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By O. Chanute

all of' level atid grade curve excepting Nos. 897, 898, 899, and 900, because of the impossibility of grouping them in the same nlonner, no two Iraving the chemical composition and physical prnprtiw as tho only v:iriubles. Phosphorus ~tnits have been taken to show the relatia h:wdnes. Of these 16 groups, 10 decidedly indicate slower wear firr tile harder rail. Of the remaining 6 groups, three (groups 2, 9, and 15) come well within the limits of error (.25 pound per yard) inherent in the palculation of the data as pointed out by Dr. Dndley; they catrnot, therefore, be considered tls exceptions. Group 2 and 15 arc but little outside of the limita of error. Rail 923 of group 9 is obviously abnornlal. This is probahly due to its being overheated, which the chemical analysis shows might easily be the case, and which the physical tc~ts and its low specific gravity tend to c-nfirm. We inry say, then, thnt 13 of these 16 groups fairly indicate, if they do not definitely point out, th:kt, under the same condition% tbe harder rail gives the slower wear. Of course, these comparisons are too few to enable us to arrive at positive ~?o-nclusions; but indications thus obtained are, I believe, fir more vsluitblc and tresttvc~rthy than those fhzt averages rvottld give us, mnde up from any ~lumhr of rails under intloy difi~rcal, conditions. Finally, it, seems to me, that the conclusions arrived at earlier in my remarks, together with, and confirmed by the last, show strong evidence that, under the same conditions, the harder rail will givc the slower wear. 0. C~~anute, New York CITY: We are very much shlipl, 1 ant sure, to Mr. Sandberg for his paper upn " Rail Ryaifications and Rail Inspertion in Europe." We have in thp United States bithhrto Been inspecting mils sonlewl~at haphazard, and we ore glad to gtbt tfie results of Mr. Sandberg's long experience. We recognize that he was an)ong the first, if not the very firwt, to iipply mare rittional and scientific rules to the designing of irou rails., niora recently, to adapt tlitve rules to the clesigtting of steel I':I~]R, to conform to the oapaljilities and rqniretnento of this new n1:ttcrial. Although we have generally adopted, in this country, sectinns for hteel rails which marly of our railway men think even bottar than those of Mr. Snlldlmrg, he is neverthelees the Ieat3er in foot.iito11~ we have followed ever since it has been est~blished

Jan 1, 1881

By H. Foster Bain

FROM time to time geologists and mining engineers, impressed by the heavy demands made on our mineral reserves' by modern industry, and particularly by the steadily mounting rate of production necessary to meet that demand, have issued warnings as to the danger of exhaustion. There can be no dispute as to the fact that mineral deposits are exhaustible. New mineral, is not created to replace that taken from the earth and when a crop of mineral is once harvested another cannot be grown in the same area. The evidence of exhaustion 'of particular oreshoots, deposits, or even of whole districts is familiar to all who have mined. If one were to judge solely from the abandoned mills and prospect holes he would rightly conclude that mining is but a short-lived industry. If one were, furthermore, to assemble the data as to known reserves of almost any of the commonly used minerals, and divide them by the annual tonnage mined, he would come to the same conclusion. If, again, one were to consider the most carefully made estimates of competent men seeking to measure the earth's reserves of minerals and plot against them a projection of the curve of past consumption, he would be justified in viewing the situation with alarm.

Jan 1, 1930

By R. Taggart, D. H. Polonis, J. C. McMillan

Thin foil electron microscopy techniques have been used to study the micros tructure of a Ti- 7.5 wt pct vanadium alloy in the quenched and aged cond_itions. Selected area diffraction has identified a (1011) twinning mode accompanying the martens ite t9.an.sfo?rn~ation. Precipitation of the 0 phase during the aging of quenched alloys has been obsevced to occuv in the form of plates and needles with preferential growth along the (1120) direction in the a' matrix. In the present work, the micro structures of quenched and aged alloys of the 0 isomorphous Ti-V system have been investigated by means of thin-foil electron-microscopy techniques. Most of the previous studies of martensitic phases in titanium-base alloys have utilized optical microscopy and X-ray diffraction techniques. The application of transmission electron microscopy is more recent, and only a few such studies have been reported.1-5 This paper is concerned particularly with the crystallographic nature of substructures formed in the martensitic a' plates. The early stages of aging or tempering have also been examined to determine the modes of precipitation from the martensitic solid solutions. Such information is essential in studying strengthening mechanisms and in determining the feasibility of high-strength rnartensitic alloys based on titanium. Liu and Margolin6 reported several types of substructures within the martensitic plates of quenched Ti-Mn alloys. It was later suggested by Liu7 that the structure of martensitic plates might be very complex and not single crystals as normally assumed. The sub-markings could not be identified with the two possible habit-plane orientations {334}ß and {344}ß, and it was not positively determined whether they are associated with mechanical twinning. The recent studies by Armitage5 on titanium martensites in a variety of commercial alloys have indicated that twinning does not generally accompany the transformation. This observation is in accordance with the Mackenzie and Bowles model for the transformation in pure titanium8 which suggests that twinning is not to be expected. However, a number of other recent investigators have reported twinlike substructures in the martensitic plates of several titanium systems including commercia1 titanium,2,3 Ti-Cu,5,9 Ti-Ta,1 and the commercial alloy Ti-8A1-1Mo-1V. Blackburn* has reported that the structure of quenched Ti-8A1-1Mo-1V depends on the prior solution temperature. He identified two types of martensitic structures, one of which is described as a heavily faulted hcp or twinned fcc structure and the other an hcp structure with a high internal dislocation density. The latter type exhibited some twinning with a (1011) twin plane. EXPERIMENTAL PROCEDURES AND RESULTS The alloy used in the present work was a 7.5 wt pct V alloy that was prepared by conventional arc-melting techniques. This alloy composition was selected

Jan 1, 1968

All the TECHNICAL PUBLICATIONS and CONTRIBUTIONS published in 1938 are available at Institute headquarters, unless otherwise noted. They are also on file in many public, university and technical libraries and, when so indicated in the list, may be found in the TRANSACTIONS. TECHNICAL PUBLICATIONS in Classes A-Metal A-Lining, B-Milling and Concen-tration, H-Industrial Minerals, and I-Mining Geology are distributed in MINING TECHNOLOGY, which is issued every other month. Technical Publications in Classes C-Iron and Steel Division, D-Nonferrous Metallurgy and E-Institute of Metals Division are distributed in METALS TECHNOLOGY, which is issued twice quarterly. TECHNICAL PUBLICATIONS ill Class G-Petroleum Division are distributed in PETRO-LEUM TECHNOLOGY, which is issued quarterly. TECHNICAL PUBLICATIONS in Classes F-Coal Division, .l-Mineral Industry Education Division, K-Mining Administra-tion, and L-Geophysical Methods of Exploration are issued as separate pamphlets. All Institute member is entitled to one copy of any TECHNICAL PUBLICATION or CON-TRIBUTION. Copies of TECHNICAL PUBLICATIONS listed have been mailed to members of the Institute according to their registration by classes. CONTRIBUTIONS and other TECHNICAL PUBLICATIONS will he sent upon request. A member may purchase an additional copy of a TECHNICAL PUBLICATION or a CONTRIBUTION at one cent. a page; in minimum charge, 256. If the TECHNICAL PUBLICATION has been published in METALS TECHNOLOGY, MINING TECHNOLOGY or PETROLEUM TECHNOLOGY, the number of either magazine containing it will be supplied at the sae cent a page (minimum charge, 25¢) rate for the particular TECHNICAL PUBLICATION requested. Nonmembers may purchase any CONTRIBUTION or a TECHNICAL PUBLICATION Of the F, J, K, or L classes at the same rate, butt the nonmember price per copy for METALS TECHNOLOGY, MINING TECHNOLOGY or PETROLEUM TECHNOLOGY is $1. TECHNICAL PUBLICATIONS (Separate pamphlet form), $2 per annum; Canadian and foreign postage 50 cents extra. METALS TECHNOLOGY, $7 per annum; Canadian and foreign postage 50 cents extra (Iron and Steel Division and Institute of Metals Division ferrous and nonferrous papers). MINING TECHNOLOGY, $6 per annum; Canadian and foreign postage 50 cents extra (metal mining, milling and concentration, Industrial Minerals Division, and mining geology papers). PETROLEUM TECHNOLOGY, $4 per annum; Canadian and foreign postage 50 cents extra.

Jan 1, 1938

By E. J. Haug, K. L. Clifford, K. L. Purdy

St. Joe Minerals Corp.'s Southeast Missouri Mining and Milling Division produces lead, zinc and copper sulfide concentrates at three of its operations. The Viburnum and Fletcher mills have been described in previous papers. The new Bushy Creek mill, dedicated in May of 1973, is an updated version of the Fletcher mill incorporating 8.5 m3 (300 cu ft) lead and zinc

Jan 2, 1979

By C. G. Dunn

This note describes a method for revealing micro-structures in tantalum through an {hkl} effect which was found during a study involving amorphous and crystalline tantalum oxides. Three steps are involved. First, an amorphous film of Ta2O5 is formed anodically1 on the surfaces of the tantalum. The amount needed depents on the thickness of the substrate tantalum; 1600Å of oxide, however, is generally satisfactory in the 1/2 -mil (12 µ) to 3-mil thickness range. The film at this point is uniform in color. Second, the anodized specimen is heated to 800°C in. vacuo during a period of a few minutes and held at temperature for 5 min. During such a treatment some oxygen leaves the oxide through dissolution into the substrate tantalum (e.g., at 10-8 Torr oxide films thinner than about 800 completely disappear on 5-mil strip). Considerable crystallization of the amorphous oxide also occurs adjacent to the metal/oxide interface but not throughout the oxide thickness. The thickness of oxide needed as a residue is not too critical; values between 500 and 1000Å (optical estimate') may be most useful. (The presence of a residual oxide layer after the heat treatment usually is not apparent; in fact, in most instances the surfaces have a metallic appearance. This can be the case also for thicker residual films needed in the detection of a crystalline oxide phase by surface X-ray diffraction—e.g., if the initial oxide film is 3000Å thick, enough crystalline oxide is formed for X-ray detection.) The third step eliminates the metallic appearance at the surface and reveals (or produces) a varied colored film of tantalum oxide. Two methods can be used and both will be illustrated. If the specimen is dipped in 48 pct HF for a few seconds, the tantalum is found to be covered with a multicolored oxide. Moreover the colors correlate with the grain structure of the substrate tantalum through an orientation dependence of the type illustrated in Fig. 1, where results of an orientation analysis by the Laue X-ray method have been plotted. Other film conditions would have provided a different set of colors for the same orientations. Any such correlation, however, provides a basis for a qualitative assessment of the distribution of orientations in a large sample. The cold-rolled structure of tantalum foil produced by a recrystallization anneal and a cold-rolling reduction of 95 pct is not easily obtained by usual metal-lographic methods.' The structure, however, is easily revealed by the present technique, Fig. 2. The alternative third step is to reanodize the specimen. The optical nature of the final anodic film depends on the presence of the crystalline oxide phase; color variations indicate optical thickness variations in the film. As the reanodization voltage is increased from zero, straw and light brown colors appear (as usual), followed now by variations in color from grain to grain depending on {hkl} orientation. Suitable end points, which are determined by voltage and time, are easily established. Fig. 3, for example, shows the grain structure developed in 5-mil tantalum strip during a 30-min re-crystallization and grap-growth anneal at 1800°C. An anodic film of 1600Å thickness was added prior to the special 800°C anneal. Reanodization was done at constant current density (near 0.2 ma per sq cm) in an aqueous solution of H3PO4 (0.01 pct) and was terminated after the initial brown colors were replaced by a deep blue at approximately 30 v. Although good grain contrast can be obtained with bright field illumination, even greater contrast for black and white micrographs may be obtained with polarized light, as in Fig. 3.

Jan 1, 1967

By A. N. Holden, J. H. Hollomon

A. H. COTTRELL* and A. T. * Dept. of Metallurgy, Birmingham Univ., England. CHURCHMAN*—We have been making some experiments recently very similar to those reported by Messrs. Holden and Holloman. Wires of Armco iron, 0.077 in. diam. were decarburized in wet hydrogen until the yield point was removed; they were then extended 31/4 pct and annealed at 880°C for 120 hr in dry hydrogen. This process produced large crystals which extended through the cross-section and were about 3/4 in. in length. Since the length of each crystal

Jan 1, 1950

By K. J. Gill, P. Chiotti, J. T. Mason

Thermal, metallographic, and vapor pressure data were obtained to establish the pkase boundaries and the standard free energy, enthalpy, and entropy of formation for the compounds in the Y-Zn system. Three coinpounds with stoichiometric formulas of YZn, YZn2, and Y2Zn17 melt congruently at 1105", 1080°, and 890°C, respectively. Four compounds with stoiclziometric formulas of YZn3, YZn4, YZn5, and YZn,, undergo perztectic reactions at 905", 895", 870º, and 685ºC, respectively. Three eutec-tics exisl in this system with the .following eutectic temperatures and zinc contents in wtpct: 875ºC, 23.2 Zn; 1015ºC, 51 Zn; 865ºC, 82 Zn. The YZn, pkase undergoes an allotropic transformation. In the two phase YZn2 -YZn alloys the trans.formation gives a weak thermal arrest at 750°C, whereas in the two phase YZn2-YZn3 alloys no thermal arrest is observed and the transformation occurs over a temperature range below 750°C. At 500°C the free mzergies of formation per lnole vavy from —18,090 for YZn to —53,430 fov YZr11 and corresponding enthalpies vary from -24,050 to -92,080. The free energies and enthalpies per g atom as a function of composition show a maximum for the YZn2 phase; the 500°C values are -9580 and -13,180, vespectively. 1 HE only information found in the literature on Y-Zn alloys was the observation reported by Carlson, Schmidt. and speddingl that Y-20 wt pct Zn forms a low melting alloy. The alloy was produced by the bomb-reduction of YF3 and ZnF2 with calcium in an investigation of methods for producing yttrium metal. The solubility of yttrium in zinc has been determined by P. F. woerner2 and reported by Chiotti, Woerner, and Parry.3 In the temperature range 495" to 685°C the solubility may be represented by the relation In these equations N represents atom fraction of yttrium and T is the temperature in degrees Kelvin. The purpose of the present investigation was to establish the phase diagram for the Y-Zn system and to determine the standard free energy, enthalpy, and entropy of formation for the compounds formed. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in the preparation of alloys were Bunker Hill slab zinc, 99.99 pct pure, and Ames Laboratory yttrium sponge. Arc-melted yttrium buttons contained the following impurities in parts per million: C-129, N-12, 0-307, Fe-209, Ni-126, Mg-13, Ca < 10, F-105, and Ti < 50. Some of the alloys containing 70 wt pct or more of Zn were prepared from yttrium containing 5000 ppm Ti as a major impurity. Tantalum containers were found to be suitable for all alloys studied and were used throughout the investigation. The pure metals, total weight about 30 g, were sealed in 1 in. diam tantalum crucibles by welding on preformed tantalum covers. A 1/8 in. diam tantalum tube was welded in the base of each crucible for use as a thermocouple well. Welding was done with a heli-arc in a glove box which was initially evacuated and filled with argon. The sealed crucibles were enclosed in stainless steel jackets and heated in an oscillating furnace at temperatures up to 1150°C. Homogeneous liquid alloys were obtained within a half hr at these temperatures except for alloys containing less than 20 pct zinc. The latter alloys were held at 1000º to 1100°C for 2 to 3 days in order to obtain equilibrium. After the initial equilibrations the tantalum crucibles containing the alloys were removed from the steel containers and used directly for differential thermal analyses. Further annealing heat treatments for alloys in which peritectic reactions were involved were carried out in the thermal analyses furnace. After thermal analyses the tantalum crucibles were opened and the alloys sectioned and polished for metallographic examination. In the following discussion alloys referred to as "quenched" were obtained by quenching the sealed stainless steel jacket containing the tantalum crucible and alloy in water. The differential thermal analyses apparatus used was a modified version of the one described in an earlier paper., The graphite crucible was replaced by an inconel crucible, the nickel standard and sampie container were separated by a 1/8 in. MgO plate, no getter was used, and provisions were made to

Jan 1, 1963

By Grafton Thrasher

For the proper discussion of this subject it is necessary to incorporate in this paper the substance of part of an article published by rite in Metallurgical and Chemical Engineering for January, 1915. CAST-IRON TEST PLUG, SHOWING LOW MOTTLED AND MOTTLED FRACTURES. Several years ago, while I was thief chemist for a malleable-iron company, it occurred to me that the mere regulation of silicon was not sufficient to produce the desired degree of chill. But only after repeatedly encountering this fact in befit open-hearth and air-furnace, as well as cupola metal, was I led to regard variation in the total carbon as the principal cause of disturbance; and I resolved to determine the total carbon as well as the sill on ill every heat, and by a carefully prepared test piece to gauge the approximate degree of chill. The test piece selected was a round plug, 2 in. in diameter and 12 in. long, cast on end

Jan 10, 1915

By P. R. Smith, R. A. Walters

Borates have been mined in the desert areas of California and Nevada for more than 100 years. To about 1890, playa surface mining provided the chief sources of boron minerals. Underground mining of colemanite and later of borax and kernite was predominate until about twenty years ago. Open pit mining of the large deposits of borax and kernite near Boron, California has been most significant for the past twenty years. Mining of colemanite in the Ryan, California area, near Death Valley, began in 1907. Following the discovery of the large deposits in the Boron area (about 1957), mining in the Death Valley area became nearly nonexistent. Only small tonnages were mined for special uses. Little mining was done in the Boraxo area near Ryan. The first claim was made in about 1915. In 1960 the area became the property of the Kern County Land Company, which was acquired by Tenneco Oil Company in 1967. In 1976 the various boiate properties and claims in this region were acquired by American Borate Corporation. The open pit mine is now approximately 122 m (400 ft) deep, 910 m (3000 ft) long and 305 m (1000 ft wide). The borates in the Boraxo pit consist primarily of three minerals. These are about 50% colemanite (CB6011 5H20), about 40% probertite (NaCaB50g 5H20), and 10% ulexite (NaCaBgOg 5H20). The colemanite, along with boric acid and high-grade colemanite ore from Turkey provide the only sodium-free borates for production of textile grade fiberglas. When heated to its decomposition temperature, colemanite decrepitates to a fine powder, which is the basis for the concentration process. The gangue minerals in this deposit are primarily calcite and clays, including bentonite. The ore body has a very low arsenic content, which is a desirable feature. Test work had been done with samples prior to the results discussed herein. This paper will discuss results of test work which were the basis for erection of a plant, and the subsequent plant operations. Laboratory Calcination and Air Tabling Tests Laboratory calcination tests showed that substantial upgrading of the borate could be accomplished by calcining followed by screening of the calcined material. Removal of the + 28 mesh calcine resulted in borate losses of less than 10% with a rejection of 40 weight % or more of the calcine. The minus 65 mesh calcine generally met the requirement of containing 48%, or more, B203. The minus 28 plus 65 mesh material contained an intermediate quantity of borate and would require additional treatment. Testing demonstrated that ore would not have to be reduced to a size finer than 19 mm (3/4 in.) prior to calcination. A temperature range from 400 to 455OC (750 to 850°F) was apparently satisfactory. Calcination at a temperature of 48Z°C (900°F), or higher, was unsatisfactory due to fusion. All laboratory calcination tests were static tests conducted by placing small covered charges in a laboratory furnace for 40 min. In all tests vapor issues from the furnace for 5 to 7 min. Following this period the ore could be heard "popping," due to decrepitation of the colemanite. The reaction generally continued for approximately one-half hour. Various size fractions of the calcination products from laboratory tests were subjected to laboratory air tabling tests, usually after removing the plus 28 mesh material. Laboratory air tabling tests were conducted employing a Whippet V-80 model air table manufactured by Sutton, Steele and Steele Co. now known as Tripple S Dynamics. Variables include both end and side-tilt, speed of vibration, and quantity of air rising through the deck. In addition to the variables in the machine itself, the feed rate is also a rather critical variable. Testing demonstrated that all - 28 mesh size fractions of the calcine could be successfully concentrated to 48% F2O3 or greater. For the finer material recoveries into the concentrate were between 85 and 90% of the borate. With the coarser material a substantial amount of middling was produced which required cleaner tabling. Laboratory calcination and air tabling tests indicated a process whereby the borate could be concentrated to about 50% B203 with borate recoveries approaching 90%. Moreover, the iron content of the concentrate was well below the required specification of 0.3% Fe2O3. Pilot Plant Calcination Following the laboratory test work described above, pilot plant testing was conducted to prove the process, provide data for engineering studies, and provide product for a prospective purchaser. The kiln used was 0.9 m-diam (3 ft) by 9.0 m (30 ft) long and had a belly section 1.2 m-diam (4 ft) by 2.74 m (9 ft) long near the discharge end. The kiln was operated at a speed of 0.7 rpm. Gas was fired into the kiln at an average rate of 27.1 m3/hr (958.4 cu ft per hr). The air to gas ratio used was 10:1. The ore was fed to the kiln countercurrent to the flame and discharged through a hopper into a screw conveyor which discharged to a 1.2 m (48 in.) Sweco separator. The separator had 28, 65, and 150 mesh screen cloths, with the plus 28 mesh fraction being discarded. The minus 28 mesh fractions were later subjected to air tabling. The exit gases, containing some calcine dust, were swept through two cyclones to recover the dust. The gases then were scrubbed in a Ducon scrubber; very little dust reported past the first cyclone. The dust from the first cyclone was also saved in drums. In addition to the gas rate, the flue gas velocity, after

Jan 1, 1981

By T. R. Armstrong

During the year 1939, Mexican production totaled 42,479,000 bbl.; a daily average of 116,381 bbl. or a little over 2 per cent of the estimated world production. The Mexican Government operates 100 per cent of the refining branch of the industry, 100 per cent of the domestic distribution, 96 per cent of the crude production and 92 per cent of the total exports. No discussion of the Mexican petroleum industry in 1939 is adequate without reference to the "expropriation" of the foreign-owned oil properties in Mexico by executive fiat on March 18, 1938. The forcible seizing of the properties culminated a long series of efforts on the part of the Mexican Government to obtain control of the oil properties developed through foreign initiative and with foreign capital in Mexico. The heart of the issue is whether the Mexican nation or any nation may with impunity confiscate the legally acquired properties of American citizens. The Department of State of our Government has in its communications to Mexico emphasized the fact that its "expropriation" of American properties was confiscatory because Mexico had failed to make "adequate, effective and prompt compensation"; that the taking was no less confiscatory "because there may be an expressed intent to pay at some time in the future," and that, consequently, "Mexico has assumed and continues to assume to exercise a right without compliance with the condition necessary to give such exercise a recognizable status of legality." Mexico has professed its willingness to pay for the oil properties but at the same time through its Supreme Court it has declared that the owners or lessees do not have the exclusive right to extract and dispose of the oil in the subsoil. This is a reversal of the Mexican position with respect to oil as set forth in the Mexican mining laws, affirmed by Mexican Supreme Court decisions, and as clarified in the Warren-Paync and the Morrow-Calles agreements, as well as in diplomatic correspondence. Efforts to Settle the Controversy Responding to suggestions from the State Department, representatives of the principal oil companies undertook in 1939 to effect a direct

Jan 1, 1940

By T. R. Armstrong

During the year 1939, Mexican production totaled 42,479,000 bbl.; a daily average of 116,381 bbl. or a little over 2 per cent of the estimated world production. The Mexican Government operates 100 per cent of the refining branch of the industry, 100 per cent of the domestic distribution, 96 per cent of the crude production and 92 per cent of the total exports. No discussion of the Mexican petroleum industry in 1939 is adequate without reference to the "expropriation" of the foreign-owned oil properties in Mexico by executive fiat on March 18, 1938. The forcible seizing of the properties culminated a long series of efforts on the part of the Mexican Government to obtain control of the oil properties developed through foreign initiative and with foreign capital in Mexico. The heart of the issue is whether the Mexican nation or any nation may with impunity confiscate the legally acquired properties of American citizens. The Department of State of our Government has in its communications to Mexico emphasized the fact that its "expropriation" of American properties was confiscatory because Mexico had failed to make "adequate, effective and prompt compensation"; that the taking was no less confiscatory "because there may be an expressed intent to pay at some time in the future," and that, consequently, "Mexico has assumed and continues to assume to exercise a right without compliance with the condition necessary to give such exercise a recognizable status of legality." Mexico has professed its willingness to pay for the oil properties but at the same time through its Supreme Court it has declared that the owners or lessees do not have the exclusive right to extract and dispose of the oil in the subsoil. This is a reversal of the Mexican position with respect to oil as set forth in the Mexican mining laws, affirmed by Mexican Supreme Court decisions, and as clarified in the Warren-Paync and the Morrow-Calles agreements, as well as in diplomatic correspondence. Efforts to Settle the Controversy Responding to suggestions from the State Department, representatives of the principal oil companies undertook in 1939 to effect a direct

Jan 1, 1940

By Riki Kobayashi, D. L. Katz

The conditions at which methane and water form solid hydrates have been extended from 4,000 to 11,200 pounds per sq. in. The curve at high pressure had been in doubt because of Villard&apos;s report of a critical decomposition temperature. The paper explains the nature of the hydrate curve at high pressure and its dependence on fluid phase behavior. Extropolation of the methane hydrate curve indicates a pressure of 40,000 pounds per sq. in. will cause hydrates to form at a temperature of 100" F. INTRODUCTION The conditions under which natural gases form hydrates when liquid water is present have been studied by several investigators up to pressures of about 4,000 pounds per sq. in. The early work by Villard on hydrates of methane and ethylene13, ethane&apos;&apos;, and propane14 included references to critical decomposition temperatures of the hydrates. Villard&apos;s work raised the question as to whether the pressure-temperature curve for methane-water hydrate continued above a temperature of 70.7°F. or whether this was the maximum temperature at which hydrates would form. This paper extends the experimental data on methane hydrate to 11,200 pounds per sq. in. A discussion of phase relations in the hydrate region for the hydrocarbons and of the methane-water system at high pressures is included. PREVIOUS WORK Villard suspected that methane hydrates could not be formed at temperatures above 21.5°C. (70.7°F.)la irrespective of the pressure of the liquid-vapor system. However, he was limited in his studies by his apparatus in 1888 to pressures not greater than 300 atmospheres (4,410 pounds per sq. in.) so that there has remained some doubt as to the existence of such a maximum temperature in this region. For the case of ethylene hydrates, however, Villard does specifically state the occurrence of what he terms a "critical temperature for the decomposition of the hydrates"13. Fig. lB shows a pressure-temperature projection of the three-phase locus, hydrate-ethylene rich liquid-vapor (H-L2-V) terminating at the critical locus in which L² and V assume similar properties. Throughout this paper the following phase designations will be used: H for hydrate, Ll for the water rich liquid. L2 for the

Jan 1, 1949

By Riki Kobayashi, D. L. Katz

The conditions at which methane and water form solid hydrates have been extended from 4,000 to 11,200 pounds per sq. in. The curve at high pressure had been in doubt because of Villard&apos;s report of a critical decomposition temperature. The paper explains the nature of the hydrate curve at high pressure and its dependence on fluid phase behavior. Extropolation of the methane hydrate curve indicates a pressure of 40,000 pounds per sq. in. will cause hydrates to form at a temperature of 100" F. INTRODUCTION The conditions under which natural gases form hydrates when liquid water is present have been studied by several investigators up to pressures of about 4,000 pounds per sq. in. The early work by Villard on hydrates of methane and ethylene13, ethane&apos;&apos;, and propane14 included references to critical decomposition temperatures of the hydrates. Villard&apos;s work raised the question as to whether the pressure-temperature curve for methane-water hydrate continued above a temperature of 70.7°F. or whether this was the maximum temperature at which hydrates would form. This paper extends the experimental data on methane hydrate to 11,200 pounds per sq. in. A discussion of phase relations in the hydrate region for the hydrocarbons and of the methane-water system at high pressures is included. PREVIOUS WORK Villard suspected that methane hydrates could not be formed at temperatures above 21.5°C. (70.7°F.)la irrespective of the pressure of the liquid-vapor system. However, he was limited in his studies by his apparatus in 1888 to pressures not greater than 300 atmospheres (4,410 pounds per sq. in.) so that there has remained some doubt as to the existence of such a maximum temperature in this region. For the case of ethylene hydrates, however, Villard does specifically state the occurrence of what he terms a "critical temperature for the decomposition of the hydrates"13. Fig. lB shows a pressure-temperature projection of the three-phase locus, hydrate-ethylene rich liquid-vapor (H-L2-V) terminating at the critical locus in which L² and V assume similar properties. Throughout this paper the following phase designations will be used: H for hydrate, Ll for the water rich liquid. L2 for the

Jan 1, 1949

By David Turnbull

IN most reactions involving solids the transformation kinetics may be represented by the combination of two processes-those of nucleation and of growth. For example, Mehl and his coworkers 1,2 in their studies on the transformation of austenite to pearlite in steels have been able to describe the kinetics in terms of the rates of nucleation and of growth. By micrographic examination of their specimens they determined the nucleation rate (rate of appearance of pearlite colonies) as a function of time, of percent transformation, and of temperature. They observed that after an incubation period in which no nuclei are observed, the number of nuclei appearing per unit time per unit of untransformed grain boundary area, increases at an increasng rate with time. When recrystallization rates have been interpreted in terms of rates of nucleation and growth and the rate of nucleation determined, an incubation period followed by an increasing rate of nucleation has also been reported. Among the studies in which this phenomenon has been observed are those of Kornfeld and coworkers3 on cold-drawn aluminum wire, of Anderson and Mehl4 on the recrystallization of aluminum sheet, and of Stanley and Mehl5 on the recrystallization of silicon ferrite sheet. The existence of an incubation period during which no nuclei are observed does not appear to have been reconciled with the generally accepted Volmer-Becker theory of nucleation in condensed systems. This theory ostensibly requires the rate of appearance of nuclei to be independent of time. VOLMER-BECKER THEORY In order to form a stable nucleus of a new phase B in a mother phase A, the molecules or atoms of the mother phase must surmount a free energy barrier whose height is determined by the volume free energy change accompanying the transformation and the energy of the surface separating the two phases. The free energy difference between nuclei of various sizes and the molecules or atoms of the mother phase is plotted schematically in Fig I as a function of the radius of the nucleus r. This free energy difference is plotted for two values of the change of free energy per atom, (fB - fA) accompanying the transformation when the volumes of the two phases are infinite. One of these values of (fa-fA) corresponds to a temperature above the temperature To at which the phases A and B are in equilibrium, and the other to a temperature below To. In order for a nucleus of phase B to be stable at a temperature T2 < To, its radius must be equal to or greater than the critical value r* for which the free energy of formation of the nucleus is a maximum, ?f*. Aggregates of phase B having radii equal to or less than r* will be called embryos. Mehl and Jetter,6 in discussing the kinetics of nucleation in solid systems, suppose that embryos of critical size are formed

Jan 1, 1948

By J. S. Aronofsky

The first step in a quantitative analysis ot the mechanism of oil displacement by water in a fractured reservoir is usually conceded to be the solution of the differential equation describing the saturation distribution of two immiscible fluids flowing in a porous medium, where the capillary pressure is taken into account. In such a system the production mechanism may consist of displacement of oil both by the flow of water due to natural or artificially imposed pressure gradients and by imbibition, which implies a flow of water not due to external pressure gradients. Owing to the presence of the two oil displacement mechanisms, the mathematical model given by the differential equation intended to describe the system may not properly represent the behavior of the physical system. In fact, in the reservoir the rate of water advance may be very slow, and in the case of a fractured reservoir with a great number of large fractures, the pressure difference determining the flow of water through the matrix may be much less than 1 lb/&apos;psi over lengths of a few feet. In such a case, imbi-bition (the exchange between oil in the matrix and water in the fractures resulting from capillary forces) may become, with time. a significant element of the production mechanism. It occurred Lo the authors, however, that without going into a physical analysis of the process of production, it might be possible by means of simple abstract reasoning to throw some light on the variation of recovery with time under conditions occurring in a highly fractured oil reservoir with rising water table. The object of this paper is to present both the reasoning and its application to a reservoir of the highly fractured type. Specifically, the analysis given here was undertaken to try to explain the increase of recovery (as defined later) with time as observed in this reservoir, without having to assume unlikely variations in the reservoir parameters with depth. This attempt has been successful as will become clear upon comparison of the computed recoveries with the actual field data. ABSTRACT MODEL Let us consider a small volume. of porous matrix saturated with oil at time, t = 0. Let the process of oil displacement by water start at time, t = t,,. At some time, t, the process will have terminated. Then a volume of oil equal to or smaller than the original oil contained in the matrix will have been produced. The first basic assumption that describes the model and guides the forthcoming reasoning is that the oil production from the small volume. dv, is a continuous monotonic function of time and that it converges to a finite limit. Such an assumption is not inconsistent with the results of laboratory waterflood tests as well as with results of imbibition tests where this is, in fact, observed. The second basic assumption is that none of the properties which determine the rate of convergence change sufficiently during the process to affect this rate or the limit. Let it be assumed that the form of the function of time relative to production from the matrix volume. dv, is given by where V,(t) is the volume of oil produced up to that time t. R is the limit toward which the recovery converges, A is a constant giving the rate of convergence, and V,(t) is the volume of oil originally in place in the volume, dv. It should be noted that recovery at time I will be understood here to he It follows that r. tends to R as t tends to infinity. CONSTRUCTION OF RESERVOIR FROM ABSTRACT MODEL Let the reservoir consist of a series of identical blocks of porous matrix stacked vertically and separated by fractures. Let each of these blocks satisfy the conditions of our abstract model. These conditions are: (1) that recovery is a continuous mono-tonic function of time converging to finite limit, and (2) none of the properties that determine the rate of convergence change sufficiently to affect the rate or the limit. Let water be rising in fractures so that oil production from any part of the block starts when the water comes in conLact with it. TOTAL RECOVERY FROM THE RESERVOIR COMPARED TO RECOVERY FROM A SINGLE MODEL ELEMENT As stipulated in Eq. 1, in the case of the abstract model,

By L. W. Bahney

MANY methods for the determination of gold or silver, or both, in cyanide solutions have been published, which with care in manipulation, and modification in some cases, will give results that are satisfactory. It is possible to classify or group these methods as follows: 1. Evaporating the solution in a porcelain or agate-ware dish containing litharge,1 or in a "boat" made of lead foil. 2. Forming a lead sponge containing the precious metals by means of zinc shavings,2 zinc dust,3 or a piece of aluminum.4 3. Decomposing the cyanide solution with an acid and precipitating the precious metals by the use of one or a combination of some of the following: Copper sulphate,5 sodium sulphite,6 hydrogen sulphide,7 cement copper.8 4. Precipitating the silver by zinc dust held in a Hooch crucible and determination with a standard solution of sulphocyanate.9 5. Electrolysis.10 6. Colorimetry.11

Jan 2, 1915

By C. G. Goetzel

Until recently porous bronzes have found many applications for self-lubricating bearings in the automotive, electrical, household appliance and general machine industries. The bulk of an annual production of several million pounds of copper powder had gone into the manufacture of these articles, of which by now more than a billion are in service. However, the war has brought severe curtailment of these bearings because of the scarcity of the two main constituents, copper and tin. The development of substitute materials of equal or superior properties has led to a large-scale replacement by products made from iron powder. In spite of the diminished interest in powdered copper-tin alloys caused by this trend, it was believed worth while to investigate some mechanical properties of these materials as a reference base for substitutes. In addition, experiments using the hot-press method were incorporated to investigate possibilities of saving vital equipment or opening new fields of applications. It must be assumed that by this time the powder metallurgy process of making porous bronzes, a development that found its first industrial applications more than 10 years ago, is well known in engineering. The patent literature and bibliography is volu- minous, most publications referring to porous, self-lubricating bronzes, containing about 10 per cent tin and I to 5 per cent graphite, with porosities in the range of 25 to 35 per cent.l-7 The excellent antifriction properties of these bearings, caused by the uniform impregnation with oil, are dependent on the interconnection of the pores and the uniform distribution of the graphite inclusions. The sintering mechanism of porous bronze, with its structural changes during the transformation of the metal powder into the sintered bearing has been shown in colored photomicrographs by Hall.* Diffusion between copper and tin was found to begin within one minute, when tin-rich transitory phases were formed. After 25 min. a homogeneous matrix of alpha was reached for an alloy containing 9.5 per cent tin and 6 per cent graphite. Price, Williams and Garrand,9 studying certain metal powder combinations in which sintering is accompanied by the cementing action of a liquid phase, including a 90-10 bronze sintered at 925°C., have found that if the treatment is carried out within the liquidus and solidus temperature range of the system, a peculiar process of alternate solution and precipitation occurs. The particles of the major solid constituent are dissolved in the minor liquid phase, but thereafter are reprecipi-tated on certain nuclei, which develop into large grains, usually rounded.

Jan 1, 1945

By Augustus Locke

Jan 1, 1923

By Augustus Locke

Jan 1, 1923