron, copper, and carbon as a function of carbon and iron content. In the same year Simpson and Bannister" and Schumacher and Souden7 described in some detail the properties of alloys containing 50 to 75 pct Cu. More recently Hodges et al.16 have developed the copper-rich alloys for use as high-strength conductors. In 1937, Iwase, Okamoto, and Ameniya8 published data on the miscibility gap in ternary alloys of iron, copper, and carbon that supported the conclusions of Maddocks and Claussen, and definitely located the two-liquid area at temperatures of 1450" and 1540°C. They also reported that additions of 1 pct Al, Ni, Pb, Sn, or Zn caused no segregation in 50 pct Cu alloys at 1540°C. The use of copper in amounts approximating 1 pct has found industrial employment to an increasing degree in both wrought and cast steels, for such steels are capable of being precipitation-hardened following normalizing, and have high yield strengths. This is summarized by Gregg and Daniloff,1 Sallitt,9 and Lorig and Adams,10 while Alexander" gives additional information on the heat treatment of copper-steel castings. Lippert12 has described Digby's two-phase steels containing copper and chromium. The work described in the present paper was done in the years 1932 to 1934, at which time much of the information was new. The excellent work subsequently done in other laboratories but more promptly published makes the present paper in part only a confirmation of what is now well known. There has not, however, been published any unified study of

Jan 1, 1951