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By Robert D. Pike

In November 1939, on behalf of the Harbison-Walker Refractories Co., the author undertook the study of the problem of utilizing the dolomite of northwestern Ohio for the manufacture of calcined magnesia suitable for use in refractories. Grateful acknowledgment is made of the unfailing assistance and encouragement throughout this work from the executive and technical staff of Harbison-Walker Refractories Company. The dolomite of the Niagara formation that is exposed or near the surface of a wide area in northwestern Ohio1 constitutes a vast supply of almost pure dolomite. It offers a virtually unlimited supply of cheap raw material of uniform dependable analysis for the manufacture of magnesia. A typical analysis of dolomite from the vicinity of Luckey, Ohio, follows: Stone Completely Calcined CaO(Sro)a............. 30.35 57.806 Mgo................... 21.55 41.050 SiO2. ................... 0.30 0.572 R2O3................... 0.30 0.572 Ignition loss............. 47.50 a SrO about 0.06 pct. Brines containing magnesium chloride or sea water can be reacted with calcined dolomite to produce magnesia.2'3 In such reactions the MgCl2 of the brine supplies some of the magnesia and the amount of dolomite required is thereby reduced by an equivalent amount, but brines of commercial importance containing magnesium chloride are some distance away from the purest grades of the dolomite of northwestern Ohio. It was decided therefore to concentrate upon the development of a suitable process for separating the lime and magnesia of dolomite, depending upon the dolomite itself as the sole source of magnesia. This would make it possible to place a plant at the dolomite quarry, thus eliminating the cost of transporting the stone and also rendering the calcined magnesia available at a most convenient production point, considering the cost of delivery throughout the steel industry. The selection of a process depending solely upon the dolomite as a source of magnesia also necessarily entails production of the lime content of the dolomite as a by-product. It was recognized that if such a lime by-product could be produced in a suitable form, a plant location in northwestern Ohio would also be advantageous for marketing the lime. The problem, therefore, was the discovery and development of a low-cost process for separating the magnesia and lime of the dolomite of northwestern Ohio and producing each in a form relatively free from the other, and meeting the respective requirements of established markets. A satisfactory solution of this problem has been found, and it is the

Jan 1, 1948

By R. S. Dean

THE commercial production of electrolytic manganese on a small scale commenced in 1939. The writer made a short report on the progress of production and utilization in MINING AND METALLURGY for January 1941. Progress during the last two years, naturally, has been more rapid. In June 1940, Congressman (now Senator) Scrugham presented a proposal to Congress for an appropriation authorizing erection of a pilot plant for "the production of metallic manganese by electrolytic or other means." As a result of this, a pilot plant, having a capacity of a few hundred pounds per day was built at Boulder City, Nev. Subsequent appropriations permitted expansion of the plant to about a ton per day. Much has been learned in this plant about electrolytic manganese, and the product even in its small way has found war uses of considerable importance. Meanwhile, the Knoxville plant of the Electro Manganese Corporation, the sole commercial producer, was expanded to about 4 tons per day to supply needed material for the war program. Other proposals for commercial plants have not been favorably received by the War Production Board. The Bureau reported on one such proposal by the American Alloys and Chemical Corporation. PRACTICE AT BOULDER CITY The present practice, as carried out at Boulder City, which is being described in more detail in a current paper by the Bureau staff at Boulder City, starts with a manganese dioxide ore containing about 20 per cent manganese. Currently this ore comes from the Three Kids deposit near Las Vegas. The steps for the production of electrolytic manganese, in general, are as follows: I. The manganese in the ore is reduced to MnO. 2. The MnO is dissolved from the ore in spent electrolyte, which contains about 38 to 47 grams per liter of free sulphuric acid, 135 grams per liter of ammonium sulphate, and 10 to 12 grams per liter of Mn as sulphate. In the leaching step the manganese is built back up to 32 to 36 grams per liter of Mn as sulphate; the pH is adjusted to neutral by means of gaseous ammonia and passed through thickeners. 3. The electrolyte is purified by adding H2S, which precipitates the heavy metals. After filtering, ferrous sulphate is added to the solution and oxidized with air and the solution is filtered and clarified on a precoat filter. 4. The purified catholyte is electrolyzed in a diaphragm cell using stainless-steel cathodes and lead-silver anodes. The current density is about 45 amp. per sq. ft. Current efficiencies of 60 to 65 per cent are regularly obtained.

Jan 1, 1944

By R. S. Dean

The commercial production of electrolytic manganese on a small scale commenced in 1939. The writer made a short report on the progress of production and utilization in Mining and Metallurgy for January 1941. Progress during the last two years, naturally, has been more rapid. In June 1940, Congressman (now Senator) Scrugham presented a proposal to Congress for an appropriation authorizing erection of a pilot plant for " the production of metallic manganese by electrolytic or other means." As a result of this, a pilot plant, having a capacity of a few hundred pounds per day was built at Boulder City, Nev. Subsequent appropriations permitted expansion of the plant to about a ton per day. Much has been learned in this plant about electrolytic manganese, and the product even in its small way has found war uses of considerable importance. Meanwhile, the Knoxville plant of the Electro Manganese Corporation, the sole commercial producer, was expanded to about 4 tons per day to supply needed material for the war program. Other proposals for commercial plants have not been favorably received by the War Production Board. The Bureau reported on one such proposal by the American Alloys and Chemical Corporation. Practice at BouldeR City The present practice, as carried out at Boulder City, which is being described in more detail in a current paper by the Bureau staff at Boulder City, starts with a manganese dioxide ore containing about 20 per cent manganese. Currently this ore comes from the Three Kids deposit near Las Vegas. The steps for the production of electrolytic manganese, in general, are as follows: 1. The manganese in the ore is reduced to MnO. 2. The MnO is dissolved from the ore in spent electrolyte, which contains about 38 to 47 grams per liter of free sulphuric acid, 135 grams per liter of ammonium sulphate, and 10 to 12 grams per liter of Mn as sulphate. In the leaching step the manganese is built back up to 32 to 36 grams per liter of Mn as sulphate; the pH is adjusted to neutral by means of gaseous ammonia and passed through thickeners. 3. The electrolyte is purified by adding H2S, which precipitates the heavy metals. After filtering, ferrous sulphate is added to the solution and oxidized with air and the solution is filtered and clarified on a precoat filter. 4. The purified catholyte is electrolyzed in a diaphragm cell using stainless-steel cathodes and lead-silver anodes. The current density is about 45 amp. per sq. ft. Current efficiencies of 60 to 65 per cent are regularly obtained.

Jan 1, 1944

By J. Stuart Warner

The reaction COSO4(c)?CoO(c) + So3(g)was investigated from 950° to 1170OK by two different methods. The sulfate was decomposed in a previously evacuated space and Pso3 calculated from the measured total pressure on the assumption that Pso2 = 2P02. The sulfate was also decomposed under conditions of controlled oxygen pressure. The difference in the results obtained by these experimental techniques is attributed to the effects of thermal diffusion. The standard free energy change for the reaction is given by ?F° = 66,292 + 17.273T log T — 102.57 T (±300 cal/mole). It was found by DTA and X-ray diffraction studies that CoS04 undergoes a transformation at 617°± 4°C. THE metal sulfates may decompose directly to the oxide or pass through one or more intermediate basic sulfates. Provided the oxidation state of the cation does not change in the course of the reaction, the decompositions may be described in general as follows: One of the major objectives of this work was to determine the validity of Eq. [3] as much of the existing sulfate data has been calculated from decomposition pressures by Eq. [5]. The type of apparatus generally used for these measurements consists of a reaction vessel at high temperature which communicates with a manometer at room temperature. A temperature gradient is thus imposed on the gas phase causing thermal diffusion which brings about a partial separation of the different gaseous species present in an initially uniform mixture. The basic theory and experimental facts associated with this phenomenon are summarized elsewhere1 and it will suffice to state here that the heavier gaseous species diffuses down the temperature gradient. Since thermal diffusion destroys the homogeneity of the gas phase, it is not necessarily true that Pso2 = 2Po2 in any particular volume element of the gas phase even though there are twice as many molecules of SO, as of 0, in the gas phase considered as a whole. Under these conditions, the decomposing sulfate gives off SO, which dissociates to SO, and 0, and all three species are distributed throughout the system by thermal diffusion. However, the sulfate will continue to dissociate until the equilibrium value of PSo3 is established on the hot zone. Thermal diffusion may distribute SO2 and O2 throughout the gas phase in any way so long as Eq. [2b] is satisfied in the hot zone; i.e. Pso2(Po2)1/2=K3pso3. When a steady state is reached, we can characterize Pso2 in that

Jan 1, 1962

By C. S. Smith, E. W. Palmer

IN 1934, when Gregg and Daniloffl wrote their excellent monograph on the alloys of iron and copper, the most recent literature on the constitution of the alloys indicated a narrow single-liquid area for 20" above the liquidus with a closed liquid mis-cibility gap above this. Since that time, however, a number of investigators have confirmed the much earlier studies of Mushet2 and Stead3 who, among others in the nineteenth century, had described the true state of affairs. Liquid copper and iron are completely miscible in the absence of carbon, but small amounts of carbon cause liquid segregation. In 1934, one of the writers' mentioned evidence for the absence of liquid separation in carbon-free alloys at temperatures up to 1700°C. Two years later, Mad-docks and Claussen5 unequivocally established the absence of liquid segregation and published a revised diagram, reproduced in fig. 1. They also studied the limits of the two-liquid area in ternary alloys of iron, copper, and carbon as a function of carbon and iron content. In the same year Simpson and Bannister" and Schumacher and Souden7 described in some detail the properties of alloys containing 50 to 75 pct Cu. More recently Hodges et al.16 have developed the copper-rich alloys for use as high-strength conductors. In 1937, Iwase, Okamoto, and Ameniya8 published data on the miscibility gap in ternary alloys of iron, copper, and carbon that supported the conclusions of Maddocks and Claussen, and definitely located the two-liquid area at temperatures of 1450" and 1540°C. They also reported that additions of 1 pct Al, Ni, Pb, Sn, or Zn caused no segregation in 50 pct Cu alloys at 1540°C. The use of copper in amounts approximating 1 pct has found industrial employment to an increasing degree in both wrought and cast steels, for such steels are capable of being precipitation-hardened following normalizing, and have high yield strengths. This is summarized by Gregg and Daniloff,1 Sallitt,9 and Lorig and Adams,10 while Alexander" gives additional information on the heat treatment of copper-steel castings. Lippert12 has described Digby's two-phase steels containing copper and chromium. The work described in the present paper was done in the years 1932 to 1934, at which time much of the information was new. The excellent work subsequently done in other laboratories but more promptly published makes the present paper in part only a confirmation of what is now well known. There has not, however, been published any unified study of

Jan 1, 1951

By Otto H. Henry, J. J. Cordiano

Though powder metallurgy is one of the oldest of metallurgical processes, it is in its infancy as a branch of the modern field of metallurgy. As early as 3000 B.C., the ancients produced implements and weapons of iron by reducing iron ore in a charcoal fire and forging the resultant sponge while still hot into the desired shape. Melting and casting soon superseded the powder metallurgy practice, and it was not until the turn of the twentieth century that powder metallurgy was applied to the commercial manufacture of tungsten lamp filaments. From this beginning, the use of the powder metallurgy process spread" to the manufacture of porous oil-impregnated bearings, cemented carbide tools, contact points, diamond grinding wheels, clutch facings, starter brushes, resin-bonded radio cores, magnets, metallic filters, and other parts. More recently, and particularly during the present war, there has been a definite trend toward the manufacture of machine parts by this process in competition with the more conventional fabricating methods. Notwithstanding these many developments, scientific progress has been slow. While many articles on powder metallurgy have appeared in the press and various publications, there have been too few contributions to our technical societies, with the result that there is a dearth of the type of information necessary for the full development of this science. It is of primary importance that the results of research and development be freely disseminated if powder metallurgy is to realize its fullest potentialities. Purpose of Investigation Excluding the refractory metal field, all commercial powder metallurgical products made by a cold compressing and sintering operation contain voids. These voids can be substantially eliminated by subsequent severe working and heat-treatment, but ' such practice has not proved economical in most applications. By applying heat during the compressing operation, plastic deformation of the powder particles is substantially increased, and the resultant compact or briquette is practically free of voids. However, hot-pressing has many attendant problems, which at present preclude its use in the manufacture of precision parts. The more important of these are to devise: 1. A die steel capable of withstanding high pressures at elevated temperatures. 2. A high-temperature lubricant capable of preventing excessive die wear and welding of the compact to the die walls. 3. A method of retaining a neutral or reducing atmosphere in the compacting zone of the die assembly. 4. A means of ejecting the hot-pressed specimen into a neutral atmosphere until reasonably cold.

Jan 1, 1946

By G. E. Agar, P. L. De Bruyn

Flotation is an important example of a chemical process by which one solid may be separated from other solids in a mixture. In contrast to other chemical processes such as leaching and smelting, separation of solids by flotation is characterized by the establishment of contact among three phases. In froth flotation these three phases are the solid to be floated, an aqueous electrolyte solution, and a gas, usually air. The gaseous phase may be re- placed by an organic liquid phase or this organic liquid phase may be added deliberately as a fourth phase. To gain an understanding of the flotation sys- tem, it is therefore necessary to study the chemical and physical properties of surfaces and to establish the effect of changes in composition of the bulk phases on the nature of the three interfaces, solid-gas, solid-liquid and liquid- gas. With very few exceptions inorganic solids are completely wetted by the aqueous phase so that the first step in flotation is to replace partially the solid-liquid interface by a solid-gas interface. This displacement process is accomplished by the addition of suitable reagents to the aqueous phase. The resultant surface reaction leaves the solid surface with a hydrophobic film. Although the primary objective of these reagent additions is to alter the solid surface, chemical reactions between the added chemical species and those species derived from the dissolution of the solids are unavoidable. For a quantitative description of such reactions and for the determination of the feasibility of a proposed reaction, we rely on available thermodynamic data. The application of thermodynamic principles to flotation systems has contributed much to our understanding of flotation. The changes in thermodynamic properties such as free energy and chemical potential are accessible to experimental determination, and a knowledge of their magnitude allows us to develop and predict a chemical mechanism oy which a solid becomes floatable. In this chapter it will be assumed that the reader has a working knowledge of the general principles of thermodynamics and solution chemistry. A complete discussion of the physical chemistry of flotation must include a treatment of solubility relations, complex ionic equilibria, reaction potential, and the elements of electrochemistry, especially those dealing with reversible electrical cells. The principles related to all of these features of the flotation system will not be discussed in this chapter. The discussion will be concerned with the thermodynamics and electrochemistry of surfaces and the electrical double layer model of the interface.

Jan 1, 1962

By Charles R. Holmes

MORE than 70 igneous pipes and dikes are known to occur in Cambrian sediments throughout an approximately circular area of about 75 sq miles in southwestern Ste. Genevieve County and southeastern St. Francois County, Mo., across the southern portion of the Farmington anticline, which is outlined in fig. 1. From evidence obtained from fossil fragments taken from some of the in-trusive~, and from the similarity in composition of the more basic intrusives to those of known age in surrounding states, these pipes and dikes are believed to be at least post-Devonian and probably Cretaceous in age. As first postulated by Rust,' these intrusives are believed to represent explosion tubes, or diatremes, punched through great thicknesses of solid rock by gaseous pressure. The particular intrusive studied is located about 1 mile north of the small town of Avon at an elevation of 880 ft in the EVz SEy4 NEY4 of see. 2, T. 35N, R. 7E. Outcrop is through the Bonneterre dolomite in two separated exposures. The larger outcrop extends east and west for about 50 ft along a tributary in a small ravine (fig. 2). The smaller exposure occurs as a few scattered patches over an area 20 ft square about 100 ft to the north. The area between the exposures is covered, but scattered patches of the Bonneterre dolomite outcrop throughout the area surrounding the diatreme. Where exposed, contact relations show the surrounding dolomite to be shattered and metamorphosed to a fine-grained rock for a distance of 15 to 20 ft from the intrusive. The igneous rock occurs as a dark greenish-gray porphyry near the center of the diatreme and as a fine-grained, greenish-gray material containing lapilli and metamorphosed fragments of dolomite near the contact with the country rock. The most abundant original mineral of the porphyritic rock is olivine now largely serpentinized as the result of extensive hydrothermal alteration at time of emplacement. The most common constituent of the fine-grained rock, which occurs near the border of the intrusive, is calcite. Mica is a common constituent of both types of rock, occurring as tufts or flakes. Magnetite makes up about 2 pct of the diatreme and occurs as small irregular grains or streaks of tiny grains. Singewald and Milton' have termed the rock of this body an "augite-free alnoite." Susceptibility measurements of pulverized specimens were made from selected samples taken from both the diatreme and the surrounding country rock. The susceptibility of the Bonneterre dolomite was found to be less than 40xlO-6 cgs (centimeter-gram-second) units and that of the metamorphosed contact dolomite less than 200x10-6 cgs. Measurements of individual samples of the igneous rock showed a wide variation in susceptibility between limits of 1000x10-6 cgs to 8000x10-6 cgs, with the maximum difference occuring in samples taken only a few feet apart. The maximum value was exhibited by a highly weathered sample taken from the northern outcrop, while minimum susceptibility was determined from a partially weathered sample taken only a few feet away. These extremes are believed to represent small local concentrations of stringers and grains of magnetite crystals in the igneous rock. A detailed magnetic survey of the horizontal and vertical components of the earth's magnetic field was made over the diatreme area. Stations were occupied at 20-ft intervals as shown by the grid on fig. 2. When greater detail was desired, intervening stations were also occupied. The field instruments were supplied by the Department of Geophysics, St. Louis University. The magnetometers are the Schmidt balance type constructed by the Ruska Instrument Co. These instruments are temperature compensated and have a standard sensitivity of 10 gamma. Calibration of the instruments

Jan 1, 1951

By M. A. El-Aouar

Drilling muds are complex colloidal systems. In an effort to analyze the physical properties that affect their performance at high temperature, an investigation was made of the hydrothermal stability of the monoionic hydrogen, calcium and magnesium forms of montmorillonite and attapulgite. Samples were heated to 400°1F in a simple autoclave and analyzed for cation exchange capacity, c-axis X-ray diffraction spacing and pH factor us sodium hydroxide titration dependence. Out of the six monoionic clay minerals tested, calcium montmorillonite and magnesium attapulgite showed the least base exchange capacities and were relatively unaffected to heat. It is concluded that, of the six clays studied, these two clays were the most suitable forms for use in drilling fluids. INTRODUCTION The drilling of deep wells is dependent upon the drilling mud, and problems frequently arise concerning the effect of mud temperature and prolonged heating. Drilling muds are complex colloidal systems. In an effort to analyze their behavior in deep, hot boreholes, it was thought desirable in this investigation to study suspension of pure, monoionic montmorillonite and attapulgite clays before and after hydrothermal heating. Chemically, clays are hydrated aluminum silicates, such as montmorillonites and attapulgites. The structure of montmorillonite is composed of units made up of two silica tetrahedral sheets with a central alumina octahedral sheet. Attapulgite consists of double silica chains running parallel to the c-axis with the chains linked together at their longitudinal edges. The apexes of the tetrahedrons in successive chains point in opposite direc-tions.4,7,10 One of the most important characteristics of clay minerals is their property of sorbing certain anions and cations and retaining them in exchangeable state. The property of exchange capacity is measured in terms of milliequivalents (meq) per 100 gm of clay. The cation-exchange capacities are taken at pH 7 from titration curves which show the relation between pH and milliequivalents of added NaoH.9,11 The following are causes of cation exchange: (1) broken bonds around the edges of the silica alumina units would give rise to unsatisfied charges, which would be balanced by adsorbed cations; (2) substitution within the lattice structure of trivalent aluminum for quadrivalent silicon in the tetrahedral sheet and of ions of lower valence; and (3) the hydrogen of exposed hydroxyls may be replaced by a cation which would be exchangeable. The primary techniques employed to study the effects of hydrothermal treatment were titration curves and X-ray diffraction analyses. Titration curves were useful in characterizing the nature of the clay mineral surface and the stability of the various samples to attack by acid or alkali before and after hydrothermal treatment. X-ray diffraction analyses were used to determine changes in the nature and crystal structure of the minerals present and to determine the cations in exchange positions on the montmorillonite samples. EXPERMENTAL PROCEDURE PREPARATION OF SAMPLES Selected samples of Wyoming bentonite and attapulgite clay from mines along the Georgia and Florida border were purified by centrifugation to remove all particles larger than 2 microns. In preparing magnesium attapulgite, first a 1.00-normal solution of magnesium acetate was prepared. The pH of the solution was adjusted to 7.0 by adding magnesium oxide. One hundred grams of attapulgite clay were mixed in a blender for 30 minutes with the magnesium acetate solution. The attapulgite solution was left overnight, and then filtered in a Buchner funnel. The suspension was leached with further quantity of magnesium acetate solution and then washed with distilled water for 20 days, after which the filtrate was free from magnesium ions. The concentration of magnesium attapulgite in the clay slurry was adjusted and determined quantita-

By B. L. Averbach, M. Cohen, C. H. Shih

The isothermal formation of martensite is studied in Fe-Ni-Mn and Fe-Mn-C alloys under conditions where the athermal transformation is completely avoided, there being no martensite present at the beginning of the isothermal reaction. The initial rate of martensite formation is extremely low under these conditions, but it increases greatly as soon as some martensite is formed. It appears that true initial characteristics of the isothermal reaction can be studied only in samples wherein the formation of martensite on cooling is completely eliminated. THE phenomenon of isothermal martensite formation is well established1 -" but the observations have been made in the presence of varying quantities of athermal martensite. Complete avoidance of athermal martensite and the formation of martensite under pure isothermal conditions have been reported by Kurdjumov and Maksimova2 in an Fe-Ni-Mn alloy (23 pct Ni, 3.4 pct Mn, and the balance Fe) and have been confirmed by recent experiments of Cech and Hollomon in a similar alloy. In each case, the isothermal transformation rate was a maximum at the beginning of the transformation and decreased as the reaction proceeded. These initial transformation rates were used by Fisher7 for the confirmation of calculated nucleation rates based on classical nucleation theory extended to include the effect of elastic strain energy. Cech and Hollomon have admitted, however, that up to 3 pct martensite formed on cooling in their samples and thus was present at the initiation of their isothermal runs. In this paper, experiments on similar alloys are described, except that care was taken to remove the incidental martensite developed at the surface prior to the isothermal reaction. It is shown here that the reaction rate at the beginning of the strictly isothermal reaction is very low. As soon as some detectable amount of martensite is produced, the transformation rate increases rapidly but ultimately decreases as the reaction proceeds. When martensite is allowed to form isothermally in the presence of about 2 pct of prior martensite, the apparent initial reaction rate is a maximum and corresponds to the observations of Kurdjumov and Maksimova and Cech and Hollomon. It is evident that the cooperative nature of the martensitic reaction results in a significant stimulating or autocatalytic effect on the isothermal reaction rate. Experimental Procedure The chemical compositions of the alloys used in this investigation are listed in Table I. The Fe-Ni-Mn alloys A and B were melted in an induction furnace, cast into ingots 2 in. diam by 4 in. long, and forged into % in. diam rods. The manganese steel (alloy C) was melted in an arc furnace and cast into ceramic molds 1/4 in. diam by 5 in. long. The rods were sealed in evacuated Vycor tubes and homogenized at 1175" to 1200°C for 50 hr. The long homogenization resulted in some manganese loss from the surface, producing a thin layer of transformed material. This surface layer was removed by grinding and the specimens were then swaged to 0.050 in. diam wire. Measurements of electrical resistance were made with a Kelvin double bridge to follow the course of the martensitic transformation. A small permanent magnet was also useful in scanning an entire specimen for small localized quantities of martensite. This test is almost as sensitive as the electrical resistance method in detecting the presence of martensite (which is ferromagnetic in these alloys) and it was especially useful in deciding whether a specimen was completely free of martensite. The wire specimens (0.050 in. diam by 2.5 in. long) were sealed in evacuated tubes and austenitized for 5 min at 1150°C. The specimens were quenched into water and, unless otherwise stated, stress-relieved for 1 hr at 650 °C in order to induce greater uniformity in the subsequent martensitic transformation. As dem-

Jan 1, 1956

By F. F. Poland

The purpose of this paper is to describe the recent applications and improvements made in the process and equipment for the recovery of metallic zinc from secondary metals by means of high temperature electric resistor furnace distillation. The process and high temperature furnace, as developed by Revere Copper and Brass Incorporated, Research and Development Department, was described in a previous paper. † Since the publication of that paper the process and equipment have been licensed to others. Consequently its field of application has been expanded, particularly for the treatment of scrap brass, galvanizers dross and scrap zinc. Other applications are being considered, particularly the melting of metallic titanium and special alloys requiring a controlled atmosphere. Consideration is also being given to modification in design that would allow the melting of copper cathodes for the production of oxygen-free and electrolytic tough pitch copper shapes without the necessity of blowing and poling. In the design of a furnace for melting copper cathodes it is intended that the fundamental principle of charging the solid material into a large pool of molten metal through a double door charging vestibule as shown in Fig 3 of the previous paper, † would be adhered to and, in addition, either dehydrated and desulphurized producer gas or commercial nitrogen, that is, approximately 96 pct nitrogen, 2 pct hydrogen 2 pct CO, also dehydrated, would be used to provide a protective atmosphere for the resistors and to flush out more soluble gases from the molten copper. The operation of a small unit producing approximately 1000 lb of copper per hr has shown that the commercial nitrogen will allow the production of tough pitch electrolytic copper when the metal is transferred from the meltdown unit contemplated to a special type induction unit where the oxygen absorption and temperature can be controlled. Standard practice in treating low grade scrap brass has been to oxidize the zinc by blowing air through the molten metal. This operation results in the recovery of approximately two-thirds or less of the zinc content of the brass in the form of an impure zinc oxide having only a fraction of the value of the zinc in metallic form. The balance of the zinc is lost to slag, fume and drosses. Fig 1 shows the revised flow sheet of the process for the treatment of scrap brass. For this application and as shown on the flow sheet a low frequency induction furnace has been substituted for the Wilkins-Poland type as a melting unit. This type of furnace has been found the most suitable for the purpose as will be shown by the following discussion. Serap Brass The melting of refinery scrap brass preparatory to distillation presents a melting problem quite different from the usual melting of brass mill scrap for recasting because refinery scrap is a heterogeneous mixture of alloys each having different melting and boiling points, and coated with a variety of corrosion products and foreign materials. In addition, brass and copper plated pieces of sheet iron, stainless steel, ceramic materials, and others are present that do not melt except at temperatures above the boiling point of the liquid bath. In the previous paper it is noted that difficulty was encountered in the melting of refinery grade scrap brass without excessive loss of zinc by volatilization and that 5 to 10 pct razorite flux was used to alleviate this condition. While this flux was successful in preventing the excessive loss of zinc by volatilization it interposed a low heat conductivity layer between the source of heat and liquid charge and resulted in lowering the melting rate of the furnace. This same problem presents itself in all types of furnaces in which the metal is heated by radiation and conduction from above the charge. It has been found in melting this type material that the melting rate per hour or per square foot of hearth area

Jan 1, 1950

By P. M. Kelly, E. P. Butler

The stability of a 70/30 Mn-Cu alloy aged to peak damping has been investigated using electron microscopy, X-ray diffraction, and torsional pendulum measurements. Storage at room temperature or at 100" C causes a reduction in damping capacity. This is shown to be due to the formation of subdomains which "lock" the main domain structure and so hinder their movement. After storage the damping capacity can be restored by a retransformation treatment, which generates structures identical to those found in newly aged specimens. Plastic deformation by rolling also causes a decrease in damping capacity. In this case the damping capacity can only be restored by retransformation if the amount of deformation is less than about 5 pct. THE general metallography and structure of these high damping capacity alloys has been discussed in Part I of this work.1 Part II deals with some of the variables that affect the damping capacity. In particular, the stability of the damping capacity of a 70/30 alloy aged for 2 hr at 425° C and quenched has been investigated. The temperature sensitivity of the damping capacity of a 70/30 alloy aged for 2 hr at 450° C has been reported by Birchon.2 The damping capacity begins to decrease with increasing temperature, and is very low above the M, temperature of 125°C. The cubic — tetragonal transformation is completely reversible and there is no apparent thermal hysteresis associated with the change in damping capacity. Another important effect was first reported by Dean and his coworkers.3 They noticed a decrease in the damping capacity with time for specimens of a quenched tetragonal alloy. More recently workers at the Admiralty Materials Laboratory 4 have studied the stability of an aged 70/30 alloy. They found that the damping capacity decreased to half its original value after about 1000 hr at room temperature. EXPERIMENTAL The techniques used for electron microscopy and X-ray diffraction have been described in Part I. The damping capacity was measured by means of a torsional pendulum, using rectangular specimens, 3 by 0.3 mm with a 6 cm gage length. The specific damping capacity, S.D.C., was calculated as a percent amplitude decay in free vibrations over 10 cycles, starting at an amplitude which corresponded to a 700 psi surface shear stress. Because of the stress dependence of the damping,' the values obtained were about a third those reported for a 5000 psi surface shear stress.' RESULTS a) Effect of Aging Temperature. The effect of aging temperature on the damping capacity is shown in Fig. 1. The damping capacity reaches a peak of 12 pct after aging at 400° to 425°C) then begins to decrease as the volume fraction of a Mn increases. At higher aging temperatures the structure becomes cubic again with a low damping capacity. b) Stability of the Aged Structure. The damping capacity of the aged alloy decreases with time at room temperature. This process could be accelerated by storing at 100°C, when about 100 hr were required for the damping to fall to half its original value. The results of room temperature and 100°C storage, for times up to 1000 hr, are shown in Fig. 2. The damping capacity starts to decrease after about 24 hr at 18° C and 1 to 2 hr at 100°C. It was found, however, that the damping could be almost completely restored by retransformation. The specimens were held at a temperature above the M, for a short time, 250° C for 5 min, and then quenched. The values of damping capacity for specimens that were aged, stored, and then retransformed are shown by the full points in Fig. 2. X-ray measurements of the c/a ratio and hardness readings on the specimens did

Jan 1, 1969

By Larry Kaufman

A useful method for estimating the entropy of NaCl type compounds has been developed by combining the Debye theory of specific heat with the Lindemann formula. This method pemnits calculation of the entropy from a knowledge of the atomic weight, atomic volume, and melting point of the compound. Comparison of the calculated and observed entropies of 35 NaCl type compounds over a wide temperature range yields good agreement thus establishing the usefulness of the method. Application of the method to other crystal types is also discussed. KUBASCHEWSKI~ has suggested a useful method of estimating the enthalpy of formation of inter-metallic compounds from a knowledge of the crystal structure, lattice parameter, and heats of sublimation of the component elements. This method is quite valuable in predicting the tendency for compound formation in a given system and is of particular value in considering systems for which no experimental data are available. In order to supplement the enthalpy calculation afforded by Kubschewski's method, it would be of value to be able to estimate the entropy of compounds so that the entropy and free energy of formation could be evaluated. Although a considerable body of such data determined by calorimetric and equilibration techniques exists at present, the difficulty of making such measurements (particularly at high temperatures) and the ever increasing number of new compounds which are of interest make the desirability of such a computational method clear. This paper deals with a method for calculating the entropy of a compound from a knowledge of the atomic weight, atomic volume, and melting point. Since these data are generally easier to determine and therefore more readily available than thermo-dynamic data, they should provide an additional tool in estimating the stability and reactivity of compounds at high temperatures. I) THE ENTROPY OF PURE METALS As a first approximation, the specific heat of a pure metal can be represented by a sum of terms where C,($/tI is the vibrational specific heat calculated on the basis of the Debye theory, lo4 TC, (0/T) is an approximation to the Cp - C, correction. T is the electronic specific heat, and Cp (p) is the magnetic specific heat. Although the Debye theory does not provide a complete description of the vibrational specific heat, i.e., the Debye temperature 0 is not a constant, it does provide a good approximation when used properly. Blackman6'7 has written several reviews on this subject discussing the different values of 0 determined by various methods (specific heat, X-rays, elastic constants, electrical resistivity, and so forth), as well as the observed temperature dependence of 0 with T. In the present case the 0 in Eq. [I] naturally refers to the specific heat 0. The variation of Debye 0 (as determined from specific heat measurements) with temperature is observed to exhibit its most radical behavior at very low temperatures. At higher temperatures the 8 values are observed to become more nearly constant. Blackman6'7 has presented the variation of 0 with temperature for several metals. His tabulation is reproduced in Table I. Reference to Table I shows that above a certain temperature level, 0 remains fairly constant. The value of 0 which is most useful in computing the specific heat, and hence the entropy, is the value of 0 in the range 0/6 « T « 0. In 1910, Lindemann' suggested a relation for estimating Debye 0 values. According to this formula, where V is the atomic volume, T is the melting point in 'K, M is the atomic weight, and CL is a constant. Mott and Jones9 present this formula and state that there is at present no satisfactory theoretical explanation, but that it does have an empirical basis. By using the valuesof 0 in Table I along with known1' values of M, T, and the molar volume VM, where the Lindemann constant can be evaluated. This

Jan 1, 1962

By T. S. Spice, H. L. Lovell, R. W. Utley

With the increased demand for lightweight aggregate, such materials have been manufactured from slags, clays, slates and, to a minor extent, the refuse of coal preparation processes. The latter source is attractive due to current interest in eliminating air pollution and improving the unsightly appearance of refuse piles as well as potential economic advantages, if a satisfactory product can be manufactured. A study has been made relating the composition of coal refuse, expressed as washability data, and the properties of a resulting aggregate. Three different refuse samples (bituminous and anthracite) were separated at gravities ranging from 1.4 to 2.96. Their chemical composition was determined. Aggregates were prepared in the laboratory from these fractions before and after ashing, at temperatures between 1250' and 1350°C. The specific gravity, expansion and compressive strength of the products were measured. The response of the refuse to bloat is related to the chemical composition of the ash to yield a glass of desirable viscosity and to the presence of a material which will form a gas in the appropriate temperature range. Carbonaceous material within the particle is a negative factor since after the glassy phase forms, oxygen cannot enter the mass thus inhibiting bloating. Precombustion of the refuse is also detrimental since it removes substances of gas-forming capability. The fraction sinking at 2.60 yielded an aggregate which had the lowest specific gravity, greatest expansion and greatest compressive strength. The purpose of this study was to seek and evaluate possible relationships between the composition of coal refuse, as expressed by washability data and factors affecting the production of a lightweight aggregate from refuse by bloating. The study was related to an intense program in the Department of Mineral Preparation at the Pennsyl- vania State University to study the possible elimination of air pollution from coal refuse fires by producing a low-carbon secondary refuse. Another phase of this program is considering possible uses of such a secondary refuse. Thus one study was to determine if a lightweight aggregate could be produced from this new refuse material and what effect the nature of refuse beneficiation would have upon the characteristics of a commercial aggregate product. It was hoped that these studies would assist in the design of a process and in establishing the optimum specific gravities at which refuse separation could be made in respect to the production of a low grade fuel from the float product and a raw material for lightweight aggregate from the sink product. The combination of producing a saleable low grade fuel and a lightweight aggregate, while at the same time minimizing disposal costs and air pollution contributions would be attractive to the coal mining industry. MECHANISM OF BLOATING Austin, Nunes and Sullivan,1 Ehlers,3 Everhart, 4 Riley7 and others, have stated that bloating is an expansion process in which two essential conditions exist simultaneously. These are: the development of a glassy phase over a relatively wide temperature range (the viscosity of this glassy phase plays a major role in the retention of the evolved gases) and the evolution of gases (SO2, SO3, CO2 and O2) from mineral decomposition in sufficient quantities at appropriate temperatures to form a cellular structure in the mass. Unless these two "type" reactions take place at the same time or in overlapping ranges of time and temperature, cellulation will not occur. In this event, the gas will escape or the melt will be too fluid to retain it; or if retained, the cells may be too large or the walls too thin for good strength in the product. The stages that occur when clays and shales are heated in an oxidizing atmosphere may be summarized as follows: 1) Drying and removal of free water to 200°C. 2) Absorbed water dehydration period (200 to 480°C). 3) Chemically-combined water dehydration period (480 to 700°C).

Jan 1, 1965

By Charles R. Holmes

MORE than 70 igneous pipes and dikes are known to occur in Cambrian sediments throughout an approximately circular area of about 75 sq miles in southwestern Ste. Genevieve County and southeastern St. Francois County, Mo., across the southern portion of the Farmington anticline, which is outlined in fig. 1. From evidence obtained from fossil fragments taken from some of the in-trusive~, and from the similarity in composition of the more basic intrusives to those of known age in surrounding states, these pipes and dikes are believed to be at least post-Devonian and probably Cretaceous in age. As first postulated by Rust,' these intrusives are believed to represent explosion tubes, or diatremes, punched through great thicknesses of solid rock by gaseous pressure. The particular intrusive studied is located about 1 mile north of the small town of Avon at an elevation of 880 ft in the EVz SEy4 NEY4 of see. 2, T. 35N, R. 7E. Outcrop is through the Bonneterre dolomite in two separated exposures. The larger outcrop extends east and west for about 50 ft along a tributary in a small ravine (fig. 2). The smaller exposure occurs as a few scattered patches over an area 20 ft square about 100 ft to the north. The area between the exposures is covered, but scattered patches of the Bonneterre dolomite outcrop throughout the area surrounding the diatreme. Where exposed, contact relations show the surrounding dolomite to be shattered and metamorphosed to a fine-grained rock for a distance of 15 to 20 ft from the intrusive. The igneous rock occurs as a dark greenish-gray porphyry near the center of the diatreme and as a fine-grained, greenish-gray material containing lapilli and metamorphosed fragments of dolomite near the contact with the country rock. The most abundant original mineral of the porphyritic rock is olivine now largely serpentinized as the result of extensive hydrothermal alteration at time of emplacement. The most common constituent of the fine-grained rock, which occurs near the border of the intrusive, is calcite. Mica is a common constituent of both types of rock, occurring as tufts or flakes. Magnetite makes up about 2 pct of the diatreme and occurs as small irregular grains or streaks of tiny grains. Singewald and Milton' have termed the rock of this body an "augite-free alnoite." Susceptibility measurements of pulverized specimens were made from selected samples taken from both the diatreme and the surrounding country rock. The susceptibility of the Bonneterre dolomite was found to be less than 40xlO-6 cgs (centimeter-gram-second) units and that of the metamorphosed contact dolomite less than 200x10-6 cgs. Measurements of individual samples of the igneous rock showed a wide variation in susceptibility between limits of 1000x10-6 cgs to 8000x10-6 cgs, with the maximum difference occuring in samples taken only a few feet apart. The maximum value was exhibited by a highly weathered sample taken from the northern outcrop, while minimum susceptibility was determined from a partially weathered sample taken only a few feet away. These extremes are believed to represent small local concentrations of stringers and grains of magnetite crystals in the igneous rock. A detailed magnetic survey of the horizontal and vertical components of the earth's magnetic field was made over the diatreme area. Stations were occupied at 20-ft intervals as shown by the grid on fig. 2. When greater detail was desired, intervening stations were also occupied. The field instruments were supplied by the Department of Geophysics, St. Louis University. The magnetometers are the Schmidt balance type constructed by the Ruska Instrument Co. These instruments are temperature compensated and have a standard sensitivity of 10 gamma. Calibration of the instruments

Jan 1, 1951

By J. M. Roberts, N. Brown

The stress-strain behavior of zinc single crystals was measured over a strain range of 10-6 to 10-2. The phenomenon of macroyielding was observed in detail and plastic strains were detected at almost zero-stress. Closed hysteresis loops were observed during loading and unloading in the strain region of about 10-5. From the hysteresis a frictional stress on the dislocation of about 6 psi was obtained. A preliminary analysis indicates that impurities are primarily responsible for the friction. Nonelastic Strains as much as 10 -4 were recovered depending on the amount of prior deformation. Part of the recovered strain occurs instantaneously upon unloading and the remainder occurs at zero stress. The time dependence of the recovered strain was measured. THIS investigation is concerned with the details of plastic deformation preceding the ordinary yield point as measured with the usual strain sensitivity of about 10-4. The approach leads to internal friction observations in the hitherto neglected frequency range below 10-1 cycles per sec. It is believed that if the phenomenon of macroscopic yielding is to be understood, then the stress-strain curve in the neighborhood of the macroyield point should be greatly magnified. It may then be possible to determine whether macroscopic yielding is a unique event or whether it is a process which begins gradually at a lower stress. In the case of low-carbon steel a unique event obviously occurs at the macroscopic yield point as indicated by a drop in the load, but copper appears to exhibit a gradual transition from the elastic to the plastic state. In zinc the yield point is rather abrupt although the data indicates that some plastic deformation precedes large scale yielding.' One of the purposes of this investigation is to determine whether there is an abrupt transition from the preyield microstrain region to the region of macroscopic deformation. Such a rapid transition would support the concept that there is a critical stress for yielding. The concept that yielding is a unique event associated with such phenomenon as activating a Frank-Read source, freeing the dislocation from solute atoms, dislocations cutting through dislocations, or dislocations moving freely by one another, has been expounded widely on theoretical grounds. It is hoped that highly sensitive measurements of strain in the neighborhood of the macroscopic yield point will shed some light on the event known as the "Yield Point". EXPERIMENTAL METHOD 1) Specimens—High-purity zinc was cast into spherical graphite moulds in air and grown into spherical single crystals by the Bridgman method under a positive pressure of Argon gas. Spectro-graphic analysis of cleaved sections from four crystals showed a purity of 99.994 pet Zn. The specimens were acid machined with an 1/8 in. gage section in a form similar to those used by Parker and co-workers.2 Bausch type grips were fastened to the specimen by Epon VI adhesive. The specimens were oriented so that only [1120] (0001) slip occurred. Fig. 1 shows two of the specimens in the grips. Prior to each test, the gage section of the specimen was given a concentrated HNO3 chemical polish followed by alcohol rinsing and air blast drying. 2) Test Method- The shear tests were performed on an Instron testing machine and the experimental set-up was made very "hard". Strain could be measured to a sensitivity of 10 -6 by means of a capacitance gage extensometer. The design and calibration of this type of extensometer to measure microstrain, as applied to pure shear and tensile tests of metals, will be the subject of a separate paper—therefore, only a brief account will be presented here. The method essentially consists of attaching a

Jan 1, 1961

By L. H. Robinson

Triaxial compression tests on Indiana limestone indicate that chemical additives in the pore fluids can increase or decrease the strength in plastic failure but not in brittle failure. Tests using a series of the sodium salts of dicarboxylic acids show that odd-number carbon-atom chains decrease the yield strength as much as 3.0 x 10 3 psi, and even-number carbon-atom chains increase the yield strength as much as 9.0 x 102 psi. ,The most effective chemical (sodium citrate) decreased the yield strength of Indiana limestone from 16.0 x 103 to 12.0 x 103 psi. The chemical additives investigated have no influence on microbit drilling rate when drilling with zero differential pressure. However, when drilling at a 2.0 x 103-psi pressure differeniial and using an odd-number carbon chain compound as the circulating fluid, the roller bit drilling rates were slower than with water whereas the drag bit drilling rates were faster. One even-number carbon chain compound added to the circulating fluid produces the opposite effect: the roller bit drilling rate is slightly faster than with water and the drag bit slower than with water. INTRODUCTION A Russian book by Rehbinderl published in 1944 generated much interest in the possibility of aiding and accelerating the destruction of solids by the action of a liquid in which the solids are deformed. This book describes a process in which microcracks are generated during elastic deformation. To describe this process, the rock is divided into three zones: (1) the zone in which the destruction takes place, (2) the predestruc-tion zone (an affected area immediately below the destroyed zone) and (3) the undisturbed specimen. Consider a load applied normally to a surface of an infinite slab of rock. Immediately below the point of application of the load, the rock is destroyed by compression or shear forces. Below this area of destruction, because of a great number of discontinuities ranging from defects to weak points in crystals of discontinuities in crystal latices, very small cracks are created in or between the crystals (often referred to as microcracks). Upon removing the load, the broken rock in the destroyed zone could be removed. In the lower predestruction zone, however, the microcracks in and between the crystals could disappear by the process of rehealing, i.e., the molecular attraction from one side of the crack to the other side being sufficient to completely eliminate the crack. Thus, a large number of these microcracks possibly exist only for a relatively short period of time. The concept of small cracks being generated within the crystals of a rock is not unreasonable. If the rock matrix is deformed below the yield point, some of the defects present within the crystalline structure could start small cracks through the interior of the grains. Upon removal of the load, these microcracks reheal (or the newly generated surfaces come back together) so that all evidence of cracks completely disappears. Under various types of loading, and in various types of fluids, the rehealing of these cracks would be time dependent. If a liquid adhered to the surface of a rock, it could penetrate into the microcracks and thus delay or prevent the rehealing process. This suggests that the prevention of healing of the microcracks may be dependent upon the wetting characteristics of the solid. Thus, rocks which are water-wet should be more easily destroyed in water than in nonpolar hydrocarbon liquid. Adsorption of a liquid could also reduce the free surface energy which could explain the decrease in strengths of materials under nonrepetitive-type loading. Rehbinder's work prompted Boozer, Hiller and Serdengecti 2 to examine the effects of pore fluids on the deformation of rocks subjected to triaxial compression over a range of confining pressures, temperatures and strain rates. Fluids which strongly adsorbed on the rock grain surfaces decreased the strength of sandstone and limestone, which deformed plastically. For certain strain

By M. J. Saarivirta

A high-purity copper-zirconium alloy system was imesti-gated. The zirconium content of the alloys studied varied from 0.003 to 0.23 pet. The solid solubility of zirconium in copper and some physical and mechanical properties of the alloys have been determined. By proper heat treatment, Cu-Zr alloy can develop a high electrical conductivity and resistance to softening at temperatures up to 500°C (930°F). This combination of desirable properties makes this alloy superior, to other com-merzcrrl copper base alloys for- use in the electrical conductor field. DEMAND for high conductivity copper alloys that retain their mechanical properties at elevated temperatures is growing rapidly. At present, copper-base alloys such as copper-silver and copper-chromium are used where these characteristics are required. As an example, commutators in electric motors are often made of these alloys. However, the life at elevated temperature of commutators made of copper-silver alloys is much shorter than the life of the same part made of copper-chromium and copper-zirconium alloys. Copper-silver alloys are subject to creep and subsequent failure when the service temperature exceeds several hundred degrees centigrade. Use of copper-chromium alloys has been known for the past several years, but little information is available in the literature concerning the properties of alloys in the copper-zirconium alloy system. Some work had been directed toward determining the solubility of zirconium in copper as well as determining properties of the Cu-Zr alloys. These investigations have revealed the superior high-temperature and electrical conductivity properties of copper-zirconium alloys over copper-chromium alloys. The United States Metals Refining Co., Carteret, N. J. has recently produced OFHC R copper-zirconium alloys for experimentation and evaluation. Because OFHC R copper contains no appreciable oxygen, no harmful oxides are formed and the full benefit of Zr as an alloying addition is obtained. This paper describes the results of this work. It contains room-temperature and some high-temperature data which have been obtained after various processing techniaues. Actual elevated temperature properties are being determined and will be reported in a separate paper. Preliminary results obtained at elevated temperatures suggest that the Cu-Zr alloy is superior to other high conductivity copper-base alloys. WORK PROCEDURE The high-purity oxygen free (OFHC R) copper-zirconium alloys with zirconium content ranging from 0.003 to 0.23 pct were cast into 4-by 4-in. wirebars by both continuous casting and conventional casting methods. Zr was added in the form of a master alloy containing 30 pct Zr and 70 pct Cu. Castings were analyzed for zirconium and nine bars containing various amounts of zirconium were selected for this study. The results of analyses and the sample numbers are given in Table I. Typical analyses of OFHC R copper are also shown. The following properties were studied: A) Solid solubility of zirconium in copper. B) Effect of zirconium on properties of copper. C) Effect of combined working and heat treating on properties of Cu-Zr alloys. The solid solubility of zirconium in copper was determined by metallographic techniques. Specimens for this phase of the investigation were hot rolled at 900oC (1650oF) to 0.250-in. rod. The rolled rods were cut into 2/3-in. long specimens and solution annealed at 950 °C (1740°F), 980°C (1795 °F). and 1020 °C (1870 °F) for 6 hr and quenched in water. In order to find the solid solubility limits at lower temperatures, the homogenized specimens were reheated at various temperatures for 1 hr and quenched. The physical and mechanical properties were determined on 0.250 in. rod, 0.132- and 0.081-in. wires. The wires were cold drawn from the 0.250-in. rods after they were solution annealed at 980 °C (1795°F) and quenched in cold water. Mechanical and electrical properties were determined on cold drawn and

Jan 1, 1961

By P. R. PaeIay, A. Slibar

Using three-dimensional, stress-deformation rate equations for a Bingham plastic, an approximate solution for the laminar flow of drilling mud between the drill pipe and casing is given for the case when the velocity gradients due to axial flow are large compared to velocity gradients due to rotation. INTRODUCTION The fact that drilling mud can be treated, to a first approximation, as a Bingham plastic has been established by several investigators12,3,4,5. A Bingham plastic is a material that is rigid until a certain combination of stresses exceeds a critical value. When the stresses are sufficiently high to initiate flow, the reduced stresses have a constant ratio to the corresponding deformation rates at each point. Prediction of pressure and torque requirements to produce the desired flow of the material have been made by analytical solutions due to Bingham6, Reiner7, and Buckingham8. One part of the present means of calculation that requires clarification is the flow between the drill pipe and casing. Present methods treat the flow resulting from the rotation of the drill pipe separate from the flow produced by the axial pressure gradient. Since the non-linear behavior of a Bingham plastic implies that solutions cannot be superposed, the present analytical investigation was undertaken to obtain a solution to the problem of combined axial and tangential flow. Equations have been proposed for the three-dimensional flow of a Bingham plastic9,10,11 and it has been shown that the proposed equations lead to the usual solutions from the one-dimensional theory". Applying these equations to the flow between two concentric cylinders the problem of axial flow only13 and tangential flow only12 have been solved. In addition to the separate problems of axial and tangential flow between concentric cylinders, the authors have determined the relationship between external torque on the inside cylinder and axial pressure gradient necessary to initiate flow". The solution given in Ref. 14 points out the complexity of the present problem. The problem considered here is the case of simultaneous axial and tangential flow. The axial flow, necessary to keep the drill bit free of removed material, results from the axial pressure gradient. Tangential flow is present since the drill pipe rotates in the hole. The solution given here is valid when the shear stresses in the drilling mud due to rotation are small compared to the shear stresses resulting from the axial flow. This case for laminar flow can be encountered in oilfield drilling. STRESS-DEFORMATION RATE EQUATIONS A detailed derivation of the equations governing the behavior of a Bingham plastic is given in Ref. 10. This section briefly outlines the physical reasoning leading to this three-dimensional formulation of the stress-deforma-tion rate law. Experiments on a certain class of materials have demonstrated the following properties: (1) when a certain combination of the stresses is below a critical value no deformation of the material occurs, (2) to a first approximation this combination of stresses is independent of the hydrostatic pressure (negative average normal stress), (3) if flow occurs the ratio of the reduced stress to the corresponding deformation rate is constant at each point of the flowing material, and (4) incom-pressibility. For the one dimensional case of shear deformation, Bingham6 formulated the governing equation as dxx, = 0 for sxx < to and µdxx = s xx = to for sxx to , . where dxx is the shear deformation rate, sxx the shear stress, to the critical shear stress, and p the slope of the sxx vs dxx curve for dxx > 0. Fig. 1 shows the behavior for pure shear between two parallel plates. Taking into account the physical properties given above and assuming the critical combination of stresses to be measured by the octahedral shear stress, the fol-lowing three-dimensional equations have been proposed.

Jan 1, 1958

By C. G. Dunn, F. W. Daniels, M. J. Bolton

IN recent investigations1. a data on relative grain boundary energies in silicon iron have been obtained. The present investigation is a continuation of this work along similar lines for the purpose of obtaining additional information on boundary energies. One aim has been to extend the data for a (110) series, which was formerly studied,&apos; to small differences in orientation, since a recent theory3,4 based on a dislocation model of grain boundaries predicts a E. ? (A-ln ? )* form of energy curve for small differences in orientation. Another aim has been to provide data for a (100) series—all grains having (100) planes parallel with the surface of sheet speci-mens—and to compare the results with the predicted form of energy curve. Finally, information on the nature of approach to equilibrium conditions was to be obtained through observations on the movements of grain boundaries. Recently published papers2,3,5 have treated the mathematical problem of expressing equilibrium conditions for grain boundaries for the general case when boundary energy depends upon boundary orientation. The equilibrium equations, which relate equilibrium angles and grain boundary -free energies, contain additional terms that express the variation of energy with boundary rotation. It has been necessary in the present investigation, however, to neglect these additional terms since no data for their evaluation were available. Dropping the additional terms leads to the following approximate equations which were used: E12/sin ?3 = E18/sin?2 =E28/sin?1 or those of the form: E28 + E13 cos ?3 + E12 cos ?2 = 0 Experimental Procedure Except for sample F1, all specimens were made from two lots of silicon iron called C and L respectively. The compositions of these are listed in table I. In the preparation of 12 three-grain specimens for the present investigation, a controlled grain growth technique, which has been described previously,&apos; was used. After preparation, the specimens were notched at the boundaries to shorten them as a means of providing more rapid approach to equilibrium in the anneals. Initial grain boundary angles were determined from micrographs taken at X500. Seven anneals, totaling about two days at 1300°C and two to four days at 1400°C, were run in an atmosphere of pure dry argon as described in a previous paper.&apos; Boundary changes generally could be followed without metallographic surface preparation, because thermal etching occurred during the anneals. These observations indicated angle changes of as much as 35" in some instances, with the major changes occurring during the first anneal. Annealing was discontinued when the angles reached stationary values. Fig. 1 gives a schematic diagram for purposes of defining crystallographic and boundary directions for three grains with common plane parallel with the sheet. Differences in orientations (expressed by A) are the angles between [00l] directions. They can be calculated with the aid of the ?&apos;s. The grain boundary angles can be calculated from the w&apos;S. Results Results are given in table 11. Types of crystal-lographic planes refer to those parallel with the sheet. Orientations are given in terms of [00l] direc-tions as shown in fig. 1. Except for grain 3 of specimen H6, which was unintentionally tilted 7" out of a (100) plane, all grains generally were within 1" or 2" of the plane specified. The directions of boundaries were measured generally to within 1" on both upper and lower surfaces, and the average direc- tions were determined for use in calculating the grain boundary angles. Variations in grain boundary directions refer to deviations from average directions. Boundaries near the junction point for all specimens generally were very close to perpendicu-

Jan 1, 1951