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By N. J. Grant, D. S. Bloom

An investigation of the Cr-Mo-Ni ternary system and attendant binaries has been completed. Some changes in the binary diagrams are shown to be necessary. The 1250°C section of the ternary and the liquidus surface have been delineated. A system of invariant reactions existing above 1250°C has been suggested. BECAUSE chromium, molybdenum, and nickel are important not only as bases for alloying systems but also as major alloying additions for other refractory metals, a study of the phase diagrams is of great interest and importance. In addition there are interesting features of theoretical value, a number of which are of prime consideration in this work. The major aim was to determine the ternary phase diagram of these metals at and above 1250°C, with sufficient attention given to lower temperatures to permit an understanding of the conditions existing at 1250°C and above. To understand ternary systems it is essential that accurate information concerning the binary systems be available, which in turn presupposes thorough knowledge of the constituent elements. On the basis of this investigation not only were significant inaccuracies indicated in the binary systems but much consideration had to be given to one of the elements, that is, chromium. The observation has been made that chromium undergoes a crystal transformation at a temperature near its melting point. Much of the experimental data leading to the detection of this transformation and the effects of this hypothesis on the form of the Cr-Ni phase diagram have already been reported' . and will not be repeated here. The experimental methods employed in the investigation have also been covered.'-" he purity of the molybdenum utilized in this work showed by qualitative spectrographic analysis that chromium, copper, iron, silicon, and tungsten were present in quantities of 0.1 to 0.001 wt pct. During the course of the investigation more than 100 melts were made, weighing from 150 to 200 grams each. Each of these melts was sectioned for chemical analysis and for specimens for examination in the as-cast and various heat-treated conditions by X-ray and metallographic means. All X-ray diffraction patterns reproduced here were made using chromium Ka radiation although iron and copper targets were used on occasions during the investigation. Experimental Results Mo-Ni-System: The most recent comprehensive investigation of the Mo-Ni system was made by Ellinger' in 1942; the diagram as shown in the American Society for Metals Handbook is based on his work. The work done on the system in this investigation substantiated the general form of the diagram although some differences were observed. These are indicated by a comparison of Ellinger's diagram and Fig. 1, the latter showing the results of pertinent thermal analyses made in this research. It can be seen in Fig. 1 that the eutectic composition is

Jan 1, 1955

By J. G. Richardson, K. H. Coats

During the initial growth of a gas bubble in an aquifer storage reservoir the injected gas tends to override the water. The resulting low displacement efficiency and high rate of gas travel down-structure make it difficult to maintain water-free production. This paper illustrates the use of two-dimensional, two-phase calculations to simulate this gas-water displacement. Calculations were performed for a stratified aquifer and for several homogeneous sands differing in permeability, porosity and thickness. Results are discussed and compared with performance predictions obtained from the simpler Buckley-Leuerett and Dietz formulas. This comparison indicates the necessity for the two-dimensional calculations in realistically simulating the gravity override of the water by injected gas. INTRODUCTION In recent years natural gas has been stored near markets in aquifers where insufficient storage capacity is available in depleted fields. Operators of these aquifer storage reservoirs have encountered technical problems relating to the gas-water displacement accompanying initial growth of the gas bubble. Injected gas tends to override the water, with a resultant low displacement efficiency and high rate of gas travel down-structure toward spill points. Low displacement efficiency makes if difficult to sustain water-free gas production. Sometimes the fingering of gas down-structure may be so pronounced that the injection rate must be severely curtailed, which excessively lengthens the time required for bubble growth. This paper is concerned with estimating — for given aquifer characteristics and fluid properties — the displacement efficiency, rate of gas movement down-structure and rate of gravity drainage of water behind the gas front. Several published articles relate to simulative capability necessary to handle this problem. The Dietz formula1 and Buckley-Leverett2 method have some applicability to the problem; Woods and comer3 reported one-dimensional, radial calculations which accounted for the two-phase flow of gas and water. Most recent research directed toward understanding aquifer behavior in relation to gas storage has concentrated on single-phase flow in aquifer.4 Douglas, Peaceman and Rachford5 presented a method for calculating multidimensional two-phase flow in reservoirs; their method has been applied in work reported by Nielsen and Tek,6 Blair and peaceman7 and Goddin.8 Refs. 5 and 7 show comparisons between experimental data and calculations similar to those employed here. One purpose of this paper is to illustrate the use of two-dimensional, two-phase flow calculations in simulating the difficult problem of water displacement by gas in a vertical cross-section. The pronounced fluid density and viscosity differences combine with the disparity in horizontal and vertical dimensions of the cross-section to pose one of the more difficult problems in reservoir simulation. The calculations described account for capillary and gravity forces, relative permeability and reservoir heterogeneity. An example reservoir is described and calculated results are presented for a variety of injection rates and values of permeability, reservoir thickness and dip angle. A second purpose is to compare the two-dimensional calculations with results obtained from the Buckley-Leverett and Dietz formulas. For this reason most calculations were performed for a simplified example reservoir to which the latter techniques might reasonably be applied. However, the computer program employed applies equally well to cases involving arbitrary spatial variations of permeability, porosity, reservoir thickness and dip angle.

By E. W. Davis

The: mysterious Lake Erie price for iron ore, established each spring, determines the maximum price that will be paid during the following season for ore of Mesabi Non-Bessemer base grade. This price is important to the ore producers, hut since most of the ore in the Lake Superior district is owned or controlled by consuming interests, the really important question to them is not the price of ore but how much it will cost them to mine and transport their season's requirements to their furnace plants. However, a few million tons are actually sold each year, and considerable quantities are traded for mixing purposes, and the negotiations lor these sales and trades usually begin with some reference to the Lake Erie price. There is no difficulty with the Lake Erie price itself or with the manner in which it is established, but the system prescribed for determining the values of ores that are not exactly base grade is incomplete. The Lake Erie price takes into consideration only the iron and phosphorus contained in the ore, but when the ore producer is negotiating a sale or trade, he is confronted by the fact that his ore must he studied and the price adjusted, not only on the basis of the iron and phosphorus analyses, as specified by the Lake Erie price, but also on the basis of silica! alumina, manganese, structure, etc. The vague and unsatisfactory methods used in making these adjustments bear some relation to the manner in which the ore is supposed to act in the blast furnace. The ore producer may not understand all of the idiosyncrasies of the blast furnace, but if the smelting-plant operators have a system more accurate than the Lake Erie price method for determining the relative values of different ores, why not pass this information on to the ore producers, so that they can make use of it and perhaps modify their practice in such a manner as to benefit both themselves and their customers? There is a lack of understanding and appreciation between these two groups that may, to some extent, be unavoidable, but in the interests of efficiency and conservation rules that are more accurate and complete than the Lake Erie price method in use at the present time should be established for the guidance of the ore producers. Recently a paper was read before the Eastern States Blast Furnace and Coke Oven Association, by Mr. G. W. Hewitt, Manager Production, Blast Furnace and Coke Oven Department, Wheeling Steel Corporation, in which he explained how his company determines the relative values of different grades of Non-Bessemer ore. This is a very important paper, perhaps not so much on account of the actual calculation methods described as because of the fact that premiums and penalties are shown on Non-Bessemer ores for silica, alumina, phosphorus, and manganese. As pointed out by Mr. Hewitt, the premium and penalty system described may not apply without adjustments to other smelting plants. However, if the various ore

Jan 1, 1941

By R. Frenkel, O. D. Sherby, J. E. Dorn, J. Nadeau

A method is shown for the study of the creep rate dependence of metals on the applied stress under the condition of constant structure. The method was applied to pure aluminum and to dilute solid solution alloys of magnesium, copper, germanium, zinc, and silver in aluminum. A linear relationship was found to exist between the true stress and the logarithm of the creep rate. ALTHOUGH extensive creep data are now avail-Aable, the fundamentals of the creep phenomena are as yet only vaguely understood. Many attempts have been made to formulate theories for creep. Eut their agreement with fact has been disappointing. It appears that merely pyramiding more of the same type of data that is now available will not provide the essential aid toward formulating a better understanding of the complicated process of creep. Perhaps attempts to construct better models for the mechanism of creep might have to be tentatively abandoned until new types of definitive creep data are uncovered. The question therefore arises regarding what type of data might be needed to provide the essential knowledge for formulating better and more realistic theories of creep. Perhaps one source of the failure to uncover an adequate theory arises from the fact that practically all theories for creep and nearly all analyses of experimental data on creep disregard the well-known fact that the structure of metals changes during creep. For example, it is customary in evaluating the effect of stress on the creep rate to correlate the secondary creep rate with the applied stress. But, as has been demonstrated recently,' the structures obtained during secondary creep tend to exhibit deformation banding at high stresses and polygoniza- tion at the lower stresses. Consequently the stress-secondary creep rate relationships found in this way are not fundamental, inasmuch as they reveal not only the effect of stress but also the effect of differences in structure on the secondary creep rates. It is the purpose of the study reported here to isolate the effect of stress alone on the creep rate in an attempt to provide new data for possible formulation of a better theory of creep. In addition an attempt will also be made to ascertain how structure, temperature, and alloying might affect the stress-creep rate relationship. The procedure that was adopted was simple: A specimen was precrept at a given engineering stress U, (initial engineering stress during creep under constant load, namely the load divided by the initial area of the specimen) and temperature T to a selected engineering strain, e (engineering strain, namely, the instantaneous gage length minus the initial gage length divided by the initial gage length), at which time the true stress was reduced to some lower value of the true stress, ^ (the true instantaneous stress, namely, the load divided by the instantaneous area). The instantaneous true creep rate, i, (the true strain rate; with E, the true strain, namely, the natural logarithm of the instantaneous over the initial gage length) following reduction of the true stress to U, was then determined. Second, third, etc., tests were conducted under identical conditions except the stress was reduced to yet lower values, us, u,, yielding yet lower instantaneous creep rates, ;, and i,. Inasmuch as the precreep conditions were identical in each series of tests, the instantaneous structures obtained immediately after reducing the stress were presumed to be identical.

Jan 1, 1955

By C. L. Meyers, J. L. Lytton, T. E. Tietz

The recovery of tensile flow stress of 99.995-pct Al and Al-1 pct Mg alloy was investigated using a fractional recovery parameter. Tensile strainirg was conducted at room temperature, and recovery treatments were made in the range from 80° to 200°C. Equal values of fractional flow stress recovery were found to result in equivalent structural states. Identical recovery treatments were found to produce constant values of fractional flow stress re covery, independent of prestrain. The activation energy for recovery of the 99.995-pct A1 between 80" and 200°C was found to be 23,000 +2000 cal per mole, and the activation energy for the Al-1 pct Mg alloy was 27,500 cal per mole. 1 HE degree of recovery of a cold-worked metal may be studied by measuring the changes which take place in any of a number of properties. Some of the properties which have been used by past investigators include X-ray diffraction phenomena, electrical resistivity, hardness, creep strength, elastic limit, and flow stress. Despite the apparent preponderance of such studies, little is known concerning the effect of recovery on the strength of metals except as deduced from changes in various types of hardness measurements. Furthermore, little information is avail- able concerning the effects which specific solute atoms have on the recovery process. Limited studies have indicated that in some cases solid-solution additions greatly decrease the rate of recovery,' whereas in at least the case of magnesium additions to alluminum an increase in the rate has been reported.2 The purpose of this investigation was to determine the effect of a 1 pct Mg addition on the recovery of high-purity aluminum. Because of the particular interest in the effect of solute additions on the recovery behavior as related to mechanical properties, the degree of recovery was evaluated in terms of tensile flow stress. For the purposes of this study, a recovery process shall be defined as any process, short of recrystallization, whereby the properties, of work-hardened metals tend toward their values ill the unstrained state. EXPERIMENTAL PROCEDURE Test Materials. The materials used in this study were a 99.995-3 A1 and an Al-1 pct Mg alloy made from high-purity base metal. The high-purity aluminum contained the following wt pct impurities: 0.001 pct Cu, 0.002 pct Fe, 0.001 pct Si, and 0.0004 pct Mg. The Pil-1 pct Mg alloy contained 0.001 pct Cu, 0.002 pct Fe, 0.003 pct Si, and 0.99 pct Mg. Both materials were obtained in the form of as-rolled 0.125-in.-thick sheets, from the Alcoa Research Laboratories, New Kensington, Penn. Tensile specimens were cut from these sheets with the longitudinal axis in the rolling direction. Both materials were recrystallized in a molten salt bath; the high-purity aluminum at 450° C for 20 min and

Jan 1, 1962

By Herbert H. Kellogg

RECENTLY the long-chain primary amines have been used extensively for the flotation of silicate minerals. The use of amines to float sulphide minerals has been investigated by several authors1-5,18 but most of this work has been done with the short-chain (less than six carbon atoms) primary amine compounds or the more expensive secondary, tertiary and quaternary amines. Perhaps the fact that the long-chain amines are good collectors for the common gangue minerals has led investigators to omit them from consideration as collectors for the selective flotation of metallic sulphides. The work reported in this paper was designed to investigate the use of a typical long-chain amine salt, lauryl amine hydrochloride, as a collector for the flotation of galena-sphalerite ores. The results show that lauryl amine hydrochloride (LAmHCI), when used in small amounts, is a good collector for the selective flotation of sphalerite and galena from the common gangue minerals. The differential flotation of sphalerite from galena was not accomplished but the amine flotation of sphalerite after the standard xanthate flotation of galena is possible. The experimental work reported herein is not complete enough to be able to say whether amine flotation of lead-zinc ores would prove superior to xanthate flotation, or whether the method is even applicable to a more complex ore than the one used for this work. However, the apparent reagent costs for the flotation operations described in this paper seem to be less than for xanthate flotation. This fact alone should be sufficient to encourage the millman to investigate the use of these amine reagents, especially as these reagents are available on a commercial scale at a reasonable price. This paper has as its secondary purposes to illustrate how contact-angle measurements have aided in this investigation, and to bring forward some evidence concerning the mechanism of the collecting action of primary amines. CONTACT-ANGLE TESTS The contact-angle measurements were made by the method described by del Giudice6 and used in recent work by Taggart and his collaborators.7-9 The mineral specimens for the contact-angle tests were carefully chosen, to avoid cracks and inclusions of other minerals. All specimens were mounted in "transoptic" plastic mounts and the surfaces were cleaned by polishing with levigated alumina on a cloth-covered glass polishing wheel. Distilled water was used on the lap during the polishing and at all subsequent steps in the contact-angle tests. The mounted mineral specimens were handled with glass forceps and special care was exercised to prevent exposure of the dean surface to air or any other source of contamination.

Jan 1, 1945

C. P. SANDBERG, LONDON, ENG : † I think we should all be grateful to the Pennsylvania Railroad Company, and to their chemist, Dr., Dudley, for spending so much time and money in order to solve an important question ; nor are we less indebted to the public spirit which leads them to impart the experience thus gained. In Europe nothing similar has hitherto been done, either by a company or by any private individual. In England the great railway companies employ their engineers in other ways, and do not keep a chemist or specialist to study rails; but even if they did they would probably not publish the results. The chief professional engineers are so occupied with their private practice of railroad construction generally, that they cannot be expected to devote their time and energies to so special a question. The German Railway Union has, in my opinion, missed the real object of its elaborate researches by falling into the error of specifying costly, impracticable tests for rails-tests at the same time which do not infallibly expose the impurities that may be in the rails under examination. There has, therefore, been nothing done on this side of the Atlantic in the way of exhaustive study to determine the best composition for steel rails. America should consequently have full credit for the enlightened example which she has set. I wish, however, to make a few remarks on Dr. Dudley's second paper, a paper which follows very much upon the same lines of argument as the first read three years ago, upon which I have previously touched in my paper on the same subject read at the meeting in August last. If Dr. Dudley had discovered a new metal he could hardly, I think, have taken more pains to prove that he was correct in his first formula for the best chemical composition of steel rails. But I have seen so much done in the way of proof by experiment that I am inclined to think that almost anything can be proved by experiments and by samples. If Dr. Dudley would only give up his formula, which would not suit any country-not even America- * For the convenience of members it has bees thought best to insert the continuation of this discussion at the Virginia meeting in tide place, rather than to delay its permanent publication until the issue of Volume X, Transactions, where it would properly belong. T. M. D., Sec'y, † Sent to the secretary in manuscript.

Jan 1, 1881

By S. R. B. Cooke, W. Philippoff, Donald E. Cadwell

THE importance of contact angles in flotation has long been recognized, but little has been done to get quantitative relationships between the surface coverage of the mineral by the reagent, the length of the hydrocarbon chain, and the contact angle. It is well known that for a complete monolayer on the surface of a mineral the contact angle 8 is determined only by the reagent1 and principally by the chain length of the hydrocarbon radical. Although for flotation the monolayer usually is regarded as being complete, early experiments of Wark and Cox&apos; showed that at very small concentrations of potassium ethyl xanthate the contact angle on galena changed in a continuous way from 0&apos; to the equilibrium value of 60". Further, Gaudin and Vincenta showed a similar continuity using heptylic acid and sphalerite. This shows that with probably incomplete monolayers, 0 varies with the degree of surface coverage. At the time these experiments were made it was impossible to measure the actual amount of surface coverage, especially since the decrease of the collector concentration in the liquor could be influenced by chemical side reactions. Through the use of the radioactive tracer method for the measurement of the amount of collector adsorbed on the surface of the mineral, Gaudin and Bloecher&apos; were able to determine accurately the actual surface coverage of dodecylamine acetate on quartz, but they did not measure any contact angles. It is believed that the relationship between the surface coverage and the contact angle is extremely important in flotation, especially as Gaudin and Bloecher showed that a 95 pct recovery is possible with a coverage of only 5 pct. Theoretical Considerations The work of adhesion W is the energy bound (in ergs per sq cm) when an interface is formed. It is determined by the difference of the free surface energies (surface tensions) of the respective phases 7j and yZ before contact and the interfacial free surface energy y, after contact. The definition of the contact angle permits the elimination of the unknown surface energy of the solid and hence the calculation of W from the surface tension of the liquid y and the contact angle 8: W = y (1 + COS0) [1] Consider a surface consisting of two components, identified as 2 and 3, 1 being the liquid. The amount of 2 in the composite surface is x, where 0 < x < 1. The respective contact angles with 1 and air are 8, and 8.. The total work of adhesion of such a surface is the sum of the values of the components multiplied by their respective areas. A formal relation can be written: Wm = x-W2+ (l-x)-W, [2] in which W, is the work of adhesion of the composite surface. Eq 1 can be introduced into Wt and Wa, but in the case of W, some discussion is needed. If the two components are segregated, each component forming an integral part of the composite surface there is no physical meaning for a contact angle 8m calculated from W,, by using eq 1. If, on the other hand, the area of each patch of the components is small in comparison with, say, the diameter of the bubble used in measuring, it could be expected that 0m would have a physical significance, because of the action of the surface tension of the liquid-gas interface tending to smooth out sharp corners. How small these patches would have to be is difficult to predict, but by using composite surfaces with microscopically

Jan 1, 1953

By R. A. Ritter, J. P. Batycky

A numerical technique has been developed to permit estimating the pressure gradient associated with laminar flow of thixotropic liquids through long Pipelines. For this purpose the pipeline is divided into a number of radial and longitudinal increments within which rheological properties of the fluid may be considered as constant at any time. Then, provided only that the fluid flow curve is defined at every duration of shear, it is possible to predict the instantaneous pressure gradient at any cross-section along the pipeline for each desired flow rate and pipe size. The technique consists of an iterative integration of shear rate to establish the appropriate value of the wall shear stress at each location. Consistency of fluid in the increment is determined by the flow history of that increment, while the radial flow associated with variations in velocity profile is accounted for by adjusting the width and radial position of the increment. A number of pressure profiles, computed at each of several flow rates, provide a convenient basis for pipeline design and pump selection. INTRODUCTION In recent years considerable attention has been given to predicting pressure drop associated with the isothermal laminar flow of time-independent non-Newtonian fluids in pipes and annuli. 6,11,12 The approach generally has been to develop analytical relationships between flow rate and pressure drop based on simple constitutive models which hopefully provide an approximate description of the rheological properties of the fluid. Analytical solutions are highly desirable since the influence of all pertinent parameters can be readily determined. Unfortunately, however, this approach is restricted to simple flow geometries and- frequently leads to erroneous results due to inadequacies in the model. In certain cases a solution may be obtained through applying appropriate numerical techniques.l,14 For example, a digital computer program is available for predicting the velocity profile and pressure drop encountered by any Newtonian or time-independent non-Newtonian fluid flowing under laminar conditions in a cylindrical pipe or annulus.l In this paper the consistency behavior of the fluid need only be described in terms of basic rheological data. Analyzing flow systems involving fluids with time-dependent rheological characteristics is considerably more complicated since substantial changes in consistency may occur because of sustained shear action. This sensitivity to shear frequently persists for several hours. Consequently, variations in pressure drop and/or flow rate resulting from the aging process and addition of unsheared or partially sheared fluid to the system must be considered for purposes of pipeline design. This paper outlines a numerical method for predicting the transient and steady-state laminar flow behavior of a thixotropic liquid in a pipeline of arbitrary length (i.e., at a specified constant flow rate, the instantaneous pressure gradient may be determined at any time after start up and at any location along the pipeline). Several such pressure gradient profiles, computed at several flow rates, may be combined to produce a complete portrait of the system response. This flow portrait provides a reasonable basis for pipeline design and for selecting a suitable pump characteristic. TIME-DEPENDENT RHEOLOGICAL BEHAVIOR The most familiar time-dependent rheological properties are those exhibited by thixotropic liquids. Many of these materials, particularly thixotropic crude oils, generally display an apparent yield stress in that a finite pressure gradient is required to initiate flow. Then, under the influence of sustained shear at a constant shear rate, the consistency systematically decreases to some final limiting value. The shear stress obtained at

By M. A. Steinberg, J. Wulff, R. Kamm

In a previous paper1 from this laboratory, the development of a lead grid method for exploring the distribution of strain and density within metal powder compacts was described. In that work thin lead foil with rectangular holes cut at regular intervals was inserted with the powder fill, the arrangement pressed and then radiographed to permit measurement of the deformation of the lead grid. Densities at each grid element obtained in this manner were plotted as a function of the die dimensions. From such plots it was found that the densest part of a compact pressed from one side (the top) is at the top outer region and the least dense at the bottom outer region of the specimen. The axial density maximum occurs more often nearer the bottom than at the top. As a result of such exploratory measurements, it appeared reasonable to conclude that variations in density could be attributed in the main to die wall friction. Thus compacts of large diameter appeared relatively uniform in density except where the die fill had been uneven. Finally it was found that lubrication of the finely finished die cavity contributed more to magnitude and uniformity of density within the compact than interparticle lubrication. Since publication of the above results, it was found that circular-hole grids could be more accurately made and, when deformed within the powder, more readily measured and analyzed. Much of the former work was repeated and new results which include the effect of lubrication, compact height, pressure, speed of pressing and vacuum pressing are reported in the present paper. Circular-hole Grids and Analyses OF Radiographs Commercial lead sheet 0.008 in. in thickness was used in all the work reported. The 0.0938-in. diam holes were punched in the sheet on 1/8-in. centers to an accuracy of 0.001 in. The finished grid used contained eight or more holes in a row and from I to 24 rows. The lead sheet was clamped between two pairs of brass strips bolted to a small milling machine table which was itself bolted to a bench in correct position near a vise which held the punch. Travel of the lead grid in two dimensions was controlled by two steel lead screws calibrated in 0.001-in. divisions. A stripper plate was used on the punch to avoid distortion of the lead foil. A high carbon-high chromium (chrocar) one-piece steel die was used throughout the work. The die cavity was 1.125 in. in diam and the clearance between plungers and die wall was 0.001 in. The die was also used for pressing from both ends with two long plungers. Finally, lapping of die and plungers gave a surface whose rms value On an Abbot profilometer was 5 micro-in. The die walls and plungers were, except where otherwise noted, lubricated with a stearic acid suspension in benzene. This was put on in multiple layers and allowed to dry before filling the die.

Jan 1, 1949

By I. W. Alcorn

The cost of drilling in the past few years of proration and ever decreasing allowables has received increasing thought and study. It seems to parallel the strides made with respect to pumping problems in 1932 and 1933. Low profit margins stimulate the search for economies. Any discussion of slim-hole drilling involves a multitude of abstract values, and the problem can be attacked only by a study of records and rational thinking. In a measure, traditional methods must be studied with a questioning attitude. The words "slim hole" may be somewhat misleading, as the term is entirely relative. For that reason I wish to define it as used in this discussion. On the Gulf Coast, I would define a normal hole as one in which 10 3/4-in. surface casing has been set and below which a 9 7/8-in. hole is dug. With this as a datum, holes of larger diameter below surface would be called "large holes," with 121/4 in. as the "extra large" class and holes of smaller diameter classed in the slim-hole range, 6 1/4 in. representing about the minimum size. The optimum size has not been definitely determined, but the preference is for a program that would call for setting 8 5/8 -in. surface casing and digging a 7 3/4 - in. hole. Different sections of the country might very properly deviate from this practice because of differences in depth, formations, regulations, or other factors. This paper will be confined to a discussion of the drilling of exploratory wells, as the drilling of this class of wells is quite a different problem from that of drilling a proven field, although many of the same considerations apply in both cases, as will be apparent. Although for many years shallow slim-hole and core-test holes of small diameter had been dug, it was not, I believe, until the fall of 1937 that serious consideration was given to its application in drilling wells 7000 ft., 8000 ft. and 9000 ft. deep on the Gulf Coast. This does not mean that nearly all such wells drilled on the Gulf Coast now are of the slim-hole variety, but only that efforts have been aimed in that direction with very encouraging results and there has been a very definite trend to reduce the size of holes, a trend that probably will continue. As to exploration policy, there appear to be two distinct and opposite views. The one usually followed in the past was more or less designed to "shoot the works" on one well. Generally on the Gulf Coast, the depth at which production might be obtained is limited by the drilling equipment and economics. With this thought in mind, wildcat wells are often planned with the idea of carrying the depth to 10,000 It., or even 15,000 ft. All of the possible hazards are anticipated and the general drilling and casing programs are so predicated. Such wells contemplate the drilling of large-diameter holes; the setting of at least one protective string of casing and an extensive coring policy, all of which finally adds up to an expensive well. AS opposed to this general policy is the slim hole. This, on the Gulf Coast, recognizes that new discoveries represent gam-

Jan 1, 1941

By A. H. Duane, A. E. Miller

The high-temperature allotropy of some heavy rare-earth metals and their alloying behavior with magnesium in the 0 to 50 at. pct Mg region was studied by thermal, microscopic, and X-ray methods. Examination of a hcc phase retained upon quenching alloys of different magnesium content confirmed the existence of a bcc high-temperature allotrope in pure gadolinium, terbium, dysprosium, holmium, erbium, thulium, and lutetium. The lattice constants of the pure metals were determined from a Vegard&apos;s Law extrapolation and .found to be 4.05, 4.02, 3.98, 3.96, 3.94, 3.92, and 3.90 + 0.02 A, respectively. In all of the systems studied, the high-temperature bcc phase decomposed eutec-toidally, when slowly cooled, into a hexagonal rare earth-Mg solid solution and a simple-cubic peritec-tic AB-type compound. In 1956, Spedding et al.&apos; observed high-temperature resistivity anomalies in the light rare-earth metals and made several unsuccessful attempts to retain the high-temperature form of these materials at room temperature by quenching the pure metals from temperatures near their melting points. High-temperature X-ray techniques were used by Spedding et a1.&apos; in 1959, to investigate the high-temperature allotropy of the rare-earth metals. This study showed that lanthanum, cerium, praseodymium, neodymium, ytterbium, and possibly gadolinium are bcc at temperatures near their melting points. Discontinuous changes in resistivity at elevated temperatures were also observed for pure gadolinium, terbium, dysprosium, holmium, and lutetium, thus indicating the possible existence of a high-temperature crystalline transformation in these metals. However, due to experimental difficulties encountered in the high-temperature X-ray analysis of these metals, their allotropic form was not identified. Spedding et a~.~ in 1960 observed that yttrium displayed a continuous solid solubility with lanthanum at elevated temperatures, thus showing the high-temperature structure of yttrium to be the same as that of lanthanum, i.e., bcc. Similarly, the high-temperature alloying behavior of gadolinium with yttrium showed gadolinium to be bcc at elevated temperatures. The bcc nature of the high-temperature form of yttrium was again recognized in 1960 by Eash and carlson4 in their study of the alloying behavior of yttrium with thorium. Gibson and Carlson, in a similar study of the alloying behavior of yttrium with magnesium, found that by quenching Y-Mg alloys from within the 0-solid solution region, Fig. l, they were able to retain the allotropic form of yttrium. It was the present authors&apos; intention to use this method to show the existence of a bcc high-temperature form of the heavy rare-earth metals gadolinium, terbium, dysprosium, holmium, erbium, thulium, and lutetium. Simultaneous with the present work, Beaudry and Daane&apos; have shown the bcc nature of the high-temperature form of scandium. EXPERIMENTAL PROCEDURES Materials. The rare-earth metals used in this study were prepared by the calcium reduction of the fluoride and were further purified by vacuum distillation. The magnesium was obtained from the New England Lime Co. and was also purified by distillation prior to its use in the preparation of the rare earth-Mg alloys. The results of chemical and spec-

Jan 1, 1964

By R. V. Colligan

[CONTENTS PACE Educating and Training Economic Geologists of the Future. By C. H. BEHRE, JR. (TP 2278, Min. Tech., Nov. 1948. Discussions by R. V. COLLIGAN and EVAN JUST) ....... I Mercury Industry in Italy. By EDWIN B. ECKEL. (TP 2292, Min. Tech., Jan. 1948. Discussion .............................. by C. N. SCHUETTE) 3 Chert in the Kingsport Formation at Mascot, Tennessee. By ARTHUR T. ALLEN. (TP 2299, ............... Min. Tech., Jan. 1948. Discussion by M. M. BUTLER) 5 Wall Rock Alteration at Butte, Montana. By RENO H. SALES and CHARLES MEYER. (TP 2400, Min. Tech., May 1948. Djscussions by C. D. HULIN, W. D. JOHNSTON, JR., and L. C. ................................... GRATON) 5] Educating and Training Economic Geologists of the Future R. V. COLLIGAN*-I can best illustrate my opinions by drafting another five year plan (Table 2). This plan is set up following the same stipulations outlined by Dr. Behre, namely: (I) the student is preparing himself for commercial work as a mining geologist; (2) he is attending an institution with a sufficiently broad curriculum (that is, engineering school and mining school as well as liberal arts college) to furnish the courses listed; and (3) he is not planning to continue his studies through to a doctor&apos;s degree before going into commercial work. A comparison of my study plan (Table 2) and that submitted by Dr. Behre (Table I) will at once point up the basic similarity, due to the obvious fact that there are so many essential courses which must be included in any outline of study. However, a more detailed analysis will show up certain differences, which, in fact, are only certain refinements on Dr. Behre&apos;s program. These I plan to discuss in order of their importance. The first and most important change is the addition of 12 hr of optional subjects, making a total of 24 hr of optional subjects as against a total of 12 hr under Dr. Behre&apos;s schedule. This of course entails the elimination of certain courses, which I shall discuss later. However, I wish to make it clear that I suggest eliminating these courses not because I feel that they are unnecessary, but rather because I feel the optional courses are more necessary to the complete education of the individual. I appreciate that Dr. Behre recognizes the importance of the cultural side of education, but I take issue with his thesis that the student will get it without credit and in his spare time. I do not think that the average college student, and certainly not the college freshman, is mature enough to know what he needs and where to get it in his spare time. I think it must be "spoon-fed"; he must be oriented through specific courses. University life (or should I say "college life") is too full of athletics, fraternity activities, dances, "bull sessions," and countless other enjoyable distractions, all of which contribute to the "full man." I fail to see how the average young American male can possibly sandwich in a necessary complement of "cultural activities" in his spare time. Since these latter activities do not fall within the pattern set by the "group," and show less promise of immediate return in enjoyment, or increased social status on the campus, they are bound to suffer in competition with the more popular, "group" activities. No doubt much of the criticism levelled against arts colleges, namely, that the cultural courses are useless, is well taken, for the culture

Jan 1, 1947

By R. L. Smith, I. G. Greenfield

The binary system Ga-Sb has been investigated by thermal, X-ray, and metallo-graphic methods. &apos;The intermetallic compound GaSb melts at 705.9OC and forms a eutectic with antimony at 11.8 atomic pct Ga. This eutectic melts at 589.8OC. A eutectic appears to be formed at 29.8°C but is too close to the composition of pure gallium to be detected. IN the course of an investigation of the semiconducting properties of the intermetallic compound, GaSb, the phase equilibrium between gallium and antimony has been investigated. Recently, the phase diagram of similar systems, such as In-Sb,&apos; In-AS,&apos; and Bi-As3 have been determined. These diagrams have the same general appearance in that an intermetallic compound is formed at 50 atomic pct and a eutectic is formed on both sides of the intermetallic compound. Jenny,& who has been investigating the semiconducting properties of intermetallic compounds, has concluded from thermal data of several alloys that the phase diagram of the Ga-Sb system resembles those mentioned previously. This paper represents a more detailed study of the Ga-Sb equilibrium. Experimental Procedure The gallium that was used to prepare the alloys was obtained from A. D. Mackay Inc. and the Aluminum Co. of America; the latter reported the purity as 99.95 pct. The antimony was obtained from Bradley Mining Corp. who specified a purity of 99.997 pct. Since the intermetallic compound of GaSb was prepared primarily to be used for further studies of the semiconducting properties, additional purification by a standard zone-melting technique under an atmosphere of hydrogen was performed. Hall-effect measurements on this material indicated an impurity content of less than 3 ppm.5 The antimony also was purified by zone melting and used in conjunction with the compound GaSb to make the necessary alloys for the determinations of the antimony-rich side of the phase diagram. The antimony-rich alloys were chill cast in Vycor tubes which were evacuated to a pressure of less than one micron. Since these alloys expand on freezing, precautions were taken to prevent oxidation of the ingot in the event the tube fractured. To insure homogeneity, the brittle alloys were ground and then placed in the furnace for the thermal-arrest determinations. Since the cost of gallium is high, the experimental procedure was complicated somewhat because of the necessarily limited sizes of the melts. In order to economize, the gallium-rich side of the diagram was determined by using a 35 g ingot of pure gallium initially and adding increasing amounts of antimony in order to obtain additional alloys. The furnace used in the determination of the cooling curves is illustrated in Fig. 1. A 2¼ in. quartz tube, sealed at one end, was fitted with a brass flange which was attached with DeKhotinsky cement. The brass collar was water cooled to prevent the cement from softening. An "0" ring was used to provide a seal between the brass collar and the furnace cover. Nichrome ribbon was wound around a 2 ½ in. asbestos-covered copper core which was used to reduce the thermal gradient in the furnace. The insulation consisted of alternate layers of asbestos and aluminum foil surrounded by sil-o-cel refractory and

Jan 1, 1956

By William M. Bowron

Thirty years ago, when I stood on the cliff of red fossil iron-ore, on Red mountain, Jefferson county, Ala., I asked what were the geological relations of this remarkable deposit. In reply I was told that it was a limestone, colored and saturated by some unknown but wholly external influences, and that at a reasonable distance from the surface the color would disappear. I could find no satisfactory explanation, either of the nature of this wonderful external permeating influence, or of the cause of such a ferrous impregnation selecting this one particular bed of limestone, to the exclusion of the higher and lower beds of the same material which are not even stained. I. The Present Theory. Referring to this subject, Dana says :&apos; "The clays, clayey sandstones and limestones of the Clinton epoch, through New York and the Appalachians, show that the mud-flats and sand-banks, and hence the shallow seas of the coast region, still continued.... The beds of argillaceous iron-ore, which spread so widely through New York and some of the other States, west and south, could not have been formed in an open sea; for clayey iron-deposits do not accumulate under such circumstances. They are proof of extensive marshes, and, therefore, of land near the sea-level. The fragments of crinoids and shells found in these beds are evidence that they were, in part at least, salt-water marshes, and that the tides sometimes reached them." At first, this explanation seemed satisfactory, but the more I studied the ore the less satisfying the explanation became. 1. In the ore itself, I found associated with the small particles of rounded matter (now consisting of iron oxide in which organic structure, if ever present, has become lost, though the

Jan 1, 1906

In 1846 a bill was pending in Congress to reduce, or eliminate, the tariff on coal; the debate caused the same writer to visit the mines on the north side of the James River and to write a letter about them to the same paper.&apos; Omitting the political arguments, his account follows: "July 13, 1846. "Early in the morning we rose, washed, combed, and ate a first-rate breakfast, and then went to the Tuckahoe, mined by Messrs. Sneed and Dietrock. Coal was first discovered here sixty years ago, and mined by Colonel Thomas Randolph, the proprietor of the land. They were worked by him for his smith-shops. Since which time they have been worked periodically, up to the war of 1812, when they were abandoned; and recommenced in 1837 under the management of Dr. W. T.- Scott. Subsequently a Company was formed called Tuckahoe Coal Mining Company, which purchased the whole track at a cost of $30,000. They commenced the sinking of a shaft and went as far as 412 feet, and then pitched the fat all into the fire by hauling off altogether in despair. In 1843 Major Sneed went to work at it, and succeeded. I may here remark that Major Sneed has been the pioneer in this business on the North side of the River, and has sunk more shafts than any other man who has pursued this vocation in Eastern Virginia. The difficulties and expense in sinking these shafts are sometimes immense. The coal on the outcrop or surface is not always a guide to where it may be found imbedded many hundred feet under earth and rock. "The Tuckahoe Pits are on the Eastern end of the coal field, within twelve hundred yards of the Canal, and about twelve miles from Richmond. They employ fifty hands and raise some three hundred thousand bushels of coal per year. It is highly bituminous and excellent for the manufacture of iron. The Tredegar and Belle Isle Rolling Mills are supplied with it. It must be good and of the right kind&apos;, or they would not use it. These pits are the only. ones on this side troubled-with gas-of course ventillation is necessary. There is not as much water in this Pit as I have found generally in many others, although they have extended their operations to a considerable distance under ground. I have observed in examining the coal mines, that, where they are sunk over four or five hundred feet, they are annoyed by gas, and where there is a less depth they are troubled with water. It is evident, therefore, that water, in the region of these coal fields, does not run through the earth to any extent, even five hundred feet deep, and the farther you go below that the greater the increase of gas. "We next visited William Cottrell&apos;s Pits, situated one mile and a half north of this. He employs some thirty hands, and raises from 4 to 500 bushels per day. "T. & R. Crouch&apos;s Pits are one hundred yards north of Cottrell&apos;s. This firm employ from 80 to 90 hands, and raise from 8 to 900 bushels per day. They are now

Jan 1, 1942

By W. F. Hosford

A series of aluminum single crystals was subjected to axially symmetric flow by drawing through dies. The orientation dependence of the drawing stress, which indicates the resistance to this type of flow, compares reasonably with predictions of Taylor and of Bishop and Hill. Measured lattice rotations likewise are generally consistent with theory. The most successful analyses of the plastic behavior of polycrystalline metal and its relationship to single crystal behavior are those of Taylor1-3 and of Bishop and Hill.4-6 The purpose of this paper is to provide a critical test of some of the basic assumptions involved in these theories. Both treatments apply to fcc metals and assume the shape change of each grain in a polycrystal to be the same as that of the polycrystal as a whole. Thus for a randomly oriented polycrystal extended under uni-axial tension each grain is assumed to undergo axially symmetric flow. dey = dez = -1/2dex, deyZ = dezx = dexy = 0 [l] where x, y, and z are a set of orthogonal axes, x being the tensile axis. Although [011.] oriented grains in bcc and fcc metals may depart markedly from this ideal behavior,7,8 the assumption is probably quite reasonable for most grains. Under a uniaxial tensile stress, ox, the work dW per unit volume expended in producing an increment of axial strain dex is, dW=oxdex [21 Since this work is expended in slip, dw =STi dyi 131 where Ti and yi are the shear stress and shear strain on the active slip systems. In both analyses Ti is taken to be the same on all slip systems, and dependent only on the total prior shear strain on all systems, so dw = Tdy [41 where t is the shear stress required for slip and y is the sum of the shear strain yi on all slip systems. Combining 121 and [4] and defining M = oX/T The ratio M is a generalized Schmid factor. It relates the tensile stress required for axially symmetric flow, ox, to the basic shear stress, 7, and it also expresses the ratio of crystallographic strain, y, to the tensile strain, Ex It depends only on the orientation of the crystal. Taylor evaluated M for various orientations by finding the least value of dy/dEx which could satisfy the shape change. Bishop and Hill, on the other hand, found M by considering the relative work (1/T)dW/dEx expended by stress states which could activate enough slip systems to produce the shape changes. The results of both methods appear to be equivalent, although certain omissions were made in Taylor&apos;s original work. The orientation dependence of M, calculated by the second method,9 is shown in Fig. 1. Taylor used the average 2= 3.06 for all possible orientations to predict the tensile stress-strain curve (oxvs Ex) for a random polycrystal from the shear stress-strain curve (t vs y) of a single crystal. Changes in M from lattice rotation were neglected so points on the ox vs ex curve were simply taken at ox = 3.06t and e = y/3.06 from corresponding points on the t vs y curve. Recent extension of the analyses of Taylor and of Bishop and Hill to crystallographically textured metals has been used to relate plastic anisotropy to textures, and to predict the potential texture hardening that could result from texture control.9 Unfortunately there have been relatively few experimental tests of the underlying theory. Taylor found that the tensile stress-strain curve of polycrystalline aluminum did agree reasonably well with that predicted from a single-crystal T-y curve. Had the single crystal undergone easy glide, how-

Jan 1, 1965

By D. K. Crampton, H. I. Burghoff, J. T. Stacy

The effect of cold-working upon electrical conductivity of copper and of copper alloys appears not to be generally known in detail. Although several papers on the subject have been presented, showing variable effects according to alloy composition, it is often assumed that the 2 to 3 per cent lowering of the conductivity of ordinary tough-pitch copper by severe cold-working is typical for copper alloys. Because of this situation it was decided to carry out the present work upon several types of copper, copper-zinc alloys over the commercial range of brasses, other binary alloys, and numerous age-hardening alloys in the quenched, and quenched and aged conditions. The large number of alloys investigated made it impossible to study every one in the detail it may have merited. Inasmuch as several interesting points that could not be satisfactorily explained came to light, further work is contemplated by the authors. It is usually considered that the normal effect of cold-work on ductile metals and unordered alloys is to decrease conductivity slightly. In alloys that are in the ordered state, as annealed or otherwise heat-treated, cold--working tends to disorder the structure, resulting in very marked lowering of conductivity. The random state of atomic arrangement produces lower con- ductivity than the ordered state for the same composition.1 Previous Work Previous work in the authors&apos; laboratory has shown the electrical conductivity of several copper alloys to be decreased by greater amounts than might have been expected, in view of the general knowledge on the subject, when cold-worked. Guillet and Ballay2 investigated the influence of cold-work upon the resistivity of several metals and alloys, including copper and some copper alloys. The increase of resistivity due to severe working w is less than 4 per cent for all pure metals tested, while the increases for the alloys were generally higher. In the copper-zinc alloys, they found that the increase of resistance due to drawing increased with zinc content, and reported a 21.7 per cent increase of resistance for an alloy contaiiiing 67.9 per cent Cu as severely worked. Masima and Sachs3 studied the change in electrical resistance of three brass crystals when stretched in the tensile test, obtaining increases in resistance of the order of 3 per cent for 30 to 40 per cent reduction of area of the specimens. The resistance decreased again when the cold-worked crystals were subsequently annealed. Bardenheuer and Schmidt4 found that the conductivity of copper was decreased by 3 to 4 per cent when reduced 50 per cent by working. The conductivity of 72-28

Jan 1, 1941

By George F. Comstock

IT has been reported recently1 that the hardenability and toughness of forging steels may be improved appreciably by the use of complex deoxidizers containing titanium, aluminum, and vanadium. In the light of these results, an investigation of similar deoxidizers containing various hardening and grain-refining elements was proposed. These deoxidizers included three manganese-silicon-aluminum-titanium al- [ ] loys with and without boron and calcium, three titanium-aluminum ferroalloys with vanadium, molybdenum and zirconium, respectively, an aluminum-zirconium ferro-alloy, and plain ferroboron. Their approximate compositions are given in Table I, and the results obtained so far in the investigation of their effects on steel are presented in the later parts of this paper. METHOD OF USING DEOXIDIZERS The deoxidizers listed in Table I were used in three series of 0.40 per cent carbon steels, which were melted in a small basic-lined induction furnace and cast in the form of I7-lb. ingots about 2.75 in. square. The basic charge for each heat was 10 lb. Armco iron and 6 lb. of clean low-carbon sheet-steel scrap. When melted, this charge was deoxidized with 15 grams of ferrosilicon, then about 500 grams of pig iron was added to give the desired carbon content. After the pig iron was dissolved, nickel [ ] shot and high-carbon ferrochromium were added if required, and additions of 80 per cent high-carbon ferromanganese and 50 per cent ferrosilicon were made to provide the proper amounts of those elements. Aluminum was added to every heat 2 min. after the silicon, for grain-size control and preliminary deoxidation. One minute later the special deoxidizer was added to the clean bare surface of the molten steel, and 2 min. afterward the steel was poured into the ingot mold, using a hot-top and pipe-preventing compound after pouring to decrease the depth of the shrinkage cavity. The special deoxidizers were used mostly in the form of about ½ to ¾ -in. lumps,

Jan 1, 1942

By J. C. Bokros

At temperatures above 950°F, zirconium which has been strained a critical amount will experience critical recrystalli-zation. The large grain size thus formed can result in a reduction in the fatigue life by a factor of 2 to a factor of 9 at both high and low temperatures. The critical strains for zirconium vary from 15 pct at 900°F to about 2 pct at 1125°F, while those for zircaloy III vary from 15 pct at 1050°F to 5 pct at 1200°F. Zircaloy II ,experiences no critical recrystallization up to 1200°F. ZIRCONIUM has become increasingly important for nuclear applications and is being employed in reactors at temperatures where recrystallization can occur. Recent work&apos; on the fatigue properties of zirconium has shown that coarse-grained structures developed in zirconium during recrystallization have much lower fatigue lives than fine-grained material. The development of these large grain sizes under such conditions is well known to be the result of critical recrystallization.2-4 Briefly, critical recrystallization occurs when a metal is strained a critical amount and annealed in the recrystallization range. The critical strain is defined as that minimum strain necessary to promote nucleation in the time unit and temperature considered. The maximum grain size occurs at the critical strain, since at this strain the fewest stable nuclei per unit volume grow into new grains. Recrystallization is not evident below this; strain since the nucleation rate is vanishingly lolw, and metal strained more than the critical amount has a higher nucleation rate per unit volume which results in a finer grained structure. This paper describes the critical recrystallization observed in reactor-grade zirconium, zircaloy 11, and zircaloy I11 as a function of annealing temperature and temperature of strain. EXPERIMENTAL The zirconium used was hafnium-free, double arc-melted sponge obtained from the Bureau of Mines. The ingots were forged and hot reduced to 0.08 to 0.10-in. sheet and subsequently cold reduced to 0.035-in. sheet with intermediate and final anneals at 1200 OF for 15 min. The zircaloy II and zircaloy III used were 0.035-in. sheets in the annealed condition. Compositions of these materials as tested are given in Table I. To determine the critical strain at a given temperature, tensile specimens having a0.065-in. taper in a 2-in. gage length were machined from the sheets parallel to the rolling direction. The specimens were polished, etched, and examined metallographically to ensure that all of them were strain-free, initially. Tukon indentations were made every half millimeter along the gage length of each specimen. These served as fiducial marks enabling the plastic strain to be measured with a microscope and micrometer stage. The specimens were pulled to failure at a rate of 0.002 in. per min in an Instron tensile-testing machine. Three temperatures were used for straining: room temperature, 500 ºF, and 900 ºF. The 500º and 900 ºF tests were run in an argon atmosphere. Since the rate of work hardening changes with temperature, a different critical strain was obtained for each temperature of strain. Specimens, prepared in the manner described, were annealed in vacuunl at various temperatures ranging from 900" to 1200 F for up to 1000 hr, after which they were examined metallographically. The critical strain and the recrystallized grain size as a function of strain were determined for each specimen. Results for the same temperature and time indicated that the critical strain measured was reproducible to within 5 pct of each other. RESULTS AND DISCUSSION Since increasing the time of anneal increases the probability of the nucleation of a new grain, the critical strain decreases with time at a decreasing

Jan 1, 1961