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By A. B. Kinzel

SILICON, unfortunately, is not in the same category as some other metals with respect to the absolute value of the highest purity material prepared. Tucker, in England, and Becket, in this country have devel-oped procedures for the purification of silicon, and Becket's process has made industrially available silicon of a purity of 99.8 per cent or better. However, even the term "silicon metal" may be a paradox to some people, although not more so than the term "amorphous" as applied to silicon. These terms come from commerce, and "metal" is used to distinguish industrially high-purity silicon from ferrosilicon, silicon-aluminum, and other high-silicon alloys. Alloys of iron and silicon with 95 per cent Si or less are known as ferrosilicon, with a designation of silicon content where necessary, and the terns "silicon metal" is invariably applied to the grades containing 96 per cent Si and higher. The Becket method of purification was referred to in a monograph on the Alloys of Iron and Silicon, and the Tucker procedure was described in some detail in that publication.1 In order to get silicon of still higher purity, a sample, prepared by the Becket method, analyzing 99.84 per cent Si, 0.020 Fe, 0.016 Al, 0.005 Ca, 0.025 C, 0.033 per cent 02, 0.006 H2, 0.006 N2, and 0.001 per cent Mn, was crushed to pass a 100-mesh sieve said further purified by a modification of Tucker's procedure. This modification differs from Tucker's method in that after treatment the 100-mesh alloy was centrifuged to remove the last traces of acid. Our directly determined analysis of this purified sample shows: Si, 99.952 per cent; Fe, 0.009; Al, 0.012; Ca, 0.003; C, 0.006; or 99.982 per cent. Silicon by difference equals 99.97 per cent. The variation between silicon by difference and silicon as directly determined is important. Although Tucker mentions the amount of insoluble matter in commercial silicon both before and after his treat-ment, he does not mention the existence of carbon in the alloy; neverthe-less, lie reports silicon by difference. Any final figure as to purity obviously results from agreement between direct determination and

Jan 1, 1939

By Joseph F. Shirley

A froth flotation plant to recover byproduct molybdenite must be designed specifically for the selected separation process and the type of ore being treated. However, some general rules concerning byproduct molybdenite plant design can be suggested that would be valid for most processes. The term byproduct molybdenite in this paper is limited to the recovery of molybdenite from copper porphyry ores, which essentially amounts to selectively separating molybdenite from copper and iron sulfide concentrates. In addition, most of the discussions would apply only to the almost universally used approach of floating the molybdenite and depressing the copper and iron sulfide minerals. Thickener It is considered essential that the feed to a byproduct molybdenite plant be thickened prior to being treated for molybdenite recovery for the following reasons: 1) Thickening allows the rougher and any preconditioning stages to be operated consistently at the optimum percent solids. 2) Generally, the size of equipment used for pretreatment and the rougher flotation is considerably smaller and less expensive than if the copper flotation concentrates were treated directly. 3) The removal of as much water as practical by thickening removes flotation reagents added in the copper flotation circuit, especially frother which can be quite troublesome in a byproduct molybdenite plant. Although thickening of the molybdenite plant feed has long been recognized as necessary to optimum metallurigcal results, very often this area has been designed poorly. The thickener should be sized so that it can produce a consistent thickened product containing 60 to 65% solids without the use of flocculants. Some plants are only able to thicken to 45 to 50% solids consistently while other plants let the percent solids vary from 45 to 60% over a 24-hr period. While the former is more desirable than the latter, in many cases better metallurgical results could be obtained if the percent solids could be held consistently close to 60%. Probably the simplest and most satisfactory system of handling the thickener underflow is to spigot it into a sump, using a sphincter type valve for the orifice, controlled by a density meter. Another satisfactory approach is to use an ODS type pump to meter the underflow. There are other methods of handling thickener underflow which work satisfactorily as long as the amount of copper concentrates entering the thickener is relatively uniform. However, they often fail to operate satisfactorily when there are large fluctuations in the thickener feed rate due to fluctuations in ore tonnage and/or copper grade. If the percent solids in the plant feed could be held close to 65%. There is the possibility the molybdenite plant tailing would not have to be thickened prior to the copper filter plant. This means that the molybdenite rougher float would have to be conducted at 45 to 50% solids with all the cleaner tailings returned to the rougher for dilution. Admittedly, in some situations this approach would be impossible, but if capital or plant area is limited, it should be considered.

Jan 1, 1981

By Charles E. Weaver

During the past few years there has been considerable activity in prospecting for oil and gas in several parts of western washington. From time to time seepages of oil or emanations of gas have been reported from various places. Several companies have been organized for the purpose of drilling, but only a part of these have actually begun operations. In certain localities very small seepages of oil occur, but up to the present time no oil or gas in commercial quantities has been obtained. In order to determine the conditions which may be favorable or unfavorable to the occurrence of petroleum it becomes necessary to know the character and extent of the geological formations in which such deposits might occur. In other regions where producing wells have been developed it is possible to know what formations contain the oil and what structural conditions influence its concentration in reservoirs or zones. It is usually possible to determine those strata which contained the materials from which the petroleum may have been derived and also the position and distribution of the more porous sandstone belts into which it may have collected. Detailed stratigraphic surveys may even determine the depth at which a certain known oil-bearing zone may be tapped at any particular place. It is also possible to recognize those formations which are presumably barren of oil, as well as those which are absolutely so. In new regions far distant from any of those which are now producing or have produced in the past, it becomes absolutely impossible to foretell whether oil may exist in commercial quantities or not. Assuming that such deposits do exist, it is extremely difficult to predict at what depth the produciqg zone or zones occur. However, in prospecting in a new and unexplored region, use should be made of such laws as have been found to govern the occurrence of petroleum deposits in other well-developed fields. Such deposits in their world-wide distribution are found almost exclusively associated with sedimentary rocks. Areas composed predominatingly of igneous and metamorphosed rocks are to be rcgarded as extremely unfavorable localities for the occurrence of commercial deposits of oil or gas. Assuming that such oil deposits are

Jan 1, 1916

By A. J. Shaler, J. Prieto Isaza, John Wulff

TANTALUM metal has a number of unique properties which give it widespread application in modern technology and in research. In electronic apparatus involving high temperatures in vacuo some of the refractory metals become brittle. Tantalum retains its ductility at elevated temperatures, and this property, together with its low vapor pressure and its ability to absorb gases, make it important in this field. Its chemical inertness in the presence of acids, halogens, and other corrosive media, makes it useful in chemical apparatus and in neuro and orthopedic surgical applications. As an addition to tungsten carbide in steel-cutting grades of cemented-carbide tools, the carbides of tantalum and of its sister element columbium have found considerable use. The present-day method1 of manufacturing tantalum is to sinter a powder compact of the metal in vacuo. Because tantalum- columbium alloys are difficult to work and since tantalum ores almost always contain columbium, the two metals must be separated chemically, the products of the separation being generally in the form of potassium tantalum fluoride and potassium columbium oxyfluoride. These salts are used in fused-salt electrolytic baths from which coarse metallic powder is deposited as a sponge at the cathode. Finer powder can be made from the coarse product or from tantalum scrap by first submitting it to an embrittling heat treatment in hydrogen and then crushing it. The fine hydrogen- containing powder may subsequently be degassed in vacuo at a high temperature. Prompted by the success of others2,3 in the magnesium reduction of titanium and zirconium halides, one of the authors under- took4 an investigation of the thermo- chemistry of the reaction between solid magnesium and gaseous tantalum penta-chloride, a subject which had not previously been studied. He found that the heat of formation of tantalum pentachloride is approximately 364,250 cal per mol at temperatures lower than the melting point of magnesium. A value of 83 units was found for the standard entropy at these temperatures. With these values, it was shown that magnesium and tantalum pentachloride are capable of reacting exothermically at temperatures less than the melting point of magnesium, and that no great violence is to be expected when these substances are heated together. The exothermic nature of the reaction indicated that the process should be efficient and should not require much externally applied energy. Tantalum pentachloride is not commonlv made commercially, and any process using it therefore involves the subsidiary problem of producing and handling this substance. A series of experiments was carried out in which dried chlorine saturated with carbon tetrachloride was passed over heated tantalum, either in the metallic state or combined

Jan 1, 1947

GENTLEMEN Herewith are transmitted reports from the Treasurer and of the principal standing committees of the Institute. To these special reports members are referred for details as to the year's work. Despite the unfavorable business conditions obtaining throughout the year, the Institute was able to carry on its various activities without curtailment and without drawing on the surplus accumulated through previous years. In fact, small additions were made to the Life, Member¬ship and various other funds. It is highly desirable that such additions should continue to be made, especially to the Life Membership fund, for reasons reported last year. At present, money must be used from current receipts in order to enable the Institute to fulfill its obligations to those who on joining the organization commuted their dues by a single payment. In addition, with the passage of years the number increases of those who have paid dues forty years or more and who, by reason of age or dis¬ability, are unable longer to practise their profession. These men have supported the Institute through their active professional life and it would be a pity to lose them as members through resignation or for failure to keep up their dues. In accordance with the By-laws the Board has authority to advance such members, on application, to the Honor Roll of Senior Members and to relieve them from further payment of dues. It has been the policy of the Board to do this liberally, but to keep up this, as well as to meet other obligations, it is necessary for money to be provided. It has been estimated by the Treasurer that nearly $50,000 additional should be placed in the Life Membership fund as soon as possi¬ble to meet these obligations without using current income and to that end it is necessary, not only to avoid running behind currently but to earn, if possible, some surplus each year. The small amount transferred to the Life Membership fund from surplus this year was, as a matter of fact, made possible by certain members paying personally bills that were properly chargeable to the Treasury. Such generosity is common among those active in Institute work and probably no year would have closed with a surplus except for it.

Jan 1, 1923

By G. E. Pellissier, C. W. Mason

Tin has long been cited as offering a classic example of polymorphism, second in repute only to the allotropy of sulphul.. The notorious "tin disease," which Cohenl has studied so exhaustively in terms of the enantiotropic transformation of tetragonal white P tin to cubic gray a tin, has apparently encouraged the expectation that one or more additional polymorphic modifications might exist. The search for confirnmntion of this idea has, as might be anticipated, led to the accumulation of a body of miscellaneous evidence, much of which would probably never have been sought, or taken seriously even by its discoverers, but fur previous assumptions. The ball apparently was started rolling iii 1880 by Trechmann,2 who reported a new modification of tin (7 tin), which was brittle and found in "hard head," a highly arsenical, slaggy material produced in a certain stage of tin smelting. A mixture of two kinds of crystals was obtained from a Cornish tin furnace, and those thought to be 7 tin were studied crystallographically. The results indicated that these crystals were rhombic and of different density from the tetragonal tin prepared electrolytically by Miller. Their analysis was given as 98.7 per cent Sn, 1.3 per cent Fe, and traces of As, Sb, Bi and S. In 1881 von Foullon4 obtained similar crystals from a Bohemian tin furnace. Headden5 examined crystals similar to those of Trechmann and von Foullon and reported them to be monoclinic, but of analysis corresponding to stannous sulphide. Later, Stevanovic,~ by goniometric measurements, proved that these crystals of SnS were really rhombic. Groth7 pictures and describes both "rhombic tin" (Fig. 9, vol. 1) ant1 stannous sulphide (Fig. 84, vol. 1); their faces and angles correspond within the accuracy of measurement. Spencers in 1921 examined the above evidence critically; lie lound similar crystals from Cornish tin furnaces, proved them to be SnS, and even was able to analyze some of Trechmann's original specimens, finding high sulphur content. (Apparently Trechmann's analysis had been based on :L second lot of crystals, not described crystallographically.)

Jan 1, 1939

By G. E. Pellissier, C. W. Mason

Tin has long been cited as offering a classic example of polymorphism, second in repute only to the allotropy of sulphul.. The notorious "tin disease," which Cohenl has studied so exhaustively in terms of the enantiotropic transformation of tetragonal white P tin to cubic gray a tin, has apparently encouraged the expectation that one or more additional polymorphic modifications might exist. The search for confirnmntion of this idea has, as might be anticipated, led to the accumulation of a body of miscellaneous evidence, much of which would probably never have been sought, or taken seriously even by its discoverers, but fur previous assumptions. The ball apparently was started rolling iii 1880 by Trechmann,2 who reported a new modification of tin (7 tin), which was brittle and found in "hard head," a highly arsenical, slaggy material produced in a certain stage of tin smelting. A mixture of two kinds of crystals was obtained from a Cornish tin furnace, and those thought to be 7 tin were studied crystallographically. The results indicated that these crystals were rhombic and of different density from the tetragonal tin prepared electrolytically by Miller. Their analysis was given as 98.7 per cent Sn, 1.3 per cent Fe, and traces of As, Sb, Bi and S. In 1881 von Foullon4 obtained similar crystals from a Bohemian tin furnace. Headden5 examined crystals similar to those of Trechmann and von Foullon and reported them to be monoclinic, but of analysis corresponding to stannous sulphide. Later, Stevanovic,~ by goniometric measurements, proved that these crystals of SnS were really rhombic. Groth7 pictures and describes both "rhombic tin" (Fig. 9, vol. 1) ant1 stannous sulphide (Fig. 84, vol. 1); their faces and angles correspond within the accuracy of measurement. Spencers in 1921 examined the above evidence critically; lie lound similar crystals from Cornish tin furnaces, proved them to be SnS, and even was able to analyze some of Trechmann's original specimens, finding high sulphur content. (Apparently Trechmann's analysis had been based on :L second lot of crystals, not described crystallographically.)

Jan 1, 1939

By Walter Renton Ingalls

Metallurgical literature has no record of any ore beneficiated for cadmium alone, and the cadmium of commerce is derived from zinc ore, with which cadmium is generally associated. Zinc ores free from cadmium—e.g., the ores of the Franklin and Stirling mines, New Jersey, and of Broken Hill in Rhodesia—are rare. Blende concentrates of 50 to 60 per cent grade have contained (in production of important tonnage) as much as I per cent Cd, which is unusually high. The concentrates from the Tri-State district average from 0.3 to 0.4 per cent Cd, which is high. The concentrates from mines west of the Rocky Mountains seldom are higher than 0.2 per cent. In the periodic system of the elements, cadmium is in the same group with zinc. Its properties and compounds are similar. Its metallurgy is also similar. Cadmium has a melting point of 320°C. and a boiling point of 778"C., while the melting point of zinc is 415'C. and the boiling point gos°C. These conditions, together with the lower reduction temperature of cadmium oxide, indicate means for. separating cadmium from zinc. Cadmium in spelter is viewed, if not as an impurity, at least as an alloying element that may be objectionable, its special effect being hardening. However, for some purposes, a little cadmium in spelter is desired, and 0.4 per cent may be permissible, even in spelter for rolling. Cadmium in spelter for brassmaking is completely volatilized at the temperature of that process, and in bygone days an immense quantity of cadmium must have been lost in the fumes from these furnaces. Pyrometalltjrgy—Early Cadmium compounds, sulphide and oxide, being more volatile than the corresponding compounds of zinc, loss of cadmium begins to occur from the first furnace operation. In normal roasting, even with Tri-State ore, this loss may not be very high. Raw ore, assaying 0.4 per cent Cd, may be expected to give a roasted product of the same assay, which would imply a cadmium loss of about 15 per cent. Roasted ore, assaying 0.4 per cent Cd when distilled at ordinary furnace temperature, yielded spelter containing about half of that in the ore charged. The first draw of spelter under these conditions may assay 0.8 per cent Cd (accounting for 22 per cent of the cadmium recovery) and after the several draws of spelter have been equalized the cadmium content may average 0.35 per cent. If, therefore, 2000 lb. of blende averaging 0.35 to 0.4 per cent Cd is roasted and distilled, there may be obtained 1000 lb. of spelter, assaying 0.35 per cent Cd or 3.5 lb. content, which entering into Prime Western spelter will be sold at the spelter price. It will be observed from the outline hereinbefore (summarizing conditions prior to the introduction of sintering) that the main loss of cadmium occurred in the distillation process and by failure to condense, which could be ameliorated by attaching a prolong to the condenser, thus collecting

Jan 1, 1944

By L. N. Cosner, C. F. Austin, J. K. Pringle

Shock wave attenuation studies with three igneous rocks are reported: a spessartite elastic to low intensity stress waves, a diorite which is anelastic, and a porous scoria. The level of shock passing through a given thickness of rock has been determined by donor-receptor methods using high speed streak cameras. Test results include shock propagation velocities adjacent to the explosive, the dependence of test results upon test geometry, and the variation in shock wave attenuation in these three common igneous rock fabrics. The utilization of explosives in rock mediums involves a series of interrelated phenomena. These are the detonation process within the explosive, the transfer of energy from the explosion products to the surrounding rock medium in the form of sound or shock waves, and the transmission of the resulting waves through the rock medium to create damage in the rock mass. The subject of this paper is the investigation of the close-in phenomena that occur in the intensely shocked rock immediately adjacent to a detonating explosive charge. The specific aspects studied include propagation velocities, free surface velocities, pulse attenuations and the determination of the equations of state for the test rocks employed. In addition, a series of tests was conducted to indicate the dependence of the test results on the charge diameter utilized. The equations of state for rock materials have been investigated by a number of authors. Lombard, ',' Grine and Fowles,3,4 Zharkov, 5 Hughes and McQueen,6 Chabai,7,8 and Bass9 have published equation of state data on rock materials similar in structure or composition to those investigated in the study. Rinehart10 has prepared a voluminous tabulation of the available equation of state data from these publications and in addition has included data on many other rock and earth materials in his compilation. The reader is referred to the extensive tabulations and bibliography of Rinehart for classical studies involving the equations of state of metals and other solids and liquids. The problems of sympathetic detonation between drill holes in hard rock environments has received the attention of various authors as have the problems of explosive rock coupling close-in stress wave attenuation and explosive diameter effects. 11 to 18 In particular, the don or-receptor geometry of this report is very similar to the geometry of adjacent drill holes in rock. Most published pulse velocity and attenuation work in rock has been devoted to velocities at much lower amplitudes than those associated with close-in explosives phenomena and most attenuation studies involve transmission and attenuation across large spans of material. Excellent work in these areas has been published by the U. S. Bureau of Mines and by many individuals and groups engaged in geophysical research. SELECTION OF TEST MATERIALS A series of rock materials was desired for this test program that would be meaningful industrially, and that would also yield comparative results from a research viewpoint. Based on the availability of a series of related petro-fabrics, for which there is an abundance of physical and shock response data, three igneous rocks were selected as the test series. The applicability of shock wave studies in igneous rocks to industrial problems is readily demonstrated. Hardrock tunneling, quarrying and mining take place in igneous rocks throughout the world. From a research point of view, igneous rocks exhibit a wide variety of grain sizes and considerable diversity in composition, yet the common igneous rocks have a general similarity in their constituent mineral structures and in their grain-to-grain bonding mechanisms. The latter is based on the concept of rock formation through magma cooling and crystallization, though the degree of liquefaction in granitic plutonic masses is indeed a moot question. Three specific types of igneous rock were chosen for study. A coarse-grained granitic textured rock was desired that would serve as a representative of the widely abundant intrusive rocks of the world and

Jan 1, 1967

By P. R. Sperry, M. L. Holzworth, P. A. Beck

The basic work of Z. Jeffries 1,2,3 has long ago established the main features of grain growth in the presence of a dispersed second phase. Working with sintered specimens of initially fine grained tungsten, to which various amounts of thoria had been added, Jeffries found that grain growth was inhibited, that is, practically prevented, up to a certain annealing temperature. When this temperature, which increased with the thoria content, was exceeded, extremely large grains developed abruptly from the fine grained matrix. such a a temperature" was later found by Gross-mann~3,14 in certain types of steel, while ~~i~ showed15 that in other steels grain growth was gradual, without inhibition and abrupt coarsening. Later work demonstrated the connection between coarsening and aluminum additions. The viewpoint that the direct cause of inhibition and coarsening in aluminum killed steels is a fine dispersion of aluminum oxide21 appears to be held quite generally, although some doubts have been voiced even very recently, 20 In steels with Ti additions the titanium carbide phase is considered responsible for the inhibition effects found.20 The coarsening temperature increases with the titanium content. That coarsening may occur, as a result of, certain heat treatments, even in low carboil rimmed sheet steel, was shown by Samuels. He also detected coarsening in a steel ingot of similar composition, after giving it the same heat treatment as that used by him for the sheet material. In this instance the identity of the inhibiting phase has not been determined. However, Tangerding found23 that even the few small carbide particles, which occur in carbonyl iron, have a very marked inhibitive effect. As a result of an oxidizing anneal at 850°C, large grains begin to form at the surface of the carbonyl iron specimen, and gradually grow inward as the subsurface oxidation of the carbide particles progresses and eliminates the obstruction. The carbide particles Can be removed also by annealing in hydrogen, with similar results. But if the oxidizing anneal of 10 hr at 850°C in air is followed between in hydrogen for 75 hr at the Same temperature, grain growth is more hibition usually the whole specimen is transformed into a single crystal (approx. 1.5 cm X 5 cm). The reversed procedure, that is, hydrogen annealing followed by oxidizing annealing leads to smaller grains. Tangerding arrived at the logical conclusion that there must have been in his specimens some additional obstruction to grain growth hibition from a minor impurity, other than carbon. It seems likely that this obstruction was caused by an oxide formed during the oxidizing anneal and gradually reduced rtain the subsequent hydrogen-annealing. Other instances of grain growth inhibition of varying severity, associated with a dispersed second phase, have been described by several authors. Notable examples: lead with 0.06 pet Cu or Ni,24 cartridge brass with 0.12 pct Cr,25 or with up to 0.15

Jan 1, 1949

By Bailey Willis, George Otis Smith

I. Summary of General Features. Location.—The Clealum iron-ore deposits occur on Clealum river, a tributary of the Yakima river; in the eastern spurs of the Cascade range, Washington.† Mount Stuart, 9470 feet in altitude, is a dominant peak of the district, which will therefore be referred to as the Mount Stuart district. By way of the valley and cañon of the Clealum, the ores are 18 miles from Roslyn, the colliery-town, which is reached by a short branch from the Northern Pacific Railroad. Where they occur the valley has an elevation of 2900 to 8000 feet above sea; that of the end of the branch railroad at Ronald is 2345 feet. The grade of the valley from near Ronald to the junction of the Clealum and Salmon Lasac rivers, 144 miles, is 20 feet per mile; thence to the iron-ores it is 130 feet per mile, through a cañon 241/2 miles long. Abreast of the deposits the western wall of the valley is formed by precipices of sandstone; the eastern slope is comparatively gentle, being cut in easily eroded

Jan 1, 1901

By Elmer A. Jones

Like the caboose on the end of a long freight train L made up of mineral and metal processing and consuming industries, the mining industry progresses according to the movement of the train to which it is coupled. Sometimes the caboose rolls smoothly; occasionally it bumps along on the ties; almost always it is under criticism from someone for being too small, too large, too expensive, foolishly progressive, or hopelessly out of date. We who ride in the caboose are used to the rough by now, but it is nice now and then to have a bit of the smooth. Last year the train of industrial production rolled ahead swiftly and smoothly, and, except for a hot-box caused by strikes in copper mines, so did the caboose. As is brought out elsewhere in this issue, the outlook for 1956 is for more of the same.

Feb 1, 1956

By R. Al-Hussainy, P. B. Crawford, H. J. Ramey

The effect of variations of pressure-dependent viscosity and gas law deviation factor on the flow of real gases through porous media has been considered. A rigorous gas flow equation was developed which is a second order, non-linear partial differential equation with variable coeficients. This equation was reduced by a change of variable to a form similar to the diffusivity equation, but with potential-dependent diffusivity. The change of variable can be used as a new pseudo-pressure for gas flow which replaces pressure or pressure-squared as currently applied to gas flow. Substitution of the real gas pseudo-pressure has a nrtmber of important consequences. First, second degree pressure gradient terms which have commonly been neglected under the assumption that the pressure gradient is small everywhere in the flow system, are rigorously handled. Omission of second degree terms leads to verious errors in estimated pressure distributions for tight formations. Second, flow equations in terms of the real gas pseudo-pressure do not contain viscosity or gas law deviation factors, and thus avoid the need for selection of an average pressure to evaluate physical properties. Third, the real gas pseudo-pressure can be determined numerically in term of pseudo-reduced pressures and temperatures from existing physical property correlations to provide generally useful information. The real gas pseudo-pressure was determined by numerical integration and is presented in both tabular and graphical form in this paper. Finally, production of real gas can be correlated in terms of the real gas pseudo-pressure and shown to be similar to liquid flow as described by diffusivity equation solutions. Applications of the real gas pseudo-pressnre to radial flow systems under transient, steady-state or approximate pseudo-steady-state injection or production have been considered. Superposition of the linearized real gas flow solutions to generate variable rate performance was investigated and found satisfactory. This provides justification for pressure build-up testing. It is believed that the concept of the real gas pseudo-pressure will lead to improved interpretation of results of current gas well testing procedures, both steady and unsteady-state in nature, and improved forecasting of gas production. INTRODUCTION In recent years a considerable effort has been directed to the theory of isothermal flow of gases through porous media. The present state of knowledge is far from being fully developed. The difficulty lies in the non-linearity of partial differential equations which describe both real and ideal gas flow. Solutions which are available are approximate analytical solutions, graphical solutions, analogue solutions and numerical solutions. The earliest attempt to solve this problem involved the method of successions of steady states proposed by Muskat.' Approximate analytical solutions' were obtained by linearizing the flow equation for ideal gas to yield a diffusivity-type equation. Such solutions, though widely used and easy to apply to engineering problems, are of limited value bemuse of idealized assumptions and restrictions imposed upon the flow equation. The validity of linearized equations and the conditions under which their solutions apply have not been fully discussed in the literature. Approximate solutions are those of Heatherington et al.. MacRobertsl and Janicek and Katz.' A graphical solution of the linearized equation was given by Cornell and Katz. Also, by using the mean value of the time derivative in the flow equation, Rowan and Clegg' gave several simple approximate solutions. All the solutions were obtained assuming small pressure gradients and constant gas properties. Variation of gas properties with pressure has been neglected because of analytic difficulties. even in approximate analytic solutions. Green and Wilts8 used an electrical network for simulating one-dimensional flow of an ideal gas. Numerical methods using finite difference equations and digital computing techniques have been used extensively for solving both ideal and real gas equations. Aronofsky and Jenkins"I " and Bruce et al.11 gave numerical solutions for linear and radial gas flow. Douglas et al." gave a solution for a square drainage area. Aronofsky 13 included the effect of slippage on ideal gas flow. The most important contribution to the theory of flow of ideal gases through porous media was the conclusion reached by Aronofsky and Jenkins" that solutions for the liquid flow case'" could be used to generate approximate solutions for constant rate production of ideal gases. An equation describing the flow of real gases has been solved for special cases by a number of investigators using numerical methods. Aronofsky and Ferris 10 onsidered linear flow, while Aronofsky and Porter 17 considered radial gas flow. Gas properties were permitted to vary as linear functions of pressure. Recently, CarteP 18 proposed an empirical correlation by which gas well behavior can be estimated from solutions of the diffusivity equation using instantaneour values of pressure-dependent gas

Jan 1, 1967

By E. C. W. Perryman

The recovery of X-ray line broadening, hardness, and electrical resistivity from cold worked AI-Mg alloys has been investigated. The results, together with those from density measurements, suggest that magnesium atoms freeze in the excess vacancies formed by cold working, and that this affects the climb of dislocations during the recovery process. PREVIOUS work1, " has shown that while 1 pct Mg increases the activation energy for recrystalliza-tion, it decreases the activation energy for the recovery of mechanical properties and decreases the subgrain size both after cold working and annealing. A similar result has been reported by Varley2 for an A1-2 pct Mg alloy. With plastic deformation at high temperatures, McLean and Farmer' and Rachinger have found that magnesium appears to retard the motion of dislocations and, furthermore, they find little or no effect of magnesium on the size of subgrains formed during high temperature deformation. In view of the apparent contradictions as to the effect of magnesium on subgrain size, the recovery process in Al-Mg alloys has been investigated more thoroughly by studying the annealing out of X-ray line broadening, hardness, and electrical resistivity from alloys cold worked at room temperature. Material Used—The chemical analyses of the alloys are given in Table I. Fabrication—The material used was cold rolled 20 pct at room temperature, the grain size prior to the last cold rolling operation being similar to that used in previous work; i.e., 230. The experimental procedure for annealing, determination of X-rav half-veak breadth. hardness measurement, electEica1 resistivity, and density and metallographic examination was exactly the same as previously described." Variation of X-Ray Half-Peak Breadth with Annealing Time—Isothermal annealing curves at 100°, 200°, and 250°C were obtained for material cold worked 20 pct. The half-peak breadth of the (333) Ka, line directly after cold working is shown as a function of magnesium content in Fig. 1. Only with the 2.87 pct Mg alloy was overlapping of the a, and n.. reflections observed to any appreciable extent. To separate these, Rachinger's method' was used. Typical isothermal annealing curves are shown in Figs. 2 and 3 for 100" and 200°C, respectively. These curves are similar to those obtained previously for super-purity aluminum except that the

Jan 1, 1957

By R. N. Upadhyay, M. Maleki, I. Fatt

Conventional laboratory core analysis tests on samples of two limestone reservoir rocks indicate that about 20 per cent of PV is in dead-end pores. These tests (electric logging formation factor, mercury injection capillary pressure and miscible displacement) were carried out on 1/4-in. diameter test plugs. Test results show a clear dilference between these samples and sandstone or homogeneous limestone reservoir rock. Although the amount of dead-end pore space can be only roughly estimated, the presence of such pore space seems clearly indicated. Pressure transient studies also show presence of deadend PV. Although they do not give quantitative results, pressure transient data yield a reasonable estimate of the size of the neck connecting dead-end pores to the main flow channels. INTRODUCTION Equations conventionally used to describe reservoir flow behavior contain the implicit assumption that all connected pore spaces contributed to both porosity and permeability. Several authors3-7 have pointed out the changes in pressure transient behavior and in electric log interpretation that may result if this assumption is incorrect and, instead, dead-end or cul-de-sac pores are present. There is a need for laboratory tests that can detect presence of dead-end pores in core samples. With such information on hand the petroleum engineer can make more rational use of the mathematical tools now available for analysis of reservoir flow behavior. This paper describes laboratory studies designed to detect and, if possible, give a quantitative measure of dead-end PV in laboratory-size core plugs. Three reservoir rocks were used, two of which were limestones suspected of having deadend pore spaces and a well-known sandstone, used as a comparison standard, in which there is believed to be little or no dead-end pore space. All the studies were designed to measure the natural dead-end PV; i.e., the pore space which is dead-ended because of rock structure. During multiphase flow in a rock without dead-end pores, some parts of one of the phases can become surrounded by the other, thereby giving (for certain flow behavior) an effective dead-end pV8,9. Such behavior will not be described here.

Jan 1, 1967

By K. O. Stamm, B. A. Rogers

Because it is the basis of the economically important operation of hardening steel by quenching, the A3 transformation in iron has been the subject of numerous investigations. Although the contributions to this subject are interesting, no general review will be given here. Readers who care to follow the matter further are referred to the comprehensive summary by Cleaves and Thompson,l which covers the literature to about 1935. Their references to 53 papers on the subject suggest that further investigation is hardly justifiable. However, considerable interest has devel oped recently concerning the reversibility of the transformation. From thermo-dynamic considerations, the transition ought to occur at the same point on heating or cooling, if the change of temperature is sufficiently slow. Yet all of the earlier investigators found a difference of several degrees. Burgess and Crowe,2 who used thermal methods, obtained average temperatures of 912" for Ac3 and 900°C. for Ar3 on electrolytic iron. Their data indicate a considerable range of temperature over which the change occurs, both on heating and on cooling. Terry3 measured the susceptibility in the critical range and estimated from the steepest parts of his curves that Ac3 came at 9I8° and Ar3 at 903°C. Ishiwara4 was one of the first investigators to report a shorter interval between the temperature of the change in the two directions. He measured the change of susceptibility of kaolin-coated samples of steel, in a hydrogen atmosphere, at rater of heating and cooling so low that about 3 or 4 hr. were required for the transformation to complete itself. His results show some variability between samples, but indicate that the difference between Ac3 and Ar3 is in the vicinity of 6°C. Roberts and Davey5 measured the space lattice in pure iron in the vicinity of 900°C. and concluded that a change occurs reversibly between 907' 3" and 910" 3°C., probably between 907" and 910°C. Wells, Ackley, and Meh16 made dilatometric determinations of the Ac3 and Ar3 points in samples of hydrogen-treated carbonyl iron maintained under a vacuum. They used three rates of heating and cooling: 2°, ½°, and .?°C. per min. and found the spread between the two points decreased with low rates. At the slowest rate, the Ac3 transition occurred at 909° to 909. 5°C. and the Ar3 change at 907°C. in three of the samples believed to contain the lowest percentages of alien elements. They concluded that if the rate of temperature change and the content of alien eiements were low enough, the A3 transformation would be completely reversible at 909.50 + 1°C. The question of reversibility is an interesting one and when some iron with especially small percentages of alien elements became available the opportunity to conduct an investigation was welcomed. This iron was prepared by the Division of

Jan 1, 1942

By B. A. Rogers, K. O. Stamm

Because it is the basis of the economically important operation of hardening steel by quenching, the A3 transformation in iron has been the subject of numerous investigations. Although the contributions to this subject are interesting, no general review will be given here. Readers who care to follow the matter further are referred to the comprehensive summary by Cleaves and Thompson,l which covers the literature to about 1935. Their references to 53 papers on the subject suggest that further investigation is hardly justifiable. However, considerable interest has devel oped recently concerning the reversibility of the transformation. From thermo-dynamic considerations, the transition ought to occur at the same point on heating or cooling, if the change of temperature is sufficiently slow. Yet all of the earlier investigators found a difference of several degrees. Burgess and Crowe,2 who used thermal methods, obtained average temperatures of 912" for Ac3 and 900°C. for Ar3 on electrolytic iron. Their data indicate a considerable range of temperature over which the change occurs, both on heating and on cooling. Terry3 measured the susceptibility in the critical range and estimated from the steepest parts of his curves that Ac3 came at 9I8° and Ar3 at 903°C. Ishiwara4 was one of the first investigators to report a shorter interval between the temperature of the change in the two directions. He measured the change of susceptibility of kaolin-coated samples of steel, in a hydrogen atmosphere, at rater of heating and cooling so low that about 3 or 4 hr. were required for the transformation to complete itself. His results show some variability between samples, but indicate that the difference between Ac3 and Ar3 is in the vicinity of 6°C. Roberts and Davey5 measured the space lattice in pure iron in the vicinity of 900°C. and concluded that a change occurs reversibly between 907' 3" and 910" 3°C., probably between 907" and 910°C. Wells, Ackley, and Meh16 made dilatometric determinations of the Ac3 and Ar3 points in samples of hydrogen-treated carbonyl iron maintained under a vacuum. They used three rates of heating and cooling: 2°, ½°, and .?°C. per min. and found the spread between the two points decreased with low rates. At the slowest rate, the Ac3 transition occurred at 909° to 909. 5°C. and the Ar3 change at 907°C. in three of the samples believed to contain the lowest percentages of alien elements. They concluded that if the rate of temperature change and the content of alien eiements were low enough, the A3 transformation would be completely reversible at 909.50 + 1°C. The question of reversibility is an interesting one and when some iron with especially small percentages of alien elements became available the opportunity to conduct an investigation was welcomed. This iron was prepared by the Division of

Jan 1, 1942

By D. A. Dukelow, G. Derge

THE Fe0-Mn0-Si0, system has many properties of fundamental interest besides its occurrence in steel-making. The system is the simplest ternary complication of the FeO-SiO, binary whose electrochemical properties have been explored. Therefore, knowledge of the conformance of Fe0-MnO-SiO, melts to Faraday&apos;s laws, as investigated by current efficiency measurements, would be of particular value in interpreting the observed variations of electrical conductivity, while at the same time furthering understanding of this type of molten oxides. Pertinent to the present study are conductivity data of FeO-SiO, and Fe0-Mn0-SiO2, and current efficiency data of FeO-SiO,. Concerning conductivity measurements, Inouye, Tomlinson, and chipman&apos; studied the specific conductivity, a, of molten wüstite as a function of temperature and oxide addition. Liquid FeO in equilibrium with an iron crucible was found to have a o whose magnitude and positive temperature coefficient were undeniably semiconductor in nature (o1400°C = 269 ohm-1cm-&apos;). Additions at 1400°C of 5 mole pct MnO decreased o to 227 while a similar addition of SiO2, dropped o to 125. Additional SiO2 produced an exponential decline of o. It was reasoned that because wüstite is known to be oxygen excess and since there is no pronounced change in oFeO upon melting, that UFeO(L)is p-type semiconduction. Björling2 gives o data for the ternary FeO-MnO-SiO, using fayalite, 2 FeO-SiO,, as the base substance. Upon addition of tephroite, 2 MnO-SiO, he noted a small decrease in o. Taking his data for 1400°C with one-half of the fayalite replaced by tephroite, o shows a decrease of some 40 pct relative to o for fayalite, i.e., 5 ohm-&apos; cm-&apos; to 3. In line with this observation, Mori and Matsushita3 reported that substituting MnO for FeO in the silicate de- creased o slightly except at high SiO, contents where the decrease was somewhat larger. Investigating the ionic nature of FeO-SiO2 melts, Simnad, Derge, and George4, found the anode current efficiency, C,, as calculated from iron anode weight loss, was temperature invariant and in general increased with SiO2 concentration. The authors suggested the possible presence of electronic conduction to explain why C+ < 100 pct. Fig. 4 includes their results as curve (b). EXPERIMENTAL METHOD Apparatus—Fig. 1 is a schematic section of the electrolysis cell used in all the current efficiency runs. The melt was contained in an iron crucible that rested on an alundum ring. A centered silica tube came within 1 in. of the surface of the melt and initially served as a thermocouple well and then as the guide for the anode.

Jan 1, 1961

By R. J. Walter, W. T. Chandler

The Ch-H phase diagram was determined for by-drogen concentrations up to ChHo.9 at temperatures below 400°P&apos;. The phase diagram includes a mis-cibility gap and a eutectoid transformation. A peri-tectoid transformation is postulated at the hydrogen-rich end of the diagram, Phase diagrams were determined for two levels oj purity, of the columbium. A single solid solution exists in the Cb-H system above 400°F. There has been considcrable disagreement among investigators concerning the system at temperatures below 400°F. Albrecht, Goode, and ~allett&apos; proposed a miscibility gap containing two bcc phases with the two lattice parameters converging at about 140°C (285-F), and Brauer and ~erman&apos; found a two-phase room-temperature region between 10 and 41 at. pct H. At sufficiently high hydrogen concentrations in the one-phase region, the hydrogen-rich phase was found to be face-centered orthorhombic. Wainwright, Cook, and Hopkills3 recently reported that the face centered orthorhombic hydride phase is derived from a unit cell which is slightly tetragonal with a small departure from 90 deg of the angle (y) opposite the r axis. The orthorhombic hydride phase was observed for hydrogen concentrations between 0.2 and 0.8 H/Cb atom ratio. Paxton and coworkers4 found that needlelike hydride plates formed in a hydrogen-charged columbium single crystal and suggested that this transformation possessed the characteristics of a diffusionless phase transformation. On the basis of room-temperature, X-ray diffraction data, komjathy&apos; suggested that an order-disorder or martensitic transformation occurs. In the present study, the Cb-H system was investigated to resolve the discrepancies found in the literature for this system. PROCEDURE The columbium specimens were prepared from two heats of wrought 1/2-in.-diameter electron-beam melted columbium rod and from two columbium powders of -80 mesh size of different impurity contents. The columbium bar stock was pur chased from Urah Chmg Corp.; the 99 and 99.5 pct purity colulnbium powders were obtained from Fansteel Metallurgical Corp. and Kern Chemical Co.. respectively. The chemical analyses of the columbium bar and powders are listed in Table I. Hydrogen charging was performed by exposing the columbium specimens to hydrogen at 1 atm pressure at various temperatures. After exposure the specimens were quenched to prevent the hydrogen pickup which would take place if cooled in hydrogen, or the hydrogen loss that would occur if cooled in an inert gas. Adequate hydrogen purity was achieved by passing high-purity tank hydrogen (maximum 5 ppm total impurities) through an Engelhard catalytic Deoxo unit, magnesium per chlorate desiccant, and finally through activated charcoal at the temperature of boiling nitrogen. Activated charcoal at -321°F has been reported6 to remove impurities from hydrogen to a nondetectable level. A schematic representation of the heat-treating apparatus is shown in Fig. 1. A metal-sheathed thermocouple embedded in the colun~bium specimen was used to control the temperature during heat treatment and to pull the specimen boat into

Jan 1, 1965

By G. H. Anderson

Cadmium-coppeR precipitate, a byproduct of the purification stage of the zinc plant, is composed mainly of zinc, cadmium and copper in varying amounts depending on the efficiency of precipitation and the cadmium and copper contents of the impure solution treated. The composition range is approximately: cadmium 10-12 pct, copper 6-8 pct, and zinc 3&35 pct. As received at the cadmium plant, the precipitate is a dark gray to black press cake produced by filter pressing the flocculent cadmium-copper precipitate formed when impure zinc solution is agitated with zinc dust. The details of the cadmium-copper precipitation are to be found in the paper "Electrolytic Zinc at Risdon, Tasmania," by W. C. Snow. Transactions AIME, 121, 501. The treatment, in addition to recovering cadmium as metal, yields a copper product as a residue for realization and recovers in solution for return to the zinc plant, the excess of zinc dust used during purification. The recovery of cadmium metal is approximately 200 tons† per year, but, with the amount of copper residue recovered, varies with the zinc production tonnage, composition of the original concentrates, degree of roasting and other operational factors. The operations involved in the recovery of the foregoing materials are carried out in a building adjacent to the purification section of the zinc plant and can best be described by dividing the process into the following stages: 1. Oxidation and Grinding of the cadmium-copper precipitate. 2. Leaching and Filtering. 3. Precipitation of cadmium. 4. Oxidation and Grinding of the precipitated cadmium. 5. Leaching oxidized cadmium precipitate and Purification of leach solution. 6. Electrolysis. 7. Melting, Casting and Packing. A feature of the process is the use of two distinct solution circuits. Spent electrolyte from the zinc plant circuit containing about 10 pct sulphuric acid is used as the primary solvent of the cadmium and zinc present in the oxidized precipitate. When the cadmium is later separated by precipitation and filtering, the filtrate, originally zinc plant spent electrolyte and now fortified in zinc, is returned to the zinc plant. The precipitated cadmium, after oxidation, is redissolved in spent electrolyte from cadmium electrolysis which solution is in closed circuit within the cadmium plant except for discards to the zinc plant circuit as mentioned in Section 5 hereinafter. (Fig 1.) Details of the various operations follow. I. Oxidation and Grinding of the Cadminm-copper Precipitate The precipitate having had a preliminary drying by compressed air in Dehne filter presses in the zinc plant is trucked to a storage platform of sufiicient length to store 3 to 4 days&apos; production separately. After 48 hr exposure to atmosphere, oxidation is sufficient to enable all cadmium and zinc but only a portion of the copper to be dissolved in dilute sulphuric acid. The oxidized precipitate is shovelled into trucks and, after weighing and sampling, is broken in size by means of

Jan 1, 1950