Search Documents

By Grover J. Holt

In order to provide a clear picture of the development of the sink-and-float process of concentration as applied to the iron ores of Minnesota, a few pertinent facts should be brought out concerning the ores and the products of concentration. Iron ore is primarily a cheap commodity handled in immense quantities. The price of iron ore at present, based on a natural iron content of 51.5 per cent, varies from $2.55 to $2.70 per gross ton f.0.b. cars at the mine or washing plant in Minnesota. Last year 92,000,000 gross tons were shipped from the Lake Superior district (Minnesota, Michigan, and Wisconsin) to the furnaces. Concentrated iron ores have no greater value per unit of iron content than ores that can be mined and shipped direct from the shafts or open pits. For years only the higher grades of concentrating ores could be treated and sold in competition with the immense reserves of direct shipping ore available. These higher-grade "straight wash" ores required only the simplest treatment; namely, the washing out of fine sand from coarse ore particles. As the exhaustion of the " straight wash " ore is reached, rock is found replacing part of this sand, and the ore no longer responds to the former sizing treatment. Substantial tonnages of this marginal (jig ore) remained to be treated. Because of the limitations placed on concentrates by the furnaces—namely, low price of product and minimum amount of fines—iron-ore concentration oil has been and must continue to be a one-pass process. Only an increase in price or a change in structure of concentrates allowed by the ore consumer will encourage departure from this practice. Faced with the necessity of handling large tonnages, with the limitations mentioned, iron-ore research men have found their search for new and more efficient methods of treatment seriously handicapped and removed from the field of fine crushing. Sink-and-float treatment appeared to offer the best field in coarse concentration and has been proved by several plants to be well adapted to our problem. The use of ferrosilicon as a medium solid was decided upon. In our present practice, the ferrosilicon metal, carrying about 83 per cent iron, 15 per cent silicon and 2 per cent carbon and nonmagnetics, is crushed to pass 65 mesh and used without further sizing. When mixed with water the specific gravity of the medium may be controlled to within 0.02 per cent above or below the required gravity. Table I shows examples of a change in solid content of the medium for varying gravities. the I is based on clean ferrosilicon, whereas some contamination is always present in the mill circuit, tending to

Jan 1, 1947

By J. L. Lummus, Frank O. Jones

A field procedure for determining graphite in drilling mud is presented which is sensitive to 0.25 lbs/bbl and accurate to 20 per cent. The method, utilizing oil flotation principles, is suitable for use in all oil-free water base muds except those containing ligno-sulfonates, lignites, or surface active agents. INTRODUCTION Graphite was proposed as a drilling lubricant as early as 1940, but has not been used extensively until recently.' Graphite has been substituted for oil in certain instances to avoid oil contamination of core samples since it has been found that graphite does not interfere with routine core analysis. A major difficulty in using graphite is the lack of a satisfactory field test for determining the concentration of graphite in mud. DISCUSSION OF METHOD Several possible methods of analysis were investigated, including chemical separation, density fractionation, radioactive tracers, and oil flotation.', ' The investigation indicated that a satisfactory method for field use could be devised using an oil flotation method. It was found that toluene shaken with a highly diluted mud sample would recover sufficient graphite to be apparent in the oil phase. Refinement and standardization of technique made it possible to detect as little as 0.25 lb/bbl graphite and to estimate graphite content to within 20 per cent by using a visual comparison method. The test is limited to oil-free water base muds. Quebracho, phosphates, or barytes in the mud do not interfere with the test but surface active agents, lignosulfonates' and lignites evidently render !he graphite water-wet so that none may be recovered by oil-flotation. PROCEDURE Instructions for determining graphite in mud: 1. Collect representative one gallon sample.- from mud stream. Transfer immediately 350 ml portions of this Sample into four mixing cans labeled A, B, C, and D. Measure out graphite (same as is used to treat mud) for addition to cans as indicated below, using either a specially designed scoop or a balance. Can: A B C D Grams Graphite to Add: none 2 4 6 Stir samples B, C, and D for 15 minutes with propeller type mixer. 2. Clean and rinse well with water four 250 ml volumetric flasks labeled I, 11, 111, and IV. Using a 5 ml hypodermic syringe, transfer the indicated volume of samples from cans A, B, C, and D into designated flasks as follows: From Can: A B C D To Flask: I II III IV Add This Volume of Mud: 4 ml 2 ml 2 ml 2 ml 3. Measure 100 ml fresh or distilled water to each flask and swirl gently to disperse mud. Add exactly 5 ml toluene to each flask. Stopper and shake each

Jan 1, 1953

By W. J. Romanow

RECENT papers by Williams, Sherwood, and Boothby,1 Seybolt et al.2 Heikes; and Roberts4 attest to the increasing importance of the hexagonal ferromagnetic compound MnBi. Since the magnetic properties of MnBi crystals are highly anisotropic, it is useful and necessary to have appropriate aids for determining their orientations—a (00.1) standard stereographic projection and a corresponding table of crystallographic angles for this structure. The tables of crystallographic angles for the hexagonal system available in the literature5 are computed for c/a ratios greater than that of MnBi and cannot satisfactorily be used to find the crystallographic angles of MnBi. A table of angles between the crystallographic planes (HK.L) and (hk.1) was calculated for MnBi from the formula0 F=are cos Hh+Kk+ 1/2(Hk+hK) + 3/4 (a/c)2Ll/v(H2 + K2 + HK + 3/4 (a/c)2L2) (h2+ k2+hk + 3/4 (a/c)2l2) on an IBM Type 650 Magnetic Drum Data Processing machine. The lattice constants used are listed in Table I and are those determined by Willis and Rooksby7 at 20°C. More recently published values obtained by both X-ray and neutron diffraction"' show no difference from these significant to the calculation. From the crystallographic angles between the basal plane (00.1) and the general plane (hk.1) in Table I, an (00.1) standard stereographic projection was made for MnBi which is shown in Fig. 1. Acknowledgments The author wishes to thank R. G. Treuting and J. N. Hobstetter for their technical assistance, and Miss D. P. Booth for programing the IBM machine for the calculations. He appreciates the opportunity to read the paper of B. W. Roberts of General Electric Co. prior to its publication. References 1H. J. Williams, R. C. Sherwood, and 0. L. Boothby: Bulletin Amer. Physical Soc., 1956 vol. 1, p. 132. 2 A. U. Seybolt, H. Hangen, B. W. Roberts, and P. Yurcisin: AIME Trans., 1956, vol. 206, p. 605: Journal oF Metals, May 1956. 3R. R. Heikes: Physical Review, 1955, vol. 99, p. 446. .B. W. Roberts: A Neutron Diffraction Study of the Structures of Manganese B.W.Roberts:ANeutronDiffractionBismuthide, Physical. Review, 1956, vol. 104, p. 607. 5 A. Taylor and S. Leber: AIME Trans., 1954, vol. 200, p. 190; JouRNal of Metals February 1954. « C. S. Barrett: Structure of Metals, 2nd Ed., p. 635. McGraw-Hill Book Co. New York and London, 1952. 7B. T. M. Willis and H. P. Rooksby: Proceedings Physical Soc., London, 1954, vol. 67B, p. 290.

Jan 1, 1958

By P. Chiotti, G. R. Kilp

IN the study of zinc-zirconium1 and zinc-uranium2 systems, vapor-pressure measurements were made in order to establish the equilibrium phase diagrams for a pressure of 1 atm. In each of these systems, only zinc has an appreciable vapor pressure over the temperature range investigated. The zinc pressure was measured over a sufficiently wide temperature and composition range to permit calculation of the standard free energy, enthalpy, and entropy of formation for the compounds ZrZn, ZrZn2, ZrZn3, ZrZn6, ZrZn14 , and U2Zn17. In these calculations the compounds were treated as line compounds. Although the exact composition range was not determined, metallographic and thermal data indicate that the solubility range for these compounds is small. It is to be noted that the compound initially reported to correspond to the formula UZn9, 2 has been shown by the crystal structure work of Makarov and vinogradov3 to correspond to the formula U2Zn17,. The crystal structure is similar to that for the compounds Th2M17, investigated by Florio,4 et al; here M represents iron, cobalt, or nickel. Therefore, thermodynamic calculations are based on the formpla U2Zn17 EXPERIMENTAL The dew-point method employed to measure the vapor pressure of zinc over uranium-zinc alloys has been described previously.2 The same procedure and apparatus were used in measuring the zinc pressure over zinc-zirconium alloys. In the case of alloys in the two-phase region consisting of a zirconium and the compound ZrZn, the Knudsen effusion method was employed to obtain a few values in the temperature range 600" to 560°C. In most cases, tantalum crucibles were used to contain the zirconium alloys. THERMODYNAMIC PROPERTIES OFU2Zn17 A least-squares treatment of the vapor-pressure data obtained for 35 and 65 wt pct U alloys in the temperature range 650° to 940°C gave lOg10PAtm = 7,713/T + 6.33 Here, as in following equations, T represents degrees kelvin and P represents the zinc vapor pressure in atmospheres. The probable errors for the two constants were calculated to be 60.68 and 0.0563, respectively. This relation represents the equilibrium dissociation pressure for the reaction U2Zn17 (s) - 2U(s) + 17Zn(v) The solubility of zinc in solid uranium is negligible and the only additional information required to calculate the free energy of formation of U2Zn17 is the free energy of vaporization of pure zinc. K. K. Kelley5 gives the relations, AF°= 30,902 + 6.03Tlog T + 0.275 X 10-3T2 - 45.03T

Jan 1, 1961

By AIME AIME

THE annual meeting of the Woman's Auxiliary to the A.I. M.E. is always held in New York, in con- junction with the annual meeting of the Institute in February. Business sessions, teas, dances, a theater party, luncheons, excursions, and many other interesting activities filled the four days to overflowing. In all ,216 women were present, from all parts of the United ,/ mates, and there were several from Canada. On Mon- ' day not only the visitors, but the New York members also, gathered around the registration desks, where Mrs. E. N. Wolfes, Mrs. S. J. Jennings, and Miss Georgene Davis saw that everyone was properly registered and provided with tickets to whatever functions she desired to attend. Greetings were eagerly ex- changed as friends met at the luncheon on the fifth floor, where the hostesses of the day were Mrs. J. D. Handy, Mrs. T. T. Read, Mrs. Sidney Rolle and Mrs. H. J. Wolf. In the afternoon, there were visits to art galleries and other interesting exhibits, arranged by Mrs. Frederick Laist. Mrs. W. H. Bassett was the hostess at a very delightful Thé damant at the Italian Gardens of the Ambassador Hotel. Many of the men attended this function also. In the evening the visiting ladies were entertained at a theater party, with Mrs. Wilbur Judson as hostess. The play that was seen was Gorki's "At. the Bottom."

Jan 1, 1930

By ARCHIBALD DOUGLAS

BY this time almost everyone knows, in a general way, the corporate income distribution policies of the 1936 Revenue Act, and many of the practical problems arising there under. This article is not intended to be a technical discussion of that act by title, subtitle, section, or supplement, nor an analysis of inter- dependent sections of the various acts over many years woven on the fiscal loom f our Congressional machine. Such a discussion would require the spinning of a web of words too long for patience. Yet ,a general statement of the underlying plan of the 1936 Act, so far as it affects dividend policies, is perhaps useful.

Jan 1, 1937

By Roman Y. Poderny, Vladimir V. Rjevskii

In the USSR, the Moscow Institute of Radio Electronics tronics and Mining Electro-Mechanics (MIRGEM) has started what it hopes will become a nationwide movement to educate mining students in the precise specialties that industry has come to require. Courses for mining engineers, the MIRGEM faculty proposes, should dovetail as exactly as possible with specific jobs available in the mining profession. Acting upon this thesis, MIRGEM revised its own curriculum in 1962 and has since presented an over-all plan for Soviet mining education before two mining school conferences as well as the Ministry of Higher Education and a number of major Soviet industrial ministries. The plan was universally approved with some suggested revisions. SOVIET MINING EDUCATION TODAY At present, mining education in the Soviet Union covers the exploitation of solid minerals and raw materials, including coal as well as ferrous and nonferrous metals. The extraction, storage, and refining of oil and gas is treated as a separate discipline. In all, there are 33 Soviet universities and institutes that train mining engineers for careers in the industrial, research and educational fields.

Jan 9, 1966

By M. A. Goudie

The deposits occur in a large salt basin of Middle Devonian age. The potash, the final deposit in the salt basin, results from several interrupted cycles of evaporation and dessication. The deposits are extensive, and, at first glance, relatively undisturbed. With more and more wells being drilled, it has now become evident that salt solution has played a large part in changing the original deposits, resulting in some cases in partial to complete removal of the potash and the underlying halite. The most dominant factor in the removal of salt by solution appears to have been tectonic movement and consequent faulting, probably of relatively minor dimensions but of major importance. Evidence which indicates the tilting of the evaporite basin to the north and northwest is shown by the changing pattern of the basin during succeeding eras of potash deposition. The potash minerals of most importance economically are sylvite and carnallite. Reserve calculations indicate that 6.4 billion tons of recoverable high grade potash in K2O equivalent exist in the basin. The Devonian salt basin, which contains the Saskatchewan potash deposits, extends from just east of the foothills in Alberta, north as far as the Peace River area, across Saskatchewan and into Manitoba as far east as Range 10 west of the First Meridian and south into Montana and North Dakota (Fig. 1). The basin is closed everywhere except to the northwest. The known potash deposits are confined almost entirely to the Province of Saskatchewan, with the exception of a small area in western Manitoba bordering the Saskatchewan boundary. The following discussion will concern only the Saskatchewan part of the basin. The evaporite series in the basin is defined as the Prairie Evaporite Formation of the Elk Point Group, of Middle Devonian age. Recent work done by potassium-argon dating methods has indicated an Upper Middle Devonian (Givetian) age of from 285 to 347 million years for the potash. The Elk Point Group consists in ascending order of the Ashern, Winnipegosis, and Prairie Evaporite Formations. The Ashern formation, with an average thickness of 30 ft, sometimes called the Third Red Bed, consists of dolomitic shales and shaly dolomites. The Winnipegosis, is a reef-type dolomite, usually with good porosity, and in many cases oil-staining, although to date no production has been obtained. The thickness varies from 50 to 250 ft. The Prairie Evaporite formation, varying from 0 to 600 ft in thickness, consists of halite with interbedded anhydrite and shale, with considerable amounts of potassium salts in the upper part of the formation. The potassium salts are chiefly chlorides, although very minor occurrences of sulfates have been re- ported. The anhydrite beds do not appear to be continuous, although generally one or two bands of anhydrite underlie the lowest potash zone and are used as marker horizons. The shale occurs as seams interbedded with the salts, as large irregular inclusions in the salts and as very fine particles in intimate mixture with the salts. The Prairie Evaporite Formation is overlain by the Second Red Bed member, the Dawson Bay Formation and the First Red Bed Member of the Manitoba Group, listed in ascending order. The Red Beds are shales which vary in color from red to green, maroon, grey, grey-black, and reddish purples. They serve as marker horizons for coring the potash. The Second Red Bed averages 14 ft in thickness, the First Red Bed 35 ft. The Dawson Bay Formation, which everywhere overlies the First Red Bed and the Prairie Evaporite Formation in the area under discussion, is a reef type of carbonate, in some places limestone, in others limestone and dolomite, with vugular to pinpoint porosity averaging 130 ft in thickness. In some parts of the area, it has a salt section near the top of the formation, usually with interbedded shales and limestones. In other parts of the area, it is waterbearing and the salt is absent. Detailed mapping has indicated that the areas in which the Dawson Bay is water-bearing are areas which have been disturbed by faulting. Where the Dawson Bay is salt-bearing, the porosity has been plugged by salt. The total thickness of the salt varies from between 600 to 700 ft in the center of the basin to zero at the northern edge of the basin (Fig. 2).* The salt-free area in the center of the Province is believed to have resulted from removal of salt by solution. Evidence from several wells suggests that salt removal has been a continuing process from the time of deposition to the present day. One well drilled between the Quill Lakes for potash information encountered

Jan 1, 1961

By M. Schwartz, S. K. Nash, R. Zeman

Knoop hardness in the rolling plane and in the longitudinal plane of hot-rolled and cold-rolled sheets of sublimed magnesiu?w was measured as a function of the angle between the long axis of the indenter and the rolling direction. These measurements were correlated with similar data taken on the (0001) and (1010) planes of a single crystal of magnesium where the hardness was measured as a function of the angle between the long axis of the indenter and the [1120] direction. The results were analyzed for compliance with the hypothesis of Daniels and Dunm to account for slip, and with a similar hypothesis to account for twinning. Some hardness anisotropy data are also presented for magnesium-indium and magnesium-lithium solid solution alloys. It is well known that the hardness of a crystalline specimen is different for its different surfaces, and also that the hardness is a function of direction within a single surface. Variations in hardness for single crystals have been found to be much larger than those for polycrystalline materials. Also, materials having low crystal symmetry were found to have a greater anisotropy of hardness than those of high symmetry. 0'Neill1 and Pfeil,2 using a 1-mm Brine11 ball, studied single crystals of aluminum and iron, respectively; and they found a variation of hardness of about 10 pct between readings taken along the principal crystallographic faces. Daniels and Dunn3 found that the Knoop hardness number varied about 25 pct as the long axis of the indenter rotated on the basal plane of a zinc single crystal. The variation on the (1450) plane was about 100 pct, and the average hardness on this plane was about twice that of the basal plane. They also studied the variation of hardness within the (loo), (110), and (111) faces of a single crystal of silicon ferrite and found variations of about 25 pct although the average values for these planes were almost identical. Single crystals of zinc were also studied by Meincke.4 He found that the Vickers hardness numbers varied about 30 pct depending on whether the axis of the indenter was parallel or perpendicular to the (1010) and (1110) planes. Mott and Ford,5 using a Knoop indenter, found a 25 pct variation in hardness on the basal plane of zinc. Crow and Hinsley6 studied heavily cold-rolled bronze, steel, brass, copper, and other metals. They found that the difference in hardness numbers based on the difference in the length of the diagonals of the Vickers indenter was from 5 to 12 pct. Some minerals and synthetic stones show a very large anisotropy of hardness. Robertson and Van Meter7 found the Vickers hardness of arsenopyrite to vary from 633 to 1148 kg per mm2. stern8 using the double-cone method on synthetic corundum found the hardness number to vary from 950 to 2070. And winchell9 reported a variation of hardness number from 184 to 1205 in kyanite. The variation of hardness as a function of direction in a given crystallographic plane in single crystals possesses a periodicity which is related to the symmetry of the lattice. Daniels and Dunn3 found a six-fold periodicity of hardness in the (0001) plane of zinc. They found that the hardness curves of silicon ferrite had a four-fold symmetry in the (100) plane, a two-fold symmetry in the (110) plane, and a six-fold symmetry in the (111) plane. Mott and Ford5 also reported a six-fold symmetry of hardness in the basal plane of zinc. And vacher10 found two-, four-, and six-fold periodicities of hardness in copper on the (110), (100), and (111) planes, respectively. The purpose of this paper is to report the results of an investigation on the anisotropy of hardness as a function of orientation in single crystals of mannes-ium, and samples of rolled magnesium, magnesium-indium, and magnesium-lithium solid solution alloys. The anisotropy of hardness of pure magnesium which had been hot rolled, and then cold rolled various amounts to fracture, was studied by means of Knoop indentation hardness numbers; and the results were correlated with the preferred orientation as determined by quantitative X-ray pole-figure data. A comparison was made of the hardness data obtained from the rolled sheets and those of single crystals of magnesium. In order to obtain a more fundamental understanding of the variation of hardness and of Knoop hardness testing, the data were analyzed by

Jan 1, 1962

By T. F. Kassner

The dissolution kinetics of type 304 stainless steel in the Bi-Sn eutectic alloy have been investigated under the well-defined hydrodynamic conditions produced by the rotating-disc sample geometry. In addition, the mutual solubilities of iron, chromium, nickel, and manganese from 304 stainless steel in the eutectic alloy were determined over the temperature range 450" to 985°C. The convective -diffusion model for mass transport from a rotating disc was used to interpret the experinlental dissolution data. The dissolution process was found to be liquid-diffusion-controlled under specific conditions of temperature and Reynolds number. Liquid penetration into the 304 stainless steel resulted in a reduction of the di,ffusion-controlled mass flux and thus precluded the calculation of the diffusion coeficients of the four components from 304 stainless steel in the Bi-Sn eutectic alloy. The convective-diffusion model for diffusional limitations of electrode reactions and mass transport at the tationssurface of a rotating disc set forth by Levich 1,2 has found wide applicability in the investigation of electrochemical and dissolution phenomena in aqueous systems. Riddiford 3 and Rosner have reviewed the model and also include numerous references on work of this nature. More recently the rotating-disc system has been applied to the investigation of hetereogeneous reactions in liquid-metal systems. Shurygin and Kryuk 5 have measured the dissolution rates of carbon discs in molten Fe-C, Fe-Si, Fe-P, and Fe-Ni alloys. Shurygin and shantarin6 also studied the dissolution kinetics of iron, molybdenum, chromium, and tungsten, and the carbides of chromium and tungsten in Fe-C solutions with a rotating-disc sample geometry. In these systems it was possible to distinguish between diffusion and reaction control mainly through experimental confirmation of the velocity dependence of the dissolution rate predicted by the model. However in the absence of dependable solubility data and the virtual lack of diffusion data in these systems, a quantitative check of the magnitude and the temperature dependence of the rate was not possible. In many instances, estimates of the activation energy for solute diffusion and the diffusion coefficient based upon the experimental dissolution data are not credible. A recent study by this author7 has resulted in a critical test of the model in a liquid-metal system. The solution rates of tantalum discs in liquid tin were measured over a wide range of temperature and velocity conditions. In addition, the solubility and diffusion coefficient of tantalum in liquid tin were determined as a function of temperature. The latter data were used with the model to predict both the magnitude and the temperature dependence of the dissolution flux. In that work it was also deemed necessary to reevaluate the solution to the convective diffusion equation to incorporate the effect of the lower range of Schmidt numbers encountered in liquid-metal systems. Good agreement between the model and the experimental dissolution data in the region of diffusion control was obtained in the Ta-Sn system. The Bi-Sn eutectic alloy is used as a seal between the reactor head and the reactor vessel in the Experimental Breeder Reactor-11. The alloy is fused periodically prior to fuel-handling operations. In that connection, it was necessary to investigate the compatibility of the liquid alloy with the type 304 stainless-steel containment material. The results of a rotating-disc study in this multicomponent system are presented. EXPERIMENTAL METHOD The 5.08-cm-diam discs were machined from 0.317-cm-thick plate. Chemical analysis information for the type 304 SS material is given in Table I. The discs were ground flat on metallographic paper and given a final polish on Linde B abrasive. A thin support rod was threaded into the disc and the region around the threads was fused under an inert gas. The support rod was fitted with a quartz protection tube and then was attached to a supporting shaft which passed through a rotary push-pull vacuum seal. The disc and supporting shafts were dynamically balanced prior to insertion into the furnace tube. The apparatus is shown schematically in Fig. 1. The 58 pct Bi-42 pct Sn eutectic alloy melts were prepared from 99.995 pct pure Bi and Sn by fusing the components in a 7-cm-ID Pyrex crucible. The system in which the melts were made was evacuated to a pressure of 1 x 10-6 Torr and back-filled with purified argon several times before melting the charge. The ingot was reweighed and placed in a slightly larger-diameter Vycor crucible used in the dissolution runs. A run was started by lowering the disc into the liquid

Jan 1, 1968

By K. H. Hiller

A rotational viscometer has been designed which perrnits the measurement of the rheological properties of drilling muds and other non-Newtonian fluids under conditions equivalent to those in a deep borehole (350F, 10,000 psi). The important mechanical features of this instrument are described, and its design criteria are discussed. The flow equations for the novel configuration of the viscometer are derived and the calibration procedures are described. The data and their interpretation, resulting from measurement of the flow properties and static gel strengths of homoionic montmorillonite suspensiom at high temperatures and pressures, are presented. Data are also presented for the flow behavier of typical drilling fluids at high temperatures and pressures. The pressure losses in the drill pipe and the annulus depend critically upon the flow parameters of the drilling fluid. This work demonstrates the need to measure these parameters under bottom-hole conditions in order to obtain a reliable estimate of the pressure losses in the mud system. INTRODUCTION The rheological properties of drilling fluids are affected by temperature and pressure, but the extent of these effects on the dynamic flow properties is not well known. Measurements of changes of the flow properties of clay-water drilling muds with temperature have been reported by Srini-Vasan and Gatlin.1 The temperatures reported did not exceed 200F, a limitation imposed by the apparatus used by these authors. The rheological properties of clay suspensions were measured at temperatures up to 100C by Gurdzhinian.' Neither the nature of the exchange ions in the clay suspensions nor the degree of purity were defined in his work, nor were the measurements extended to currently used drilling fluids. The lack of systematic measurements of dynamic flow properties at high temperatures and pressures seems the more surprising since during the last decade the importance of the control of the hydraulic properties of drilling fluids has come to be widely recognized. Very good mathematical treatments of the friction losses in drill pipe and annulus have been developed.3 4 These treatments are based on the assumption that drilling fluids behave as Bingham plastic fluids. Quite often this assumption is justified, while in other cases a power law equation pro- duces better fit than the Bingham model does. For convenience in applying viscometer data to pressure-drop calculations, the Bingham plastic flow equation is preferable and, therefore, has been applied to the data reported in this paper, although other equations may fit these data more accurately. In a Bingham plastic fluid the relationship between the shearing stress 7 and the rate of shear D is given by the following equation: where is the plastic viscosity and 4 the yield point. If 4 = 0, the equation for simple Newtonian flow, 7 = pD, is obtained. Two empirical constants are required for the description of laminar flow of a Bingham plastic fluid, and calculations of the flow behavior at high temperatures and pressures cannot be better than is permitted by the accuracy with which these constants are known. For this reason a high-pressure, high-temperature rhe-ometer has been designed to measure the plastic viscosity the yield point +, and the static gel strength S, at pressures up to 10,000 psi and temperatures up to 350F. The important features of its design will be described. The results of measurements on homoionic clay slurries will be discussed insofar as they are relevant to an understanding of the general flow behavior of clay-water drilling fluids. The results of measurements on some typical drilling fluids will be presented also, and their practical implications will be briefly discussed. DESCRIPTION OF EQUIPMENT MECHANICAL FEATURES A viscometer designed to measure the plastic viscosity, yield point and gel strength of non-Newtonian fluids must permit the measurement of the shearing stress t at any given rate of shear D. This is possible only if t and D are approximately uniform throughout the entire sheared sample. A Couette apparatus is the most convenient method of realizing this condition, as has been pointed out by Grodde." The "high-pressure, high-temperature rheometer" described in this paper is basically a rotational Couette viscometer that is immersed in a cell in which pressure and temperature can be controlled over the range of interest. Fig. 1 shows schematically the important features of the pressure cell and associated equipment. The heart of the instrument is the rotating cup. It is shown more clearly in Fie. 2. which revresents the lower one-third of the pressure cell (below the input drive shaft shown in Fig. 1), and it is shown in detail in Fig. 3. For measurements of dynamic flow properties, the rotating cup is driven by a 1/2-hp electric motor, which operates through a Vickers

By W. A. Oates, J. A. Lambert, P. T. GaIIagher

Monte Carlo methods have been used to compute the arrangements of interstitial atoms dissolved in tetrahedral sites in bcc lattices. It is assumed that the presence of an interstitial atom "blocks " a certain number of neighboring sites and prevents their occupancy. Sites "blocked" by more than one filled site are allowed for. The computed values of. the mean occupation number (defined as the ratio of the total number of sites blocked to the number of solute atoms are used to calculate the configurational entropies of the solutions. These entropies are compared with those resulting from previous theoretical studies of this problem and also with available experin~ental data for the p Zr-H, Nb-H, V-H, and Ta-H systems. Evidence is also given that the "blocking" explanation of low limiting compositions in these systems, rather than this being due to initial limitations on the number of sites available, is probably correct. THE ideal partial configurational entropy of mixing of an interstitial solute in a metal is given by: where p is the number of interstitial sites per metal atom and Xi is the atomic fraction of the interstitial. For the bcc lattice. which we shall be concerned with in this paper, the interstitial positions are shown in Fig. 1. It can be seen that for the tetrahedral sites, p=6. whereas for the octahedral sites, p = 3. Different emphasis has been placed on the relative importance of energy and entropy effects in determining deviations from ideality in interstitial solid solutions. In some cases the same system, e.g., Fe-C, has been described by the contradictory regular and athermal solution models indicating that the enthalpy and entropy functions, derived from equilibrium data, are frequently not accu.rate enough to differentiate between these treatments. However, for certain metal-hydrogen solutions the equilibrium data is available over sufficiently wide ranges of temperature and composition to permit a reasonably accurate determination of the compositional variation of the heats and entropies. Hoch&apos; has attempted to interpret the results of interstitial solid solutions in terms of a regular solution model. In the case of the Ta-H system where 13 = 6, this model entails fitting the experimental relative partial entropies of solution, asH, to the equation: where ASgs is the relative partial excess entropy of solution of hydrogen. Hoch found that the results of Mallett and Koeh1 could be fitted to this equation with an approximately constant value of AF up to XH = 0.25. However, it is apparent from the solubility isotherms in this system which become asymptotic to the composition TaH that, since (Xh /6 - ~Xh ) becomes infinite only at TaH6, it is necessary that AS<&apos; tends to infinity at TaH. In other words, the low saturation composition of TaH, instead of the anticipated TaH,, eliminates the possibility of applying regular solution theory to such systems. Rather large negative excess configurational entropies must exist at higher hydrogen concentrations in order to explain the lower saturation values. To account for these low limiting compositions and excess entropies two distinctly different approaches have been followed. Rees and many others1-l2 have assumed that not all interstitial sites are crystallographically equivalent with respect to the interstitial addition; that is, in Eq. [I] p is less than the value anticipated from geometrical considerations. To describe, say, a bcc metal-hydrogen system with a limiting composition of MH by this approach one would consider that p = 1 in the first instance instead of p = 6.&apos;j3 In some cases, nonintegral values of B have been taken in order to improve the fit with the experimental data over limited ranges of composition. The other approach which has been used to explain the low saturation compositions is to assume that, although all sites are available for occupancy, strong repulsive interactions exist between the neighboring interstitial atoms, and hence occupancy of any site excludes or blocks a certain number of neighboring sites from being occupied. Earliest treatments of this concept considered the exclusion of an integral number, of nearest-neighbor sites from being occupied at all concentrations. In this case, the partial configurational entropy is given by: These early treatments failed to allow for the overlap of the blocked sites which will arise at all but the very lowest concentrations. More recently attempts have been made to calculate the effect of this decrease in the number of blocked sites on the configurational entropy. Using the quasichemical treatment of interstitial solid solutions as given by Lacher and assuming that an infinite repulsive interaction energy existed between the solute atoms. atom obtained an approximate configurational entropy applicable to the blocking with overlap case:

Jan 1, 1970

By J. B. Conway

Stress-vuptuve data for several of- the refractory metals are frequently found to yield a linear relationship between the Larson-Miller parameter and the logarithm of the applied stress. In such cases linear stress-rupture isotherms result with slopes bearing a definite relationship to the temperature. It also follows that the stress to produce rupture in a certain period of time will be linear in temperature. Data for several refractory metals have been reviewed and excellent linearity is shown in this type of isochronal plot. In addition, the af ore - mentioned lineavity leads to a linear relation between the log of the stress to produce rupture in a certain time and the homologous temperature. This has been illustrated for the Group VI-A metals, tungsten and molybdenum. EXTENSIVE use has been made of the Larson-Miller&apos; parameter in the interpolation and extrapolation of stress-rupture and creep data. In those cases where this particular parametric approach is applicable a convenient and fairly straightforward procedure is made available for the correlation of experimental stress-rupture data. It is quite common to employ this parameter in the form of a master rupture plot in which the parameter, T(C + log tr), is expressed as a function of log stress. In many cases this functional relationship in log stress is linear within acceptable accuracy and hence the following relation results: where P is the parameter, C is the Larson-Miller constant, T is the absolute temperature, t~ is the rupture time, a is the stress, and a and b are constants. Examples of such a relationship are contained in the work of Green, Smith, and 01son2 dealing with high-temperature rupture behavior of molybdenum and in the work of Green&apos; dealing with the high-temperature behavior of tungsten. In addition, pugh4 has shown a similar linearity for some fairly low-temperature data for molybdenum. It can be shown that when the relationship in Eq. [I] is exhibited certain generalizations can be made concerning the form of the stress-rupture isotherms. For example, rearranging yields: For a given material (constant C) at a given temperature the first term on the right-hand side of Eq. [2] is a constant and hence this equation defines a straight line when log stress is plotted as a function of log-rupture time. This is recognized as the standard form usually employed in this type of data presentation. Such linearity then suggests the linear form of the Larson-Miller parameter. Or, in other words, the linear parametric relationship in Eq. [2] results only when the stress-rupture data are linear on a log-log plot of stress vs rupture time. Another interesting observation can be made in regard to Eq. [2]. It can be noted that the slope of the stress-rupture isotherms is given by - T/b and hence a direct calculation of the constant b is available. It also follows that since the value of b is the same for all temperatures the slopes of the various isotherms on the log-log stress-rupture plot cannot be the same. Indeed, the existence of the relationship in Eq. [2] precludes a system of parallel lines on this common stress-rupture plot. As a matter of fact it further specifies that in addition to being nonparallel the slope of these isotherms must decrease (i.e., become more negative) with increasing temperature. Such a condition is indeed found to exist in the case of the stress-rupture data reported for molybdenum.&apos; As a corollary to the above, it may be stated that stress-rupture data which do not lead to a linear log-log stress-rupture plot or whose isotherms do not exhibit a decrease in slope as the temperature increases will not yield the linear relationship of Eq. [I]. Applying Eq. [2] to two different temperatures and solving for C yields: Eq. [3] affords a simple and rapid method for calculating the Larson-Miller constant from the log-log stress-rupture plot. The slope of a given linear isotherm is measured and the value of "b" calculated based on Eq. [2] as: slope = - -Tb Then at an abscissa value of 1.0 hr (making log tr in Eq. [3] equal to zero) read the stress corresponding to rupture for two different temperatures. Substitution in [3] yields: A value of the Larson-Miller constant can thus be calculated from a few simple mathematical procedures employing data read directly from the log-log plot of the stress-rupture data. Of course, it is not to be overlooked that the above reasoning has been based on the linear relationship of Eq. [I] being applicable. However, if as mentioned above the log-log plot is

Jan 1, 1967

By J. F. Martin, L. M. Melnick, R. Rapp, R. C. Takacs

Recent studies on the determination of hydrogen in steel have shown that the hot-extraction method for removing hydrogen from a solid sample is preferable to its removal from a molten sample by vacuum fusion or by fusion in vacuum with tin. A number of techniques are available, however, for determining the hydrogen so extracted. They include: thermal conductivity, gas chromatography, pressure measurement before and after catalytic oxidation of the hydrogen to water and removal of the water, and pressure measurement before and after diffusion of the hydrogen through a palladium membrane. These techniques have been evaluated on the basis of initial cost, maintenance, speed and accuracy of analysis, and applicable concentration range. The results of this study showed that the palladium-membrane technique is best suited for routine use. FOR some time investigators have been concerned with the origin, form, and effect of hydrogen in steel. In such stdies&apos;, the analysis for hydrogen constitutes one of the most important phases. It is quite apparent that the results for hydrogen concentrations in a given steel are dependent on the method of obtaining the sample, storage of the sample until analysis, preparation of the sample, and analysis of the sample, including all the facets inherent in the calibration and operation of an apparatus for gas analysis. There are a number of means available for determining hydrogen. This is a critical study of some of the more common techniques in use today. In most conventional melting and casting methods, hydrogen concentrations of 4 to 6 parts per million (ppm) in steel are quite common. Because of the undesirable effects of hydrogen on steel there has been increased use of techniques such as vacuum melting,&apos; vacuum casting, and ladle-to-ladle stream degassing, which lower the hydrogen content to levels on the order of 1 to 2 ppm. Therefore, the method used for determining hydrogen in steel must be sensitive and precise. In any analytical procedure for gases in metals there are two distinct operations—the extraction of the gas from the metal and the analysis of the extracted gas. To extract the gas from the steel, three methods have been employed: 1) fusion of the sample with graphite at high temperature; 2) fusion with a flux, such as tin, at a lower temperature; and 3) extraction of the hydrogen from the solid sample at a temperature below the melting point of the steel. Fusion with graphite is the least-acceptable method. The blank in this method is higher and more variable than in either of the other two methods. The hydrogen fraction of the total gas composition usually is between 10 and 50 pct; thus, a larger analytical error is possible. The vacuum-tin fusion4 extraction of hydrogen is probably the most rapid method in use today; the extraction time is usually about 10 min. However, with this system a bake-out of the freshly charged tin for 2 hr is necessary and a change of crucible and a charge of fresh tin are required after each day of operation whether one or thirty samples have been analyzed. In addition, frequent checks of blank rates are required since CO and Na are continually being given up by the steel samples dissolved in the tin bath. The composition of the gas in this method lends itself readily to analysis; although the hydroge concentration may fall to as low as 50 pct, more often it is above 90 pct, thus allowing a more precise analysis (because of less interference from other gases). In 1940 ewell&apos; published the hot-extraction method for extracting hydrogen from the solid sample, comparing analysis for hydrogen extracted at 600°C with similar analysis for the gas extracted at 1700°C by fusion with graphite. Good agreement for hydrogen was obtained between these two methods, provided sufficient time was allowed for extraction at the lower temperature. carsone obtained good results in his comparison of this hot-extraction method with vacuum-tin fusion. Subsequent work by Geller and sun7 and Hill and ohnson&apos; has shown that steel samples should be heated to at least 800°C to effect the release not only of the diffusible hydrogen but also of the "residual" hydrogen that may be present as methane. Since the rate of evolution of hydrogene9l0 depends on such factors as sample size and composition, thermal history, and extent of cold work, a fixed extraction time is not possible. Extraction times of 30 min are normal, but 2 hr are not unusual. Induction or resistance heating may be used in the hot-extraction method. With resistance heating the

Jan 1, 1964

By F. Selig, A. S. Odeh

A second-order approximation to the exact solution of the diffusivity equation corresponding to the pressure build-up of a well producing at a variable rate is derived. This approximation is applicable when the well&apos;s shut-in time is larger than the total time elapsed since the well was first produced. The resulting equations are compact in form and easy to use. Thus, the need for Horner&apos;s&apos; theoretically precise but rather laborious solution to the above problem is eliminated. In addition, these equations apply where the use of Horner&apos;s widely known approximate method is questionable. From a practical point of view, the reported method is best suited for analysis of drill-stem tests and short production tests conducted on new wells. INTRODUCTION The utility of drill-stem and short production tests in reservoir studies has long been recognized by the reservoir engineer. If interpreted correctly they could lead to a wealth of information upon which may depend the success or failure of reservoirs&apos; analyses. Initial reservoir pressure and the average flow capacity are two quantities that are normally sought from a drill-stem and/or a short production test analysis. Pressures are the most valuable and useful data in reservoir engineering. Directly or indirectly, they enter into all phases of reservoir engineering calculations. Therefore, their accurate determination is of utmost importance. The flow capacity kh of the reservoir is indicative of its commercial capability. In addition, it can indicate the presence of a darnaged zone around the wellbore and, thus, the necessity for remedial measures. Of the several methods used to analyze drill-stem and short production tests, Horner&apos;s&apos; method is by and large the most common. It applies to an infinite reservoir and or a limited reservoir where the effect of production has not been felt by the boundary. Horner&apos;s method makes use of the so-called "point-source" solution of the diffusivity equation. The point-source solution is approximated by a logarithmic function and the superposition theorem is utilized to give the familiar pressure build-up equation where is the shut-in time, q is in reservoir barrels per day and the rest of the symbols conform with AIME nomenclature. Eq. 1 was derived for a well which produced at a constant rate q from time zero to time t and was then shut in. In actuality, such a constant rate of production does not normally obtain. Therefore, a correction must be applied to Eq. 1 to account for the varying rates of production. Horner suggested two methods. The first, which results in a theoretically accurate solution, is rather lengthy and laborious and, thus, it is not suited for routine analysis. The second which has been termed a "good working approximation" is the one used by the majority of the reservoir engineers. In the second method, Eq. 1 is modified by simply introducing a corrected time t, and writing where q is the last established production rate prior to shut-in, and t, is obtained by dividing the total cumulative production by the last established rate. Horner&apos;s original paper does not give any indication that this method of correction is based on any theoretical justification. In addition, there is a question as to what constitutes the last established rate. In case of a drill-stem test some engineers use the average rate obtained by dividing the total fluid produced by the total flow time, while others calculate the average rate by dividing the total fluid produced by the last flow-period time. Obviously, different results obtain for the different flow rates used. Because of this, a simple method to the varying-rate case was developed which is theoretically sound and which defines clearly the flow rate and its associated time to be used in the calculations. The final equation arrived at is where q* and t* are a modified rate and time, respectively, and can be easily calculated. In addition, it is shown theoretically that Horner&apos;s approximate method, if used for a variable-rate case, gives the correct pressure but would not be expected to give the correct flow capacity. MATHEMATICAL ANALYSIS The general equation governing the flow of slightly compressible fluid in porous media may be written as The elementary solution to Eq. 4, representing an instantaneous withdrawal of Q units volume of fluid at the origin at t = 0, is known as the instantaneous sink

By Robert Baschwitz, John Chipman

The distribution of silicon between liquid silver and Fe-Si-C alloys has been studied at 1420oand 1530°C. The data are consistent with earlier studies. New data of Hager on the liquidus lines of the system Ag-Si and the distribution data are used to obtain the activity coefficient of silicon in both liquid phases. Data on the heat of mixing in iron permit accurate extension to 1600°C. Equilibrium data involving SiO2 and silicon in liquid iron together with revised data on the free energy of SiO2 are used to fix the activity of silicon in the infinitely dilute solution. The binary system exhibits strong negative deviation from ideality. At infinite dilution ? Si at 1600" is 1.25 x 10&apos;3, and at concentrations up to NSi = 0.4 the slope d InySi/dNSi has a constant value of r; = 13. It is found that logysi in the ternary solutzon is approximately but not exactly the same function of Nsi + NC as of NSi in the binary. The results are consistent with currently available data on the free energy of Sic and its solubility in molten iron. LIQUID solutions of the system Fe-Si-C have acquired considerable importance as the laboratory prototypes of blast furnace hot metal. Equilibrium studies involving such solutions and slags approximating those of the blast furnace have yielded useful information concerning the thermodynamic properties of blast furnace slags. In studies of this kind great importance attaches to a knowledge of the thermodynamic activity of silicon in the solution as a function of temperature and composition. An attempt was made by Chipman, Fulton, Gokcen, and askey&apos; to evaluate all of the pertinent data on this system and to deduce the desired relation between activity, composition, and temperature. These authors published data on the solubility of graphite and Sic in molten Fe-C-Si solutions and on the distribution of silicon between liquid iron and liquid silver. They showed further how the activity of silicon in very dilute solutions in liquid iron could be calculated from equilibrium data involving the molten alloy and solid SiO,. These calculations rested on the published thermodynamic properties of SiO, in- cluding its heat of formation which at that time was recorded as -209.8 kcal. This value has been under suspicion for some time and has recently been replaced by the concordant results from two independent laboratories2,3 which place the heat of formation of a-quartz at -217.6 kcal. This revision necessitates a re-evaluation not only of the activity of SiO2 in slag but also of silicon in molten iron. It is the purpose of this paper, therefore, to recalculate the activity of silicon, and in furtherance of this objective to present new data on its distribution between liquid Fe-Si-C alloys and liquid silver. HEAT OF SOLUTION OF SILICON IN IRON In order to determine the effect of temperature upon the activity coefficient it is necessary to know the heat of solution of silicon in iron as a function of composition. This is found in the data of Korber and Oelsen4 shown in Fig. 1. The curve corresponds to the following equation, which is of a form suggested by Wagner:5 Here AH is the heat absorbed in kilocalories in forming one gram atom of molten alloy from its molten elements and the N&apos;s are atom fractions. The relative partial molal enthalpies of the components, each referred to its pureliquid state and defined as zFe = aFe - PFe and zsi = HSi — -psi, are shown graphically. At low concentrations zSi = -28.5 kcal, in agreement with Kijrber and Oelsen&apos;s computation. This is in good agreement with the value of -29.3 kcal obtained by Chipman and Grant6 using an entirely different method. ACTIVITY AT INFINITE DILUTION From the known free energy of SiO, it is possible to obtain the activity of silicon in dilute solution in liquid iron from equilibrium studies. The heat of formation of a-quartz is —217.6 kcal and the heat capacity and entropy data are given by Kelley and ~ing.&apos; The free energy of formation of ß-cristo-balite at temperatures above the melting point of silicon is expressed by the following equation: Si(Z) + O2(g) = SiO2 (crist); AF" =-226,500 + 47.50T [I] The value of the deoxidation product for silicon [%Si] x [%O]2 at 1600°C according to Gokcen and chipmans is 2.8 x 10"5, in agreement with results of Hilty and Crafts.9 More recent works of Matoba,

Jan 1, 1963

By R. I. Jaffee, R. M. Evans

IN recent years, the interest in liquid metals as heat-transfer media for power plants has been very great. The possibility of the development of nuclear power plants has increased this interest and served as the impetus behind much research on low melting metals and alloys for such purposes. The principal reasons for consideration of liquid metals as heat-transfer media lie in their high thermal conductivity and consequent high heat-transfer coefficients, stability at high temperatures, and the high ranges of temperature possible. The element gallium possesses some of the requisite properties for a heat-transfer liquid. It is a unique material, having a low melting point and a high boiling point. Pure gallium melts at 29.78oC, and suitable alloying will produce a metal which melts below room temperature. The boiling point is about 2000°C. As it is a liquid metal, the heat-transfer characteristics would be good. Gallium is not now readily available, due in part to a lack of uses for the metal. Nevertheless, it is not a rare element, and a sufficient supply of gallium exists to permit its consideration for this use. Since gallium has some promise as a heat-transfer liquid, owing to its unique properties, research on the subject was carried on at Battelle Memorial Institute at the request of the Bureau of Ships, U.S.N. The research had as its objectives the determination of the effect of alloying on the melting point of gallium, and the study of the corrosion of possible container materials. In this research, alloys were found which had significantly lower melting points than pure gallium, but none which simultaneously fulfilled other additional requirements, chiefly the corrosion problem. Neither was it found possible to reduce the melting point of certain otherwise suitable alloys appreciably by small additions of gallium or gallium alloys. The results gave little hope that gallium alloys can be developed which enhance the good properties and minimize the undesirable characteristics of elemental gallium. Thus, gallium now appears less promising than other metallic heat-transfer media. The experimental thermal-analysis techniques used in this work have been described.&apos; Experimental Results As a first approximation, the development of low melting gallium alloys was based on alloying elements suitable for use in a nuclear power plant, which also lowered the melting point of gallium. Information from the literature, summarized in Table I, indicates that. tin, aluminum, and zinc are the only suitable elements which cause a lowering of the melting point of gallium. Indium and silver also lower the melting point of gallium, but are of little interest for use in nuclear power plants. Of the elements reported not to lower the melting point of gallium, there is some ambiguity on the behavior of copper. Weibke3 obtained solidus arrest temperatures of 29°C for Cu-Ga alloys from 60 to 90 pct Ga, 0.8C lower than the generally accepted melting point. This may be the effect of a eutectic close to gallium, or, more likely, the result of impurities, or experimental error. The seven elements listed in Table I whose effects were not known were of potential interest if they lowered the melting point of gallium. Their effects were determined experimentally for this reason. Binary alloys containing nominally 2 pct of each of these elements were prepared in the form of 2-g melts by placing the components in a graphite crucible and holding them in an argon atmosphere at 370°C for 5 hr. These melts were then subjected to thermal analysis. In all cases. the solidus temperature was the melting point of gallium. Since these elements (As, Ca, Ce, Mg. Sb, Si, and T1) did not lower the melting point of gallium, they were not considered further as components of a eutectic-type alloy. Ga-Sn-Zn Alloys Preliminary considerations of this system for low-melting alloys were encouraging. All three binary systems were of the simple eutectic type. The composition and melting points of the eutectics were as follows: Sn-9 pct Zn (199°C), Ga-8 pct Sn (20°C), and Ga-5 pct Zn (25°C). Therefore, the probability of a ternary eutectic was high. For reasons to be discussed later, aluminum could not be used as an alloying constituent, leaving the Ga-Sn-Zn system as the only one of interest for low-melting gallium-

Jan 1, 1953

By F. Weinberg

The relative concentration of 1" at grain boundaries in controlled orientation bicrystals has been examined by autoradiographic techniques, and by activity measurements of grain boundary surfaces exposed by preferential ,melting. The autoradio-graphs indicate that thallium is concentrated at grain boundaries in as-grown bicrystals, but not in zcell-annealed bicrystals. They also indicate that the solute concentration and the distribution on as-grown bicrystal surfaces are markedly different than that of the bulk material. The boundary surface measurements are in agreement with the autovadiographic evidence. On the basis of these measurements, as-grown bicrystals containing approximately 100 ppm of Tl, solidified at rates between 5 and 30 cm per hr and with tilt boundaries greater than 10 deg, exhibited grain boundary segregation equivalent to roughly 10 atomic planes of pure solute. Higher solute concentrations (equivalent to 140 atomic planes of pure solute) were obtained in bicrystals solidified slowly (0.6 cm per hr); slightly higher values were obtained in specimens containing a large angle nantilt boundary. Annealing for various times over a range of temperatures eliminated grain boundary segregation within the experimental uncertainty of the results (equivalent to 1 atomic Plane of pure thallium at the boundary). The results for the as-grown bicrystals can be qualitatively accounted for by assuming the presence of a groove on the solid-1iq;id interface, at the grain boundary. SOLUTE segregation at grain boundaries may be considered in two parts, namely, nonequilibrium segregation associated with the solidification process, and equilibrium segregation in fully annealed materials.&apos; There is much indirect evidence for nonequilibrium segregation, based on preferential etching at grain boundaries and the mechanical properties of as-cast alloys. In addition, some direct observations have been reported in which radioactive tracers were used as solute additions and segregation detected at the grain boundaries by autoradiographic techniques. However, there is little detailed quantitative data on solute concentrations related to grain boundaries, particularly for different freezing conditions and grain boundary configurations. Equilibrium segregation at grain boundaries has been considered both theoretically and experimentally. cean&apos; has made an estimate of the maximum equilibrium solute concentration that might be expected at a grain boundary, based on the lattice distortions in the boundary region. He arrived at a concentration which was equivalent t a monatomic layer of pure solute. A similar value, based on thermodynamic arguments, was calculated by Cahn and Hilliard for the segregation of phosphorus in iron. Experimentally, much higher values of solute concentration at grain boundaries have been reported recently by both Inman and iler&apos; for phosphorus in iron, and Ainslie et 1.&apos; for sulfur in iron. They observed concentrations equivalent to as much as 20 to 100 atomic layers of pure solute at the grain boundaries. However, in both cases it was shown that the observed segregation was not due solely to equilibrium segregation at the grain boundary. In the former case, precipitation effectss due to trace impurities in the material were believed to account for the large amount of solute present at the grain boundary. In the latter case it was shown that a high density of dislocations in the boundary region could provide a large number of additional sites for solute atoms, other than at the grain boundary. Thomas and chalmera have reported on the equilibrium segregation of po210 in grain boundaries of Pb-5 pct Bi alloys. Using autoradiographic techniques, they observed a concentration of polonium along the boundary trace on the surface of annealed bicrystal specimens grown from the melt. The concentration only appeared after annealing, and varied with boundary angle, increasing as the boundary angle increased. Their conclusions have been questioned by Ward," who pointed out that the segregation they observed along the boundary trace was much too wide to be compatible with the usual concepts of the thickness of a grain boundary of several lattice spacings. Also, Maroun et al.,l1 with specimens similar to those of Thomas and Chalmers, found that segregation could only be detected on the specimen surface, suggesting that Thomas and Chalmers&apos; results were associated with an oxidation effect of polonium, and not equilibrium segregation. Thomas and Chalmers replied12 that they did observed segregation at the grain boundary in the bulk material and suggested further experiments were necessary to resolve the difference. The purpose of the present investigation was to examine both nonequilibrium and equilibrium grain boundary segregation in melt grown bicrystal specimens as a function of boundary angle, growth rate, and solute concentration, and to de-

Jan 1, 1963

By H. P. Rassbach, E. R. Saunders

MUCH progress has been made in recent years in the theory and practice of making stainless steel. By effective utilization of oxygen for decar-burization and more suitable alloying agents, it has been possible to attain consistent production of very low-carbon stainless steel. In order to facilitate economical production of stainless steels, the Electro Metallurgical Co. has carried out an extended experimental program that has clarified some of the complex interrelations of temperature and composition under decarburizing and reducing conditions. These results&apos;-:&apos; have been founded in large part on small experimental heats, and in order to confirm their validity and significance under commercial conditions, a survey of stainless steel melting practice has been made with the cooperation of stainless steel producers. Conditions required for decarburization and associated oxidation of chromium, manganese, and iron have been fairly well established in relation to the beneficial effect of the highest practicable temperature. The recovery of chromium and manganese from highly oxidized slags by reduction with silicon has been indicated with somewhat less precision and this study has shown significant deviation in large commercial heats from the small experimental heats. In spite of an unsatisfactory degree of accuracy in estimating the conditions affecting reduction of metallic values, it has been possible to calculate a slag weight in reasonably good agreement with the results observed in large heats. While there still is much to be learned about both the qualitative and quantitative aspects of stainless steel melting, this survey has indicated the manner by which the efficiency of the production process may be measured. Oxidation Period In order to establish practices for the recovery of chromium and manganese from the slag the amounts of these metals oxidized should be known. Moreover, since reduction of oxidized chromium and manganese must necessarily be accompanied by similar reduction of iron, knowledge of the total quantity of metallics oxidized is essential. The relations between carbon, chromium, and temperature under oxidizing conditions were developed by Hilty in 1948.&apos; While it had been realized previously that retention of chromium in the metal during carbon oxidation is favored by high temperatures, the Hilty relation provided quantitative information useful for evaluating melting procedures. For example, it was shown that decarburization to moderate carbon levels can be achieved while retaining substantial amounts of chromium. However, in decarburizing to the low-carbon level necessary for producing 0.03 pct maximum carbon stainless steel, very little chromium remains in the bath at the temperatures generally employed. For this reason, Hilty, Healy, and Crafts&apos; later projected an extension of the chromium-carbon relation to the low-chromium region. Although this chromium-carbon-temperature relation defined the composition of a chromium steel bath at the end of the oxidizing period, it did not provide a direct means for estimating the total amount of metallic oxidation occurring during decarburization of a stainless steel heat. This subject was investigated by Crafts and Rassbach³ and, later, by Hilty, Healy, and Crafts" who demonstrated that metallic oxidation is a function of the chromium content of the initial furnace charge, the minimum carbon content attained, and the temperature. It was further demonstrated from data on 1-ton heats that an empirical relationship exists between the ratio of chromium plus manganese to iron in the slag (S) to the corresponding ratio of these components present in the metal bath. The following expression was derived to permit the calculation of the amount of metallics oxidized during decarburization of a given charge: W-2000 (Cr1 + Mn1)-(Cr2 + Mn2) 1 100s/s+1-(Cr3 + Mn2) where W is the pounds of chromium, manganese, and iron oxidized per ton of charge; Cr1, the percentage of chromium in the charge; Mn1, the percentage of manganese in the charge; Cr2, the percentage of chromium in the bath after oxidation; Mn2, the percentage of manganese in the bath after % Cr + % Mn oxidation; and S =%cr+ % Mn/%Fe in the slag after %Fe oxidation. In order to establish whether the slag ratios of commercial heats are consistent with those found in the experimental heats, the slag and metal analyses shown in Table I were evaluated. These data represent samples taken after the oxidation of two 1-ton and seven 15 to 25-ton heats of types 303, 304, and 304L stainless steel made in chromite, acid, and basic hearths. Fig. 1 illustrates that the results for the commercial heats correlate reasonably well with the relationship originally established for experimental 1-ton heats. It will be noted that in the range of metal composition of these heats, the slag values generally lie above the line. As was suggested by

Jan 1, 1954

By C. H. Mathewson

CHARACTER OF THE WORK IN HAND IN planning the present experiments, we have made a particular effort to secure that adjustment of working conditions which would render the forthcoming tests most serviceable by way of indicating the comparative properties of the three different commercial grades of copper used. More specifically, we have endeavored to obtain certain definite information with respect to the relative behavior under test of ordinary electrolytic copper and furnace-refined lake copper containing (a) a moderate percentage of arsenic and (b) a rather large percentage of arsenic, in addition to the usual content of silver and other impurities. These comparisons were made systematic and comprehensive by testing throughout a series of (eight) reductions running from 0 to 70 per cent. in the case of cold-rolled metal, and throughout a series of (15) temperatures running from 100° C. to 1,000° C. in the case of annealed metal. In other words, a survey of properties similar to that made by Grard,1 in the case of electrolytic copper, was here repeated (with modifications) and extended to two other commercial varieties of copper.

Jan 7, 1916