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By J. J. Bowman

The term "secondary aluminum" frequently is used loosely and often is considered synonomous with "inferior quality." Under war conditions, when every pound of material must contribute its share to the job at hand, this type of thinking is most unfortunate. Actually, given a supply of segregated scrap, an experienced smelter can produce remelted ingot of good quality, comparing closely to the analysis of the original material, and of considerable value of the war effort. The alloys he can produce are, of course, somewhat controlled by the analysis of the available scrap and, by the very nature of things, some of his production is not suitable for indiscriminate use. However, remelted scrap ingot provided about 273,2 per cent of this country's domestically-produced 1942 aluminum supply and probably will comprise about 39 per cent of the 1943 supply. (Canadian production is excluded from these figures.) That this part of the supply remains important is indicated by a recent report that "requirements" for the second quarter of this year were about 14 per cent greater than the supply, even though that supply will be almost twice the prewar annual production. (And those requirements, incidentally, were prepared after many conservation measures had been taken into account.) Since W. Bonsack recently has published a paper2 on the effects of the various alloying elements and impurities on the properties of aluminum, and such con¬siderations really are the important ones in a discussion of the metallurgy of secondary aluminum, it is planned to restrict this discussion more to a consideration of the sources, general characteristics and possible uses of these materials. For the purpose of this discussion, mill (or run-around) scrap may be disregarded and only plant scrap and obsolete scrap considered. Plant scrap, of course, is that scrap which is generated during the production of some part or assembly from a fabricated form of aluminum, such as sheet, tubing, forgings, castings or the like, and it may consist of solids (including rejected parts or subassemblies) or of machinings. To the extent that the several alloys are effectively segregated and the material is properly identified, the composition after remelting can be rather closely controlled or predicted. Obsolete scrap, on the other hand, is the "junk" which accumulates because of the wearing out or breakage of some piece of equipment. Although it is almost always in the form of solids, the accumulation includes many different alloys (often in the same assembly) and may include a considerable amount of nonaluminum material. The "metallics" recovered from drosses also contribute a portion of this class of material. The composition after remelting, therefore, may vary over rather wide limits and can not be very accurately predicted in any specific instance. SEGREGATION OF PLANT SCRAP Unfortunately, perhaps, it was not very common practice before the war to

Jan 1, 1943

By J. S. McNeil, J. U. Messenger

In the drilling of oil wells the control and prevention of lost circulation of the drilling- fluid is a oroblem which is frequently encountered; in many cases existing materials and methods for alleviating this condition have not been adequate. For severe cases of lost circulation in which the simpler methods, such as application of various bridging materials to the mud system, have proven unsatisfactory. a new material and method for applying to the loss zones have been developed which appear to he superior to existing techniques in many respects. The material, called a clay cement, is capable of being handled as a drilling fluid after initial mixing of the solitl ingredients with water and may be pumped down the drill pipe and squeezed into loss zones. After a short period, the material develops a very high gel strength which seals off the zone against further losses of the drilling fluid. In field tests, the process has been demonstrated to be a very effective method for combatting lost circulation. INTRODUCTION Methods of treating lost circulation in rotary-drilled wells by the addition of special materials to drilling fluids have long been in the process of development and are continuing to improve.' However, the annual drilling costs which can be traced directly to lost circulation difficulties still run into the millions of dollars. The loss of mud materials into highly permeable zones may range up to $50,000 per well in some areas. In addition to mud costs, excessive requirements of casing, cement; rig time, and the attendant blowout hazards further emphasize the importance of the need for improved methods of combatting lost circulation. The shortcomings of presently-used materials and methods have led to the development of a new lost returns material in the form of a time-setting clay cement. In field tests this material has proven very successful in plugging off loss zones. which other more conventional materials had failed to do. REVIEW OF PRESENT CORRECTIVE MEASURES The proper control of such operating factors as pump pressure, clearance between pipe and hole, and speed of running pipe in a holez is of primary importance in preventing and minimizing lost circulation problems. These factors, however, concern matters of drilling technique and do not directly involve lost circulation materials. Aside from setting casing past loss zones, three principal methods are generally employed for the purpose of avoiding or combatting lost circulation: (1) adjustment in properties (principally density) of the drilling fluid, (2) addition of fibrous, flaky, granular or other types of bridging materials to the mud system, and (3) the application of cements to the loss zones. The latter method is usually employed only after the first two have proven unsuccessful. In Table I are listed some advantages and disadvantages of the common corrective measures. Frequently, a combination of bridging material and cementing material is used." This combination is based on the premise that a bridge will

Jan 1, 1952

By Charles H. Moore

In the study of the properties of rutile pigments it became apparent several years ago that certain physical and optical properties could not be determined on particles of pigmentary size. Since reflected light is the dominant type which reaches the eye from small particles, the true color of pure rutile was not known. Most rutile pig-ments are acicular in habit, elongated parallel to the "c" axis. It was considered important to know the nature and tone of light transmitted, for example, by a basal plate. Further, as shown by spectrophotometric curves, there is a very strong absorption of light of 4000 A as measured on particles with random orientation. It would be interesting to see whether this absorption position varied with predetermined and selected orientations. Also, since the behavior of titanium pigments in a vehicle is important, a knowledge of the surface wettability of single crystals by various media should prove very fruitful. Finally, the optical properties of rutile are such that it should show, in a single pure crystal, greater fire and brilliance than the diamond. Mineralogists had long speculated that this would be the case and curiosity was strong to produce a single crystal large enough to cut. In light of the above, a project was initiated for the formation of single crystals of rutile. Method of Formation of Rutile Single Crystals Fortunately, purification of TiO2 produced from both titanium tetra-chloride and titanyl sulphate solutions had reached the stage where spectro-graphically pure starting material could be made. Spectrographic analysis of the feed material used in the initial experiments is compared with the present feed material in Table 1. It is apparent that the present large scale purification is approximately as good as the original experimental, small scale purification. Verneuil1 produced synthetic ruby and corundum in 1904 by the well-known flame fusion process, which today bears his name. Except for mechanical improvements the present commercial production of synthetics by flame fusion is essentially unchanged from his initial method. His burner consisted of an inner orifice through which was fed the feed material and oxygen. Surrounding this was a larger outer orifice through which was fed hydrogen at lower pressure. This arrangement consists then of a lance of oxygen burning in an atmosphere of hydrogen. The proportions of hydrogen to oxygen usually used in corundum production is about 3:1, providing there is sufficient temperature to reach the 2050.°C required for the fusion of alumina. From work done in the Titanium Division Laboratories2 and from the published work of Erlich3 it was known that rutile appears to lose oxygen near its melting point and that it would not be possible to grow single crystals in a strongly reducing environment. Consequently, in order to determine whether single crystals could be grown at all, an Airco oxygen-acetylene torch with

Jan 1, 1950

September 20, 1917. As this meeting terminates the year's agreement under which the Engineering Foundation has appropriated its income to the National Research Council, a brief summary of what has been accomplished seems called for. The Research Council was organized Sept. 19, 1916. The Executive Committee was appointed at that meeting; since that date two other meetings of the Council have been held, one in Boston, on Nov. 13 and 14, the other in Washington on April 19. During the intervals between the meetings of the Research Council, the Executive Committee has conducted all of the business of the Council. There have been 29 meetings of the Executive Committee, 13 in New York up to the first of May, 15 in Washington subsequently, and one in Boston. The meetings in New York were devoted to the organization of the Research Council and especially to appointment of committees. At the outset, the Council had no very clear idea of the way in which it was to organize; there were several other groups of scientific men at work, among them, the Research Committee of the American Association for the Advancement of Science and the Engineering Committee of the Advisory Commission to the Council of National Defense. Time was spent in straightening out these two principal complications, both of which were satisfactorily adjusted. The upshot of these negotiations is to leave the Research Council as the only representative, national body of research men, assisting the Government. During the period up to May, the Executive Committee in New York selected carefully the personnel of some 25 principal committees, and of a large number of sub-committees; so carefully were these chosen that of the entire number, several hundred, there have been only one or two declinations. Some of the important steps in the development of the Research Council are the establishment of the Military Section, composed. of the members of the Council connected with the Government and resident in Washington. This Section put the Research Council into close contact with the most important officials of the Army and Navy. From it has grown the Washington office of the Council, and the recognition of the Research Council as the "Department of Science and Research of the Council of National Defense; " and the establishment of the Washington office after the Council of National Defense had officially recognized the Research Council. About this time Dr. Hale, Chairman of the Council, appointed Dr. Millikan to be Vice-Chairman to represent the Council in Washington, and Dr. Millikan has since then been in charge of the work of the Council. At the request of the Secretary, Dr. Millikan has prepared a brief report of some of the work of the Research Council during its first year, which is appended to this report. It shows that the Research Council has been active in much of the important work. under way in our preparations for war, and that it has rendered effective services to the Government.

Jan 12, 1917

By H. O. Jahns, R. A. Greenkorn, R. E. Haring, L. K. Shallenbarger

This paper is a study of the effects of heterogeneity on flow in an analog of porous media, the Hele-Shaw model. l-3 A set of experiments in heterogeneous Hele-Shaw models showed streamlines through and around heterogeneities of various sizes, shapes and levels. (A level, we define as the ratio between the transmissibility of the heterogeneity and that of the rest of the model.) The heterogeneities were restrictions or expansions of the flow stream analogous to variations in the transmissibility of porous media. The experimental data agreed well with numerical results and with an analytical solution, which we derived for a circular heterogeneity in an infinite field. This study considers the flow-stream distortion due to the shape, size and level of heterogeneities. Size and level are much more important than shape provided the heterogeneity is not long and narrow. Our analytical solution shows that a circular heterogeneity in a large field can be replaced by an equivalent circle of either zero or infinite permeability. The radius of the. equivalent circle is a simple function of size and level of the actual circle. INTRODUCTION With the availability of high-speed computers and numerical procedures to predict reservoir behavior, we are faced with an important question. How much information about the reservoir do we need to justify the cost of the computer in any given case? To answer this question, we have to know how various reservoir parameters affect flow behavior. Reservoir heterogeneity is one of these parameters. In this study, we used a simple, two-dimensional model of porous media, the hele-shaw model, to investigate the effect of heterogeneity on flow behavior. We restricted ourselves to linear, single-phase, steady-state flow in a rectangular field with a single heterogeneity at its center. The analogy between flow in Hele-Shaw models and in porous media is easily verified. Let us first consider a homogeneous Hele-Shaw model with constant plate separation h. (The Hele-Shaw model is constructed by placing two plates, usually glass, very close together and allowing liquid to flow between them. Streamlines are made visible by introducing colored fluid into the space between the plates at a number of points across the model.) We assume a cartesian coordinate system with its origin in the middle between the plates and the z axis directed perpendicular to the glass plates (Fig. 1). The fluid flow is always in a direction parallel to the glass plates and varies from a maximum value to zero in the very small distance from the middle (z = 0) to either plate (z = h/2). For slow motion of an incompressible fluid, neglecting inertia and body forces, we have the viscous flow equation: where p is the fluid pressure, p the viscosity, and v the velocity vector with components u, v and w in the x, y and z directions, respectively. In our rase. and the derivatives of 3 with respect to x and y are small as compared with the derivative in the z direction. Therefore, approximately, with Vp and v being two-dimensional vectors in the x-y plane. Two integrations with respect to z give

Jan 1, 1965

By C. W. Hazelett

This paper is a resume of some of the accomplishments in direct rolling of strip from molten metal, and a description of some experimental developments in recent years. In all the early developmental work, we used a pair of rolls with a bath of metal between them, maintained by flanges or plates at the ends of the rolls. These flanges produced an excess cooling of the metal and built up enormous pressures at this point as the metal went through the bight of the rolls. Many means were tried for compensating for this excess cooling, such as thickening the strip at the edges, heating the end dams directly or by flowing more of the molten metal against them, leaving an open crotch below the end dam and above the bight of the roll, where the excessive pressures built up could be relieved by some of the metal squeezing out at this point, and so forth. All of these helped somewhat to solve the problem, so that very large heats of many metals melting up to 200°F., having commercially uniform gauges, could be rolled up to 24 in. in width. The rolls were made by mounting heavy rings on heavy shafts, and pressures up to 75,000 lb. per inch in width were used. Cooling of the rolls was generally done by spraying water on the outside surface of the rolls that came in contact with the molten metal. Roll life was commercial with brass, barely satisfactory with copper, and totally impractical with steels. The greatest difficulty encountered in all this work was caused by lack of uniformity in the product, owing to a folding action in the mill. Those who are familiar with the operation of a rolling mill know that a bar entering a mill moves at a lower speed than the peripheral speed of the roll. However, the metal solidifying from a bath in a direct rolling mill is cast at exactly the peripheral speed of the roll. This results in irregular folding of the metal, some irregular remelting of the previously solidified sections, and it is difficult, if not impossible, in some cases to exert enough pressure to weld these folded sections sufficiently into a sound product. In addition to this melange of solid, semisolid and liquid metal in the bath, we know that pressure near the freezing point of any alloy in which the constituents have different melting points—and I believe all of them have—causes the lower-melling-point constituent to be squeezed back until it becomes cold enough to solidify and go through the mill. This segregates all alloys, the segregation increasing with the pressures and the freezing ranges of the metals. Add to these problems the excessive roll-maintenance costs with high-melting-point metals and then, the greatest difficulty of all, the vanity of homo sapiens where a matter of possibly large importance is being considered, and the problems seemed almost insuperable. It was long ago obvious to me that something much more than the size of a corporation's money and self-assuradce was necessary if this process was to be made commercial. I should like to show you first the performance of the only mill we ever really designed and built, to see what might be done with a well constructed mill. We accomplished something new in history with this prccess, first, by producing at Scovill Manufacturing Co. coils of brass

Jan 1, 1945

By E. C. W. Perryman

On electropolishing, high-purity Cu-Sn and Cu-Sn-P alloys with more than 5 to 9 pct Sn were found to contain many grain boundaries with a ridge-and-furrow profile. The effect was not eliminated by solution treatment and was present at the new boundaries in recrystallized material. It could be produced by diffusing tin into the 3 pct Sn alloy and it is concluded that the effect is due to enrichment of certain boundaries in tin, or possibly in an impurity present in the tin, in solid solution. IN the hot working of tin bronzes, especially those with moderately high tin contents, considerable difficulty is frequently encountered from intercrystal-line weakness, which results in cracking at the edges in sheet on strip rolling and in the unsupported regions of the rod in rod rolling.' These difficulties are not at all pronounced with up to 3 pct Sn, but at 5 pct Sn impose serious limitations and at higher tin contents, especially if the phosphorus content is also high, they may become very severe. In some work carried out at the laboratories of The British Non-Ferrous Metals Research Association it was found that a notable lack of ductility in tension at elevated temperatures, associated with intercrystal-line failure, was characteristic of tin bronzes even of relatively high purity. That the intercrystalline fracture is not due to a brittle or molten impurity phase at the grain boundaries was shown by the fact that the temperature at which intercrystalline fracture first occurred decreased with decrease of rate of straining. Tensile tests on some commercial tin bronzes, reported by Goetzel,² show a similar fall in ductility with increasing temperature. As no visual evidence had been obtained showing that the grain boundaries of the tin bronzes were different from those in copper, a more detailed microscopical examination was carried out, and the results of this are given in the present report. Several workers"' have observed that electrolytic polishing is a powerful tool for detecting small amounts of a second phase and in particular for detecting high solute concentrations, "equilibrium segregation," at grain boundaries. Since it had been found that the suggested solutions for electropolishing bronze and the standard solutions for brass and copper did not give satisfactory results it was first necessary to find a suitable electropolishing solution.' Experimental Procedure Materials Used: The cast and wrought materials used for this work were the same as those used for the mechanical tests referred to above. They comprised 3, 6, and 9 pct Sn alloys without phosphorus and the same three basic alloys with 0.03 and 0.4 pct P. A 5 pct Sn alloy without phosphorus, of similar purity, was also examined. The basis materials were Chempur tin, high purity 15 pct phosphor-copper and cathode copper, and spectrographic analyses are given in Table I. Treatment: The cathode copper was first melted under charcoal, degassed by plunging marble chips beneath the surface, and cast through a coal gas flame into sand molds to produce a number of small ingots which after machining were of a suitable size for subsequent vacuum melting. Chill cast bars of the alloys, approximately 1¼ in. in diameter, were then made by melting and casting in vacuo, the tern-

Jan 1, 1954

By W. C. Ellis

Growth directions of tin, zinc, and cadmiun whisker crystals grown spontaneously fi-om the solid are summarized. In tin the edge and diagonal directions of the unit cell are jound with the exception oj- the [110] diagonal. In cadmiurn and zinc the usual dip-ections are a or a + c. The c direction has not been ohserwed. The gvouth directions from the solid are for the most part the same as those found for vapor-grozun crystals and are the ohserz:ed glide directions in plastic j-lou. Whisker crystals of these elements grown from the solid are not twinned. Specular lateral reflections are associated with planes of snall crystallographic indices. WHISKER crystals of tin, zinc, or cadmium grow spontaneously at room temperature in periods from months to years from thin electroplates and other prepared films of the respective metals.''2 It has been established that these crystals are single, but the question of twinning, such as occurs in whisker crystals of silicon,3'4 has not been resolved. Studies of morphology have been restricted to determinations of growth directions.5-' Whisker crystals are both straight and kinked. A few studies have been made on kinked whiskers including measurements of kink anglesa and determinations of growth directions,' but unfortunately not both on the same crystals. The kink angles, for the most part, for each species are grouped closely about a few unique values, but these values are not always those between observed growth directions in a single crystal. To supplement existing data, the growth directions, identification of lateral features, and presence or absence of twinning were determined with a Weissenberg goniometer by a method described elsewhereg on eight whisker crystals of tin, five of zinc, and five of cadmium. One kinked cadmium whisker was examined in detail. The specimens were needlelike, a few microns in cross section, and of the order of a millimeter in length. They were removed from electroplated substrates on laboratory specimens and commercial equipment after several years of growth as described in Table I. Since the specimens were less than 10 p in cross section they were ideally strong with no attendant risk of plastic deformation or damage in handling. Only deformation twinning has been reported for these elements. Therefore, twinning probably should not be expected in whisker crystals of these metals, particularly a twin plane containing the growth direction. A twin plane oriented in this direction was the one sought in this study. No examination was made for twinning at the boundary between kink segments except for one cadmium crystal. Well-defined reflections occur as a whisker crystal of tin, zinc, or cadmium is rotated about its growth direction when illuminated by a beam of light Although these reflections had been noted in earlier investigations, no study of them was made, probably because the earlier studies had disclosed also that

Jan 1, 1967

By N. A. Gokcen, M. N. Dastur

In metallurgical process industries a knowledge of true melting and casting temperatures is very essential for increasing the operating efficiency as well as improving the quality of the finished product. Optical pyrometers are widely used for the purpose because of their cheapness and ease of operation. It is an unfortunate fact, however, that this mode of measuring temperature entails a source of severe error inasmuch as with all non-black bodies, the temperature observed is always below the true temperature owing to deficient emissive power. Hence, the need for emissivity correction arises. In 1913 Bidwell1 obtained emissivity values of 0.36-0.48 for a temperature range of 1520-1800°C. He measured the true temperature of molten iron by sighting into a carbon cavity immersed in the iron under an atmosphere of hydrogen. In 1914 Burgess2 determined the emissivity of a smooth surface of liquid iron free from oxide to be 0.37 under an atmosphere of hydrogen. He claimed to have attained an accuracy of within 5°C at 1500°C with an optical pyrometer using monochromatic light. He reported that no difference appeared to exist between the emissivities of pure iron and of steels containing considerable percentages of carbon, nickel or manganese; nor was there any appreciable variation of emissivity with temperature from 1530 to 1571°C. Wensel and Roeser3 found an elnissivity value of 0.4 for temperatures above 1375°C for cast iron. The average emissivity value for carbon steels reported by Leiber,4 odd,5 Hase6 and Umino7 range from 0.4 to 0.45. Knowles and Sarjant8 made an extensive study of emissivity of molten iron and steel over a wide range of workshop and laboratory conditions. Observations of true temperature were made with immersion thermocouples, and correlated with apparent temperatures indicated by optical pyrorneter readings taken on the pouring stream as it passed over the lip of the crucible. The emissivity of Armco iron was shown to be of the order of 0.4, rising slightly with increasing temperature. But for plain carbon steels containing up to 1.0 pct carbon the emissivity was shown to fall slightly with increasing temperatures. The results of their investigation are in agreement with those of Guthmann.9 Naeser,10 Spencer," Todd5 and Hase6 in regard to the relation between emissivity and temperature for plain carbon steels. However, Goller12 has found a rise of emissivity with increasing temperature for the same steels. Results of several investigations are given in Fig 1. Measurement of True and Apparent Temperatures The necessity for an accurate optical temperature scale for liquid iron in studies of gas-metal equilibria led to this investigation. Experimental measurements were carried out in the induction furnace used by Dastur and Chipman13 in their studies of the reaction of hydrogen with oxygen in liquid iron. The furnace as modified for this work is shown in Fig 2. The atmosphere of the furnace was a mixture of purified argon with hydrogen containing a small controlled amount of water vapor. Gases were preheated by means of a platinum-10 pct rhodium resistance coil. The stream of hydrogen sweeping across the surface of niolten iron vir-

Jan 1, 1950

By AIME AIME

EVER since Henry Bessemer, nearly 100 years ago, developed the steelmaking process that bears his name, occasional variation has been noted in the quality of steel made in the acid converter, owing largely to the difficulty of stopping the ? refining-which takes only ten to twelve minutes -at precisely the right moment. Principally as the result of this, the amount of Bessemer steel made in the United States gradually declined over the years until it is now about 7 per cent of the total.

Jan 1, 1943

By R. M. Waterstrat, B. N. Das, Paul A. Beck

The central region of the Ti-Mn system was studied by means of x-ray diffraction and metallography. The following intermediate phases were found: an MgZn2-type Laves phase having a wide range of homogeneity, the p-phase of unknozvn structure, and the + -phase with a large tetragonal unit cell, stable at 930°C and lower temperatuves. MaYKUTH, Ogden, and jaffee1 determined the soh-inh bility limits of manganese in and titanium. They also confirmed the structure of the intermediate phase TiMn2 which was previously identified as a Laves phase of the MgZn2 type.2 In the equiatomic region they found an additional intermediate phase, y, which presumably formed by a peritectic reaction at approximately 1200°C. This last observation was disputed by Rostoker, Elliott, and McPhers0n,3 who reported the formation of TiMn by a peritectoid reaction between 900" and 1000° C, but found no evidence of any intermediate phase other than the Laves phase at higher temperatures. Elliott and Rostoker4 reported furthermore that the X-ray diffraction pattern of TiMn could be identified as that of a o phase, although their data were not consistent with this inter~retation. Margolin and Ence6 presented X-ray diffraction data for the and TiMn, phases, and obtained metallographic indications for the existence of additional intermediate phases. They concluded from metallographic observations that two Laves phases are formed, separated by another phase, designated as &. A phase diagram for the Mn-Ti system has recently been published by Savitskii and Kopetskii,' which shows considerable disagreement with the work of Hellawell and Hume-Rothery,' in particular with regard to the terminal solid solutions based on the allotropes of manganese. The present investigation was undertaken primarily to clarify the phase relationships in the equiatomic region of the Ti-Mn system. The metals used in preparing the alloy specimens Were iodide titanium and electrolytic manganese, the latter having a nominal purity of approximately 99.9 pet. The electrolytic manganese was covered with a thick coating of a brown manganese oxide which was reduced by heating the manganese flakes for several hours at a temperature of 1100°C in an atmosphere of dry hydrogen. Three alloys, see Table I, were made using sponge titanium and manganese not treated in hydrogen. The alloys were prepared by arc-melting in an atmosphere of helium or argon. The composition of each alloy was calculated by assuming that the entire weight loss during melting was due to evaporation of manganese. Subsequent chemical analysis of certain alloys indicated that the compositions calculated in this manner were usually correct within 1.4 pct, as shown in Table I. All alloy specimens were wrapped in molybdenum foil before sealing them in silica tubes containing argon at a pressure of 1 atm at the annealing temperature. After quenching in cold water, the alloy specimens were bright and clean, with no evidence of any surface reaction. The alloys listed in Table I were examined metallographically, using an etchant consisting of 20 pet HNO3, 20 pet HF, and 60 pet Glycerine. powder for X-ray diffraction examination was prepared by crushing a portion of each annealed alloy

Jan 1, 1962

By Richard J. Fruehan

ThE thermodynamic activities of nickel and chromium in liquid Ni-Cr alloys have not been previously reported. There have been several investigations on the solid alloys.1-3 In the present investigation the activity of chromium in liquid Ni-Cr alloys at 1600° C was determined by the use of the following galvanic cell, The use of galvanic cells employing solid oxide electrolytes for determining the activity of metals in solid alloys was first demonstrated by Rapp and Maak4 on Cu-Ni alloys between 700° and 1000°C. Recently Schwerdtfeger5 tested the performance of the ZrO2(CaO) electrolyte at 1600°C and found it satisfactory for oxygen pressures as low as 10"12 atm. He also demonstrated the use of solid oxide electrolytes for determining the activities in liquid metal systems in measuring the activity of manganese in Fe-Mn alloys at 1500°C. Extensive investigations have been carried out in this laboratory, exploring the oxygen partial pressure lower limit at which ZrO2(CaO) electrolyte can be used satisfactorily in oxygen galvanic cells at 1600°C. In a paper to be published at a later date,9 it is demonstrated conclusively that ZrO2(CaO) exhibits insignificant electronic conductivity at oxygen pressures down to about 3 x 10"13 atm which is lower than the oxygen partial pressure in equilibrium with Cr-Cr2O3 at 1600°C. Therefore, the activity of chromium can be related to the measured reversible electromotive force of the cell in the present investigation since no electronic short circulating will occur. Fig. 1 is a schematic diagram of the cell used. The Cr-Cr2O3 electrode was made of equal weights of chromium and Cr2O3 powders which were mixed and packed into a recrystallized alumina crucible. A Pt-wire lead was embedded into the Cr-Cr2O3 compact to insure good contact. A ZrO2(CaO) crucible, supplied by the Zirconium Corp. of America, contained the Ni-Cr melt equilibrated with solid Cr2O3. The ZrO2(CaO) crucible was placed on the Cr-Cr2O3 electrode and additional Cr-Cr2O3 mixture was packed around it. Contact with the Ni-Cr alloy was made with a Cr2O3 tube, which is a weak electronic conductor. A platinum wire lead was attached to the Cr2O3 tube. The galvanic cell was lowered slowly into the hot zone of the furnace tube in order to avoid too large a thermal shock which could break the ZrO2 (CaO) crucible. The furnace was con- tinuously flushed with purified argon during the experiment. The temperature was measured with a Pt-Pt/10 pet Rh thermocouple and maintained at 1600° ± 5°C. The electromotive force was measured with a recording potentiometer. The furnace was turned off when measurements were being made in order to avoid induction effects and the reversibility of the cell was demonstrated in the usual manner. The electromotive force was measured several times over a period of approximately 1 hr. During that period the electromotive force remained constant within ± 3 pet and did not continuously drift in any one direction. After the experiment the alloys were analyzed for chromium in the usual manner. The measured electromotive forces of the cell at 1600°C, (2912°F), are listed in Table I. The activity of chromium, with solid pure chromium as the reference state, (a), was calculated using Eq. [l], , n F E I, n lna RT- U] where E is the measured electromotive force, F is the Faraday constant, and n is equal to 3, the number of equivalents per mole, (nF/RT = 18.59 volts'1 at 1600°C). The resulting activities are listed in Table I. The activity of chromium relative to pure liquid chromium was also calculated. The free energy of fusion of chromium at 1600° C was calculated using

Jan 1, 1969

By Fred C. Bond

The Standard method of determining the crushing resistance of rocks consists of crushing prepared shapes under slow compression, and expressing the ultimate crushing resistance at the load causing failure in pounds per square inch of cross-sectional area perpendicular to the crushing force, with the height approximately equal to the diameter. One-inch cubes or cylindrical drill cores are commonly used. Cubes and drill cores are cut by a highspeed steel disk with diamond dust embedded in the edges, and running under a water spray. such a saw will cut one square inch or more of hard stone per minute. An oiled, spherical, swivel compression block of small diameter should be used to equalize the pressure. Each sample is crushed between sheets of cardboard or blotting paper extending about one-half inch beyond the edges of the stone. A cloth is wrapped around it to prevent dangerous explosive shattering. It is probably preferable to place the swivel block below the specimen, with either a rigid head or another swivel block above. Whatever the arrangement, the conditions should be selected that will develop the maximum crushing strength of the specimen, even though its top and bottom planes may not be precisely parallel. The cardboard pads may be dispensed with if the ends of the specimens are polished smooth. The use of lead pads was discontinued because of the observed tendency to split the material. The samples are weighed and measured before breaking, and the density is calculated. Cubes that contain bedding lanes or veinlets are usually placed with these vertical and parallel to the crushing force, in order to develop the maximum resistance possible. A number of compression tests were made on Canadian ores, by Forrest Nagler, of the Allis-Chalmers Manufacturing CO., and are listed alphabetically in Table I. These tests were made on one-inch cubes or on diamond-drill cores approximately one inch in diameter and One inch long. The drill cores represent virgin rock, while the cubes may have been previously weakened by explosives. compression tests have been made in the Allis-Chalmers Milwaukee Laboratory on a number of ores and other materials. These are listed alphabetically in Table 2. In test NO. 1339, on limestone from the Hanna Coal Co., comparison was made between 2 by 2-in. diamond-drill core segments and one-inch cubes cut from the cores in the same strata. Results for the cylinders are tabulated directly below those for the cubes. The bedding planes were normal to the compressive force in breaking the cylinders and parallel in breaking the cubes, which accounts for the lower strength obtained from the cylinders. The percentage of net linear compression at the ultimate pressure was measured in test No. 1055 for Fontana TV A quartzite as 0.30 for cube A, and 0.37 for cube D.

Jan 1, 1947

By Olaf N. Rove

YEAR 1951 has been bright for the mining geologist. He has arrived after struggling for a generation or two to sell his wares through service to the operator, the mine superintendent, and the manager. But as he establishes himself on the operating front, he is faced with even greater challenges; namely, the development of basic geologic principles governing ore-forming processes and the occurrence and distribution of mineral deposits. These principles are needed to guide his ever-widening search into new areas. He must now stimulate the interest, confidence, and imagination of the mining executive and layman in fostering the research essential to expand rapidly the basic science of geology and its more specific applications to the mining industry. The hallowed time-tested tools of the prospector and the industry are no longer adequate. New basic data, principles, and ideas are needed to guide industry's exploration. The entry of Government into exploration, by lending money to prospectors and operating companies to partly finance exploration, is one of the major events of the year. This was one of the activities for which the Defense Minerals Administration was established in the Department of the Interior. DMA was staffed largely with men from industry, but the Bureau of Mines and the Geological Survey have acted as its technical advisors and have provided its field staff. Since the start of this work in May 1951 to November 19, 1951, the DMA has approved 208 exploration projects while denying 318 others. The contracts involve about eleven million dollars worth of exploration, of which Government's share is about sixty percent. A few contractors have already made discoveries and are into production to repay their loans; others have completed their projects without making a discovery. In November, the DMA was split into two successor units. The Defense Minerals Exploration Administration was set up in the Interior Department to carry out the exploration program. The Defense Materials Procurement Agency was organized as a separate agency to carry out the other functions of the former DMA, as well as general strategic materials procurement. The strategic materials group of the Economic Cooperation Administration was transferred to DMPA in order to centralize the procurement from foreign sources into one agency, although the authority and scope of activities of this group have not been announced as of the middle of December. The DMA-DMEA-DMPA programs are making large demands upon the technical manpower of the Geological Survey and Bureau of Mines. It is still too early to evaluate with confidence the productiveness of this diversion so far as the immediate and long-range effects are concerned. Many of the individuals associated with these programs, as well as others in the industry, are convinced that from a long-range national viewpoint, the regular programs of both the Survey and the Bureau equal or even exceed in importance the current emergency mineral activities of these two agencies. Uranium Uranium continued to be the glamour-girl metal of the mineral industry, and at the request of the Atomic Energy Commission uranium and thorium were included in the DMA exploration program. Industry's intensive prospecting and mining activities in 1950 were further expanded early in 1951 when the Atomic Energy Commission announced an increased price schedule and a new bonus payment

Jan 1, 1952

By J. R. Johanson

With the continuing development of automatic operations, it is important that reliable discharge rates through hoppers and bins be obtained for bulk solids. In most applications a feeder is used to control the feed rate. The selection of this feeder size is usually based on the rated ability of the feeder to move material without regard to the capability of the material to flow through the opening in the hopper onto the feeder. The dis charge rate through a given hopper opening may vary from zero to a theoretical maximum depending on the flow properties of the material. This paper presents an equation for the maximum discharge rate for a bulk material as a function of the hopper shape, the opening size and the flow properties of the material. Discharge-rate tests on various materials indicate good agreement with calculated values for opening sizes from a fraction of an inch to several feet. As part of a program to develop improved design criteria for bulk storage and handling facilities, a specific study of the methods involved in calculating the rate of discharge of bulk solids from hoppers and bins has been made. This study is closely related to earlier work done on the prevention of flow problems through the choice of proper design geometry of hoppers and bins1. The present paper is an extension of this earlier work, and therefore many of the concepts previously derived and explained will be used without explanation. Two types of flow will be considered: plane-strain flow in a wedge-shaped hopper and axial-symmetry flow in a conical hopper. The literature contains many studies on discharge rate for regular-shaped dry particles2*3 such as glass beads, lead shot and coarse dry sand. However, the work is empirical in nature, and it is difficult to extrapolate the given information to apply to moist, sticky materials typical of many industries. Some studies4 have shown a decrease in discharge rate with an increased moisture content of the material. However, no attempt was made to correlate the discharge rate with moisture. The method of calculating discharge rate presented in this paper was derived analytically from the basic knowledge of the flow of frictional, cohesive, granular solids, The equation includes the effect of material cohesion (stickiness), hopper configuration, opening size and bulk density of the material. THEORETICAL WORK The basic assumptions made in deriving the discharge rate equation are as follows: 1) The material is a frictional, cohesive, granular solid. 2) The flow is considered continuous and without significant density change. 3) The material at the hopper opening forms a continuously failing arch that is in dynamic equilibrium. 4) The strength of the material in the arch, which must be overcome for the arch to fail, is caused by the pressure in the flowing mass near the hopper opening. 5) This pressure at the hopper opening can be calculated5. If we consider the dynamic equilibrium of an arch of uniform thickness such as that shown in Fig. 1,

Jan 1, 1965

By M. Prats

This paper presents a method for obtaining the correct values of the breakthrough sweep efficiency of the staggered line drive, taking into account the proper shape of the breakthrough streamline. Results obtained were different from those previously published, which were obtained by using an inexact shape of the breakrhrough streamline. INTRODUCTION In Section 9.31 of Muskat's' The Flow of Hotnogeticous Fluids Through Porous Media, it is stated that in a staggered line drive flood "the streamline of highest average velocity [is] the line of centers between input and output wells" (see Fig. I). Muskat used this concept to determine the relationship between the breakthrough sweep efficiency and the geometry of the staggered line drive pattern. Although it is clear from symmetry considerations that the breakthrough streamline passes through the midpoint between input and output wells, it is equally clear, as shown in Fig. 239 of Ref. 1, that the breakthrough streamline is not represented very well by the straight line joining the input and output wells. Therefore, it is desirable to determine the proper relationship between the breakthrough sweep efficiency and the pattern geometry by using the proper shape of the breakthrough streamline. METHOD OF SOLUTION It was found that the effect of the geometry of the staggered line drive on the breakthrough sweep efficiency can be investigated easily by making use of the method developed in Ref. 2. With this method, it can be shown that the general complex potential for the staggered line drive, which can be considered as a rectangular five-spot, is given in the coordinate system of Fig. 1, by O(z) = In cn(z\m) = +(x,y) + i $(x, y) . (1) where z = x + iy, +(x, y) is the potential distribution and $(x, y) is the stream function. The function cn (zm) is a Jacobian elliptic function of parameter m and has simple zeros at z,. = (2n + 1) K + 21iK and simple poles at z, = 2nK + (21 + 1)iK. Thus, the complex potential behaves like a(z) = ln(z - zr.) in the neighborhood of the production wells and behaves like a(z) = - ln(z - Z,) in the neighborhood of the injection wells. Since (z - z1.v) = rll.ei, we note that the potential + has the proper logarithmic behavior near the two wells, while the stream function $ varies with the angle, decreasing clockwise around the production well and increasing clockwise around the injection well. The functions K(m) and K'(tn), related by K(m) = K'(m,), where m + m, = 1, are known as the complete elliptic integrals of the first kind. By use of other properties of the Jacobian elliptic functions, the general stream function distribution for the staggered line drive can be obtained from Eq. 1: From the Jacobian elliptic function values, sn(0lm) = 0 dn(O(m) = cn(0jm) = 1, and f[K'(m)Iml = 03, it follows that the stream function given by Eq. 2 satisfies the proper symmetry conditions near a production well P located at [K(m), 01 and an injection well I located at [0, K' (m)]. That is, the line IOP in Fig. 1 is a streamline with value G (0. 0) = -0. and the straight lines connecting I and P to the point [K(m), K' (m)] is a streamline of value $[K(m), K' (m)] = -7/2. Similar symmetry conditions are obtained near other wells. It should be nuled that for m = m1, = 0.5, Eq. 2 reduces to the stream function distribution of the regular five-spot given in Ref. 7. SHAPE OF THE BREAKTHROUGH STREAMLINE It is apparent, from symmetry considerations, that the breakthrough streamline ($,) passes through the point [K(m)/2, K' (m)/2]. Its value there is so that the shape of the breakthrough streamline $,, is given by

Jan 1, 1957

By Walter J. Karplus

By means of a finite difference expansion a fluid flow field in cylindrical coordinates with axial symmetry, is simulated by a network of electrical resistors. A series of DC analog computing units, connected to the network bounrlary corresponding to the free surface effectively adjust the network parameterr to satisfy simultaneously Laplace's equation and the borrndary conditions. The system automatica1ly "re1axes" to the correct boundary shape in a fraction of a second. A detailed application of the method to the water coning problem in oil wells is presented. INTRODUCTION The water coning problem in petroleum production is a prime example of a class of problems known as free surface problems. A free surface arises in fluid flow regions when the shape of the boundary of a single phase flow region is affected in some manner by the pressure or potential gradients within the region. When there exists an interface of two fluids of different densities, the shape of this interface will be determined by the relative velocities of the two fluids and will therefore comprise a free surface. Other free surface problems of interest to petroleum engineers include the gas coning, water injection, and gravity drainage probIcms. In each case it is desired to predict the shape of the boundary of the oil zone as a function of the flow rate, the well penetration and the physical parameters and dimensions of the system. Such problems do not lend themselves to the classical analytical treatments of boundary value problems because in this case the boundary of the potential field and the potential distribution within the field are interdependent and must be calculated simultaneously. A further difficulty arises from geometric considerations. Since the fluid flow is of the radial type in most cases, such effective methods as conformal transformation and the hodograph are not applicable. It is the purpose of this paper to present a method whereby free surface problems of this type may be solved rapidly to the desired order of accuracy by means of a combination of a network of electrical resistors and conventional analog computer units. The water coning problem is treated in some detail. Then the procedure for extending the technique to other free surface problems is indicated. FORMULATION Most commercial oil reservoirs consist of an oil-saturated sand, bounded above by an impermeable strata and below by a water-saturated sand. Gravimetric separation results in a horizontal oil-water interface. When an oil well is drilled so that it partially penetrates the oil zone, and production is initiated at a constant rate, the oil-water interface will assume a new shape as a result of the pressure gradients in the oil zone. It should be emphasized that this is a steady phenomenon. After an initial transient period the water phase will be completely static and only the oil will be in motion. The new steady-state shape of the interface, as shown in Fig. 1, depends upon the depth of penetration, d, the thickness of the oil zone, I, the production rate, q, the hydraulic permeability zone of the sand, k, the viscosity of the oil, µ, and the densities of the oil and water, p.,. and pw.. The problem is to determine this relationship. Darcy's law + = - (P f g p z).....(1) it.

Jan 1, 1957

By A. Rosenzweig, M. M. Karnowsky

The generalized binary diagram of the Au-Sn-Pb system is presented. The chief characteristic is the pseudobinary between lead and AuSn. On the high-gold side of the pseudobinary, four reaction isotherms were found at 363°, 274°, 225°, and 204°C. On the low-gold side of the pseudobinary, three reaction isotherms at 277°, 205°, and 176°C were found. A vertical section from the eutectic solder composition to gold was developed from the isothermal sections generated. METALLURGICAL problems arising from the intentional or accidental formation of Au-Sn-Pb alloys in soldering applications have indicated a need for information on the phase equilibria in this ternary system. The literature indicates that a complete diagram presenting this information has not been prepared. Even the recent excellent work by prince' entitled "The Au-Pb-Sn Ternary System" actually extends only to the AuSn or 50 at. pct Au range. There are more events in the 50 to 100 at. pct Au than in the less than 50 at. pct range. This article by Prince furnished much guidance in preparing this report. Initial efforts with the isopleth from the eutectic solder composition 61.9 wt pct Sn-38.1 wt pct Pb and 0 to 90 wt pct Au indicated that extensions of the work to the whole of the diagram (even if in less detail) were necessary to understand this system. In undertaking the construction of such a diagram, this study used differential thermal analyses (DTA) and metallography with verification and identification of phases by electron microprobe analyses. EXPERIMENTAL PROCEDURE The procedure began with the development of a cell which would be unreactive with lead, tin, and gold, retain its strength to 1100°C, exclude oxygen, and also furnish a suitable well for insertion and protection of a thermocouple to monitor temperature changes in the material. Such a cell would make it possible to reuse the sample should a repetition of determination be desired. Fig. 1 is a photograph of two such quartz cells as finally developed. The specimens have been run many times. The cell is made up of an inner sample bucket and an outer capsule with a thermocouple well which the sample surrounds. The DTA unit was an assembly devised from available instrumentation. The sample holder was a 3-in.-long cylinder of nickel, 2 1/2 in. in diam, fitted securely in a vertical tube furnace. Two holes 7/8 in. in diam were symmetrically located to receive the quartz cells. A dummy cell with nickel powder was used as the reference. The absolute temperature was recorded with a Pt/Pt 10-pct Rh thermocouple with an automatic Kaye ice bath compensator. (Calibration indicated the compensator to be accurate to better than ±0.5° over the 100° to 1000°C range.) The absolute temperature was measured in the sample and recorded on an L&N mul-tirange recorder with a full-scale display of 1 mv and automatic ranging of 99 mv. The differential signal between the sample temperature and the reference temperature was amplified with an L&N microvolt amplifier and recorded on an L&N Speedomax G recorder. Since two charts were obtained, the chart speeds were equalized and each event was noted on the differential chart, and the temperature at that time was obtained from the temperature record.

Jan 1, 1969

By H. R. Ogden, E. S. Bartlett, A. G. Imgram

Notched and unnotched tensile specimens of wrought and recrystallized, oxygmted and hydro-genated tantalum and columbium were tested over a range of temperatures selected to encompass the ductile-to-brittle transition. Increasing the oxygen content of tantalum and columbium increased their strength, and raised their ductility transition temperature, but did not cause a marked deterioration of notch properties below that of commercially pure material. The adverse effects of oxygen were more pronounced for recrystallized structures than for wrought material. The effects of hydrogen are complicated by strain aging or slow strain rate hydrogen embrittlement at -105°F. However, in general, hydrogen had only a minor effect an strength, but markedly increased the effective transition tem-terature and caused a deterioration of notch properties . BCC metals including the refractory metals in Groups Va and VIa (V, Cb, Ta and Cr, Mo, W) can be expected to undergo a ductile-to-brittle transition and exhibit brittle fractures at low temperatures.' Notch embrittlement is associated with this phenomenon, and can be a serious design problem. Table I compares the tensile transition behavior and notch sensitivity of commercially pure Group Va and VIa refractory metals. The Group VIa refractory metals have considerably higher transition temperatures, and become notch sensitive at higher temperatures, than do the Group Va refractory metals. In addition, the Group VIa refractory metals are sensitive to metallurgical structure. Recrystallized structures generally have higher transition temperatures than wrought material of the same composition. The relatively poor transition behavior of the recrystallized structures of these metals is generally attributed to the segregation of interstitial impurity atoms at grain boundaries. Pronounced sensitivity to structure is not evident with commercially pure Group Va refractory metals, however. Since these metals have higher solubilities for interstitial elements than do the Group VIa metals ,4 it can be expected that higher total interstitial concentrations are necessary to develop a comparable degree of grain boundary segregation and to produce a similar sensitivity of transition temperature to structure. Increasing only the concentration of interstitial atoms in solution would tend to increase the flow stress of a metal in relation to its cleavage fracture stress and thereby raise its transition temperature, but would not be expected to cause a marked sensitivity of transition temperature to structure. A research program has been conducted at the Battelle Memorial Institute to evaluate the effects of interstitial oxygen and hydrogen on the transition behavior and notch sensitivity of tantalum and columbium, and to evaluate the effects of structure on "contaminated" material. EXPERIMENTAL PROCEDURES Notched and unnotched tensile specimens of oxygenated and hydrogenated tantalum and columbium with both wrought and recrystallized structures were tested over a range of temperatures selected to encompass the ductile-to-brittle transition Oxygen levels selected for study in both tantalum and columbium were nominally 500 and 1000 ppm, whereas nominal hydrogen contents were 150 and 500 ppm in tantalum and 150 and 300 ppm in columbium. Oxygen and hydrogen additions were made directly to 6-in. lengths of 1/2-in.-diam electron beam melted wrought bar stock, in a Sieverts Apparatus. Subsequent high-temperature annealing was required for homogenization of the oxygenated material, but was not necessary in the case of hydrogenated stock. The oxygenated and hydrogenated bars were then swaged to 1/4-in.-diam rods. Tensile specimen blanks were cut from the 1/4-in.-diam rods and annealed to achieve stress-re-

Jan 1, 1963

By E. E. Anderson, R. L. Newacheck, J. Kohl

Radioactive materials were used underground before the advent of the nuclear reactor. Radium containing ores have been mixed with cements and other materials for later location in oil wells by gamma ray logging since 1940.1 Perforating bullets have been marked with radium salts,, and radioactive materials have been added to drilling muds to find the cause of "lost circulation."' More recently colloidal suspensions of radioactive cobalt-60 and silver-1103 and solutions of 1-1314 have been used in waterflooding operatiorns to determine injection profiles, flow paths and water velocities. In this paper a recent and interesting underground tracer application is discussed. Development work and field engineering were carried out under the direction of Tracerlab, lnc., with assistance from personnel of the client. A gaseous tracer, argon-41, was used in an attempt to determine the cause of leakage from an underground gas storage reservoir. STATEMENT OF PROBLEM This gaseous tracer application was carried out for the Natural Gas Storage Co. of Illinois. This company has developed an underground gas storage field 1,750 ft below the surface of the earth near the village of Herscher, Ill., about 60 miles south of Chicago. The total volume of gas stored in the field was estimated to be about 13 billion cu ft in the spring of 1954. The field has a maximum estimated storage capacity of 90 billion cu ft. The gas is contained in the Galesville sandstone, previously a water bearing formation of about 25 per cent porosity. The water as it is pushed out by the gas forms a barrier for the gas around the edge of the reservoir. Over the top and beneath the bottom of the reservoir are located several layers of impervious rock, which barring cracks or unplugged and unknown wells should act as seals. Twenty-one injection and withdrawal wells were drilled into the Herscher reservoir and gas injection was begun during the summer of 1953. After a few weeks of gas injection, evidence of gas leakage was detected at the surface; water wells began bubbling and losing prime, and dry spots in the fields indicated gas leakage from uncharted oil wells. In every case, the leakage could not be traced back any further than the water bearing formations a few hundred feet below the surface. An extensive search was made to locate uncharted oil wells which were believed to be possible channels for the gas from the storage formation to the water containing formation. Long-time residents in the area assisted in the location of several abandoned oil wells. The wells when located were cleaned out and either used as vent wells to relieve the gas pressure in the water formations, or were plugged with cement. None of the wells even approached depths which would endanger the soundness of the storage reservoir. All of the injection wells were tested for leaks in the casings by conducting neutron surveys and by other techniques. To detect any leakage up through the cement-filled annulus surrounding the casing, a section of the casing wall in one well was milled out. Then, plugs were installed above and below the cut-out section and pressure applied to the annulus, which proved conclusively that the cement was sound in that well. The well was then plugged with cement and abandoned. In another well, ammonia was injected into the well and a temperature log was made. It was hoped that a leak would be re-

Jan 1, 1956