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By Alec M. Crowell, Thomas D. Bailey

Although natural gas was first discovered in Northwest Arkansas in 1887, . near Fort Smith, Sebastian County, the literature contains very little information on the region, which is separated distinctly from the oil area of Southern Arkansas. For that reason this brief and concise report is a summary of developments from discovery to the present time. Northwest Arkansas produced 5,736,-ooo,ooo cu. ft. of natural gas during 1942, the trend of production having been generally upward over the past five years, as is shown in Fig. I. Since 1904 a reserve of 237 billion cubic feet of natural gas has been discovered in Northwest Arkansas, of which approximately 162 billion cubic feet have been expended, leaving a reserve of approximately 75 billion cubic feet available as of Jan. 1, 1943. A prolific new field discovered in Pope County Oct. 23, 1942, will add to the reserve of the region materially. Per well reserves, over-all, are unusually high because of the practice of multiple completion. As yet no commercial deposits of oil have been discovered in Northwest Arkansas. but the gas deposits have proved of immense value industrially, principally in the processing of zinc ore mined in the local area as well as that imported from distant states. With the war, new interest in the exploitation of the metallic ores of the region lends new significance to the gas reserves tabulated herein. Geological Discussion The region covered in this report comprises the Arkansas Valley from Pope County weslward to the Arkansas-Oklahoma state line as shown in Fig. 2. This valley is a westward trending structural trough with sharp-topped ridges and mesa-like mountains rising above the valley's undulating surface. It is bounded on the north by the Ozark Highlands and on the south by the Ouachita Mountains. The sedimentary beds of the Arkansas Valley are composed mainly of noniossil-iferous shales and sandstones. The rocks contain a high content of carbonaceous material and many coal beds are found in the region. The Gxed carbon ratios (ratio of fixed carbon to volatile combustible matter of surface coals) are very high and average about 80 per cent over the region covered in this report. Little or no calcareous material is present. Rocks of the Arkansas Valley are sharply folded, and igneous intrusive rocks cut the sedimentary beds at a few places. The Arkansas Geological Survey' made a detailed reconnaissance survey of the Arkansas Valley province in 1927, the purpose being to delineate the major structural features (Fig. 3) and to point out the possibilities of discovering addi. tional gas deposits. More than fifty anticlines were mapped as a result of this survey. The information gained by this

Jan 1, 1943

By Thomas D. Bailey, Alec M. Crowell

Although natural gas was first discovered in Northwest Arkansas in 1887, . near Fort Smith, Sebastian County, the literature contains very little information on the region, which is separated distinctly from the oil area of Southern Arkansas. For that reason this brief and concise report is a summary of developments from discovery to the present time. Northwest Arkansas produced 5,736,-ooo,ooo cu. ft. of natural gas during 1942, the trend of production having been generally upward over the past five years, as is shown in Fig. I. Since 1904 a reserve of 237 billion cubic feet of natural gas has been discovered in Northwest Arkansas, of which approximately 162 billion cubic feet have been expended, leaving a reserve of approximately 75 billion cubic feet available as of Jan. 1, 1943. A prolific new field discovered in Pope County Oct. 23, 1942, will add to the reserve of the region materially. Per well reserves, over-all, are unusually high because of the practice of multiple completion. As yet no commercial deposits of oil have been discovered in Northwest Arkansas. but the gas deposits have proved of immense value industrially, principally in the processing of zinc ore mined in the local area as well as that imported from distant states. With the war, new interest in the exploitation of the metallic ores of the region lends new significance to the gas reserves tabulated herein. Geological Discussion The region covered in this report comprises the Arkansas Valley from Pope County weslward to the Arkansas-Oklahoma state line as shown in Fig. 2. This valley is a westward trending structural trough with sharp-topped ridges and mesa-like mountains rising above the valley's undulating surface. It is bounded on the north by the Ozark Highlands and on the south by the Ouachita Mountains. The sedimentary beds of the Arkansas Valley are composed mainly of noniossil-iferous shales and sandstones. The rocks contain a high content of carbonaceous material and many coal beds are found in the region. The Gxed carbon ratios (ratio of fixed carbon to volatile combustible matter of surface coals) are very high and average about 80 per cent over the region covered in this report. Little or no calcareous material is present. Rocks of the Arkansas Valley are sharply folded, and igneous intrusive rocks cut the sedimentary beds at a few places. The Arkansas Geological Survey' made a detailed reconnaissance survey of the Arkansas Valley province in 1927, the purpose being to delineate the major structural features (Fig. 3) and to point out the possibilities of discovering addi. tional gas deposits. More than fifty anticlines were mapped as a result of this survey. The information gained by this

Jan 1, 1943

By R. S. Moehlman

IN recent years, exploration and development by diamond drilling has become a popular attack on the problem of finding new ore shoots and developing extensions of known shoots. Diamond drilling has been used in recent years in extensive sampling of disseminated copper deposits, in preference to churn drilling. At the Harvard gold mine, near Jamestown, California, Philip R. Bradley, Jr., general superintendent, reports that: "The Harvard work was a singular example of the reliance that can be placed on diamond drilling in evaluating an ore body." Drilling at the Harvard mine will be discussed in a subsequent section of the paper. So popular has diamond drilling become, indeed, that many who have had slight experience with drilling are inclined to regard it as a cheap cure-all. This paper proposes to show some of the limitations on the application of drilling and some of the steps that should be followed in drilling programs to obtain reliable results. COST OF DRILLING Drilling has the advantage, over shaft sinking and drifting, of lower cost and greater speed. As compared with churn drilling, the advantage of bringing up a coherent sample instead of fine cuttings for a sample is obvious. Diamond drilling is generally more expensive, however, and more engineering effort is required in combining the average of core and sludge samples. Exploration of drift walls by hammer drills to a depth of less than 50 ft. is generally cheaper than diamond drilling, but beyond this depth the diamond drill is cheaper and more efficient. The principal factor in determining cost of drilling is the character of the ground drilled. Broken ground with many fissures is most expensive to drill. Hard ground is less of a problem with diamond drills than with ordinary machine drills. Hardness or softness affects only the speed of drilling. Caving, easily washed, sandy or clayey ground requires continual cementing and casing, which is the greatest cost problem. Thus, soft, incompetent ground is more costly to drill than hard, massive ground. Cost of drilling per foot in good to fair ground varies from less than $1 per foot, achieved in some districts in Ontario, the Mother Lode, and Missouri, to $5 per foot in many western states. In bad drilling ground, costs may range from $5 to $15 or more per foot, thus approaching the cost of drifting. Other factors that increase the cost per foot are: I. Short total length of hole drilled, so that the cost of moving in crews and equipment must be spread over a relatively few feet. 2. Cost of drilling per foot increases with depth beyond about 500 ft., as more time is consumed in pulling rods. 3. Cost of preparing drilling stations, getting air underground to stations, etc. 4. Inaccessibility and lack of water on the job make for higher costs.

Jan 1, 1946

By K. K. Rao, M. E. Nicholson

IN a recent paper on the solubility of carbon in Ni-Cu alloys,' Nicholson reported that the carbon solubility appeared to be limited by the electronic structure of the alloys and that the solubility was propor- tional to the density of states at the Fermi surface of the "3d" band. In order to determine whether or not this relationship is a general one, the study has been extended to other systems. One of these is the CO-Ni system. This system was chosen for study because 1) it is adjacent to Ni-Cu system in the periodic table, 2) the alloys of cobalt and nickel do not form stable carbides at 1000°C, and 3) the system exhibits no pronounced change (less than 1 pct) in lattice parameter from cobalt to nickel,' see Fig. 1. The alloys were prepared from -200-mesh 99.92 pct Ni furnished by the International Nickel Co. and spectroscopically pure -200-mesh cobalt sponge obtained from Johns on-Matthey and Co. The powders were weighed, mixed, and pressed using a pressure of 40,000 psi. The samples were sintered for 24 hr at 900° C in dry hydrogen and then cold rolled to a thickness of 0.010 in. (Samples containing more than 70 wt pct Co had to be annealed after cold reductions of about 20 pct to avoid cracking.) The alloys were carburized at 1000°C in an alun-durn boat containing Acheson AUC powdered graphite in an atmosphere of carbon monoxide cylinder gas which had been passed through Ascarite to remove carbon dioxide. After carburizing for either 12 or 24 hr the samples were moved to a cool zone of the furnace to cool. Cooling required about 5 min. The samples were filed to remove about 0.005 in. from the surface and then analyzed using a conventional combustion-gravimetric analytic method. The results of this investigation are shown in the lower portion of Fig. 1 and Tabulated in Table I. The nickel percentages for these alloys were determined from the weights of the powders from which the alloys were made. The solubility of carbon in pure cobalt at 1000°C (fcc) is 0.25 wt pct. This is somewhat less than the 0.33 wt pct measured by Boecker.3 From his data, it would appear Boecker's samples were supersaturated before the equilibrating treatment and that a 20-min treatment was not long enough to achieve equilibrium. Since in the present investigation the 12 and 24 treatments produced essentially equal carbon contents, our figure is presumed to represent more nearly the equilibrium value. The solubility of carbon in nickel of 0.19 wt pct agrees quite well with the value of 0.21 wt pct

Jan 1, 1963

By W. M. Bertholf

In 1945 tests were made in the coal washery of the Colorado Fuel and Iron Corporation, at Pueblo, Colo., to determine the value of the Humphreys spiral. So far we have demonstrated that it is of definite value to us in rewashing a portion of our table middlings; and we are fairly certain that this is not necessarily the only place in which it can be used to advantage. Because of manpower and material shortages, experimental work has been discontinued for the present. Three of the spirals are being installed for use in rewashing the middlings, and testing and experimental work will proceed when this installation is completed. All evidence secured so far points to the fact that the spiral call make an effective separation of heavy material below 8-mesh; but that it is ineffective in removing larger, heavy material. This, of course, will limit its use to fine coal or a classified feed containing no heavy material larger than 8-mesh. In considering the results of our tests, it should be noted that the feed was our table middling, and that any real separation of this material is a "moral victory)" as there is little material that could be properly called coal and practically no heavy rock, the consequence being that previous attempts to clean the middlings have not been at all successful. Several articles dealing with the spiral and its use in treating heavy minerals have already been published,' but for the benefit of those who have not seen these we include a brief description of the spiral and of the way it operates, taken from Bulletin 4 of The Humphreys Investment Co.: The Humphreys Spiral Concentrator consists of a spiral conduit of modified semicircular cross section. Ore pulp is fed to the top and, as it flows downward, the heavier particles concentrate in a band along the inner side of the pulp stream (Fig. I). Outlets for removal of products are located at the lowest points in the cross section of the conduit. Wash water, added at the inner edge of the stream, flows outwardly across the concentrate band. The width of concentrate band removed at the outlets is controlled by adjustable splitters. Concentrate is usually removed from the upper portion of the spiral and middling from the lower portion. Tailing is discharged from the lower end. Tests are usually made in closed circuit, since this provides a maximum of information with a minimum amount of sample. Fig. 2 shows the spiral set up for closed-circuit testing, and gives a good idea of the general arrangement of such an installation. The small cyclone separator is used to provide clean wash water without introducing additional water into the circuit.

Jan 1, 1947

By W. M. Bertholf

In 1945 tests were made in the coal washery of the Colorado Fuel and Iron Corporation, at Pueblo, Colo., to determine the value of the Humphreys spiral. So far we have demonstrated that it is of definite value to us in rewashing a portion of our table middlings; and we are fairly certain that this is not necessarily the only place in which it can be used to advantage. Because of manpower and material shortages, experimental work has been discontinued for the present. Three of the spirals are being installed for use in rewashing the middlings, and testing and experimental work will proceed when this installation is completed. All evidence secured so far points to the fact that the spiral call make an effective separation of heavy material below 8-mesh; but that it is ineffective in removing larger, heavy material. This, of course, will limit its use to fine coal or a classified feed containing no heavy material larger than 8-mesh. In considering the results of our tests, it should be noted that the feed was our table middling, and that any real separation of this material is a "moral victory)" as there is little material that could be properly called coal and practically no heavy rock, the consequence being that previous attempts to clean the middlings have not been at all successful. Several articles dealing with the spiral and its use in treating heavy minerals have already been published,' but for the benefit of those who have not seen these we include a brief description of the spiral and of the way it operates, taken from Bulletin 4 of The Humphreys Investment Co.: The Humphreys Spiral Concentrator consists of a spiral conduit of modified semicircular cross section. Ore pulp is fed to the top and, as it flows downward, the heavier particles concentrate in a band along the inner side of the pulp stream (Fig. I). Outlets for removal of products are located at the lowest points in the cross section of the conduit. Wash water, added at the inner edge of the stream, flows outwardly across the concentrate band. The width of concentrate band removed at the outlets is controlled by adjustable splitters. Concentrate is usually removed from the upper portion of the spiral and middling from the lower portion. Tailing is discharged from the lower end. Tests are usually made in closed circuit, since this provides a maximum of information with a minimum amount of sample. Fig. 2 shows the spiral set up for closed-circuit testing, and gives a good idea of the general arrangement of such an installation. The small cyclone separator is used to provide clean wash water without introducing additional water into the circuit.

Jan 1, 1947

By R. Schumann

THE expression "unit process " comes up with increasing frequency in discussions among metallurgists and mineral engineers, especially among those concerned with training the next generation. The unit process approach characterizes a significant advance along the road from metallurgy as an empirical art to metallurgy as a branch of engineering. The purposes of this paper are to define and list the unit processes in specific terms, to indicate the scientific and engineering principles basic to all the unit processes, and finally to show how these ideas have been applied to a reorganization of instruction in chemical metallurgy. UNIT OPERATIONS AND UNIT PROCESSES Metals are extracted from ores and other raw materials by stepwise procedures. In general, each metallic element is extracted by a different procedure. For many of the metals there is a choice of several flowsheets. However, the procedures all have steps in common. In fact, the many different flowsheets are all made up of a relatively small number of steps which are combined in different groups and sequences. For example, crushing, screening, roasting, sintering, melting, and gaseous reduction are steps which each appear in the flowsheets for extracting the majority of the metals. The individual steps or flowsheet units can be designated as unit operations or unit processes. These terms are well established in the field of chemical engineering, as the American Institute of Chemical Engineers' definition of chemical engineering shows: " Chemical engineering is that branch of engineering concerned with the development and application of manufacturing processes in which chemical or certain physical changes of materials are involved. These processes may usually be resolved into a coordinated series of unit physical operations and unit chemical processes. The work of the chemical engineer is concerned primarily with the design, construction, and operation of equipment and plants in which these unit operations and processes are applied. Chemistry, physics, and mathematics are the underlying sciences of chemical engineering, and economics its guide in practice."1a In this definition, the distinction between unit operations and unit processes is that the unit operations are physical while the unit processes are chemical. Table I gives a list of the principal unit operations and unit processes of chemical engineering, taken from Shreve. lb Table 2 lists the principal unit operations and unit processes used for metal extraction. The division between unit operations and unit processes is similar to the chemical engineers' distinction and also corresponds approximately to the division of labor between mineral dressing and chemical metallurgy which has been customary in the past. Furthermore, it will be noted that in the proposed classification the unit processes primarily involve chemical reactions and/or changes in state of aggregation; the unit operations, primarily do not involve either bulk

Jan 1, 1948

By V. S. Tuman

In the first part of this paper, an estimate is made of the magnitude and extent of the thermal stresses which result from mud circulation. Our study is made for the period of relaxation, i.e., when the drilling operations are terminated and mud circulation is discontinued. In the second part, we have shown how the thermal stress can affect the wave propagation. An example is worked out for a Carbondale sandstone (Illinois basin). It is concluded that, in extreme cases when differential temperature is about 100°F, the travel time will be affected by about 2 microsec/ft. For more refined permeability studies, such corrections would be desirable. MAGNITUDE AND EXTENT OF THERMAL STRESSES RESULTING FROM MUD CIRCULATION When geological beds are penetrated by boreholes, it is observed that the formation temperatures increase with depth; however, the temperature profile varies considerably from place to place. During drilling operations, mud pumped from a pit at atmospheric temperature absorbs heat from the lower beds. As a result, the drilling fluid returning to the surface is at a higher temperature than the surrounding beds. The temperature gradient in a well depends on the rate of mud circulation and other factors; normally, this temperature gradient is smaller than the natural gradient in the formations. (See Fig. 1.) The temperature difference between the mud column and the surrounding beds gives rise to therma1 stresses (which are also important in the phenomenon of fracturing), and it is expected that they will affect the transit time of the sonic front in velocity logging.1 It is evident chat beds near the surface will undergo various cycles and will have a complicated dynamical and thermal-stress history. A limestone bed which is just penetrated will act as a source of heat, warming up the cold mud pumped down a few minutes earlier from the surface pit. The same limestone bed a week later will act as a sink, absorbing heat from the drilling mud which has already warmed up sufficiently to be at a higher temperature than the bed in question. No doubt a large section of the hole will undergo a heat treatment, which will make the calculation of the exact magnitude of the thermal stresses very difficult. In the solution of wellbore thermal equation, it is assumed that the rock around the wellbore is elastic and isotropic, and that the system is radially symmetrical. A complete dynamical solution of the thermal stresses set up at different horizons during the drilling operations would require a comprehensive history of the mud circulation, the surface temperature of the pit and the number of hours in which mud was not circulated. CONDUCTION OF HEAT AND THERMAL EQUATION OF STATE

By S. Leber, R. F. Hehemann

This investigation describes the kinetics of alloying in a (Cb-15 wt pct W. 5 wt pct Mo, 1 wt pct Zr) powder-metallurgy alloy. The degree of homogeneity obtained in hydrostatic ally pressed and vacuum-sintered samples is described by composition distributions resulting from analysis of X-ray dvfraction line profiles. Sintering variables and degvee of powder dispersion were evaluated. The utility of single-value parameters obtained from composition distributions is disaissed. The spatial distribution of composition, as revealed by anodically tinted metallographic sarrzples, was used to provide diffision models based on a concentric-sphere geometry. Diffusion equations developed from these models were found to be in general agreement with experimental results. The powder-metallurgy method for the production of refractory metal alloys has the ability to produce an inherently fine-grained, fabricable structure. The more general use of this method is inhibited, in part, by the presumed difficulty in obtaining homogeneity on a microscale. The degree of homogeneity therefore is an important, but usually neglected, variable in specifying the quality of a powder-metallurgy alloy. Convenient techniques for measuring the degree of homogeneity are now available,' and have been used to develop a model describing the process of alloying in a simple binary mixture.' In this investigation, the process of alloy formation has been studied in a more complex system. PROCEDURE The columbium-based F-48 mixture was prepared from the constituent powders shown in Table I. The particle sizes tabulated were provided by the vendors of the individual powders. Standard laboratory techniques utilizing a jar mill were employed for blending. The blended powders were hydro-pressed into 1-in. diam rods which were then sliced into thin discs for vacuum sintering. All samples were given a preliminary treatment at 1700°C for 2 hr. Varying degrees of homogeneity were obtained using additional treatments at higher temperatures. The degree of homogeneity obtained by a specific sintering treatment was evaluated metallographi-cally using the anodic-tinting technique described by olff,' and quantitatively by the analysis of X-ray diffraction line profiles using the X-ray diffraction technique developed by udman.' The diffraction technique is strictly valid only for binary systems. However, the relatively small difference between the lattice parameters of tungsten and molvbdenum when compared with columbium permitted the treatment of the complex composition of F-48 as a (W, Mo)-Cb pseudobinary. Calculations were weighted in accord with the W-Mo ratio in the F-48 composition. The contribution of the 1 pct Zr was ignored since it could not even be detected in the blended powder. Two factors are required to convert an X-ray line profile into a composition distribution. The variation of these factors with composition is shown in Fig. 1. Curve A was used to convert angular posi-

Jan 1, 1964

By A. H. Geisler, J. H. Keeler

Preferred orientations in unalloyed zirconium were determined by the Geiger-counter spectrometer X-ray diffraction technique. With increasing P-annealing temperature the following textures were obtained: l—a retained a-annealing texture, 2—additional orientations predictable from the a-p (Burgers) relationship, and 3—a texture derived from a cube texture in the p phase. Earlier work on cold-worked and a-annealed zirconium was reappraised to show a quantitative dependence of rotations on temperature and to identify spurious areas of some of the pole figures. IN a previous paper,' the preferred orientations of high purity zirconium sheet were described for cold-rolled and annealed samples. Annealing temperatures up to 900°C, which is slightly above the allotropic transformation temperature, were explored. Of interest was the observation that the orientation of the hexagonal-close-packed material after annealing in the temperature range of the stable body-centered-cubic phase was similar to that of the material which had been annealed in the a temperature region, although a change in texture would be expected because of the many new orientations based on an orientation relationship between the two forms of zirconium. The reversion to an original orientation after an allotropic transformation cycle is not unusual. It has been found for titanium,"* for thallium," and for cobaltB among the hexagonal metals. Burgers found in his original work7 that, when zirconium was cooled through the allotropic transformation and then reheated, the body-centered-cubic phase reverted to the original orientation. Additional experimental work has been carried out to further explore the textures of zirconium after annealing in the temperature range above the allotropic transformation. In addition, a reappraisal was made of the earlier results for zirconium' in light of recent work on titanium4 which has shown that the texture type depends quantitatively on the temperature of annealing and that spurious areas may be encountered in the pole figures of hexagonal metals determined by the X-ray spectrogoniometer technique of analysis. Experimental Procedure Crystal-bar zirconium prepared by the iodide process was the material used in this investigation. The major impurity was hafnium which was less than 0.3 pct. The composition obtained by spectro-graphic analysis is given in Table I. Cold-rolled specimens were prepared from crystal bar by a series of reductions of approximately 0.010 in. until the sheet reached a thickness of 0.010 in., after which it was cold rolled to 0.001 in. thickness between sheets of alloy steel. The total cold reduction amounted to about 99.8 pct. Specimens were annealed for % hr at 1000" to 1100" to 1200°C or 1 hr at 1400°C in an evacuated Vycor or quartz tube. The transmission pole figures were obtained by

Jan 1, 1956

By R. W. Bartlett

The rates of oxidation of tungsten have been determined at temperatures between 1320" and 3170°C and oxygen pressures to 1 amn using a surface -recession measurement technique. Above approximately 2000°C and 10-6 atm the rate is independent of temperature and can be calculated from gas collision theory assuming a constant reaction probability, e, of 0.06. Oxygen molecules react at surface sites where oxygen atoms have previously chemisorbed. This provides a direct pressure dependence at low pressures but at high pressures tungsten oxide molecule s form an adjacent gas boundary layer which lowers the PO2 at the tungsten surface. A correction for this effect using free-convection theory fits the rate data over the entire oxygen-pressure range from 10-8 to 1 atrn as well as data using O2-A mixtures. Below 10-6 atrn and above 2000°C, e decreases with increasing temperature because of desorption of oxygen atoms. Below 2000°C the rate decreases with decreasing temperature at all oxygen pressures following an apparent activation energy of 42 kcal per mole and depending on (Po2)n with n varying between 0.55 and 0.80. MOST of the previous tungsten oxidation studies have employed gravimetric methods and have been limited to temperatures below 1000°C where the weight loss associated with evaporation of tungsten oxides is negligible compared with the weight gain from oxidation.' At higher temperatures, oxygen-consumption rates have been determined from pressure measurements, usually at constant flow rates, by Langmuir,2 Eisinger,3 Becker, Becker, and Brandes,4 and Anderson.5 The sensitivity of this method decreases with increasing pressure and, with the exception of Langmuir's work, these investigations were confined to pressures below 10-6 atm. Above approximately 1300°C, depending on the oxygen pressure, the rate of oxide evaporation is greater than the oxide-formation rate and the recession of the tungsten surface can be measured optically without interference from an oxide layer. This was first done by Perkins and crooks6 who heated tungsten rods in air pressures from 1 to 40 torr at temperatures between 1300" and 3000°C. The present investigation of the oxidation kinetics of tungsten at high temperatures emphasizes oxygen pressures from 10-6 to 1 atm. This is the range of interest for earth atmosphere re-entry applications of tungsten for which little data were previously available. APPARATUS The apparatus is a modification of the type used by Perkins and crooks.' Ground tungsten seal rods, 6 in. long by 0.125 in. diam, were mounted vertically between two water-cooled electrodes, one fixed and the other having free vertical travel. The movable counter-weighted electrode is prevented from undergoing horizontal displacement by three sets of runners mounted at 120-deg intervals. Electrical contact is made by means of a water-cooled mercury pool. A 24-in. vacuum bell jar having a volume of approximately 267 liters was used as the reaction chamber with the sample holder mounted in the middle of the chamber. Power was supplied from an 800-amp dc variable power supply. Temperature readings were made by means of a Latronics automatic two-color recording pyrometer. With this instrument, corrections for emissivity are not necessary provided the spectral emissivi-ties at two closely spaced wavelengths are equal. Supporting measurements were made with a micro-optical pyrometer corrected for emissivity of bare tungsten and window absorptivity. The micro-optical pyrometer was calibrated against a National Bureau of Standards calibrated tungsten lamp and both pyrometers were periodically checked against the melting points of tungsten and molybdenum using the oxidation apparatus. Above 10-6 atm, pressures were measured with an Alphatron gage calibrated against a McCleod gage. At 10-6 atm, a hot-filament ionization gage was employed. A magnified image of the self-illuminated tungsten rod was formed using a 360-mm objective lens mounted outside the bell jar. When the experiment exceeded 1 hr, the image was focused on a ground-glass plate about 10 ft from the tungsten rod at about X8 and the recession of the thickness of this image was monitored with a Gaertner cathe-tometer. When faster rates were encountered, a 35-mm time-lapse cinecamera with a telephoto lens and bellows extension was substituted for the ground-glass plate and cathetometer. Diameter recession rates were determined from the photograph image projected on the screen of an analytical film reader. EXPERIMENTAL PROCEDURE After installing the rod in the apparatus and cleaning it with acetone, the system was evacuated to 5 1 x 10-5 torr. Before oxygen was introduced,

Jan 1, 1964

By E. I. Larsen

Powder metallurgy has been described as being "as old as the pyramids and yet as new as the latest bomber." While this may be true literally, it has been only in the last Io or 1 5 years that widespread use has been made of this method of fabricating various articles One of the first items fabricated by powder metallurgical methods on a commercial scale was electrical contacts, which were fabricated from metal powders as early as 1920. The reason why these contacts have been made for so many years by powder metallurgy is because the compositions of most of these materials arc such that they could not be made by the conventional methods of melting, casting, rolling, drawing, etc. Classes of Contacts In general, electrical contacts fabricated from metal powders fall into two classes, both from the point of view of the method of fabrication and the components that make up the chemical composition. One class is composed of silver or copper and a refractory metal such as tungsten, molybdenum, or compounds thereof such as carbides. The second class contains a predominant amount of silver and a semi-refractory material such as cadmium oxide, nickel, cobalt, or graphite. Electrical contacts of the first class have been developed primarily as facing materials for heavy-duty circuit-interrupting devices. This class of material unites the high melting point, high boiling point, great resistance to electrical erosion, and the refractory characteristics of molybdenum, tungsten, or their carbides with the high thermal and electrical conductivities and low contact resistance properties of silver or copper. The second class of material is used for lighter duty or specialized applications such as heavy-duty, direct-current aircraft relays. Varieties Electrical contacts fabricated from metal powders are made in a wide variety of compositions, shapes, and sizes. In general, the sizes of electrical contacts fabricated from powders vary from contacts weighing approximately 0.001 oz. up to those weighing 3 to 4 Ib., the contacting face being as small as 0.001 sq. in. up to approximately 6 sq. in. in area. The shapes consist of: sound or rectangular buttons, some of which have radii or bevels on the contacting faces; rings, cups, rectangular bars, the contact face of which may have a radius across the width and/or at one end; and form-pressed pieces of a wide variety such as angles, both acute and obtuse, irregular shapes comprising a radius blended into a flat, which in turn may have steps. The size or shape of the contact is dictated principally by the mechanical design of the manufacturer, who in turn may have problems to be met such as: (I) size, weight, or space limitations; (2) electrical conditions such as blowout coils arc chutes, baffies, gas passages.

Jan 1, 1945

By G. L. Craig

In order to meet the unprecedented demand for copper it has proven necessary not only to develop every primary source, but also thoroughly to exploit the vast reservoir of metal in use that is not directly serving the war effort. To accomplish this, industry has been called upon to use its resourcefulness for developing methods of recovery that have not been previously utilized. It is in this connection that we have been asked to review the methods suggested for recovering the basic constituents of various types of the so-called clad or composite steels. As a background for a discussion of recovery processes, it seems appropriate to consider clad materials in general and their processes of manufacture. A composite steel has been defined as one consisting of two or more component parts of which the smallest shall comprise at least 3 per cent of the total mass. Clad materials or composites are produced commercially by several different methods of which the most important may be classified as: I. The Blacksmith or Forge Weld Method. This method is limited to carbon steels or low-alloy steels as the presence of even small amounts of common alloying metals prevent the formation of a satisfactory weld. The principle is the application of pressure to sections in contact at elevated temperatures. Because of the tendency of the iron to oxidize, borax is generally used as a flux to absorb the iron oxide. 2. Casting Process-In this method a composite ingot, billet or cake is produced by pouring one metal onto or about another. The bond may be accomplished by the action of the molten metal against a solid, in which case the bond may be referred to as mechanical; while in other instances alloying occurs at the interface producing an anchor by the formation of component parts of the two materials. 3. Cementation Process.-In this process any number of combinations of metallic and nonmetallic constituents which are mixed together may be used as a bonding agent. The combinations, whatever they may be, are placed between the materials to be joined and subjected to pressures at elevated temperatures to produce the desired bond. 4. Fusion Welding Processes.-Gas and electric joining for direct use or subsequent fabrication. 5. The, Assembly Process.-This method involves the joining together of prefabricated bars or plates followed by hot and/or cold working the assembly to the desired finished form. This method is advantageous in many cases because of its flexibility on small quantities as compared to the casting method. It is also possible to control the relative proportion of components more accurately. In this discussion we are concerned only with the scrap resulting from the manufacture of clad materials and our interest,

Jan 1, 1943

By C. J. McHargue, J. C. Ogle

Lightly deformed columbiun single crystals which contained only parallel hoins or purullel and intersecting trains were annealed at 1000' and 1600"C. No re-crystallizntion occurred in specimens hawing only parallel twins. Only noncoherent twin boundaries nzipated at 1000°C but both coherent and noncoherent ones moved al 1600°C. Recrystallization occurred within a few minutes at twin intersections at 1000°C. The orientation 01 the recrystallized grains differed front that of both the matrix and deformation twins, but could he derired by (110) and/or(112) rotations. ALTHOUGH twinning in metals has been extensively studied, there have been no definitive studies of the annealing behavior of crystals containing deformation twins. Some effects observed after annealing deformation twins have been summarized by Cahn1 and Hall2. Any or all of these phenomena are observed: 1) The twins may contract so that the sharp edges of the lens become blunted, and eventually the twin may disappear entirely. 2) The twins may balloon out at an edge, giving rise to a large grain having the same orientation as the twin. 3) The specimen may recrystallize; i.e., new grains are nucleated and grow at the expense of the twins and the crystal immediately adjoining the twin. Such grains have orientations which are not present before. Contraction has been observed in iron,3 titanium,3, 4 beryllium,5 zinc,8, 7 Fe-A1 alloy,' and uranium.9 Long anneals at high temperatures are required to have any appreciable effect in these metals and only thin twins are absorbed. Lens-shaped twins are absorbed from the edges: the thin, almost parallel-sided twins are usually punctured in several places and each piece contracts independently. Absorption is very gradual and no sudden cooperative jumps have been observed. The expansion of a twin into a larger grain of identical orientation is unusual, but such growth has been observed in iron,"'" zinc,6 and uranium." Crystals which have been deformed simultaneously by slip and twinning recrystallize first in the area adjacent to the twin. New grains appear faster where the twins intersect: but isolated twins, especially if thick, can also give rise to new grains. This type of recrystallization occurs in zinc.6, 7, 12, 13 and beryllium.14 Reed-Hill noted, in a single crystal of magnesium, the nucleation of a recrystallized grain at a twin intersection which had the same orientation as the second-order twin and which grew into the highly strained matrix.15 Short-time annealing has been reported to cause no change in the deformation twins in vanadium,16 columbium, 17, 18 tantalum,19 tungsten,'' and zinc.7 The purpose of this investigation was to note the effects of annealing on the coherent and noncoherent boundaries of deformation twins in columbium and to locate the nucleating sites for recrystallization. The orientation relationships, which the new recrystallized grains have with the parent crystal and the deformation twins, were also determined. EXPERIMENTAL PROCEDURE Single crystals of columbium were obtained by cutting large grains from electron-beam-melted buttons which contained 10 to 50 ppm C, 10 to 100 ppm O,, 1 to 10 ppm H2, and 10 to 15 ppm N2. The crystals were hand-ground and chemically polished until all grain boundaries were removed. The specimens were mounted in an epoxy resin and a face of each crystal was mechanically polished on a Syntron polisher using Linde A and then Linde B polishing compounds. After all faces were mechanically polished, the crystal was electrolytically polished to remove all distortion due to cutting and grinding. Laue photographs were taken of all faces of the crystals to determine the quality and orientation of each crystal. The crystals were compressed about 10 pct at -196 C in a specially constructed compression cage with an Instron tensile machine. Each crystal was separated from the top and bottom anvils by teflon films which acted as a lubricant. With the specimen crystal in position, the entire cage was cooled to -196°C by being submerged in a Dewar containing liquid nitrogen. The crystals were compressed at a rate of 0.02 in. per min and the load was recorded on a strip-chart recorder. After deformation the crystals were mechanically polished on 600-grit paper and Pellon cloth with Linde A and Linde B polishing compounds. The crystal faces were chemically polished and then etched. The twin planes were identified metallographically from an analysis of the twin traces on two surfaces. Annealing was carried out by placing each crystal in a columbium bucket made from the same electron-beam-melted material as the crystal itself and suspending the bucket by a tantalum wire in a quartz tube. After a vacuum of 10-7 Torr was attained, a furnace at 1000" or 1600 C was raised into position and the crystals held for various lengths of time. The crystals were repolished and etched after annealing to remove any surface contamination. Approximately 0.010 in. was removed during this process. The resulting surface was examined metallographically for microstructural changes due to annealing. A microbeam Laue camera mounted on a Hilger Micro-focus X-ray unit was used to determine the Orientstions of the recrystallized grains. This X-ray micro-beam camera had a 0.002-in.-diam collimator and incorporated the ideas of both and and chisWik21 and Cahn.22

Jan 1, 1967

By J. N. Hobstetter

It is widely believed that the nucleation of phase transformations in solid metals is accomplished by some type of local atomic fluctuations in the parent phase which arise from spoutaneous difiusion in the metal or alloy system. Under appropriate conditions, these fluctuations are believed to be stable in the sense that the free energy of the entire system is lowered if the fluctuations, or nuclei, grow. Under other conditions they are thought to be unstable in the sense that the free energy is lowered if they redissolve. The criterion for stability is usually taken as the size of the fluctuation. This view has been rationalized by Beckerl in terms of the free energy released by the volume of the nucleus and the free energy associated with the formation of a new surface surrounding the nucleus. The qualitative result of this reasoning is shown in Fig I where the changes in free energy for the surface and volume effects are plotted together with their sum against the radius of the nucleus. There is evidently always a critical size r, beyond which the release of free energy which is proportional to the volume always dominates the increase of free energy which is proportional to the surface area. Borelius2 has also attempted to rationalize the stability criterion for binary alloys, but in terms of the internal concentration of the fluctuations. He has found that, if surface energies are entirely ignored, the fluctuation must still reach a critical concentration if it is to become stable and avoid subsequent dilution. Although the Borelius theory fails to predict many observed nucleation phenomena such as the vanishing of the nucleation rate at the critical temperature, the major premise must certainly be valid. In this paper a reconciliation of the Becker and Borelius views is made by means of a search for nuclei which are at once stable with respect to both size and internal concentration. The increase in free energy per mole accompanying the formation of a nucleus which is just stable, AF., is independent of the path whereby the nucleus is brought into being. It is thus appropriate to seek critical nuclear attributes without reference to the fluctuation mechanism. The rate of nucleation, however, cannot be treated without a detailed understanding of the exact fluctuation process which produces stable nuclei. In this and succeeding papers the purpose will be to find the size, shape and internal concentration of the stable nucleus which is formed with a minimum increase in free energy in a wide variety of systems. The Nature of the Nucleus It is necessary ti have rather detailed knowledge of the nature of a nucleus if AF, is to be computed. Fortunately, enough facts are known or suspected about the nucleus to make possible a detailed analysis. X ray diffraction studies have shown

Jan 1, 1949

By W. G. Pfann

THE problem of forming points on wires that were from 0.002 in. to 0.010 in. in diam arose in the recent appearance of silicon and germanium point contact rectifiers as elements in microwave radar.1 In these devices a pointed tungsten wire makes a delicate contact with the surface of a semiconductor. Because the quality of such rectifiers is largely determined by the nature of this contact, considerable attention has been given to the formation of the metal point. Reproducibility of contour and freedom from burrs and even microscopic irregularities are considered essential. The operations involved must be simple and rapid enough for mass production. Previously tungsten wires had been provided with conical points by a grinding method which involved rotating a wire about its axis and causing it to bear at an oblique angle against a spinning abrasive disc. This was later complemented with an electrolytic polishing treatment which removed irregularities from the ground point and also rounded it off at the tip-a desirable feature. Finally, these operations were supplanted by the electrolytic pointing method described here. MECHANISM OF POINT FORMATION The wires to be pointed are partially immersed- in an electrolyte in a .vertical position whereupon they are provided with smooth rounded points entirely by electrochemical action. The process is independent of the depths to which the wires penetrate the electrolyte because the points are formed at the surface level. It may be used to point a single wire or many of them simultaneously and is applicable to wires of different diameters within a limited range. Solution of the immersed portion of a tungsten wire is accomplished by making it the positive electrode in an electrolytic cell, as shown in Fig I. While the wire is maintained at constant voltage the current through the cell falls continuously, principally because of the decrease in wetted area which results from solution of the tungsten. This increase in resistance occurs in a reproducible manner and is used as a control in the process. As the immersed portion of the wire dissolves, it remains cylindrical in shape except for the short section which is wetted by the meniscus. Here the rate of solution is lower and decreases as the top of the meniscus is approached. The result is the formation of a tapered section inside the meniscus. As solution continues, the cylindrical section either dissolves entirely or drops off just before complete solution, leaving only the taper which is now sharply pointed. Further action causes this point to become rounded and then quite blunt, until finally the end of the wire is almost plane. Fig 2 shows the stages in this development. Contour PF is most representative of those used in point contact rectifiers. Thus a variety of point

Jan 1, 1947

By S. Whinery

I am indebted to L. E. Bryant, of Danville, Ky., President of the Virginia Mining Co., operating coal-mines in Scott county, Tenn., for the following information relating to the existence of the Clinton iron-ore under the NW. slope of the Cumberland Plateau in Kentucky and Tennessee. During the past 15 years quite an important oil-field has been developed in a region having Wayne county, Ky., as its center, and a large number of wells have been drilled in that and adjacent territory in the search for oil. Many of these wells have been carried to considerable depths below the recognized oil-bearing horizon, and one of them was drilled by Mr. Bryant at Pine Knot, a station on the Cincinnati, New Orleans & Texas Pacific railroad, a few miles north of the point where that road crosses the Kentucky-Tennessee State-line. The elevation of

Jan 1, 1913

By O. W. Bilharz

INTRODUCTION ACID mine-water drainage is a serious problem with many mines in the Tri-State zinc and lead mining district. Particularly is this true when large volumes must be considered in unwatering old mines that have refilled with water which has dissolved the products of oxidation and has become chalybeate in character. The experiences discussed in this paper have to do specifically with the unwatering of a comparatively small area west of the town of Baxter Springs, Kans., where the pumping job was complicated by water of this type and where the extremely high sulphate content particularly effected that phase of mine drainage having to do with stream pollution. LOCATION, GEOLOGY AND HISTORY The Baxter Springs area of the Tri-State mining field is situated just west of the town of Baxter Springs and is a northeasterly extension of the main mineralized zones of the Oklahoma part of the district (Fig I). The mining area is traversed with well defined shear zones which provide easy circulation of ground waters and the ore bodies are found along these shear zones as localized enrichments wherever the structural conditions are favorable (Fig 2). The ore-bearing strata is Mississippian with an overlain capping of shale of Pennsylvanian age. This shale strata carries much pyrite and marcasite at its base and undoubtedly was a contributing factor to the subsequent high iron content of the water. The area originally contained a sulphide water which discharged as an artesian flow in springs within the town and gave Baxter Springs its name. These springs were famed for many years for their mineral water. This original sulphide water was first removed about 1917 and active mining was carried on west of the town during subsequent high metal price periods. Many small mines were opened, with each localized enrichment becoming a separate mine. During the depression mining ceased and all mines in the west Baxter area were allowed to flood. No serious effort was made to again unwater until higher prices caused from the demand for metal for World War II once more focused attention on this part of the field. ORIGINAL MINING RESULTS IN OXIDATION As plans for unwatering progressed, it soon developed that the mine-water pools had become strongly acid in character and carried large amounts of sulphates in solution. This occurred in the following way. When the original sulphide water was removed, shafts sunk, and mining carried on over a number of years, ferrous sulphate was formed by the spontaneous oxidation of the pyrite beds in contact with air admitted through churn-drill holes and mine openings. These products of oxidation can be seen today in the old mines of the district as crusts of crystalline sulphates

Jan 1, 1947

By R. F. Krueger

Results are presented from tests of dynamic fluid-loss rates to cores from clay-gel water-base drilling fluids containing different commercial fluid-loss control agents (CMC, polyacrylate or smt,ch), organic viscosity reducers (quebracho and complex metal lignosulfonate) and oil at several different levels of concentration. In the dynamic system the most effective individual additives to the clay-gel drilling fluid, based on cost-equalized concentrutiom, were found to be starch and the viscosity reducers. These results do not conform with the rankings determined by API fluid-loss rests, which indicate CMC, polyacrylate and starch to be the most effective and comparable. Generally, minimum dynamic fluid-losr rates were attained at cost-equalized concentrations of additive (including thinner) of about $1.00/ bbl, or less. For chernically treated clay-gel drilling fluids, both the standard and the high-pressure API filter-loss tests were found to he inaccurate indicators of trends in dynamic fluid-loss rates under the test conditions used, particulurly for drilling muds containing viscosity reducers. From a practical field viewpoint, restrictions on the applicability of the API fluid-loss test are such that it is open to question whether or not results of this test can be used routinely with confidence as an indicator of control of down-hole fluid loss under field treating conditions. INTRODUCTION The petroleum industry spends large sums of money during drilling operations to control the fluid-loss properties of drilling fluids based on the standard API filter-loss test,' which is a static filtration system. Laboratory studies' ' of dynamic filtration have shown that in a given time period filtrate loss from a circulating mud stream is greater than from a static system and that it is a function of linear mud velocity, pressure and the properties of the drilling fluid. Ferguson and Klotz' and Horner, et al," observed that (I) the dynamic fluid-loss rates for the drilling fluids used were not related to the extrapolated API filter loss and (2) the drilling fluids with the lowest API filter losses did not have the lowest dynamic fluid-loss rates. However, there has been no published information on the relative effects on dynamic fluid-loss rate as a given drilling fluid is treated with increasing amounts of chemical additive to reduce the API filter loss. Such information is economically important because drilling-fluid costs rise rapidly as chemical requirements increase. This paper presents the results of a study of dynamic filtratioi rates to cores from a clay-gel water-base drilling fluid treated with various commercial viscosity reducers and chemical fluid-loss control agents. The dynamic fluid-. loss rates to cores are compared with the standard API filter-loss values at several different levels of additive concentration. Dynamic filtration rates were obtained in each experiment under two different simulated wellbore conditions: (1) filtration just above the bit through a new mud cake laid down dynamically on a freshly drilled formation and (2) filtration up-hole through a mud cake formed by deposition of a static filter cake on top of the initial dynamically formed cake. The latter case corresponds to the bottom-hole conditions existing above the bit when mud circulation is restarted after a stand of pipe has been added or a round trip has been made to change the bit. Except for the short-duration, high-rate filtration beneath the bit where no mud cake can form, these two conditions probably represent the two extremes of dynamic filtration. Because thickness of a dynamic mud cake formed on freshly exposed formation is limited by the shearing action of the mud stream, the filtration rate for this condition is high. On the other hand, once circulation is stopped and a static mud cake forms on top of the dynamic cake, re-starting circulation has only a small effect on the cake properties and filtration rate is much lower thereafter. A discussion of the mechanics of mud-cake deposition and dynamic filtration is outside the scope of this paper but may be found in more detail in publications by prior investigators. APPARATUS AND EXPERIMENTAL CONDITIONS The test equipment used to simulate the dynamic flow conditions existing during drilling was a modification of that described previously by Krueger and Vogel: A schematic flow diagram is shown in Fig. 1. In general, a power-driven, high-pressure mud pump capable of delivering up to 60 gallmin was used to circulate drilling fluid parallel to the faces of 1-in. diameter sandstone cores mounted in a 2 3/4-in. ID high-pressure test cell. Pump rates were controlled by means of a magnetic clutch to maintain an average axial fluid velocity of 110 ft/min in the annular space between the cell wall and a 1 1/2-in. rod positioned on the center line of the cell. The core specimens were Berea sandstone plugs sealed with plastic inside 1 1/8-in. OD tubes and were fluid-saturated prior to use. Burettes were used to accumulate fluid discharged from the cores. The mud sump shown was used for treatment and storage of the drilling-fluid samples during a particular test. The valve arrangement permitted either (1) circulating drilling fluid through the by-pass line while treating with

By N. Brown

From the theories of flow and fracture it is shown that the difference in reciprocals of the transition temperatures (OK) is a quantitative measure of temper ernbrittlement. Experimental data are given which support this conclusion. STUDIES of temper embrittlement have been made with various viewpoints; some involved a study of the kinetics of the reaction,',2'" others were concerned with changes in the mechanical properties," . and still others investigated the structural differences between the embrittled and unembrittled states by means of the microscope," -ray ,' measurements of electrode potential," and electrical resistivity." In all these studies, the difference in impact properties was the criterion for distinguishing between the embrittled and unembrittled states. By common agreement the difference in transition temperatures is now taken as a measure of the degree of embrittlement, and this measure is used as the quantitative measure upon which studies of the phenomenon are based. Vidal and Jolivet"' suggested that the degree of embrittlement was the same whether measured by impact or by a slow bend test. Their conclusion was based on tests at constant temperature. Jaffe and Buffum" using the impact and slow bend test showed that, for a given degree of embrittlement, the difference in transition temperatures varied with the method of testing. Hultgren and Chang" showed that the difference in transition temperature produced by the V-notched Charpy impact test was not the same as the value produced by the keyhole-notched impact test. This is a very fundamental point because there can be no true measure of temper embrittlement unless it is invariant with respect to the test method. Theory The purpose of this analysis is to show how the transition temperature depends on the stress distribution and the state of the material. The criterion for fracture may be stated as follws: where iF is some function of the principle stresses and F is a critical condition depending on the state of the metal. Similarly yielding occurs when Where is another function of the prin-ciple stresses and Y is a critical value depending on the state of the material. There is some controversy as to the exact form of the function f,.(u,, u,, us) but most experimental data give the following criterion:= where 8, and 6, = 21 or 0. Combinations of 6, and 8, give the various criteria such as the normal stress, the hydrostatic tension, and the maximum shear stress laws. Agreement is general that the octahedral shear stress law adequately describes the yield condition. where the bracketed factor will be called the design factor and depends on the stress distribution. Whether the metal decides to yield or fracture is given by the condition that The effect of temperature and strain rate upon Y has been studied by various investigators, It has been shown by MacGregor and Fisher" that

Jan 1, 1955