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By F. L. Fayers, J. W. Sheldon

It has been a matter of concern to the petroleum industry to determine what effect the capillary term has on saturation profiles, since these profiles determine ultimate economic oil recovery. In their original solution of the non-capillary two-phase flow problem, Buckley and Leverett&apos; showed that solutions of the two-phase flow equations became multiple-valued in saturation. Since it is physically unrealistic for saturation to have more than one value at a given position, Buckley and Leverett resolved this difficulty by introducing a saturation discontinuity or "shock". They evaluated the strength and position of the shock from material balance considerations. Recently Sheldon, Zondek and Cardwell&apos; have demonstrated that the method of characteristics can be used to solve this and related problems. Owing to capillarity it is physically unlikely that saturation shocks occur in an oil reservoir. Buckley and Leverett suggested that the effects of interfacial tensions should be included in the fluid flow equations, if the solutions are to give continuous single-valued saturation distributions. An analogy to this problem is encountered in the theory of wpersonic compressible flow where the introduction of the viscous term eliminates shock behavior. However, the mathematical form of the capillary term in the porous medium fluid flow equations differs from the viscosity term in the Navier-Stokes equation. This paper demons~rates that capillarity does eliminate the triple-valued behavior and indicates the magnitude of capillary and gravity effects on the saturation profile for a variety of systems. DERIVATION OF LAGRANGIAN AND EULERIAN FORMS OF THE DISPLACEMENT EQUATION The equations representing capillary, two-phase flow are given by applying Darcy&apos;s law and a material balance condition for each phase. The familiar Darcy and material balance equations are as follows. ^U*^0......<3, ^^r=°......c« S is the saturation of the water phase, and B the inclination of the porous medium. Pressures in the oil and water phases differ by the capillary pressure associated with the interfacial tensions, P.-P.=pAS)..........(5) where p, is determined experimentally. The porous medium is said to be oil-wet if P, > Po and water-wet if P, < Po. If the fluids are incompressible and the total volumetric flow rate, q, is constant, then v, f v,, = q...........(6) By eliminating P.. /»,, and v, from Eqs. 1, 2, 5 and 6 it follows that It is convenient to normalize the variables in the problem after the manner of Handy and Hadley% so that Eqs. 3 and 7 become where j,, = —, the fractional flow of water; (F, is a capillary pressure normalizing constant.) Substitution of Eq. 9 into Eq. 8 gives In this partial differential equation for an initial value

By F. R. Brotzen, L. D. Whitmire

Single crystals of high-purity molybdenum were de-formed at temperatures from 195°to 473°K, and the effect of deformation on the electrical resistivily was deler-mined. To separale the resislivity components of point and line defecls some cryslals were annealed at 473°K. The vale of resislivily increase wilh strain was nearly linear and was strongly dependent upon the deformation temperature. Point dejects are annealed out without any effect on the flow stress. At low temperatures the flow stress is a linear function of the square root of the resistivity increase attributable to dislocations. ELECTRICAL-resistivity measurements have been used successfully to gain information on structural changes in metallic materials. During plastic deformation the electrical resistivity rises because of electron scattering from newly created lattice defects. Such measurements lend themselves, therefore, to corroborating results from direct observation of lattice defects and, to a certain extent, to correlating defect densities and distribution with mechanical properties. Published information on research with single crystals of the bcc metals of Group VI, particularly molybdenum, is still limited. Yet, molybdenum single crystals of relatively high purity can be readily prepared by electron-beam-melting techniques. Furthermore, some valuable information on the defect structure of deformed crystals by direct observation is available. Lawley and Gaigher,1 for example, have examined dislocation configurations in deformed molybdenum crystals by means of transmission electron microscopy. Their results revealed that the dislocation density and distribution were strongly dependent upon the deformation temperature. These findings differed from those by Keh and weissmann,2 who found that the average dislocation density in polycrystalline iron deformed between 138° and 298°K depended only on the degree of strain and not on the deformation temperature. Martin3 and peiffer4 showed that point defects introduced in polycrystalline molybdenum by cold work can be eliminated by annealing at a relatively low tempera-ture. In view of their work it became apparent that resistivity measurements of suitably annealed crystals could disclose changes in their dislocation structure and contribute to the understanding of the work hardening of molybdenum crystals. EXPERIMENTAL PROCEDURE Crystals were grown by electron-beam zone melting5,6 of 0.062-in.-diam molybdenum rods (99.99 pct) supplied by General Electric Lamp and Wire Division, Dover, Ohio. The crystals, about 4 in. long, were prepared by using five zone-refining passes at a speed of about 6 mm per min in a vacuum of about 5 X l0-6 Torr. The resistivity ratio of the crystal, p(4.Z°K)/p(273°K), was generally near 10-3. These crystals were used as tensile specimens of uniform diameter in the "as-grown" condition. They were oriented for maximum shear on the (011)[111] slip system (Schmid factor >0.49). The specimens were held in spherically seated Templin-type grips so as to minimize bending. Samples were deformed on an Instron machine at a strain rate of about 5 X 10-5 sec-1 in an isopentane bath with dry ice at 195°K, in ice water at 273°K, and in a vegetable-oil thermostat at 373° and 473°K. The temperature in the latter was maintained constant within +2°K. Resistance measurements were carried out with a Kelvin double bridge. The resistance of the potential leads was kept low by using large-diameter wires outside the low-temperature bath. Many of the resistance data were checked by measurements made with an ac bridge. Current and potential leads were spot-welded to the specimens. The distance between the potential leads, about 3 in., was also considered to be the gage length for the strain measurements. Diameter and gage length of the samples were measured optically with an error of less than 2 pct. These measurements were used also to insure that the deformation had been uniform over the gage length of the specimen. Resistivity changes were then determined from the resistance measurements at 4.2°K assuming constancy of volume. In the course of a test, the crystal diameter, gage length, and resistance at 4.2°K were determined first in the initial state and subsequently for various amounts of elongation.

Jan 1, 1968

By Cyril Stanley Smith, W. Earl Lindlief

A study of the mechanical properties of the alloys of copper and silver led to the discovery that the solubility of silver in copper was greatly different from that generally supposed, therefore some work was done to determine the solubility with greater accuracy than had previously been achieved. After the work had been completed, two papers were published&apos; giving solubility figures which agreed closely with one another and with the work described herein. A detailed comparison of that work with the present will be given later. Preparation of Allots The copper used in making the alloys was electrolytic ingot of high purity. The silver was prepared by precipitation as chloride from nitric acid solution, followed by fusion of the washed precipitate with sodium carbonate and potassium nitrate. This method gives metal containing at least 99.99 per cent silver. The copper was first melted under charcoal in a small electric resistance furnace and the silver added as pure silver, it being unnecessary to make any intermediate alloys. After thorough stirring the metal was poured into a mold of suitable form. The alloys contained between 0.008 and 0.015 per cent of oxygen. Small amounts of oxide were visible under the microscope, but it is not believed this would have much effect on the results. Copper-silver alloys are notorious for segregation, consequently a few experiments were carried out to find a form of casting with as little segregation as possible. A mold 6 in. long and 1/2-in. dia. was first used, and an alloy nominally containing 5 per cent silver was cast in it, while some of the same alloy was poured directly into water to obtain the maximum rate of cooling possible. Analyses were made both on this sample and on turnings from the top and bottom of the 1/2 in. dia. cast-ing, the turnings being separated into three parts according to the position

Jan 1, 1932

By J. S. Vanick

AN extremely hard, tough, and strong, white or chilled cast iron has been applied for the past several years to industrial and mining services in which its unusual properties have been confirmed by its ability to deliver in many instances much better performance than plain chilled iron, or other wear-resistant materials. It is being produced regularly by alloying a good base composition of chilled or white cast iron with essentially 4 to 6 per cent of nickel and 1 to 2.5 per cent of chromium. Such a material can attain a hardness exceeding 600 to 750 Brinell as against 380 to 530 for corresponding grades of plain chilled iron. The strength is approximately doubled and the toughness significantly increased. These properties make it especially useful for many applica-tions requiring a high hardness for resistance to wear, abrasion, attrition, deformation; to some extent to high compressive loading and to a lesser but important degree to corrosive action. A wide variety of commercial castings is being successfully produced from this iron, ranging in size from the small-grain grinding plates or burrs through medium-sized castings such as sand pumps up to large, heavy castings such as rolls for metal rolling or cement grinding. The composition of this white cast iron may be roughly bracketed within the range shown in Table 1.

Jan 1, 1933

By M. W. Hayward

THE object of this paper is to record and tabulate the data and field observations obtained by the writers and their associates during 10 years of intensive study of lead-zinc deposits in the Cretaceous limestone areas in Northern Mexico, particularly in mines owned by the Cia Minera de Peñoles, S. A. At the El Paso meeting of the Institute in October, 1930, J. G. Barry made the suggestion that a committee be appointed to correlate the ideas and theories which have been put forth by the numerous engineers and geologists who, during recent years, have made a study of the ore deposits in the area under consideration. The first step in a work of this nature would be to record all of the observed facts, and these facts would have to be accepted by those who attempted to formulate a theory of ore deposition. It is with this idea in mind that the writers have described as accurately as possible the actual, observed facts pertaining to the occurrence of the lead-zinc ores in dolomites or dolomitic horizons. By most writers the term "dolomite" is loosely used to designate magnesium-bearing limestones, regardless of the percentage of MgO present. Since no true dolomites exist in the areas to be described, we shall also loosely use the terms dolomite or dolomitic limestone to desig-nate those beds having a magnesia content of 5 per cent MgO or more. For a number of years the writers have been impressed with the fact that in areas where dolomite beds occur a large percentage of the lead ore is found in these beds, in spite of the fact that such beds may be overlain or underlain by pure limestone, which one would assume to be just as favorable for replacement as the dolomite, if not more so on account of its being more soluble in acid solutions than the dolomite. It is true that in some limestone areas, such as the Erupcion-Ahumada districts, Chihuahua, and Providencia, Zacatecas, where no dolomite beds have been found, large tonnages of lead ores have been mined. We venture to predict, however, that had there been dolomitic beds in these areas, the

Jan 1, 1932

By Bernard MacDonald

Of the treatment of the slime-pulp of gold- and silver-ores by cyanidation, agitation is an essential part. When prepared for treatment, this pulp, consisting of ore reduced to such fineness that approximately 80 per cent. of it will pass through a 200-mesh screen, is mixed with a certain proportion of water, carrying in solution the cluantity of cyanide (KCN) and other chemicals required. The water-constituent of the pulp thus prepared usually ranges from 1 to 2 parts by weight to 1 of the dry ore. Thus constituted, the pulp is charged into treatment-tanks, the shape and capacity of which vary, according to the quantity of pulp to be treated daily and the method of agitation to be employed. Tanks have no other function in a cyanide,plant than that of being economical and corlvellient containers or receptacles for holding the pulp, solutiou, or water used in the operations. It is by agitation that the solids in the pulp charged into the tanks are kept in suspension in, and mixed with, the solution in the proper proportions required for the treatment. If the proper mixture of solution to dolids be determined to be 2 to 1 by weight (which is, approximately, 5 to 1 by volume), this proportion should be maintained in every part of the charge; that is, each solid particle of the pulp, whether it be of&apos; 180- or 400-mesh size, should be surrounded by five times its own volume of solution throughout the whole period of treatment. The reason is, that the amount of chemicals ascertaiued to be necessary for dissolving the gold and silver contained in the solids, is held in uniform solution in the water-constituent of the pulp, and, therefore, the determined proportions of solution and solids must be maintained at all times during treat-

Jan 1, 1912

By A. A. Smith, J. S. Smart

THE controlled amounts of phosphorus, arsenic, sulphur or selenium found in commercial coppers perform a variety of highly useful functions. Indeed, a large segment of modem copper technology is essentially dependent upon the presence of one or more of these elements. Consequently, the literature contains many references to their effects but the scope is broad and has been only partly covered. New data are presented herewith directed toward a better understanding of the basic behavior of these elements in copper, with particular emphasis on the composition range 0 to 0.05 per cent. These data are a part of a general program of research on the effects of impurities on the properties of oxygen-bearing and oxygen-free copper, other portions of which have been reported previously.1-2-3 Schematically, the behavior of individual elements is determined from measurements of conductivity and softening temperature,1, 2 and the binary alloys employed are synthesized from high-purity copper in order to eliminate interference from the effects of extraneous impurities. Alloys of selected composition were first prepared in the oxygen-free form by continuously casting the melts in the form of 3/8-in. diameter rod. Oxygen was added subsequently to portions of the alloys, either by remelting or by diffusion at 850°C. from a surface scale. Test wires were drawn one B. and S. number per pass, using four 30-min. 600°C. anneals at o.3125, 0.257, o.204 and o.162 in., and a final cold reduction of 95 per cent t0 0.081 in. Oxygen-bearing slugs made by remelting were hot-rolled to 5/16 in., drawn to 0.162 in., annealed for 30 min. at 600°C. and cold-drawn 95 per cent to 0.081inch. The alloys containing phosphorus, having been compounded very early in the program, were prepared in the form of 5/16-in. rod, and processed to wire with only the last three intermediate anneals listed above, all of these having been conducted in commercial nitrogen. In addition, the conductivity anneals on these alloys were also performed in the same atmosphere, and the small amount of oxygen present as an impurity in the gas resulted in some loss of accuracy at temperatures of 700° to 800°C., as will be shown later. Subsequently, the anneals for all oxygen-free alloys were conducted in hydrogen to prevent oxidation, and purified nitrogen was employed only for oxygen-bearing samples. All conductivity anneals were of one hour duration followed by a rapid quench in 10 per cent H2SO4. EFFECT OF PHOSPHORUS The widespread use of phosphorus as a deoxidant has resulted in universal appreci-

Jan 1, 1945

OUTSTANDING symbol of the machine age, the steam shovel needs no introduction. Few individuals there are, in the United States at least, that have not watched with fascination the almost human motion, the more than human strength, the rhythm of the whole steam-shovel cycle of crowding, digging, swinging, dumping, swinging, and crowding again. A mass of steel with some copper and other metals, fed with water and coal, guided by a single alert and dexterous operator, or perhaps two, does the work that would require 50 to 500 men or even more. The largest shovels working in the copper mines have loaded into waiting railway cars as much as 10,000 tons of ore in a single 8-hour shift. With no equipment but hand shovels, it would, in fact, be impossible to duplicate the work with any number of men; first, because they would be in each other&apos;s way, and second, because the steam shovel can lift single pieces of rock weighing 5 or 10 tons with effortless ease. Of recent years, internal-combustion engines and electric motors have displaced steam as a motive power in many instances; and of course the detailed design of the shovels has been improved immensely. Whereas the largest dippers used 30 years ago had a capacity of 3 ½ to 4 cu. yd., today the 350-ton shovel used at Chino has an 8-yd. dipper, as has the 320-ton shovel at Chuquicamata. Incidentally, for stripping at coal mines a shovel having an 18-yd. dipper is in use. However, the principle of operation of the modern shovel, regardless of the size and type of motive power, is essentially the same as that of the earlier shovels. It is fair to say that the indispensable of open-cut mining is the steam shovel, or, to be more precise, if perhaps less picturesque, the power shovel. Somehow the electric shovel seems to lack the glamour that

Jan 1, 1933

By L. W. McKeehan, W. C. Elmore

The magnetic powder method, long used for roughly mapping magnetic fields, has recently been refined1, "or investigating the microscopic variations in the surface magnetization of ferromagnetic crystals. Bitter2 first discovered regular powder patterns connected with the crystal structure of such specimens. Several other investigators:&apos; have used Bitter&apos;s original technique, with slight modifications, to study the variation of the patterns with variations in the magnetizing field applied parallel to the surface, and their dependence upon the state of strain, of polish and of crystal cut. All of the explanations of these patterns on metallic ferromagnetics have been couched in general terms. In a preliminary report we have described an improvement ill the powder technique which led us to the discovery of a new effect throwing considerable light on the magnetic secondary structure of alpha iron4 and of nickel5 single crystals. We now report additional evidence confirming the existence and stability of a magnetic block secondary structure. Specimens The following list describes the specimens used in the present investigation. Designation Description A1 Silicon ferrite furnished to us by Dr. W. E. Ruder, of the General Electric Co., for which lie gave the following typical analysis: C, 0.05; P, 0.038; S, 0.026; Mn, 0.15; Si, 3.24. Disk, 0.60 cm. diameter, about 0.05 cm. thick. By X-ray analysis angles between disk normal and [100] 75o, [0101 76" [00l] 21o. A2 Same as A1 except: diameter 0.75 cm. A, Same as A1 except: diameter 0.68 cm.

Jan 1, 1936

By L. W. McKeehan, W. C. Elmore

The magnetic powder method, long used for roughly mapping magnetic fields, has recently been refined1, "or investigating the microscopic variations in the surface magnetization of ferromagnetic crystals. Bitter2 first discovered regular powder patterns connected with the crystal structure of such specimens. Several other investigators:&apos; have used Bitter&apos;s original technique, with slight modifications, to study the variation of the patterns with variations in the magnetizing field applied parallel to the surface, and their dependence upon the state of strain, of polish and of crystal cut. All of the explanations of these patterns on metallic ferromagnetics have been couched in general terms. In a preliminary report we have described an improvement ill the powder technique which led us to the discovery of a new effect throwing considerable light on the magnetic secondary structure of alpha iron4 and of nickel5 single crystals. We now report additional evidence confirming the existence and stability of a magnetic block secondary structure. Specimens The following list describes the specimens used in the present investigation. Designation Description A1 Silicon ferrite furnished to us by Dr. W. E. Ruder, of the General Electric Co., for which lie gave the following typical analysis: C, 0.05; P, 0.038; S, 0.026; Mn, 0.15; Si, 3.24. Disk, 0.60 cm. diameter, about 0.05 cm. thick. By X-ray analysis angles between disk normal and [100] 75o, [0101 76" [00l] 21o. A2 Same as A1 except: diameter 0.75 cm. A, Same as A1 except: diameter 0.68 cm.

Jan 1, 1936

By E. Luttgen

The substance referred to in the title is the artificially prepared basic carbonate of magnesia, a compound of the carbonate with the hydroxide. It is the "block-magnesia " of commerce, the magnesia alba of the pharmacist. Its composition, though somewhat indefinite, may usually be expressed by the formula : 4MgCO3,Mg(OH)2, 5H2O; it is found to vary slightly with the details of the method of preparation. This substance has been employed recently with much reported success, as a non-conductor of heat. It is moulded to form coverings suitable for steam-pipes and their fittings and sectional jackets for boilers and cylinders; it is furnished also in forms suitable for lining refrigerators, walls and roofs of buildings, fire-proof safes, etc. It was with a view of ascertaining the efficiency of this material as a non-conductor, or, rather, its relative efficiency among the various non-conducting materials in use, that the writer made the experiments about to be described. A block of magnesium carbonate or magnesia alba exhibits some interesting physical qualities. It is a smooth, white, close-grained solid, in outward appearance resembling a block of Paris plaster. It possesses the lightness of cork, the porosity of sponge, and withal a degree of firmness and strength that, in view of its levity, is quite remarkable. To examine more closely the properties of this substance, a number of 1-inch cubes were sawed from the commercial block-carbonate, also some bricks, that is, blocks measuring accurately 2 x 4 x 8 inches, the dimensions of an ordinary brick. The cubes weighed from 2.2 to 2.7 grammes, the bricks weighed 140 to 175 grammes (5 to 6 ounces). The bricks were carefully measured and weighed, and placed in vessels containing distilled water, in which they became gradually submerged, owing to the displacement by water of the air inclosed in the structure of the magnesium carbonate. After twenty-four hours the blocks were removed from the water, dried superficially by contact with filter-paper and weighed. From the increase in weight, the volume of the water absorbed, and consequently that of the air displaced by it, were obtained. For example: a block which when dry weighed 155

Jan 1, 1887

By D. W. Akins

The case history of a combination gas and water flood instituted early in the life of a field is described. It was recognized from the beginning that recovery would be low, under normal production methods, from the several separate, thin beds of porous limestone which had such poor native permeability that the wells would not produce without acidizing. It is thought that the combination flood gives excellent recovery efficiencies for this type of reservoir. The chief function of the gas flood now is to maintain bottom hole pressure in that part of the reservoir which will not be affected by the water injection program until later. Present estimates are that ultimate recovery will be approximately double the recovery expected under the original solution gas drive mechanism. Wide (80-acre) spacing has enhanced the economics of the over-all field program by the elimination of more than $5,000,000 worth of unnecessary wells. INTRODUCTION The Haynesville Pettit Field was discovered in November, 1941, with the completion of T. L. James Co.&apos;s Callie Akin No. 1, located in the W 1/2 of the NE 1/4 Section 27-23N-8W, Claiborne Parish, La., at an approximate depth of 5,300 ft. The center of the field is about two miles north and a mile west of the town of Haynesville, La. A total of 189 producing wells have been drilled on 14,500 acres. An additional nine dry holes were drilled. The Louisiana-Arkansas state line divides the field so that 34 wells are in Arkansas and 155 are in Louisiana. Governmental sections are divided equally to contain eight production units making 80-acre spacing where the sections are regular. Along the state line in Louisiana there is an irregular tier of sections, each of which contains approximately 456 acres. When divided equally into eight production units the spacing is 57 acres per well for these three and a fraction productive sections. All Haynesville Pettit wells are identified by their section number followed by their position in the section as determined by numbering the production units counterclockwise beginning in the upper right corner of the section. All of the producing wells in the field except two are unit-ized and operated by the Haynesville Operators Committee. These two wells are located in the extreme northern part of the field in Arkansas. Efforts to bring them into the Unit are being continued. The Pettit operators organized the Haynesville Operators Committee and the field became a unit operation May 1: 1944. GEOLOGY The Pettit is Lower Cretaceous in age and is defined as the uppermost porosity in the Sligo formation. The unitized area known as the Haynesville Pettit Field is composed of two separate zones of porosity approximately 40 ft apart and without connection between the two, except in wells. These zones are known as the Upper Pettit and the Lower Pettit. The Upper Pettit is separated into two sections throughout most of its area by a relatively thin but quite impervious shale streak. These are called the "A" and "B" sections of the Upper Pettit. All of these lenticular zones are composed of coquina limestone and a small percentage of normal oolites. The large

Jan 1, 1951

By D. W. Akins

The case history of a combination gas and water flood instituted early in the life of a field is described. It was recognized from the beginning that recovery would be low, under normal production methods, from the several separate, thin beds of porous limestone which had such poor native permeability that the wells would not produce without acidizing. It is thought that the combination flood gives excellent recovery efficiencies for this type of reservoir. The chief function of the gas flood now is to maintain bottom hole pressure in that part of the reservoir which will not be affected by the water injection program until later. Present estimates are that ultimate recovery will be approximately double the recovery expected under the original solution gas drive mechanism. Wide (80-acre) spacing has enhanced the economics of the over-all field program by the elimination of more than $5,000,000 worth of unnecessary wells. INTRODUCTION The Haynesville Pettit Field was discovered in November, 1941, with the completion of T. L. James Co.&apos;s Callie Akin No. 1, located in the W 1/2 of the NE 1/4 Section 27-23N-8W, Claiborne Parish, La., at an approximate depth of 5,300 ft. The center of the field is about two miles north and a mile west of the town of Haynesville, La. A total of 189 producing wells have been drilled on 14,500 acres. An additional nine dry holes were drilled. The Louisiana-Arkansas state line divides the field so that 34 wells are in Arkansas and 155 are in Louisiana. Governmental sections are divided equally to contain eight production units making 80-acre spacing where the sections are regular. Along the state line in Louisiana there is an irregular tier of sections, each of which contains approximately 456 acres. When divided equally into eight production units the spacing is 57 acres per well for these three and a fraction productive sections. All Haynesville Pettit wells are identified by their section number followed by their position in the section as determined by numbering the production units counterclockwise beginning in the upper right corner of the section. All of the producing wells in the field except two are unit-ized and operated by the Haynesville Operators Committee. These two wells are located in the extreme northern part of the field in Arkansas. Efforts to bring them into the Unit are being continued. The Pettit operators organized the Haynesville Operators Committee and the field became a unit operation May 1: 1944. GEOLOGY The Pettit is Lower Cretaceous in age and is defined as the uppermost porosity in the Sligo formation. The unitized area known as the Haynesville Pettit Field is composed of two separate zones of porosity approximately 40 ft apart and without connection between the two, except in wells. These zones are known as the Upper Pettit and the Lower Pettit. The Upper Pettit is separated into two sections throughout most of its area by a relatively thin but quite impervious shale streak. These are called the "A" and "B" sections of the Upper Pettit. All of these lenticular zones are composed of coquina limestone and a small percentage of normal oolites. The large

Jan 1, 1951

By J. N. Ong

The oxidation of tantalum is assumed to occur by four simultaneous first-order chain reactions; solution of oxygen in the metal, nucleation and growth of a suboxide phase at the metal surface and two phase boundary processes which give rise to two different modifications of Ta2O5. A rate equation is then formulated which accounts for all principal details of oxidation behavior, unifies and correlatss the results of the principal investigations, and expresses the rate as a function of pressure, temperature, and time. For purposes of practical application, the expressions: may be used below and above 700T respectively to determine the regression rate of tantalum in cm per hr, where T is to be expressed in "K and P in atmospheres pressure of oxygm. The equations will reproduce within a factor of two all reported experimental rates in the temperature range 475" to 1400°C and pressure range 0.000026 to 40.8 atm 0. 1 HE oxidation kinetics of tantalum have been investigated thoroughly in the temperature range 50" to 1400 and pressure range 1.32 x l0-&apos; to 40.8 atm pressure of 0,and as a result, the principal features of the oxidation of tantalum are known and have been described in considerable detail. The exposition of the characteristics of the behavior of tantalum in oxygen has been largely descriptive, with considerable attention being devoted to elucidating the structure, composition, and morphology of the resulting oxide products. The weight change vs time results have usually been reported graphically. With the exception of the linear rate below 700 C and the process of diffusion of interstitial oxygen into the metal,6&apos;9 no effort has been made to characterize the reaction rates in functional form. It is the purpose of this paper to demonstrate that when the fundamental principles of chemical kinetics are rigorously followed, the results of the principal investigations will be correlated and unified and the oxidation rale may be expressed as an analytic function of pressure, temperature, and time. In addition to accounting for the temperature and pressure dependency of the oxidation rate, the following minor features will be accounted for as a result of the basic analysis: the initial period of nonline-arity in rate at low temperatures, which decreases with increasing temperature;3&apos;5&apos;7 the rate vs temperature cusps obtained at constant pressure"5 the concentration gradient of oxygen interstitially dissolved in the metal.5&apos;7 The analysis will also be consistent with the overall chemistry of reaction and with all visual, microscopic, and X-ray observations. DEVELOPMENT OF RATE EQUATION As a fundamental basis for the treatment of metal-oxygen reaction kinetics, it will be regarded that the rate of reaction is determined by the concentration and not the activity or chemical potential. It is further assumed that all metal-oxygen reactions are first order complex chain reactions" whose rate is dependent on the concentration of an intermediate species which is a complex function of the oxygen concentration, or oxygen pressure, only. The basic rate equation is therefore: is the weight of oxygen consumed by the reaction, A is that portion of the area of the metal over which the reaction is occurring (cm2), t the time (sec), kf the rate constant for forward reaction, C the intermediate species concentration and f &apos;([Oz]) and f (Po,) are complex functions of oxygen concentration and Oxygen pressure respectively. Reverse reactions may usually be neglected in metal-oxygen systems since a large negative free energy generally accompanies these reactions. Eq. [I] takes different forms when the rate of reaction is controlled by diffusion into or through a phase or at a phase boundary. For diffusion into the metal phase, the rate is given by1&apos; Di is the diffusion coefficient of species diffusing into the metal phase (cm2/sec), and Q is the corre-

Jan 1, 1962

By Douglas Bunting

In the anthracite fields of Pennsylvania, mine fires occur with more or less regularity and their existence is an ever-present hazard in coal mining. In all probability 90 per cent. of the mine fires can be ascribed directly or indirectly to the ordinary miner&apos;s open lamp. Other causes may be smoking, electrical installations, gas explosions, gas feeders, and the communication of fire to the outcrops from ash dumps, culm banks, timber and brush fires. Fires in pump rooms, engine rooms, and barns have been largely eliminated as a result of the Act of Assembly, approved June 15, 1911, which provides that all inside buildings, including engine rooms, pump rooms, barns, etc., shall be constructed of incombustible materials. Smoking of pipes, cigars, and cigarettes should be prohibited in the mines and too much care cannot be exercised in preventing fires by enforcing all rules designed for that purpose. Mine fires that involve underground fighting are invariably dangerous, and all fires, irrespective of the method pursued in extinguishing them, involve property loss and expense. Each fire generally presents a more or less original problem, dependent on the particular conditions. Generally mine fires may be divided into two classes: Those occurring in inaccessible workings and those occurring in accessible workings. The methods pursued in extinguishing or controlling mine fires are as follows: (I) direct attack, (2) smothering by sealing, (3) flushing with silt or other solids, (4) flooding with water, (5) cutting off, (6) surrounding with incombustible materials, (7) digging out by stripping from the surface. Most fires arc extinguished in their incipiency by direct attack and failure to extinguish by this method is due to late discovery, lack of water, and facilities for fighting, or improper procedure in the initial attack. Should the method first pursued be unsuccessful, careful consideration should be given in determining next the method to be adopted; then the work should be carried on as rapidly as possible and under the supervision of the most competent persons. Materials and supplies should be furnished without delay and in sufficient quantities for the work to be accomplished.

Jan 1, 1922

By H. B. Pulsifer

.ABOut 1.5 varieties, or tnodifications, of the best rnagnesiurn available were prepared and subjected to etching tests, then examined for micro-structure. Of the 30-udd etching reagents that were tried, nearly half, mostly ammonium salts, etched the metal satisfactorily. The surfacing and etching of magnesium is shown to be a very simple and quick operation. The density and hardness of magnesium were determined. The most interesting new observations relate to the finding of the hexagonal etch figures, the crystal laminations, and the fact that the metal is plastic, cold, when restrained or quickly deformed. Under slowly applied pressule cold metal deforms slightly, then shears to fracture without plastic flow. The chief structural features of magnesium arc presented in two reduced photographs and 30 photomicrographs. Materials Tested There are only two sources in the United States from which new metal can be procured: the American Magnesium Corpn. and the Dow Chemical Co. No pronounced structural or property differences in the metals from these two companies were disclosed by the work of this investigation. The following materials were obtained from the manufacturers: 1. Massive crystals of distilled metal (American Magnesium Corpn.). 2. Rods of hot-extruded metal, ½-in. squares and 5/8-in. rounds (American Magnesium Corpn.). 3. Sheet magnesium, 0.005-in. thick (American Magnesium Corpn.). 4. Cast stick metal, 13/8-in. dia. (Dow Chemical Co.). 5. Magnesium-aluminum alloy, hot-rolled plate, ½-in. thick (American Magnesium Corpn.). From these materials, were prepared: 6. Sections from a furnace-cooled ingot made from clistilled crystal. 7. Cold-strained pieces from (6), (4) and (2). 8. Pieces cold-squeezed to fracture from (6), (4) and (2). 9. Hammer-struck pieces from (6), (4) and (2). 10. Steam-hammer struck pieces from (6), (4) and (2). 11. Sections from furnace-cooled ingot of the magnesium-aluminum alloy.

By F. R. Morral, E. P. Miller

Hot-dipped heat-treated zinc coatings on sheet steel were examined with X-rays. The phases identified were compared with those listed in the modern literature 01 the zinc-iron system. The zeta (FeZn13) phase is shown to correspond to the phase found by Schueler (1925) in heat-treated zinc coatings. An investigation was undertaken to determine the phases present in hot-dipped heat-treated zinc coatings on steel sheets and wire. This kind of coating on wire was studied some years ago by Schuelerl by microscopic and chemical methods. He reported a new phase, FeZn10. Later, Clark and Stillwell,2 using X-ray crystal analysis, identified a new phase in ordinary galva. nized wire, which was assumed to be the FeZn10 phase. Since the extensive review of the iron-zinc alloys presented a few years ago,3 much new work has been published, some of which5-l6 was too late to be included in the recent edition (1939) of the American Society for Metals&apos; Handbook.4 Figs. 1 and 2 are reproductions of the latest iron-zinc diagram proposed by Schramml1 as a result of his investigations by microscopic, thermal, magnetic susceptibility and X-ray methods. Table 1 summarizes all the known published X-ray data of the phases Present. The solubility of iron in zinc has been determined by x-ray methods.10 In the same manner the homogeneity range of the P phase was studiedlo using the principle that the parameter of an intermetallic compound changes while the concentration of One of the constituents changes. Schramm10 has found some 80 alpha lines in X-ray powder photograms of phase d1, and from these he believes that this phase is related to the P phase. Previous investi-

Jan 1, 1941

OPEN-HEARTH refractories are not merely an accessory to the furnace. They themselves ore the furnace, to all intents and purposes. The steel work of the main structure is merely a frame which helps to support the refractories; and the regenerators, a necessary part of the furnace system, consist almost entirely of refractories with very little supporting structure. Not only do refractories constitute the essential part of the furnace, but they also carry the liquid steel all the way to the point where it begins to solidify. On leaving the furnace the liquid passes through a refractory runner into a refractory-lined ladle, then through a refractory nozzle closed by a refractory stopper on the end of a refractory- protected rod. The liquid is sometimes sent through an additional refractory-lined tun-dish, a supplementary ladle, or a refractory runner for bottom pouring, until it finally enters the iron mold in which it solidifies. Even in the mold, refractory materials are sometimes used to provide a non-conducting "hot top." These materials, from ladle to hot top inclusive, are often referred to as the "pouring-pit refractories." CAUSES OF FAILURE Compared with the equipment used in most industrial processes the open-hearth furnace has a relatively short life. The most important quality of an open-hearth refractory, therefore, is its rate of failure. The discussion here of the individual refractory materials will therefore keep uppermost the question "Why, how, and where does it fail?" The principal causes of failure of open-hearth refractories are, in their order of importance: 1. Reaction with iron oxides. 2. Reaction with slag. 3. Flow and failure under load. 4. Melting. 5. Spallimg. 6. Mechanical breakage. Reaction with Iron Oxides and Slag. This is by far the most important cause of failure. Liquid iron oxide comes very near to being the

Jan 1, 1944

By E. P. Miller, F. R. Morral

Hot-dipped heat-treated zinc coatings on sheet steel were examined with X-rays. The phases identified were compared with those listed in the modern literature 01 the zinc-iron system. The zeta (FeZn13) phase is shown to correspond to the phase found by Schueler (1925) in heat-treated zinc coatings. An investigation was undertaken to determine the phases present in hot-dipped heat-treated zinc coatings on steel sheets and wire. This kind of coating on wire was studied some years ago by Schuelerl by microscopic and chemical methods. He reported a new phase, FeZn10. Later, Clark and Stillwell,2 using X-ray crystal analysis, identified a new phase in ordinary galva. nized wire, which was assumed to be the FeZn10 phase. Since the extensive review of the iron-zinc alloys presented a few years ago,3 much new work has been published, some of which5-l6 was too late to be included in the recent edition (1939) of the American Society for Metals&apos; Handbook.4 Figs. 1 and 2 are reproductions of the latest iron-zinc diagram proposed by Schramml1 as a result of his investigations by microscopic, thermal, magnetic susceptibility and X-ray methods. Table 1 summarizes all the known published X-ray data of the phases Present. The solubility of iron in zinc has been determined by x-ray methods.10 In the same manner the homogeneity range of the P phase was studiedlo using the principle that the parameter of an intermetallic compound changes while the concentration of One of the constituents changes. Schramm10 has found some 80 alpha lines in X-ray powder photograms of phase d1, and from these he believes that this phase is related to the P phase. Previous investi-

Jan 1, 1941

By Yves Dardel

The literature concerning the remelting of alunlinum and its alloys is very rich. Unfortunately the majority of the papers on this subject have no scientific value, for the theories or explanations are too often in opposition to the laws of physical chemistry. Furthermore only a few of the methods of purification are considered in the literature. Hence it has seemed necessary to the author to sketch a general theory of the purification of secondary aluminum. The purpose of the purification is to eliminate the impurities that the charges, and the atmosphere of the furnaces bring into the bath during the successive remelt-ings. Indeed scrap as well as metal can be used when soiled with oil, greases, water, or others, if it has been sufficiently dried and contains oxides. At the melting point of the metal, the oils and greases are decomposed into their constituent elements H², O2, H²O, co², CO, CH,, and others. These gases are added to the corresponding gases in the atmosphere of the furnace. The impurities introduced into the metal during the remelting will accordingly be the products resulting from the action of these gases on the liquid bath. The quantity of hydrogen that is soluble in aluminum and its alloys is given by the relation of sieverts3 as a function of its partial pressure PH2 in the atmosphere m = K vPH² [I] where K is a constant, which depends only upon the temperature and increases with it. The experiments of Rijntgen and Braun4, RÖntgen and M611er5, Bircum-shaw6 and Winterhagerl have rendered it possible to determine the value of K, when the temperature is less than 1.000°C. One obtains: log K = - 4,702.5T + o 238 [2] Besides its usual significance, the term Ph~ represents also the internal pressure of dissolved hydrogen, since in the equilibrium, that is1 when no gas exchange Occurs between the two phases, the Pressures of hydrogen in the metal and in the atmosphere must be equal. Eq I shows that when the partial pressure of H2 increases the amount of dissolved hydrogen in equilibrium increases, and that, if the contrary Occurs, the quantity of H² should diminish. However, if for any reason the diffusion of hydrogen is hindered and the total amount of dissolved gas remains constant while the temperature decreases, the internal pressure of H² increases until it reaches the value of the hydrostatic pressure. At this point, bubbles of hydrogen appear in the bath and escape out of it. The amount of hydrogen in the metal is then limited by a a depending On the hydro- static pressure, which is practically equal to one atmosphere. Indeed hydrogen does not accumulate in the form of a hydride appearing as a separate solid phase. However1 even the mechanism of the solubility is not yet elucidated. One does not know exactly as yet, whether the

Jan 1, 1949