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By F. W. Glaser

Metal-carbon-boron powder mixtures were hot pressed and the resulting specimens were studied by X-ray diffraction. It was found that regardless of the starting combination of the metal, carbon, or boron powders, a metal boride phase was always the major component in these samples. In the absence of carbon the boride phase formed on hot pressing depended only on the amount of boron present. Two new phases of the system Ti-B were found. They are Ti2B and Ti2B5. The existence of a controversial face-centered cubic phase of formula TiB was confirmed. Electrical resistivities were measured for various boride phases. It was found that the diborides are generally better conductors than the monoborides of the same metal. THE carbides and borides of the transition elements have very high melting points, in the range 2500° to 4000°C, and are therefore of interest as high temperature materials. The literature on the stability or chemical reactivity of these carbides and borides is very scarce. Various investigators'-" have demonstrated a relative instability of certain carbide phases in the presence of boron or boron-containing substances. In a recent publication, Glaserl demonstrated the stability of zirconium-boride (ZrB,) in the presence of carbon at temperatures in excess of approximately 2900°C, while during a preliminary investigation of boride phases, Steinitz' concluded that the diborides are stable in the presence of carbon while the monoborides of the fourth and fifth group are not, forming diborides plus carbides instead. Nelson, Willmore, and Womeldorph" have elaborated on the reaction B,C + 2TiC = 2TiB, + 3C, which was known to occur because of a relative instability of B,C and the great tendency towards TiB, formation at relatively low temperatures (approximately 1200°C). A similar study, involving as starting materials TiO, and B,C and resulting in TiB,, was recently described by Honak4, who observed the beginning of an exothermic reaction of a Ti0,-B,C powder mixture, which, when preheated in a hydrogen atmosphere to approximately 950°C, was carried to about 1600 °C by the heat of reaction. To shed more light on reactions of this type (Metal-C-B), the final product apparently always resulting in a boride phase at the expense of a carbide phase," a systematic investigation was started * Boride phases of various metals, as reported to date, are listed in Table I. and the following is an account of some of the results that were obtained. Materials, Preparation of Samples, Testing Methods The raw materials employed for this work consisted of various carbide, boride, and metal powders. as well as of boron and graphite powders. In cases where commercial grades of carbides were considered unsuitable because of low purity or excessive amounts of graphitic carbon, such carbide powders were prepared by this laboratory. The procedure for the preparation of carbide powders (zirconium carbide, titanium carbide, tantalum carbide, and niobium carbide) consisted of mixing graphite and the respective metal hydride powders in stoichio-metric proportions and subsequent heating of such mixtures in a hydrogen atmosphere in carbon crucibles. The heating was by high frequency to temperatures ranging between 1700" and 2100°C. The resulting carbide was then comminuted and screened to the desired particle size. ZrB, and TiB, powders were produced by the electrolysis of fused salt baths, according to the method described by Andriex.. The borides of niobium, vanadium, tantalum, molybdenum, chro-ium, and iron were obtained by mixing the respective metal and boron powders in the desired proportions. Such metal-boron mixtures were heated in a high frequency furnace to form boride powders. For each metal-carbon-boron group (Tables I1 through XI) a metal, its hydride, carbide or boride were mixed with carbon, boron or boron carbide powders. The additions of carbon, boron or boron carbide powders to any of these metals or metal compounds were calculated to satisfy a particular carbide or boride phase that according to the literature (Table I) had definitely been established by X-ray diffraction work. Samples of powder mixtures were hot pressed in graphite molds that were heated by direct conduction. The specimen dimensions were approximately 2.5X1X1 cm. Hot pressing temperatures were measured optically and maintained for approximately 30 sec under a constant pressure of about 1.3 ton per sq in. Wherever possible, an attempt to obtain maximum specimen density was made by temperature variation. Electrical resistivity testing was done by measuring potentiometrically the voltage drop over a length of 1.5 cm for a current of 10 amp, at room temperature. To obtain electrical resistivities for specific carbide or boride phases, values were plotted as a function of the respective sample densities

Jan 1, 1953

"Located on the Big Hole River, three miles from Divide, Montana, and 21.75 miles from Butte.Built in 1899.DAM: Rock-filled wooden crib, 512 ft. long and 57.5 feet high.SPILLWAY: Equipped with flash-boards 189 ft. long, 8 ft. 10 inches high.PENSTOCKS: Two 8 ft. diameter of steel, each branching and supplying two wheels.WHEELS: Four double horizontal, double discharge turbines, made by The James Leffel & Co., 1,000 h-p., 180 r. p. m., direct connected to generators, operating at 60 ft. head. GENERATORS: Four G. E., revolving field, 750 k-w., 180 r. p. m., 800 volt, 3 phase, 60 cycle alternators.EXCITERS: Two water-wheel driven exciters.TRANSFORMERS: 12 250-k-w. G. E. air blast, primary 15,000 volts, Secondary 800 volts.OPERATION: The plant operates essentially as a peak load plant. Except in flood period, there is insufficient water to operate at full load continually. In December its average output is about 500 k-w."

Jan 1, 1913

Executive Committee, Board of Directors C E Reistle, Jr, Chairman, H DeWitt Smith, Vice-Chairman, T B Counselman, Grover Holt, A W Thornton Finance Committee, Board of Directors Andrew Fletcher, Chairman, R B Caples, C R Dodson Investments Erle V Daveler, '57, Chairman, Henry Krumb, '59, John E Warren, '57, G F Moulton, ex officio as Treasurer, Andrew Fletcher, ex officio as Chairman, Fi¬nance Committee Endowment W W Mein, Jr, Chairman, N G Alford, E V Daveler, W J Coulter, J V N Dorr, R B Gilmore, J B Haffner, 0 H Johnson, Henry Krumb, D H McLaughlin, J R McMillan, J B Morrow, L F Reinartz, Wilfred Sykes, C E Weed Honorary Memberships Andrew Fletcher, Chairman, L F Reinartz and H DeWitt Smith, ex officio as Past Presidents, C E Reistle, Jr , ex officio as President, M L Rai¬der, '60, Henry Krumb, '58, D H McLaughlin, '57, P D Merica, '59

Jan 1, 1956

By J. E. Tobey

UNDER war conditions coal immediately assumes a position of highest importance for coal must carry the basic load for industry. The upward trend in production continued through 1941. Bituminous coal production alone about equaled the total output of bituminous and anthracite in 1940. The figures for 1941 approximated 500,000,000 tons for bituminous, and 54,000,000 tons for anthracite, and production of by-product and beehive coke exceeded that of the previous year. The coal industry, under the National Bituminous Coal Act, is going through a period of readjustment, and is beginning to stabilize itself under the statute. The Federal Mine Inspection Nill became law during the year.

Jan 1, 1942

By R. W. Raymond

The immense commercial value of the Gayley dry-blast process has been established beyond controversy. The testimony of practical blast-furnace managers, on both sides of the Atlantic, agrees that it reduces the cost of pig-iron about $1 per ton; but from the same testimony it appears that this direct economy does not by any means cover its commercial advantages—in fact, that under conditions frequently encountered in practice, it presents other benefits of even greater immediate financial importance. To this point I shall recur in a later part of the present paper. The history of the reception given to this invention, especially on the other side of the Atlantic, has repeated an experience familiar to American engineers. First, the reports of our practice were rejected as theoretically impossible, according to generally accepted notions and formulas; then the figures were reluctantly accepted; and finally the attempt has been made to explain how they could have been obtained. As to the Gayley dry blast, me Americans have been for several years in the last stage of the discussion, and the rest of the professional world is rapidly coming to it. Meanwhile, the remark has been repeatedly made that, whatever Mr. Gayley's process may turn out to be worth, it was not an invention on his part, but simply the energetic and persevering execution of a procedure already proposed by others. This question I wish to discuss first in the present paper. I. What Did Mr. Gayley Invent? Realizing that this is not the place for detailed argument on an issue of patent law, I shall not undertake to quote and criticise the publications prior to Mr. Gayley'a first patents. It may be admitted, without such critical analysis, that the possible advantages of removing moisture from the air forced into an iron blast-furnace were recognized and talked about a hun-

Jan 1, 1909

By D. Walton, W. C. Winegard, W. A. Tiller, J. W. Rutter

It is shown that the cellular substructure observed in binary alloy crystals grown from a melt of known concentration can be eliminated by the proper choice of growth conditions. For a given solute concentration, there exists a critical ratio of temperature gradient G in the melt to the rate of solidification R of the crystal, i.e., of G/R, which must be exceeded before the cellular structure can be eliminated. A secondary substructure is observed which is related to the cellular substructure. IN crystals grown from the melt, a prismatic substructure has been observed by Buerger,1 Pond and Kessler,2 and Rutter and Chalmers." This structure is columnar in the direction of growth and appears as a network of hexagonal cells in the plane of the solid-liquid interface. Rutter and Chalmers3 have shown that this substructure occurs as a result of the presence of a layer of high impurity concentration in the melt adjacent to the solid-liquid interface. The formation of the substructure is accompanied by a redistribution of this impurity in the neighborhood of the interface. The structure can be controlled by proper adjustment of the variables in the solidification process such as a rate of solidification and the temperature gradient in the liquid. The redistribution of solute during the solidification of metal crystals has been treated theoretically

Jan 1, 1956

By Gustav Egloff

AN unexpected and unprecedented demand for its products now challenges the petroleum industry. Between 1939 wand 1946, domestic oil demand increased nearly 45 per cent and in the first half of 1947 it was 10 per cent higher than in 1946. In 1939 the United States produced 1,264,962. 000 bbl of crude oil and indications are that about 1,860,000,000 bbl will be produced in 1947, a 47 per cent increase. Runs to stills are more than keeping pace with production. The crude capacity of 365 operating refineries is rated as 5,400.000 bbl daily and almost 100 per cent of this capacity was running crude oil in August 1947. The oil industry is cognizant of our need for a greater volume of petroleum products and is expending the huge stun of four billion dollars on exploration. production. transportation, refining. and marketing of petroleum. Of this amount about half will be spent on exploration and production. a billion on refining. and another billion on transportation and marketing facilities.

Jan 1, 1947

By E. S. Leaver

The authors of the paper above mentioned have sent the following statement to correct erroneous com-ments and implications in their article with the re-quest that it be published: "In the above mentioned article the reference to Bendelari jigs is used in the generic sense as applying to the mechanically driven diaphragm jigs. No attempt was made to dif-ferentiate between the various machines as installed on different dredges. The Natomas Company use a jig of their own manufacture. The Yuba Company installed the Placer jig as manufactured by the Pan American Engineer-ing Company. "The Pan American Engineering Company also manufactures the Crangle jig under their own name. This is a diaphragm jig in which the pulsations are produced by intermittent flow of water through the patent Crangle Valve and it has no driving mechanism."

Jan 1, 1937

By Vince Poxleitner, John Delaney

Introduction In the mining industry, comminution typically begins in the mine with a blast of explosive to break rock so that it can be handled by the avail- able equipment. Though the breaking of the rock is essential for material handling in the mine and plant, this is not the only reason for ore reduction in the mineral industry. Comminution is primarily required to liberate minerals from ore so that they can be concentrated into valuable products or to prepare minerals, such as talc, for market as mined. The size of the equipment used for comminution ranges from small to massive. Regardless of equipment size, the power required to reduce the rock is a major expense. Years ago, mineral deposits could be mined more selectively and required less grinding to produce saleable products. However, as richer deposits were depleted, it has become necessary to mine low-grade deposits, with the valuables dispersed throughout the rock. Comminution equipment evolved in physical size and capacities to meet the new mine and process requirements. A modern, modestly sized mining operation, with a capacity of 25.000 TPD may use crushers two stories high weighing over a million pounds, SAG mills 36 feet in diameter driven by dual motors putting out 10.000 horse- power, and ball mills over 16 feet in diameter . Because of the increasing size and weight of modern equipment, the builder is faced with the problems of erecting massive foundations and field assembling equipment on these foundations. As equipment costs and plant construction costs increase, builders are finding that owners are asking for more detailed progress and cost data. Comminution construction projects are generally classified as grass roots plants or expansions or modifications to existing plants. It is estimated that 60-702 of the jobs involve existing plants. Today ' s costs for construction of small, new comminution plants can reach tens of millions of dollars; larger plants can cost hundreds of millions of dollars. Modifications, on the other hand, usually run from a few thousand to several million dollars. Though many problems are common to the construction of both new plants

Jan 1, 1982

[Alphabetic Section: The letter immediately following a member's name indicates grade: M-member, A-associate, J-junior. The numerals following member's grade indicate year of election. The letter following year of election indicates primary divisional affiliation: A. Mining & Exploration F. Coal B. Minerals Beneficiation G. Petroleum C. Iron and Steel H. Industrial Minerals D. Extractive Metallurgy J. Council of Education E. Institute of Metals K. Council of Economics Geographic Section: An asterisk (*) preceding a member's name indicates availability for consulting work:]

Jan 1, 1961

By A. L. Mular. Discussion by G. A. Parks

G. A. Parks (Associate Professor, Dept. of Mineral Engineering, Stanford Univ., Stanford, Calif.) - Professor A. L. Mular in his paper Effect of Impurities on the Flotation Behavior of Zinc Oxide (T.P. 65B206) has made a most interesting and thought provoking contribution. In view of his recognized lack of measurements of the ZPC's of the doped samples and lack of direct evidence for participation of semi-conducting electrons in collector adsorption an alternate explanation should be considered. The alternate also

Jan 1, 1967

By Robert Glass Cleland

[PARTIAL LIST OF DIRECTORS OF THE NICHOLS CHEMICAL COMPANY AND NICHOLS COPPER COMPANY: G. H. Nichols William H. Nichols, Sr. William H. Nichols, Jr. Charles W. Nichols E. Remington Nichols George Martin Luther John Brown Francis Herreshoff]

Jan 1, 1952

By F. A. Crossley

The additions: o, Sn, Zr, Cb, Mo, and V were studied for their effects on the a/a + Ti3A1 boundary of Ti-A1 base ternary alloys. These additions were chosen because of their importance to commercial titanium alloy practice—oxygen as the major impurity (in terms of influence on mechanical properties) and the others as major alloying additions. The composition and temperature ranges of investigation varied according to the system as shown in Table I. The principal means of investigation was light-microscopy. The basis of the ternary studies was the recently determined titanium-rich end of the Ti-A1 system.' MATERIALS, METHODS, AND PROCEDURES Ingots were prepared in 15 g size for all alloys except those of the Ti-Al-Mo and Ti-A1-V systems which were prepared in 20 g size. These alloys were prepared from high-purity, electrolytically refined titanium obtained from the Bureau of Mines, Boulder City Metallurgical Laboratory, Boulder City, Col., and Chicago Development Corp., Riverdale, Md., for the 15 g and 20 g ingots, respectively. The alloying additions were obtained from commercial sources, and were at least of 99.9 pct purity, except the V-15 wt pct A1 master alloy for vanadium additions. This alloy was of 98.2 pct purity; the major impurities were 0.37 wt pct Fe and 0.38 wt pct Si. The ingots were prepared by multiple melting in a nonconsum-able-electrode arc furnace. The ingots were covered with Markal coating "CR-T22" (Markal Co., Chicago) to protect them from scaling. Markal coating is applied as a slurry of solids in a volatile carrier liquid. The coated article is air dried. Upon heating to the hot working temperature the coating fuses to form a glassy, protective film. The ingots were heated to 1000°C and rolled to 0.16 in. thickness, reheating after each pass. The glassy film was removed by sand blasting. Ten mils were removed from all surfaces by grinding and/or pickling (3 pct HF, 30 pct HN03, balance water). Grinding was always followed by pickling to remove traces of the grindmg medium. Hydrogen removal was accomplished by vacuum annealing at 1000°C for 2 hr to a final pressure of about 0.02 µ Hg. This was followed by annealing in evacuated Vycor bulbs (800°C, 2 hr, ice brine quenched (IBQ)) in order to maximize ductility. The materials were then lightly pickled and cold rolled to 0.12 in. thickness or cracking, whichever occurred first. After rolling, 1/2 by 1/4 in. specimens were cut for the equilibration anneals given in Table 11 and carried out as previously described.1 Final polishing of the specimens for metallographic examination was done by electrolytic means. Specimens were first examined without etching under bright field and polarized light illumination, for this is the only means of detecting the "two-phase" phenomenon.1,2 The term "two-phase syndrome" refers to Ti-A1 al-loys which appear on the bases of their chemical, phys-ical, and mechanical properties, to be two-phase, but are actually single phase and inhomogeneous in composition. Since processing and heat treatment of the alloys of the first group were completed before the two-phase syndrome was discovered, a number of the specimens were found to exhibit this phenomenon—80 pct of those of the Ti-Al-Zr system, 5 pct of those of the Ti-Al-Sn system, 30 pct of those of the Ti-Al-Zr system. The affected specimens were homogenized by heating above the ß transus temperature and quenching. The heat treatment and working schedules to accomplish this are given in Table 111. After rolling, specimens were pickled (3 pctHF, 30 pct HNO3 in water) to remove 1 to 2 mils from the

Jan 1, 1970

By H. J. Morel-Seytoux

The influence of patten, geometry on assisted oil recovery for a particular dispIacement mechanism is the object of investigation in this paper. The displacement is assumed to be of unit mobility ratio and piston-like. Fluids are assumed incompressible and gravity and capillary effects are neglected. With these assumptions it is possible to calculate by analytical methods the quantities of interest to the reservoir engineer for a great variety of patterns. Specifically, this paper presents (1) very brieily, the methods and mathematical derivations required to obtain the results of engineering concern, and (2) typical results in the dorm of graphs or formulae that can be used readily without prior study of the methods. Results of this work provide checks for solutions obtained from programmed numerical techniques. They also reveal the effect of pattern geometry and, even though the assumptions of piston- like displacement and of unit mobility ratio are restrictive, they can nevertheless be used for rather crude but quick, cheap estimates. ,These estimates can be refined to account for non-unit mobility ratio and two-phase flow by correlating analytical results in the case M = 1 and the numerical results for non-piston, non-unit mobility ratio displacements. In an earlier paper1 it was also shown that from the knowledge of closed form solutions for unit mobility ratio, quantities called "scale factors" could be readily calculated, increasing considerably the flexibility of the numerical techniques. Many new closed farm solutions are given in this paper. INTRODUCTION BACKGROUND Pattern geometry is a major factor in making water-fIood recovery predictions. For this reason many numerical schemes have been devised to predict oil recovery in either regular patterns or arbitrary configurations. The numerical solutions, based on the method of finite difference approximation, are subject to errors often difficult to evaluate. An estimate of the error is possible by comparison with exact solutions. To provide a variety of checks on numerical solutions, a thorough study of the unit mobility ratio displacement process was undertaken. To calculate quantities of interest to the reservoir engineer (oil recovery, sweep efficiency, etc.), it is necessary to first know the pressure distribution in the pattern. Then analytical procedures are used to calculate, in order of increasing difficulty: injectivity, breakthrough areal sweep efficiency, normalized oil recovery and water-oil ratio as a function of normalized PV injected.

Jan 1, 1967

G. McMEANS*—This paper is a very good demonstration of the use of a new tool for the solution of industrial problems of a physical nature. To have solved this problem without the use of radioactive tracers would have required a far greater amount of investigation and work. The authors have described their work in such detail and in such a manner as to suggest the possibilities of the use of such tracer studies in the solution of many perplexing problems of industry. R. E. BREWER †—The authors are to be congratulated on this very excellent paper, which describes the results obtained by utilizing radioactive tracers in investigating the complicated reactions in the coking process. The paper has especial merit because the study was made under typical operating conditions in a commercial coke oven. Considering all the difficulties involved, the results obtained are excellent. My brief comments will relate primarily to the method used for determining the sulphur in the gas and to the value of the data obtained in stimulating further research. In discussing their results, the authors state (p. 17) that "Of the total sulphur charged to the oven in the coal 95 pct was accounted for in the coke and gas. Most of the sulphur unaccounted for is believed to have been lost in the gas, since the gas sampling system removed all the H2S but probably only part of the organic sulphur compounds present in the gas. Although sulphur in the acid-insoluble tar residue in the gas scrubbing bottles was determined and added to the total sulphur determination of each sample, it is doubtful whether an aliquot portion of tar for each sample was obtained." The reviewer believes that the authors might have obtained a better sulphur balance had they used an improved procedure for determining sulphur in the gas. The absorption train should have included a trap to remove the tar and am-moniacal liquor and a wash bottle containing 5 pct sulphuric acid to remove ammonia in the coke-oven gas before it entered the gas scrubbing bottles containing the ammoniacal cadmium chloride solution. Sulphur in the tar and

Jan 1, 1950

By Leonard Grimshaw

THE idea of bonding two dissimilar ferrous metals, and making use of both, is an old one. Tips have been brazed onto tool shanks for many years. The bonding of larger pieces to form whole bars and sheets has also been accomplished, but has received little attention in the technical literature, although a number of patents have been issued covering various methods for its accomplishment. There are three main motives behind the manufacture of composite steels. One is that the physical properties of one steel may supplement those of another; a useful, but at the same time, hard, brittle steel may be backed by a soft ductile one, or a stainless steel may be backed by a steel possessing greater strength. Another motive is direct lowering of cost; an expensive steel may be backed by a less expensive one, bringing down the cost of the piece as a whole. The third motive is an indirect lowering of cost, as when a useful steel is backed by a steel that is easier to machine, so that machining cost on a finished product is lowered considerably. Often more than one of these motives lead to a decision to use a com-posite steel.

Jan 1, 1936

By J. Alfred Berger, O. M. Katz

The Zv-Hf-H ternary system was studied between 500° and 900°C at pressures less than 1 atm of hydrogen gas between 1 and 60 at. pct H. A new and unique microgravimentric apparatus was used. Cizanges of slope on pressure-hydrogen composition isothernis delineated phase boundaries. These boundaries separatecl the three regions, a, 0, and y—so designated to correspond to the regions of the Zr-H binary system—from the multiphased areas between them. A eutectoidal decomposition was found with the ß region phase or phases decornposing into a lamellar product on quenching to rool ter,zperatuve. Reproducible decomposition-pressure hysteresis occilrved lnainly at lower hydrogen cornpositions and at lower temperatures across multiplzase vegions between a and 0 and a and y. Tire effects of hqfniur7z on the hydriding charactevistics of zirconiurrz weYe as follows: 1) stabilization of the a and y vegions while destabilizing the 0 region; 2) a/?preciable elevation of the decomposition pressrkres in the multiphase region between the a and /3 field; 3) ~nouenzent of the eutectoid reaction to high te~nperatures; 4) reduction in the total qiiantity of hydrogen absorbed under one atmospheve of Hz p7-essure; and 5) introduction of a split deconzposilion at the eiitectoiclal poinl in pa?? of the ternavy. Assuru~ptions based on an ir-2terstitial vandonl-solulion rtioclel 0.f hydrogen in metals slzowed that the bindit~g energy between solute sites prednnzinatecl at low /i?!dvogen concentrations. However, at high hydrogen contents the entropy was the predorninatlt factor in determining the stability of the Zr-Hf-H al1o.s. This was interpreted to mean a scarcity of filrtlzer itltevslilinl solute sites caused by hydrogen-hydvogen intet-actions in the metal lattice. INTEREST in the reaction of hydrogen with metals has increased in the past few years for the following reasons: 1) the formation or use of high hydrogen potential environments in nuclear reactors; 2) the reaction of hydrogen with alloys in nuclear reactors with the accompanying deleterious effects on the mechanical and corrosion properties; 3) the theoretical implications of thermodynamic data on the theory and rules of alloy formation in the metal-hydrogen systems; 4) the use of hydrogen-containing fuels in rocket engines; 5) the need for a process of making fine metal powders of high-melting reactive metals; and 6) the beneficial impregnation of superconducting alloys with hydrogen. In nuclear pressurized-water reactors, the problem exists of limiting the hydrogen pickup of zirconium alloys which are utilized as fuel cladding, heat shields, and support members. In general, zirconium alloys have good mechanical and corrosion-resistant properties in high-temperature water. However, hydrogen is absorbed from the corrosion reaction between metal and water, greatly accelerating the formation of the corrosion product ZrOz as well as mechanically embrittling the underlying metal. In addition, recent observations1 at zirconium to hafnium welds showed that secondary elements in zirconium can have an appreciable, and somewhat unexpected, effect on hydrogen absorption. This paper lists the thermochemical data in the range 500" to 900°C for the equilibrium reaction of four high-purity Zr-Hf alloys with hydrogen. Phase boundaries and thermodynamic functions are determined while the structural data will be presented in a future paper. In general, the Zr-Hf-H system approximates the well-known, eutectoidal, Zr-H diagram2,3 with modifications introduced through the behavior of hafnium.4,5 The Hf-H system,' published while this work was in progress, provided a consistent trend with the Zr-Hf-H data. PREPARATION OF Zr-Hf ALLOYS Table I presents a complete flow chart of the preparation procedure. The zirconium and hafnium crystal bars were completely immersed in high-purity kerosene and slowly cut into thin wafers. Wafers were then cold-sheared into approximately 1-g pieces, thoroughly cleaned, weighed, and inserted into the furnace. The alloys, B-2, B-4, B-6, and B-8, were then nonconsumable arc-melted under 500 mm of purified argon. Additional purification of the argon was accomplished by melting a large titanium button each time an alloy was re-melted or a different alloy melted. Each alloy button, which weighed 25 g, was remelted four times in an approach to complete homogeneity. Material losses were less than 0.02 wt pct. Alloy buttons were alternately cold-rolled and vacuum-annealed into 10- and 20-mil sheets. Table I1 gives the composition of the four alloys used. Very little elemental segregation existed be-

Jan 1, 1965

By E. Mille, R. Geffken

The Mg-Si and Mg-Ge phase diagrams were rede-levtnined by thermal analysis, and the existence of a single congruent melting compound in each system was confirmed. The melting points of the two compounds Mg2Ge and ,Wg2Si were found to be 1117.4° and 1085.0°C respectively. The euteclics for the Mg-Ge system occur at 635.6°C (1.15 at. pcl Ge) and 696. 7°C (64.3 at. pct Ge); for the Mg-Si system the eutectics are at 6376°C (1.16 at. pct Si) and 945.6°C (53.0 al. pcl Si). The phase diagrams and known thermodynamic data were used to calculate activity values for both systems. The activities calculated for the Mg-Ge system agreed very well with those previously published. Partial molar enthalpy values for the Mg-Si systetn were calculated from the phase diagram for the composition region where no experimental values have been reported. THE phase diagram for any system is an important source of thermodynamic data. Steiner, Miller, and Komarek1 have derived equations which permit calculation of the activity in binary systems with an inter-metallic compound! if the liquidus and enthalpy data are known. The thermodynamic properties of the Mg-Ge and Mg-Si systems have recently been determined in this by by an isopiestic method, and it was considered that it would be interesting to compare these directly determined values with those computed from the phase diagram. The basic features of the Mg-Ge and Mg-Si systems are essentially similar. The one intermediate compound present in each system. Mg2X, crystallizes in the antifluorite structure and melts congruently. Raynor4 has accurately determined the temperature and composition of the magnesium-rich eutectic in both the Mg-Ge and Mg-Si systems. Klemm and West-linning5 investigated the entire Mg-Ge liquidus, employing sintered alumina crucibles; the purity of the magnesium and germanium starting materials was not reported. The melt was not stirred, and the temperature was automatically recorded to an accuracy of ±3°C. The authors reported large weight changes due to magnesium evaporation between 50 and 67 at. pct Mg. The Mg-Si system has been studied by a number of investigators, and the results have been compiled by Hansen and Anderko.6 Significant discrepancies exist between the two principle investigations of voge17 and Wohler and Schliephake.8 Two different grades of silicon were used by Vogel, one of 99.2 pct purity and the other quite impure, containing 6 pct Fe and 1.7 pct Al. The magnesium purity was not specified. The melts were contained in graphite crucibles with porcelain thermocouple protection tubes under an atmosphere of hydrogen. Samples weighing 10 g were rapidly heated to 50° to 100°C above the liquidus: held, and then rapidly cooled without stirring. Accuracy was ±1 at. pct which is equivalent to a maximum error in temperature of ±18°C. Wohler and Schliephake used 97.9 pct Mg and 99.48 pct Si. The graphite crucibles contained a stirrer and the 15-g samples were melted under an atmosphere of streaming hydrogen. The samples were chemically analyzed after each run. Because of the scarcity of the data, the impurity of the starting materials, and the resultant uncertainty and inconsistency in the published liquidus values, it was decided to undertake a reevaluation of the Mg-Ge and Mg-Si phase diagrams by thermal analysis. EXPERIMENTAL PROCEDURE Alloys were prepared from 99.99+ pct Mg (Dominion Magnesium Ltd.) with impurities in ppm: 20 Al, 30 Zn, 10 Si, <1 Ni, <1 Cu. <10 Fe; 99.999 pct Ge (United Mineral and Chemical Corp.), and 99.999 pct Si (Wacker Chemie Corp.). All graphite parts were machined from high-density (1.89 g per cu cm) G-grade graphite obtained from Basic Carbon Corp. with a total ash content of 0.04 pct. Boron nitride parts were machined from rods of National-grade H.B.N. boron nitride. All graphite and boron nitride pieces were baked out under running vacuum at 1100°C for 24 hr before us Cylindrical graphite crucibles (1; in. OD, 23/4 in. long, l3/8 in. ID) were tightly closed with threaded graphite covers which had 21/4-in.-long thermocouple wells and 1/4-in.-diam off-center holes for stirrers. The cover and thermocouple well were machined from a single piece of graphite. A stirrer was made from a flat cylindrical graphite plate perforated with five 3/16-in.-diam holes and a 1/2-in.-diam central hole, and was held parallel to the crucible bottom by a 1/4-in.-diam. 4-in.-long graphite rod which screwed into the plate and extended up through a tightly fitting hole in the crucible cover. An iron core enclosed in a glass capsule was attached to the stirrer with an 18-in.-long molybdenum wire, so that the stirrer could be magnetically raised and lowered from outside the system. One crucible and stirrer with essentially the same dimensions given above was made entirely of boron nitride. Chunks of magnesium were premelted, cast into 11/2-in.-diam. rods, and then cut into lengths varying from a to 1 in. A 5/16-in. hole was drilled through the center of each piece to accommodate the thermocouple well and the individual pieces were then cleaned and rinsed with acetone. The total weight of an alloy was 50 to 70 g in the Mg-Ge system and 40 to 60 g in the Mg-Si system. The pure components were weighed to an accuracy

Jan 1, 1969

By L. A. Schrider, J. A. Wasson

A method of predicting waterflood performance has been developed that combines certain facets of several previously published prediction techniques. The manner of combination has required the development and use of some new and some little-known relationships and has eliminated several of the weaker assumptions inherent in the original individual prediction methods. This approach, which was designed for computer solution, has removed the necessity of referring to plotted curves and permits the analytical prediction of water flood performance for a five-spot well pattern in either homogeneous or stratified reservoirs. The Predicted values are expressed in common oilfield units rather than in abstract or dimensionless terms. The calculation procedure has been programmed in FORTRAN IV and the entire program listing is available to potential users.* Introduction Prior to initiation of secondary recovery of oil by waterflooding, the possibilities of economic success or failure must be evaluated with the greatest practical accuracy. Although many prediction techniques are available, most, if not all, have serious limitations. In recent years, the Bureau of Mines has attempted to stimulate interest in the secondary recovery of oil from Appalachian pressure-depleted reservoirs. Waterflooding, because of its widespread acceptance and success, is the principal secondary-recovery method considered. During the life of the project, several performance prediction methods have been studied and applied. Because these methods, individually, have inherent assumptions and limi-tations, portions of some of them have been selected and combined in an effort to eliminate such shortcomings wherever possible. We believe that the resulting technique is as accurate as the necessary available data will permit and that it has several distinct advantages over previously published methods. Development of the Method The fractional flow equation developed by Buckley and Leverett&apos; from Darcy&apos;s law is the fundamental mathematical statement describing immiscible fluid-fluid displacement in porous media. A generalized form of this relationship, whose derivation is readily available in the literature, is The formation dip, a, is usually very small in those petroleum reservoirs being considered for pattern waterflooding in the Appalachian area. Therefore. in many cases. a has an almist negligible value. In addition, Ap, the difference between the density of water and the density of oil, is relatively small. For these reasons the gravitational term may often be neglected. Capillary pressure is a function of saturation, which is in turn a function of distance from the upstream boundary of the system or the injection well. In this study it is assumed that the frontal zone of the waterflooding (or zone of capillarity) has negligible length and that only those saturations in the water-swept zone at breakthrough and later are of interest. As the distance in a waterflood pattern is comparatively large and the change in water saturation with distance is usually small, the change in capillary pressure with distance is negligible. The simplified form of the fractional flow equation is appropriate, therefore, in this application. Three variables must be considered in determining that fraction of the total fluid flow that consists of water: the viscosity ratio, saturation, and relative permeability ratio.

Jan 1, 1969

By Raymond Wilson

GRINDING costs are an important item in cement manufacture, and the cost of power is one of the large items in grinding costs. Even where power is of secondary importance, cost items dependent on mill capacity are influenced by the efficiency with which the mill uses power. Tube mills typify the grinding mills most generally used in cement plants, though other types are in use. Tube mills have been widely criticized as being extremely inefficient, and this feeling regarding them has led to many attempts to design more efficient grinding equipment. Other types may be an improvement over tube mills, but the improvement has certainly not been revolutionary, at least as applied to clinker grinding. The very fact that there is doubt regarding the relative efficacy of various types of mills is an indication that an adequate basis for an analysis of performance is lacking. The development of methods of analyzing mill performance has been hampered by the lack of a suitable method for measuring the work actually done in pulverizing. There has been no acceptable standard to which mill performance might be compared. As a consequence, it was not known whether the margin of possible improvement in pulverizing operations was large or small. Even direct comparison of different types of mills was seldom possible because most plants had only one type of mill for each type of service. Comparisons between plants were difficult because of differences in the grinding characteristics of various clinkers. Some recent developments complete a chain of circumstances that place the cement industry in a particularly fortunate position for the study of its clinker-pulverizing operations. Modern investigators of grinding phenomena have generally agreed that the best measure of mill performance is the production of new surface. For most materials this measure of performance is largely theoretical and has a rather remote connection with the practical aims of the grinding operation. In clinker grinding, on the other hand, surface area is intimately connected with the properties conferred on the cement by grinding. Moreover, the determination of surface area is rapidly coming into routine use as at test

Jan 1, 1937