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By R. F. Mehl, B. Lustman

The formation of intermediate phase layers in cementation processes has been subjected to extensive qualitative investigation though to relatively little quantitative study; this work has recently been fully summarized by F. N. Rhines.' It is necessary here only to cnumerate the general conclusions drawn concerning the kinetic laws governing the growth of intermediate layers and to state what is known concerning the structural changes accompanying the generation of phase layers. I. When the intermediate phase is protective in type—i.e., when its density is less than that of the base metal, so that a continuous coating is formed and maintained—the isothermal growth of the phase follows a simple parabolic equation: X2 = kt [i] where X is the thickness of the alloy layer, k thc reaction rate constant, and t the time. The applicability of this equation to diffusion processes is tested by plotting the square of the thickness versus time, or by plotting the thickness versus the square root of time; the resultant achievement of a straight line in such a plot has been considered sufficient proof of the validity of this equation. Exceptions have been found where liquid phases are involved in the reaction, where the diffusion layer is cracked,2 and where thin semimetallic oxide and sulphide coatings are formed on metals.$ In the first two cases the thickness increases linearly with time, and in the latter it is a logarithmic function of time. 2. The rate of thickening varics with temperature according to the Arrhenius equation: k = Ae-Q/RT [2] where k is the parabolic rate constant of Eq. I, or some other rate-descriptive function, A is the action constant, e the base of natural logarithms, Q the heat of activation, R the gas constant, and T absolute temperature. This equation has been found to be generally valid except when transformations occur during reaction in either the base metal or in the reaction layer; in such instances Eq. 2 is still applicable with different values for the constants A and Q above and below the transformation temperature. 3. Ali phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two components. In some cases certain of the phases may be too thin to be observed and identified easily. Nonequilibrium phases have never been noted in thick reaction layers; i.e., layers of a thickness that may be discerned microscopically. The relative thickness of each phase in a diffusion layer is proportional to the concentration gradient and to the rate of diffusion in that phase.4 The reaction layers tend to have a

Jan 1, 1942

By R. F. Mehl, B. Lustman

The formation of intermediate phase layers in cementation processes has been subjected to extensive qualitative investigation though to relatively little quantitative study; this work has recently been fully summarized by F. N. Rhines.' It is necessary here only to cnumerate the general conclusions drawn concerning the kinetic laws governing the growth of intermediate layers and to state what is known concerning the structural changes accompanying the generation of phase layers. I. When the intermediate phase is protective in type—i.e., when its density is less than that of the base metal, so that a continuous coating is formed and maintained—the isothermal growth of the phase follows a simple parabolic equation: X2 = kt [i] where X is the thickness of the alloy layer, k thc reaction rate constant, and t the time. The applicability of this equation to diffusion processes is tested by plotting the square of the thickness versus time, or by plotting the thickness versus the square root of time; the resultant achievement of a straight line in such a plot has been considered sufficient proof of the validity of this equation. Exceptions have been found where liquid phases are involved in the reaction, where the diffusion layer is cracked,2 and where thin semimetallic oxide and sulphide coatings are formed on metals.$ In the first two cases the thickness increases linearly with time, and in the latter it is a logarithmic function of time. 2. The rate of thickening varics with temperature according to the Arrhenius equation: k = Ae-Q/RT [2] where k is the parabolic rate constant of Eq. I, or some other rate-descriptive function, A is the action constant, e the base of natural logarithms, Q the heat of activation, R the gas constant, and T absolute temperature. This equation has been found to be generally valid except when transformations occur during reaction in either the base metal or in the reaction layer; in such instances Eq. 2 is still applicable with different values for the constants A and Q above and below the transformation temperature. 3. Ali phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two components. In some cases certain of the phases may be too thin to be observed and identified easily. Nonequilibrium phases have never been noted in thick reaction layers; i.e., layers of a thickness that may be discerned microscopically. The relative thickness of each phase in a diffusion layer is proportional to the concentration gradient and to the rate of diffusion in that phase.4 The reaction layers tend to have a

Jan 1, 1942

By C. A. Gibbons

AFTER nine years of extremely de- pressed business, marked mostly A with red ink on the balance sheets of most coal companies and with an increasing internal competitive struggle for diminishing markets, somewhat of a change appeared during 1939. Shipments increased and prices generally firmed, giving the coal industry increasing optimism and encouragement for the future. Specifically, it now appears that bituminous coal production for 1939 will approximate 378,000,000 tons, and anthracite production will approximate 47,500,000 tons, bituminous production being around 14 per cent ahead of 1938 and anthracite production 12 per cent better. The curve on p. 31, showing both bituminous and anthracite production, furnished by the bituminous coal division of the Department of the Interior, shows graphically most of the 1939 monthly production and clearly illustrates the increased production.

Jan 1, 1940

By P. W. Bridgman

DURING the war, the Navy undertook the construction, under my direction, of an experimental gun embodying features designed to lessen the cost and time of production. These experiments were initiated after representations as to their, desirability had been offered by myself, by the Naval Consulting Board, and by the National Research Council. The first drawings were made in June, 1917, and the experiment was completed in November, 1918. For the sake of clearness it will pay to recapitulate briefly the fundamental idea of gun construction. It is well known that if a hollow cylinder is subjected to internal fluid pressure, the maximum stress occurs in the inside layers, the outer parts carrying much less than their due share of the stress. This inequality of stress is more pronounced the thicker the walls of the cylinder. If such a cylinder is pushed to the elastic limit, failure in elasticity will take place long before the outer layers have reached the limit of their capacity. Economical use of the material would demand, however, that all parts of the cylinder reach the limits of their capacity simultaneously. This may be brought about, at least in cylinders of not too great thickness, by producing in. the inner layers an initial compression, and in the outer layers an initial tension. The effect of internal pressure is at, first to relieve the compression of the inside layers, while increasing the tension of the outside layers. If the initial stresses are properly distributed, all parts of the cylinder will reach their elastic limits simultaneously, thus giving a cylinder of maximum strength for its weight. In gun construction as hitherto practiced, this initial distribution of stress is produced either by winding the inner tube with wire, a common English practice, or by shrinking hoops over the inner tube, which has been the standard American practice. Either process is long and expensive, particularly with the larger guns, 12- or 14-in., which require

Jan 2, 1920

By G. G. Oberfell

THOUGH the largest volume use of natural gas has been, is. and in all probability will continue to be as a fuel for domestic and industrial heating, it has various market outlets, both as a fuel and as a raw material for the chemical industry. Natural gas is a preferred type of fuel where ease of control, fuel uniformity, and freedom from ash are of primary importance. Other industrially important uses are as a source of carbon black and as a fuel in various low-cost heating operations. Many other uses are of varying importance and new potential uses are continually being uncovered, some being of economic importance to the gas indus¬try as a whole, but most of them involve such small volumes of gas that they are only of passing interest. Since various products extracted from natural gas and recovered as by-products from petroleum refining, such as liquefied petroleum gas and fuel oil, are being utilized in many industrial and domestic heating applications, some consideration will have to be given such materials in order to present a reasonably complete story of the importance of natural gas. Some of these materials may prove to be transient competitors and will not be available when more profitable uses are found for them. Meanwhile, however, the potential volumes of such materials available, the current volumes being marketed, and the nature of the utilization are considered as constituting an essential part of the over-all fuel picture.

Jan 1, 1946

By A. B. Cox, L. W. Wark

An attempt has been made to compare the influences of the two most widely used depressants—alkalis and sodium cyanide—and the most widely used activator—copper sulfate—on the air-mineral contact induced by five sulfur-bearing compounds: (1) sodium di-ethyl dithio-phosphate (sodium Aerofloat); (2) potassium ethyl xanthate; (3) sodium di-ethyl dithiocarbamate; (4) potassium iso-amyl xanthate; (5) potassium di-n-amyl dithiocarbamate. Three different organic types are included in lhis group and for two of these types a higher and a lower homologue have been tested. The study of potassium ethyl xanthate, the preliminary results of which have been described,' was continued until there had been obtained a comprehensive account of the influence of variations in pH value and in the concentrations of xanthate, sodium cyanide and copper sulfate on the adsorption of this xanthate by galena, sphalerite, pyrite and chalcopyrite. With concentrations of copper sulfate and collector that the work with ethyl xanthate indicated would give the most illuminating. results, the other four collectors were tested, in a less exhaustive way. The same general principles determine the influence of alkalis, cyanide and copper sulfate, no matter to which type the collector belongs, but there is a gradation in the quantitative measure of such influence. In the list above, the five collectors are cited in the order of their capacity to withstand the depressants, sodium Aerofloat being the least resistant, potassium di-n-amyl dithiocarbamate the most resistant. This order coincides substantially with that of the solubilities of the heavy metal salts formed by double decomposition with the collectors, those formed from sodium Aerofloat being most soluble. There is little difference between the third and fourth members of the series, and under certain conditions their positions are reversed. In general, then, of the three types of collectors investigated, the dithiophosphate type is most easily influenced by depressants, and the

Jan 1, 1935

By William Mikulas

LITTLE work has been done in the field of the nickel-tin binary system. The complete diagram has been investigated on two occasions, but the results are in very poor agreement. The structure of a compound NiSn, and the solubility of tin in nickel have been determined by X-ray methods. Several investigations have been made of the liquidus curve, and the compositions of the eutectics have been determined. A study of the literature, however, shows that there is no satisfactory agreement between the data presented in the various papers. The present investigation was undertaken in an attempt to determine the equilibrium conditions, and to correlate X-ray with metallographic data. The equilibrium diagram was determined by thermal and metallo-graphic means, and the solubility of tin in nickel further investigated with X-rays. Powder diagrams were made of the intermetallic com-pounds, and three of the structures were partly determined. No attempt was made to determine the range of homogeneity of the inter-metallic compounds.

Jan 1, 1937

By Evan Evans

WITH the expiration on April 30, 1941, of the agreement between the anthracite operators and the United Mine Workers of America, a new agreement was entered into, providing for a general wage increase of 7 1/2 per cent effective May 1, to be brought to a total of 10 per cent on Oct. 1. Contract rates were increased from the rates established under the agreement of September 1923, and hourly rates were raised above the agreement of May 1936 as modified from the eight-to seven-hour day in May 1937. The new rates are to be in force for the duration of the agreement, ending April 30, 1943.

Jan 1, 1942

By Howard H. Fields

Any mining engineer with a desire to operate independently, with some financial backing, and with no fear of heavy responsibility and long hours, should be able to make a comfortable living in Mexico. Barring a few inconveniences such as a lack of satisfactory liability or accident insurance, the difficulty of obtaining repair parts or vehicles, and the length of time required to receive returns from shipments, the operation of small mine is not at all difficult. It is, in fact, a little easier to find a good prospect in Mexico than in the U.S.

Jan 1, 1950

By C. E. Wood, E. P. Barrett, T. L. Joseph

The invention of the Bessemer converter process in 1856 added great impetus to the manufacture of steel and is one of the outstanding contributions to process metallurgy. Although the process of refining pig iron by passing air through the molten metal bears the name of Henry Bessemer, it should be mentioned in passing that William Kelley of Eddysville, Ky., worked on the process as early as 1847. Kelley was granted a patent on the process in 1857, inasmuch as he was able to prove priority in discovery.' After considerable litigation in 1865 the respective interests of Kelley and Bessemer were combined. On Sept. 10, 1856, Robert Mushet of England obtained his first patent on the application of manganese to cast steel. Mushet anticipated trouble in purifying iron by passing currents of air through it: His patent specified that steel made in this way often contained flaws and was red short or cold short. Mushet understood the refining of pig iron into steel well enough to realize the difficulties likely to be cncountered from oxidation of the iron. Mushet was not only an inventor; he was also an investigator. He understood the principle of selective oxidation which takes place in the converter process, and he realized therefore that the remedy for over-oxidation was attainable if a suitable metal could be found at a reasonable cost and in sufficient quantities. His first experiments were made in small crucibles holding a few ounces of metal. Later his work was conducted on a larger scale and with complete success. Manganese had been used in making steel a quarter of a century before the converter

Jan 1, 1927

By Frank Clemes Smith

The study of the so-called refractory gold-ores of the Potsdam sandstone, ores which are probably of wider occurrence and of much greater economic importance in the Black Hills than is generally supposed, has led the writer to formulate in the present paper some of the results obtained in the course of a special examination of these particular ores, conducted at the State School of Mines at Rapid City, So. Dak. Various circumstances have interrupted the work, and it will easily be seen that relatively little has yet been accomplished; but it is hoped that this little may be of sufficient interest to justify a later supplement. Tellurium, discovered by Muller von Reichenstein in 1781, is generally classed as a very rare metal; it is further mentioned by one of our late writers as " of comparatively little importance," and as obtained from its ores by a " complicated process.'' Concerning its rarity, we have some trustworthy evidence below. Its commercial importance, particularly in connection with electrical appliances, has been passed upon by Mr. Edison ; * and it is certain that, in some metallurgical processes for the treatment of gold- and silver-ores, it may be saved as a byproduct at a relatively reasonable expense. The importance of tellurium as a mineralizing agent is emphasized by the remarks of one of our leading metallurgists,jwho, in his own practice and by a wide series of experiments, has found its occurrence to be much more general than has been supposed. Recently the same writer has discussed the occurrence of tellurides and oxidized tellurium compounds in the gold-ores of Cripple Creek, Colo., and in those of the Black

Jan 1, 1897

By Nestor Torres-Acuña, Fathi Habashi

Metallic copper of purity equal to commercial electrolytic copper is deposited during the anodic dissolution of technically available white metal, Cu2S, in m acidic solution of' copper(II) sulfate as electrolyte and copper sheets as cathodes. The process may be applied on commercial scale since it has the advantage of by passing the converting and poling steps, decreasing pollution problems due to SO, and recovering the sulfur of the white metal in the elemental form. The anodic dissolution is believed to take place in three steps: The working conditions that lead to 98 pct cathodic current efficiency are: 30 gpl Cu2+ and 100 gpl H2SO4 in electrolyte, current density 1.0 amp per sq dm, and tetnperature of bath 40°C'. DURING the smelting of copper, nickel, lead, and zinc sulfide ores, large amounts of sulfur dioxide are produced. Because the release of this gas in the atmosphere causes pollution problems, many attempts were made in the past for its recovery either in liquified form or processed to sulfuric acid. Although these two forms of sulfur are the usual forms that are consumed by the chemical and metallurgical industries, their storage and transport usually raise economic problems. It was realized, long ago, that a process by which sulfur can be recovered directly in the elemental form would be most attractive. Elemental sulfur is easily stored and transported, and is readily converted to SO2, H2S, or H2SO4 when needed. Processes aimed to recover the metals from their sulfide ores, and at the same time by-product sulfur in the elemental form, were recently reviewed.' As early as 1882, Marchese2 patented a process in which a matte having the composition: Cu 15, Pb 14, Fe 41, and S 25 pct was electrolyzed. According to cohen3 the process was applied on a pilot scale by the Aktiengesellschaft fur Bergbau-, Blei-, und Zinkhiitten-betriebe at Stolberg, Rheinland, Germany. The process was unsuccessful, however, owing to the contamination of the electrolyte during electrolysis. Studies in this field were reported by Bernfeld4 and Egli.5 Borchers et a1.6-8 developed the process further by using white metal (Cu 78.2 pct, S 19.6 pct) instead of the matte, and a pilot plant was operated by the Mansfeldschen Kupferschiefer Co. at Eisleben, German~.~ It appears, however, that the process never went into commercial operation. Further studies in this direction were carried out by Russian workers.10-23 The International Nickel Co. of Canada erected a pilot plant at Port Colborne in 1951 to apply the process to nickel matte which is essentially pure nickel sulfide."'- 26 Full-scale plant went into operation at the Thompson Refinery in Manitoba in 1964.27 In this method nickel sulfide matte is melted and cast into anodes analyzing 76 pct Ni and 20 pct S with small amounts of copper, cobalt, and iron. These anodes are then electrolyzed in an aqueous solution of NiS04 at pH 4. Further work on this method was reported in the literature.28-31 In this paper, experiments on the anodic dissolution of white metal in aqueous copper sulfate solution are reported. EXPERIMENTAL White metal, Table I, obtained from The Anaconda Co., was cast in form of anodes 10 by 7.5 by 1 cm, Fig. 1. The anodes are mechanically strong and do not break easily; when polished they gave a shiny gray metallic appearance. From the chemical composition shown in Table I, it can be seen that the atomic ratio Cu:S corresponds approximately to the formula CU2.06S. The copper in excess to the formula Cu2S is most probably present as a separate phase since metallic copper could be seen under the microscope, Fig. 2. Fig. 3 shows the X-ray diffraction pattern of white metal which matches fairly well with that of reagent-grade Cu2S.

Jan 1, 1969

By Thomas T., Read

IN this survey of the progressive development (of education for the mineral industries throughout the United States, the review of .the history of each school has usually been completed wherever it is first mentioned, but the history of the schools in the cities of the eastern seaboard was not carried beyond 1870. It is necessary now to cover what happened during the period of approximately the last quarter of the nineteenth century in several of the schools in the east. Philadelphia Of Philadelphia, it has been related in chapter 4 that the Polytechnic College of Pennsylvania began offering a curriculum leading to the B.S. in mining in 1853; that the school did not prosper, and finally closed about 1890. The establishment of a Department of Mining, Arts, and Manufactures at the University of Pennsylvania in 1855-56 was also mentioned, but its history was not carried beyond 1860. In 1859 J. Peter Lesley was appointed professor of mining in the University of Pennsylvania. The son of a cabinetmaker, born in Philadelphia Sept. 17, 1819, he had taken his A.B. degree at the University of Pennsylvania in 1838 and then secured a position on the Geological Survey of Pennsylvania under H. D. Rogers. When the Survey was discontinued, in 1841, he went to Princeton to study theology, was ordained a Presbyterian minister and followed that career until 1852, when the Pennsylvania, Geological Survey was again started and he rejoined its staff. He published "A Manual of Coal and its Topography" in 1856, and studied at the École des Mines, Paris, in 1856-57. He published an 800-page "Iron Manufactures Guide" the year that he was appointed to the staff at the University of Pennsylvania. In 1863-64 a College of Agriculture, Mines, Arts and the Mechanic Arts was established, but it was not a separate school

Jan 1, 1941

By DR. DOUGLAS

Discussion of the Paper of Dr. Douglas, presented at the Toronto Meeting of the Institute, July, 1907 (Trans., xxxviii., 455 to 471). EDGAR HALL, Silverspur, Queensland, Australia (communication to the Secretary*) :-Dr. Douglas has written on this subject before, and his influence has had a powerful effect on the side of freedom among the younger generation of engineers. Moreover, it is not the first time that he has attributed the decline of the copper-smelting industry in Swansea to the secrecy maintained by the firms there engaged in smelting-operations. In this latter statement I think his conclusions are open to criticism. Whether the firms referred to have suffered by their secrecy is their own business-I. bold no brief for them ; but that the decline of the copper-industry at Swansea was inevitable seems to me to be proved conclusively by Dr. Douglas's own writings. In his paper on The Copper Situation,1 Dr. Douglas says "In comparing iron and copper mining, . . . it must be remembered that 2 tons of average iron ore from the most prolific source now available will make 1 ton of metal; whereas from 33 to 75 tons (say an average of 50 tons) of copper ore must be mined to produce 1 ton of copper." And further: "Last year's production of iron was made from approximately 50,000,000 tons of ore. Our copper mines, to yield a production of 900,000,000 pounds, must have handled approximately 22,000,000 tons of ore, or nearly half the quantity raised from our iron mines." Is not this the key to the whole situation ? In transporting the 50,000,000 tons of iron-ore, 25,000,000 tons of the metal iron were carried so much nearer to the market, but the transportation of 22,000,000 tons of copper-ore would have carried only 450,000 tons of the metal copper nearer to its ultimate destination. The small percentage of copper available in its ores makes

Sep 1, 1908

By A. U. Seybolt

Experiments on both suljidation and hot corrosion have been carried out using ternary Ni-Cr-X alloys and commercial nickel-base superalloys. It has been shown that lhere are certain micro structural similarities between sulfidation using H,S/H2 mixtures and hot corvosion using Na,S04 in "crucible" experiments or hot corrosion tests using a flame tunnel apparatus. It is proposed that two key processes in the hot cowosion process are: 1) formation of chromium sulfides which deplete the alloy matrix, and 2) oxidation which can be accelerated because of chromium depletion. Other processes play an important role in the hot corrosion process, such as accelerated oxidation attack due to the presence of a N& S04 or N&SO,- NaC2 film which inhibits the formation of a protective external oxide scale. However, this latter phenomenon was not studied in this work. THE term hot corrosion has come to mean a combination of sulfur and oxygen attack on nickel-base or cobalt-base superalloys used as gas turbine blades or partitions. This attack can be initiated by any combustion process in air involving fuel containing sulfur if the sulfur level is sufficiently high. Levels of 5 pet SO2l for example, in the combusting gas have been observed to produce hot corrosion attack on nickel-base alloys. The important immediate corroding medium in aircraft gas turbines, however, has been established to be Na2S04, formed from reaction between NaCl from sea air and sulfur in the fuel.' The Na2S04 concentrates the sulfur sufficiently so that superalloy parts heated in the range 1400" to 1900°F can become sulfided by reducing the Na2S04 film which forms on the parts, and this reaction allows sulfur to gain access to the alloy. The sulfur thus released diffuses into the superalloy and forms primarily chromium sulfides of various compositions, but frequently Cr2S, has been identified. Figs. 1 and 2 show the morphology typical of hot corrosion of a cobalt-base superalloy X-45 (25 Cr, 10 Ni, 7.5 W, 0.25 C) and a nickel-base alloy, Udimet 500 (19 Cr, 19 Co, 4 Mo, 3 Ti, 2.9 Al, 0.07 C). Both alloy samples were subjected to the same hot corrosion conditions: 616 hr at 1600°F in a combusted 2.9 pct S distillate oil containing 125 ppm Na as NaC1. It will be noted at once that the nickel-base alloy is much more severely attacked. The depth of corrosion is much greater and the number and size of the sulfides present are much greater. Both alloys show a duplex oxide scale, which is more noticeable in the X-45 alloy. The external scale is probably a spinel in both cases, with CrQ3 lying next to the alloy. Many investigators1 -"ve been concerned with hot corrosion phenomena, but there has been a lack of unanimity of opinion as to the details of the hot corrosion mechanism. More than one definition of hot corrosion is possible. Some investigators con- sider as a measure of hot corrosion only the weight gain due to an accelerated oxidation. However another point of view is that the total depth of affected alloy may be used as a measure. While it is recognized that surface oxidation attack is greatly accelerated by the presence of salts like Na2S04 or Na2S04-NaC1 mixtures, sulfur penetration into the alloy also undoubtedly produces very important effects. The region of sul-fide penetration which is so prominent in Fig. 2 is one of the outstanding characteristics of hot corrosion. For highly stressed parts, such as first-stage buckets, this sulfur-penetrated region can be more significant in mechanical property loss than the reduction of cross section produced by the formation of the massive external scale. In addition, evidence will be presented that this sulfided region can be less resistant to subsequent oxidation attack. Since it appears that the sulfided region below the surface oxide scale plays an important role in the overall corrosion process,

Jan 1, 1969

By Dilip K. Das, Douglas T. Pitman

ONE of the major uses of barium in metallic form is as a getter material in vacuum tubes. Because of the high chemical reactivity of the metal, Ba-Al alloys are extensively used. Numerous methods for the preparation of Ba-Al alloys have been published, a few of which1-4 are cited here. Most of these methods were found to be quite elaborate, involving the reduction of BaO, and not too well adapted for the close control of the final composition of small amounts of alloys prepared for laboratory use. A simple laboratory method for the preparation of Ba-A1 alloys in small batches starting from pure metals was devised, so that it was possible to control the desired compositions to within 1 pct. The pertinent features of the alloy system Ba-Al5 are 1) an intermediate compound BaAl, with the melting point of 1050°C, and 2) a eutectic between aluminum and BaAl4 at 98 pct Al. The accompanying sketch shows the experimental arrangement for the preparation of the alloys. Weighed amounts of aluminum and barium were placed in an alumina and a stainless steel crucible, respectively. According to the supplier's specification, the purity of the metals used in the alloys is as follows: a) aluminum rods—99.9 pct Al, and b) barium rods—99.5 pct Ba. The stainless steel crucible, tapered at the bottom and having a 1/16 in. diam hole, rested on top of the alumina crucible. The assembly was placed inside a graphite sleeve which rested on a refractory platform. The platform moved the assembly up and down through the field of a radio frequency coil. A glass bell jar was placed between the crucible assembly and the radio frequency coil to maintain a steady flow of helium around the melt. A small window was cut out on the wall of the alumina crucible to observe the progress of the re- action and to record the temperature with an optical pyrometer. The platform was first raised high enough to move the barium out of the radio frequency coil field in order to allow only the aluminum to melt. The assembly was then lowered so that the barium began to melt and flow out through the small orifice into the molten aluminum. In order to keep the violence of the exothermic reaction under control, the rate of flow of barium was carefully regulated by raising or lowering the crucible assembly. All the samples prepared by this technique were examined by a Norelco X-ray diffractometer using CuKa radiation, The diffraction specimens were prepared by placing the finely powdered samples in flat specimen holders. The Ba-Al alloys prepared with a high barium content were found to consist mainly of BaAl4. The structure of BaAl4 has previously been reported by Alberti and Andress.8 They found that BaAl4 was body-centered-tetragonal with an a0 = b0 = 4.530Å and c0 = 11.14Å. An alloy whose composition was found by chemical analysis to be almost 100 pct BaA1, was used to determine the relative intensities. The d-spacings were obtained from the same alloy to which a small amount of tungsten had been added as a calibrating material. Accurate values for a, and c, were calculated according to the method proposed by Taylor and Floyd.' The calculated values are: a, = b, = 4.566Å and c0 = 11.250Å. The measured d-values for BaAl4 are shown in Table I along with relative peak intensities above background and hkl indices. Acknowledgment The authors are grateful to L. J. Cronin, the head of the Techniques Dept., for suggesting the problem and for his constant interest. References 1Froges and Camargue: German Patent No. 809107, 1951. French Patent No. 935324, 1949. 2E. Bonnier: Annales de physique, 1953, vol. 8, pp. 259-312. 3M. Orman and E. Zemhela: Prac Institute of Metals; 1952, vol. 4, pp. 437-445. 4E. Fujita and H. Yokomizo: Reports Gov. Chemical Industrial Research Institute, Tokyo, 1952, vol. 47, pp. 291-297. 5E. Alberti: Ztsch. fur Metallkunde, 1934, vol. 26, p. 6. 6E Alberti and K. R. Andress: Ztsch. fur Metallkunde, 1935, vol. 27, p. 126. 7 A. Tnslor and R. W. Floyd: Acta Crystallographica, 1950, vol. 3, p. 285.

Jan 1, 1958

By H. J. Ramey

Conventional calculation of total system isothermal compressibility for a system containing a free gas phase involves, among other things, evaluation of the change of oil and gas formation volume factors and the gas in solution with pressure. Preferably, this information should be obtained from laboratory measurements made with particular oils and gases. Often, experimental measurements are not available. In this case, it is necessary to obtain pressure-volume-temperature relationships from general correlations such as those of Standing' for California oils. In order to speed estimates of compressibility, generalized plots have been prepared of the change of both oil formation volume factors and gas in solution, with pressure from Standing's correlations. A generalized plot for estimating the change in the two-phase (oil and gas) formation volume factor with pressure is also presented. Usually, the effect of gas dissolved in reservoir water upon the total system compressibility is neglected for gas saturated systems, due to the low solubility of gas in water. Results of this study indicate that the increase in total system compressibility caused by solution of gas in water is often as large as the compressibility of wafer, and can be magnitudes larger for low pressure systems. Generalized results for estimating the change of gas in solution in water with pressure are presented in tabular and graphical form. INTRODUCTION During the past decade, pressure build-up and drawdown techniques have gained an important place in reservoir engineering. Build-up and drawdown analyses are only two special applications of the broad field of transient fluid-flow theory. All solutions of transient fluid-flow problems contain a parameter called the total system isothermal compressibility. This property of fluids and porous rock is a measure of the change in volume of the fluid content of porous rock with a change in pressure, and it may vary considerably with pressure. Evaluation of total system isothermal compressibility is not difficult, but it is tedious and time-consuming. Often compressibilities are estimated roughly, or transient flow methods are neglected completely. The benefits of using accurate system compressibility in properly-executed build-up or drawdown analyses are: 1. Better planning of pressure build-ups may be achieved to avoid unnecessary loss of revenue due to excessively long shut-in periods, or to shut-in periods too short to yield useable data. 2. Better and more reliable estimates of static formation pressures for reserves estimates and rate performance estimates. 3. Reliable information for evaluation of well completion effectiveness, and planning and interpretation of well stimulation efforts. The purpose of this paper is to clarify the nature of the total system isothermal compressibility, and to present useful methods for estimation of compressibility, particularly for systems containing a gas phase. DEVELOPMENT Numerous publications have presented solutions to transient single-phase flow of slightly compressible fluids, stressing pressure build-up applications. In transient flow, a compressibility* term arises to permit volume content of fluids in porous rock to change as pressure changes. The basic nature of the compressibility term is usually taken for granted. Problems arise in practical applications of transient fluid theory because most published works consider only one flowing fluid—in an ideal porous system containing only one fluid. In 1956, Perrine2 presented an intuitive extension of single-phase flow pressure build-up methods to multiphase flow conditions. Later, Martin- established conditions under which Perrine's multiphase build-up method had a theoretical foundation. Perrine has shown that improper use of single-phase build-up analysis in certain multiphase flow situations can lead to gross errors in estimated static formation pressure, permeability and well condition. It is likely that, much pressure build-up data for oil wells should be analyzed on the basis of multiphase flow. For both single-phase and multiphase build-up analysis, the isothermal compressibility term in dimensionless time groups often should be interpreted as the total system compressibility. All real reservoirs contain one or more compressible fluid phases. In addition, rock compressibility can contribute in an important way to the total system compressibility. The proper total system compressibility expression may contain terms for compressibility of oil, gas, water, reservoir rock and terms for the change of solubility of gas in liquid phases.

Jan 1, 1965

By S. W. Zehr, G. S. Murty, W. A. Backofen

AN observation by Squires, Weiner, and phillipsl has stimulated interest in a mechanism of deformation at high temperature (above -0.5 of the absolute melting point) that is not usually thought to be involved in the creep of metals. They found precipitate-free or "denuded" zones along grain boundaries normal to the stress axis in tensile specimens of a hydrided Mg-1/2 wt pct Zr alloy after slow straining at 450° and 500°C. Their suggestion that the zones were a result of directional diffusion of magnesium atoms was supported with calculations from Harris and Jones2 which also tended to identify the process as Nabarro-Herring (N-H) creep3,4—a process that is characterized by Newtonian viscosity, with stress (o) directly proportional to strain rate (C), and one that proceeds by lattice diffusion. Material transport by diffusion along grain boundaries is an alternative basis for Newtonian viscosity, as demonstrated by Coble,5 and is favored over N-H creep for fine grain size and lower temperature.6 In either case, the strain rate sensitivity of flow stress, defined as m = d log o/d log E (which commonly appears in the empirical a = KEW), is unity. The experiments to be described here gave metallo-graphic indications of diffusional creep which were no less clear than those just cited, but the associated m (as measured by the method of Ref. 7) was much more like that of a Bingham material. For true Bingham behavior, (a — ao) E, where oo is an initial yield stress. Therefore, even if flow after yielding should occur by diffusional transport, m must increase from 0 as < is raised to reach unity only in the limit as One result is that the resistance to tensile necking conferred by Newtonian viscosity is lost, which would become increasingly apparent through the formation of more sharply defined necks as 6 is lowered. That trend appeared in these experiments. Most of the work was done on an extremely finegrained alloy of magnesium with -6 wt pct Zn and ½ wt pct Zr (Mg ZK60); the initial mean-intercept grain diameter, L, was 0.55 µ. Shown in Fig. l(a) is a germanium-shadowed carbon replica of the surface of a specimen that was coated with silicone oil,* heated to 270°C under a helium atmosphere, and then stretched locally -200 pct at an initial E = 3.3 x 10-5 sec-1. Under

Jan 1, 1969

The Jeffrey operation of Canadian Johns -Manville Co. , Ltd., at Asbestos, Quebec, is considered to be the world&apos;s largest asbestos mine. It accounts for approximately 37% of Canadian production of chysotile asbestos and about 13% of world production. Rated capacity is over 600,000 stpy (540,000 mtpy) of fiber, of which well over 90% is exported to the United States and seventy other countries. During the early 1970&apos;s the company completed a five-year modernization and expansion program which included the installation of a unique 72 in. by 93 in. gyratory crusher to handle the extremely blocky serpentinized peridotite ore. Because of the large diameter of this crusher the top ring of the shell was made in two halves which were bolted together. Hundred-ton trucks dump from two sides of the crusher into the 200 st (180 mt) dump pocket which is equipped with dust collecting ducts in the walls of the other two sides. The installation was designed to accommodate the eventual use of 200 -ton trucks. Crushed ore at a. size of 7 ½ in. (191 mm) falls into a uniquely designed crushed ore pocket equipped with three sloping steel sides and one vertical side, which make it totally live. Infrared heaters installed in back of the hopper sides prevent the ore from sticking to the steel. Another interesting feature is an eccentric removal bridge which is permanently mounted inside the crushed ore pocket. The two halves of the bridge are let down by electric winches to form a platform on which the eccentric cart travels and from where maintenance is done. Level indications in the crushed ore pocket are by radioactive indicators. Under the crushed ore pocket is a 72 in. by 28 ft (1.83 m by 8.5 m) apron feeder which operates at 7. 2 to 50 fpm (2. 3 to 15. 3 mpm). Crushed ore is discharged to a picking belt for tramp removal. A crossbelt magnetic separator is also mounted over this belt. Permanently mounted belt reels are also situated over the picking belt to facilitate the changing of this unit. A 60 in. (1. 52 m) wide takeaway belt then elevates the crushed ore to t.he surface facilities. Instead of discharging to a crushed ore stockpile, the takeaway conveyor delivers the ore to a 300-ton distribution bin. The ore is then screened and secondary crushed; and the plus ¾ in. (19 m) is "stored in a 3,000 ton bin while the minus ¾ in. is dried and then sent to storage. This system of directly screening primary crushed ore is similar to that used at both the Endako molybdenum and Gibraltar copper operations in British Columbia. While it would seem connecting processing equipment directly to a primary crusher would have an adverse effect on the crusher availability, the 94% of scheduled time this crusher

Jan 1, 1978

YEAR or ELECTION 1913. FRANK DAWSON ADAMS Montreal, Canada. 1933. KARL EILERS New York, N. Y. 1922. FEDERICO GIOLITTI Q. Torino,Italy. 1906. SIR ROBERT A. HADFIELD London, England. 1921. FRANK WILLIAM HARBORD London, England. 1917. HERBERT HOOVER New York, N. Y. 1931. WALDEMAR LINDGREN Cambridge, Mass. 1921. C. MCDERMID London, England. 1913. EZEQUIEL ORDOAEZ Mexico City, Mexico 1935. ROBERT PEELE New York, N. Y. 1938. A. M. PORTEVIN Paris, France. 1937. Joan V. W. REYNDERS New York, N. Y. 1937. GEORGE S. RICE Washington, D. C. 1911. ROBERT H. RICHARDS Cambridge, Mass. 1934. T. A. RICKARD Victoria, B.C., Canada. 1933 Cambridge, Mass.

Jan 1, 1938