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By J. D. Milburn, H. J. Hill

In quantitative interpretation of electrical logs the presence of clay minerals introduces an additional variable which further complicates an already complex problern. Although recognizing the difficulties introduced as a result of the heterogeneity of natural sediments and despite the present incomplete state of knowledge regarding electrochemical behavior of shales, dissemirzated clay minerals and concentrated electrolytes, it was felt that useful empirical correlations might be obtained from experimental investigation. Six typical sandstone formations, having a wide variety of petrophysical properties, were selected for the study. Approximately 45 samples from each formation were selected to satisfactorily represent the range of pore size distribution within the particular formation, As a matter of general interest, four limestone formations were also included in the investigation. Previously proposed equations relating to resistivity, SP and interrelationship of the two phenomena have, where possible, been tested with data obtained in this investigation. These equations do not satisfactorily describe experimental behavior of samples through all degrees of shaliness or throughout the range of brine solution resistivities normally encountered in logging practice. An empirical equation has been developed which quantitatively relates formation resistivity factor to satirrnting solution resistivity, porosity, and "effective clay content." This relation is indicated to be uniformly applicable to clean or shaly reservoir rocks. It is shown that both the SP and resistivity phenomena of shaly samples are related to the sample cation exchange capacity per unit pore volume. The independent chemical determination of this parameter is thus a means of determining the "effective clay content" of samples. Some implications regarding theory and electric log interpretation of shaly sands are discussed. INTRODUCTION The use of electrical resistivity logs as a means for estimating formation porosity is based upon the original work of Archie1. It was shown by empirical methods that the resistivity of a rock, when 100 per cent saturated with brine solution, could be related to rock porosity through the equation, F = Ro/ RW = f-m.......(1) where F, the formation resistivity factor, is defined as the ratio of the resistivity of the 100 per cent water saturated rock, Ro, to the saturating solution resistivity, Rw; f is the ratio of pore volume to bulk volume; and m is the slope of the average line when the data are plotted on log-log paper. This relation was established for relatively shale-free formations containing water having high salt concentrations, and under these conditions F may be considered constant for a given rock sample. Applications of Eq. 1 to interpretation of logs of shale-free formations has been quite successful when satisfactory formation water resistivity data could be obtained. The most readily available means of estimating formation water resistivity is the self-potential log. Conventional methods of SP log interpretation involve correct.

Jan 1, 1957

By D. C. Jillson

THE data on the critical resolved shear stress for zinc single crystals published by Rosbaud and Schmid1 showed many irregularities, as seen in fig. 1. There have been subsequent investigations,2,3 but no one has repeated this work with a wide range of orientations, with specimens of a higher degree of purity and perfection, and with improved experimental techniques in order to determine whether these variations were entirely experimental or whether they might have been due, at least in part, to some feature of the mode of deformation not known or understood. Mathewson4 and others have long felt that the glide observed in a [100]* direction between two (001)* planes in the zinc lattice might be actually the net effect of many consecutive unit glides or movements in two alternating [210] directions (fig.

Jan 1, 1951

By John Gjers

Being on a visit to your great and prosperous country, and having been favored with an invitation to attend this meeting of your Institute, the author has been requested by your Secretary to give a short account of his invention of the " soaking-pit," which he has great pleasure in doing. The object of the soaking-pit is the rolling of steel ingots with their own initial heat, that is, to supply the missing link in that chain of metallurgical operations which Sir Henry Bessemer began in 1857, when he proved how it was possible to produce malleable iron or steel direct from the fluid cast-iron out of the blast-furnace, without any further direct use of fuel. The great Bessemer invention has revolutionized iron and steelmaking throughout the world; but it stopped short at producing the ingot, which, it was found, had afterwards to be heated in a furnace to enable it to be rolled or hammered; and it is only lately, twenty-five years after Mr. Bessemer's announcement, that the author of this paper has been able to show that furnacing can be dispensed with, and that it is practicable to roll a steel ingot into say a bloom, a rail, or a billet, with its own initial heat. It has no doubt suggested itself to many that there ought to be heat enough in the ingot just cast, for the purpose of rolling; and from time to time attempts have been made to utilize this heat; but such attempts always ending in failure, it became a settled opinion in the trade that it could not be done—an opinion which the author is aware that your late lamented countryman, Mr. Holley, than whom there was none more conversant with Bessemer steel-making, also entertained. But settled opinions sometimes prove to be great fallacies. As an instance, it is not many years since the opinion prevailed in the trade that steel ingots could not be rolled successfully, that is, so as to make good rails, unless they were first allowed to get quite cold, and afterwards heated. No greater boon was ever conferred on the

Jan 1, 1885

By W. B. Humes

The use of high vacuum on a large industrial scale in the ferrosilicon process for the production of magnesium marks the coming of age of an important new metallurgical technique. The economical production of reactive metals, such as magnesium, which combine with all the well-known furnace atmospheres, has until recently been successfully carried out only by electrolytic methods. It is now apparent that, through the use of high vacuum, the distillation or sublimation of many metals can be done industrially at much lower temperatures, and hence in much simpler equipment, than heretofore has been thought possible. At the beginning of the present emergency, when the ferrosilicon process of producing magnesium was brought to the fore, little was generally known about vacuum engineering, practices, and techniques. In a comparatively short time, the available equipment has been adapted, new equipment designed and built, and a fund of know-how evolved to make possible the production of thousands of pounds of magnesium per day at pressures less than 1/ r0,000 of an atmosphere. Pilot-plant operations have been consistently maintained at pressures even as low 2s one micron (0.001 mm.). These low pressures, which previously were regarded as prohibitively costly or impossible to attain, have been demonstrated as economically feasible on an industrial scale. Necessity for Vacuum The main function of vacuum in the ferrosilicon process, and hence in most vacuum smelting processes, is to lower the temperature at which the metal may be distilled or sublimed from the reduction mixture. A secondary function is to protect the distilled metal from attack by the furnace atmosphere and to permit the formation of a dense condensate. In the ferrosilicon process, magnesium is formed by the reaction between dolomite and ferrosilicon: 2(Mg0-Ca0) -\- HFeSU / t=> aMg + MFe + (CaO)2-SiO2 The metal is distilled from the pelleted charge at a free air pressure of about 0.100 mm. of mercury (100 microns). This low pressure is not needed for the reaction, but rather serves to protect the metal vapor from the oxygen or nitrogen of the atmosphere and permits the formation of a condensate free of pyrophoric material. The reaction proceeds at air pressures as high as several millimeters of mercury, and evidence has been offered to show that the actual equilibrium pressure of magnesium at operating temperatures of 2I50°F. is somewhat higher. Experimentation indicates that the yield begins to decrease at pressures above 500 microns. While no real operating data are yet available on the relationship between

Jan 1, 1944

By B. C. Craft

Oil and gas development in Arkansas during the year 1933 has been marked by considerable wildcat drilling, considering the overproduction prevalent in the oil industry. Arkansas showed an increase in drilling operations during 1933. There were 45 completions from 10 counties resulting in 7 oil wells and 38 dry holes, compared with 37 completions resulting in 4 oil wells and 33 dry holes during 1932. Miller County continued to be the most active area, with 18 completions resulting in 3 oil wells and 15 dry holes. Extensive exploration around the Miller County field has more definitely established the producing limits. It has confirmed the belief that produc-

Jan 1, 1934

By David H. Browne

The use of coal-dust fired reverberatory furnaces, or indeed of rever-beratory furnaces of any description, was for the Canadian Copper Co. a matter of necessity, and not of choice. For 20 years smelting had been done in blast furnaces alone, and with the Herreshoff furnaces used prior to 1904 there was no trouble in treating fine ores. But little flue dust was produced, and this, following the time-honored custom, was wetted down and put back with the charge. Whether the flue dust really smelted, or whether it was worn out by being chased around in a circle, was a problem that troubled no one. With the installation of modern blast furnaces and high-pressure blowing engines, in 1904, flue dust commenced to assert itself. Evidently more dust was made than could be smelted, but so many vital. problems engaged our attention at that time that this minor question was pushed to one side. In 1906, the details of blast-furnace smelting and the conversion of matte had been worked out to a satisfactory conclusion, and the ever-increasing piles of flue dust and fine ore on the stock yard demanded serious consideration. Numerous experiments in sintering, briquetting, mixing with converter slag, forming blocks of flue dust with green-ore fines and cement, and so on, were undertaken. None of these showed much promise. Our problem was still further complicated by the question of treating converter slag. The ore was basic, the slag was not needed as a furnace flux, and it was felt that under these conditions the old method of pouring slag in molds and resmelting in the blast furnace was an unnecessary expense. If the converter slag could be settled in basic-lined reverberatory furnaces, in which at the same time flue dust and green-ore fines could be smelted, two problems might thus be solved. Reverberatory practice with our ores was, however, an unknown factor. As carried on in the West, on siliceous ores and concentrates, at least 25 per cent. of fuel was required, and even this ratio depended greatly

Jan 1, 1915

By B. L. Landrum, J. Simmons, J. M. Pinson, P. B. Crawford

Patentiometric model data have been obtained to estimate the effect of vertical fractures on the areas swept after breakthrough in water flooding and miscible displacement programs such as gas cycling where the mobility is near one, The data are presented for the case of the fire-spot pattern in which the cemer well is fractured various lengths and orientations, the data indicate that for 10-acre spacing, fractures extetidirrg over 1300 ft in either directior1 from the fractured well may re.srrlt in reductions in sweep efficiencics from 72 to approximately 34 per cent. However. the area swept after break through may be quite largr and only 10 or 12 per cent 1ess than would be obtained if the reservoir were trot fractured. For the specific case when the volume of fluid injected is equivalent to 100 per cent of the pattern vol-unie, the swent area may vary from 80 to 88 per cent, depending on the lenght of the fracture. The former value is that which occurs when the break through or sweep efficiency was orrly 34 per cent and the latter figrrre of 88 per cent is that which is obtained if the reservoir were unfrac-ttm'd. It is pointed out that although the sweep efficiency may he very low in vertically fractured five-spot patterrz.s, the area swept at low water-oil ratios may be only 5 to 10 per cent less than those achieved if the reservoir were unfractured. INTRODUCTION Since the initiation of commercial reservoir fracturing techniques it has been desirable to determine the effect of fractures on the areas swept after breakthrough. Most water flooding or gas cycling projects are continued for substantial periods after the brcakthrough of the injected fluid. Although the sweep efficiency serves as one criterion for rating various flooding patterns. the area swept after breakthrough for various water-oil ratios or percentage wet gas, if cycling. is of perhaps more importance than the sweep efficiency alone. Sweep efficiency data on the vertically fractured five-spot have been presented3. Previous work on the line-drive pattern has shown the effect of vertical fractures on the area swept after breakthrough for the case in which the distance between injection and producing wells divided by the distance between adjacent input wells was equivalent to 1.5 (see lief. 2). The data indicated that for the line-drive pattern it may be desirable to flood or cycle substantially perpendicular to the fractures in order to achieve the greatest recovery for the smallest volume of fluid injected. For this study the center well of a five-spot is assumed as the fractured well. All fractures were assumed to originate at this well and extend into the reservoir for various distances and orientations. All the fractures are straight and are of large permeability compared to the matrix proper. These data are presented to aid the engineer in estimating fractured five-spot pattern performance. ANALOGY The potentiometric model was used in making this study. The model used was 20 20 in. by approximately 1-in. deep. For certain portions of the study one corner of this model was considered to be an injection well and the opposite corner a production well. To simulate vertical fractures a copper sheet was soldered to the wire well and made to conform to the desired length and orientation. In other studies the same model was used except that the four corners of the model might be considered as the corner wells of a five-spot pattern and a fifth well was placed in the center of the model. The well placed in the center of the model was fractured. The total fracture length is L and the well spacing. d. The complimentary fracture angles will be obvious from Figs. 3 and 4. The data obtained on the potentio-metric model assumes the pay to be uniform and homogeneous, the mobility ratio is one, steady-state conditions exist and gravity effects arc neglected. The permeability of the fractures is very great compared to that of the matrix proper. The po-tentiometric model has been used widely both in water flooding and gas cycling projects, and may be used for miscible displacement; how-ever. it is believed that the poten-tiometric model data are more properly applicable to gas cycling than water flooding because the model as-

By Philip D. Shelton

INTRODUCTION Traditional design of support for permanent underground mine excavations place great emphasis on the magnitude of the maximum radial load which a specific support or lining must sustain. However, this depends upon so many factors that reliable prediction in advance of excavation is very difficult except in strong-self supporting ground. Some of the factors affecting the loads acting on a support are illustrated in Table 1. [ ]

Jan 1, 1984

By E. K. Soper

Introduction It has been observed that where veins or other types of orebodies are intersected by cross faults, the continuation of the ore deposit below the fault is often of lower grade than that portion above the dislocation.1 In some mines, the reverse of these conditions has been noted, and the richest ore is found to occur in that portion of the vein beneath the fault intersection. Such instances seem to be less frequent than those where the richest ore is above the offset. The important and widespread influence of fault and vein intersections upon the localization of ore shoots is well known 2 but the factors that govern the position of the ore shoot relative to the fault intersection seem to be less clearly understood. The richest ore may be above or below the fault,. or it may occur at-the point of intersection, or there may be no change. Recent observations made by the writer in mines in Idaho and Montana suggested a possible explanation for the changes in the richness of ore below certain types of fault intersections. These observations have been supplemented by a study of the literature containing detailed descriptions of ore deposits at a large number of mines in North America. The results of these studies are presented herewith in the hope that they may lead to further discussion of this important phase of ore deposition.

Jan 10, 1917

By W. S. Gresley

The traces of fossils herein described were discovered in or upon piles or heaps of iron-ores upon the docks at Erie, Pa. The author has worked among these ore-piles since 1890, when his attention was first directed to what looked like organic remains upon certain specimens collected. All the specimens described and figured herein were found by him, and, as no ironore is used at Erie, and no other iron-ores, save those of the Lake Superior region, find their way to the stock-piles at this place, there can be no question but that the specimens in question are genuine ore transported from that region over the great lakes, and cannot have been brought in from other ironore regions. The author has reason to think that no fossil remains have been reported hitherto as occurring in the iron-ores of the Lake Superior region, and he believes that these specimens, however imperfect, rank among the oldest forms of which man has any knowledge. The illustrations are engraved from photographs of drawings. The specimens themselves have not been photographed, because their condition would have prevented bringing out, by that process of reproduction, all the markings as clearly as is necessary, and would have rendered the specimens otherwise less distinct by reason of the blotchy character of their colors, the presence of cracks, or of marks more or less in contact with those of the organisms. In drawing these remains, therefore, I left out everything upon the specimens of ore that did not seem to belong in any way or contribute to their value as illustrations of the fossils. According to information obtained from the dock superintendent at Erie, Pa., the majority of these specimens came from the Chapin mine, Iron Mountain, Menominee range, Mich. As to the rest of them, I stupidly failed

Jan 1, 1897

By William Colby

INCREASING governmental control of human activities seems inevitable. Within the present generation railroad rates and the public sale of water, gas and electricity have been subjected to rigid regulation. The field of control is slowly but surely being enlarged, and it is the object of this paper to outline in brief space this tendency toward increased governmental regulation, as far as mineral resources are concerned. Our, dual form of government complicates the problem. We must deal not only with the powers of the Federal Government, but also with those of the individual States. In order to approach this question intelligently we must have some conception of the powers and jurisdiction of the States and the United States, respectively, over mineral lands and mineral production. Starting with the Federal Government we find it never owned any public domain within the States that formed a part of the thirteen original colonies and, for historical reasons, the same is true of Tennessee and Texas. The Mid-Western States were erected out of the public domain which was acquired by the United States through cession from the original States or by purchase from foreign nations. Congress early in the last century adopted a policy of leasing public lands containing lead deposits in a portion of this Mid-Western territory, but later abandoned that policy and disposed of such public, lands, mineral and non-mineral, outright so that they long since have practically all passed into private ownership and become subject to the general jurisdiction of the respective State governments. In the great public domain lying west of the Mississippi River, and in portions of some of the Southern States, the Federal Government adopted a new mineral land policy following the discovery of gold in California. (Acts of Congress of 1866, 1870, and 1872.) The mineral lands within these States, instead of being disposed of on the game basis as agricultural lands, as occurred in the Mid-Western States, were segregated from agricultural lands and sold under special laws intended to encourage mining, giving the miner the free right to locate and work these mineral lands without paying any royalty to the Federal Government. A miner could also obtain at slight expense a complete

Jan 1, 1930

By C. A. Allen

FOR over three years we have been endeavoring to reduce the number of fatalities and minor accidents in Utah. The physical condition of the o? Represents the average of 4 States mentioned excluding the catastrophes indicated. FIG. 1.-NUMBER KILLED PER MILLION SHORT TONS OF COAL PRODUCED IN COLO¬RADO, NEW MEXICO, UTAH, WYOMING, AND BITUMINOUS MINES OF THE UNITED STATES, 1914 TO 1920. mines, concentrators, and smelters is good, yet the number of accidents,

Jan 5, 1922

By J. F. Myers, F. M. Lewis

THE selection of the proper type of flotation machine involves the consideration of a wide variety of factors. Under any condition, all types of machines will promote some kind of separation. Obviously, the correct way of deciding which type of machine is best suited for a particular problem would be to set up all types of machines and test them out in a competitive manner, but the vast number of small concentrating plants are unable to make such complete and exhaustive tests. The experience of the authors of this paper indicates that if all the factors involved in any particular problem can be determined, and if all the flotation-machine characteristics are understood, some basis for selection could be arrived at other than actual comparison. This paper is presented to show how the process factors and machine characteristics have been combined at the mills of the Tennessee Copper Co. from studies of several types of flotation machines. At the two mills of the Tennessee Copper Co. in the Ducktown Basin of Tennessee, four distinct flotation separations are made on the complex sulphide ore. Three different concentrates are produced from the ore-in the order of their importance: iron concentrate, copper concentrate, and zinc concentrate. Four different types of flotation machines are used. The selection of these four machines, for the plant operation, was based upon the study and operating experience of the machine units shown in the following list: Fagergren machine; square cell, size 56 inches Fagergren machine; level type, size 56 inches Denver machine; conical disk impeller, size 24 inches Denver machine; receded disk impeller, size 24 inches Minerals Separation Sub-A, size 24 inches Munro-Pearce deep cell, pneumatic Southwestern air machine, Hunt principle To date the study of flotation machines has been confined almost entirely to the rougher circuits. The various cleaning operations, being relatively a much simpler matter, have not been investigated so thoroughly. Table 1 shows a typical analysis of the two ores as well as of the mineral content. []

Jan 1, 1944

By A. J. Phillips, A. A. Smith, J. S. Smart

THE preparation of a sufficient quantity of high-purity copper for extensive laboratory use in the study of impurity effects has been an integral part of a research program in progress at the Central Research Laboratory of the American Smelting and Refining Co. for the past several years. Initially the degree of purity desired was that necessary to meet two essential requirements for experimental accuracy: (I) no impurity was to be present in the copper in an amount capable of producing a detectable effect on the properties to be studied, (2) even the minor changes in properties caused by the addition of extremely small amounts of individual elements were to be measured without significant interference from contaminants. In the course of the investigation, evidence has accumulated to justify the conclusion that this copper is of exceptional purity; in fact, no impurity can be detected by any chemical method or spectrographic technique known to the authors. The present paper describes the method of production of the copper and presents some of its properties. PREPARATION OF HIGH-PURITY COPPER The elimination of impurities from commercial electrolytic copper is accomplished by a three-step purification process. The first operation consists of an electrolysis through a purified CuS04-H2SO4 electrolyte using bagged anodes, low current .density (5 amp. per sq. ft.) and low temperature (25°C. max.). The electrolyte is prepared from commercial Cu2SO4 and is purified by heating the solution and adding I gram Fe as Fe 2(S04)3 to each 100 grams dissolved copper; sufficient hydrated oxide of copper, prepared from Cu2SO4 and NaOH, is supplied to precipitate Fe(OH)3, which carries down arsenic, antimony, tin, selenium, tellurium and other minor constituents. Silver and remaining traces of lead are removed by addition of Na2S to the acidified filtrate, which is then refiltered after standing hot overnight. The cold solution is made up to 30 grams per liter Cu and 150 grams per liter H2S04 and introduced without addition agents into the electrolytic system, which consists of a double row of hard-rubber battery boxes with the inside webbing and partitions removed, arranged in seven steps of ascending height. Electrolyte is uniformly supplied to the two highest cells by glass siphons operating from a constant-level reservoir, and flows by gravity through the bank of seven cells, entering each at the bottom and leaving at the top. Glass air lifts continuously supply the returning liquid to the constant-level reservoir for recirculation. Each cell contains three 434 by 43a by I-in anodes cast from high-quality electrolytic wire bar copper, various lots of which have been used with equal success. The anodes are pinned to sheet copper hangars shaped to prevent crawl of the electrolyte to the multiple-wired bus bars-which would result in fouling of the contacts and hang inside wool flannel bags stretched over open wood frames. The deposit

Jan 1, 1941

By W. M. Small

Austria.—Austria produced some 430 cisterns of 10,000 kg. each of crude oil of a 0.9428 sp. gr. during 1934. Gosting II well near Zis-tersdorf was placed on the pump in August and at the end of the year was still producing about three cisterns daily. This well is owned by the Erdöl-Produktionsgesellschaft while Gösting I is owned by Raky-Danubia. Only five wells were completed in the republic during the year. These accounted for 1783.5 meters of the 2225 meters drilled. The only producer completed was Gosting 11. At the close of the year, four rigs were in operation and one rigging up. At least 8 or 10 new wells are planned in Lower Austria for 1935. The European Gas & Electric Co. put its 6-km. gas line into operation in May and has sold 12,301,550 cu. m. of gas to the Vienna City Electric Works. A 2-km. pipe line was built from Gösting II to the railway loading rack near Zistersdorf. Hungary.—No oil or gas was produced except a small amount of gas trapped from flowing artesian wells. The Government completed and abandoned a 1500-m. hole at Tisztaberek in northeastern Hungary and is drilling at 967 m. near Bogáes, 120 km. northeast of Budapest. It is unofficially reported it plans to drill two new wells in 1935. The European Gas & Electric Co. has a rig up for a test at Mihalyi in Transdanubia. Czechoslovakia.—In Gbely (Egbell) there were produced 1283 cisterns of 10,000 kg. of 0.935 sp. gr. oil and a small amount of gas used for fuel. This field is operated by the Government; 17 shallow producing wells and three dry holes were drilled, with a total of 3351 m. of hole completed. In Hodonin (Goding) there were produced approximately 1300 cisterns of 10,000 kg. each of 0.91 sp. gr. oil and a small amount of gas used for fuel. The field is operated by the Apollo, which drilled four producing wells averaging 460 m. in depth, one small gas well of 550 m., one small gas well 260, and one dry hole 230 m. Two wells were deepened a total of 80 meters. The Government is drilling below 800 m. in a wildcat test in eastern Czechoslovakia near the Rumanian frontier.

Jan 1, 1935

By Charles Catlett

(Chattanooga Meeting, October, 1M.) THE terms " developed " and " undeveloped " are necessarily relative and cover a wide range; but the latter is here applied to cases in which the information at hand falls short of a clear demonstration of values, and conclusions must be reached from a study of the geological conditions of the particular deposit, interpreted in the light of similar and closely related deposits. Such an inquiry might be characterized as an effort to reach reliable conclusions from insufficient data. But the engineer engaged in commercial work finds himself often face to face with apparently such problems; and while he may realize with regret that a small amount of intelligent development would add enormously to the value of his conclusions, he is compelled to recognize the demand of a business situation for a prompt decision as the basis of immediate action. In a case within my knowledge, the question involved was the purchase of 50,000 acres of coal-land, and 10 days was the limit within which this question must be decided. Of course, it was impossible to make a satisfactory examination within that time; but the 'instructions were "to make the most complete examination and the most positive recommendation possible." Such instructions are often given; for, no matter how much time an investor may have, he is likely to put of his decision until the last moment, and then discover that he needs more light and advice. It does not follow that engineers, after full explanation and mutual understanding of the situation, should decline to undertake examinations thus limited. In the case just mentioned, while only the broadest view was possible, half the time available was sufficient to show that the property was a good purchase. The timber alone was subsequently resold for more than the entire purchase-price of the

Mar 1, 1909

By Arnulf Muan

PHASE relations in three isothermal sections (l000°, 1100°, 1200°C) of the system Ag-Fe-Pd have been determined as part of a program to develop improved crucible materials for containing low-melting iron silicates at low oxygen potentials. The following experimental method was used: Two- to 3- g samples of each of forty different alloys within the system Ag-Fe-Pd were made up from metals of 99.9 pct purity. The mixed metal powders were contained in a 1-cc crucible of dense recrystal-lized alumina and heated in a protective atmosphere (90 vol pct A, 10 vol pct H2), first to complete melting for approximately 30 min and subsequently at the desired equilibration temperature (1000°, 1100°, or 1200°C) for approximately 24 hr. The samples were then quenched rapidly to room temperature and examined metallographically as well as by X-ray techniques. Unit cell dimensions were compared with standards obtained by study of one-phase alloys of known compositions. The results are summarized in diagrams (a), (b), and (c) shown in Fig. 1. Heavy solid curves outline areas comprising compositions of mixtures consisting of the phases labeled for each area. Mixtures in which liquid is the only condensed phase present are confined to very narrow areas adjacent to the Ag-Pd join at high silver contents. An enlarged, distorted picture of the phase relations prevailing in these areas is shown in the upper-left circular insert. Particular attention is directed toward the misci-bility gap which occupies major parts of the composi-

Jan 1, 1962

By R. J. Borg, C. E. Birchenall

The self-diffusion coefficients for a iron have been deternzined between 980° and 1167° K using Fe55 as the tracer. With decreasing temperature the diffusivity was found to decrease more rapidly than predicted by the Arrhenius equation in the region of the Curie temperature. The diffusion coefficients obtained well above the temperature of the magnetic transformation are more precise ard differ substantially from all the previously reported values. In the temperature region beginning at least 50" above T,, the diffusion coefficient is given by D = 118 (±2) exp 1 HE self-diffusion coefficients for a iron have been reported previously as the result of four independent investigations The general lack of agreement and the poor precision of most of the previous work prompted the redetermination by the present authors. The possible effect of the onset of ferromagnetism upon the diffusivity5 provided an additional impetus for this investigation. The earlier measurements of Birchenall and Mehl1 gave low values for the diffusion coefficient at temperatures below the Curie temperature, Tc. However, the precision of these measurements is not sufficient to establish an indisputable correlation between the low values and the magnetic transformation. The results of this investigation along with all the previous ones are shown in Fig. 1. EXPERIMENTAL Small rectangular samples, approximately 1 by 0.5 by 0.3 cm, of high-purity iron (Vacuum Metals Corp., "Ferrovac") are first heated in hydrogen at 900°C for24hr in order to remove possible trace amounts of dissolved carbon and oxygen. The small

Jan 1, 1961

By Earl A. Gulbransen, Kenneth F. Andrew

DRY oxidation of zirconium has been studied by several groups.'" The present work extends our early study1 to the high-temperature studies of Cubicciotti2 and Belle and Mallett.8 ulbransen and Andrew1 showed that the parabolic rate law fitted the 2-hr experiments between 200" and 425°C after an initial deviation. An energy of activation of 18,200 cal per mol was calculated. Cubicciotti,' in a study between 593" and 880°C, showed that the parabolic rate law fitted the data and an energy of activation of 32,000 cal per mol was calculated. In contrast to these studies on sheet specimens, Belle and Mallett3 studied the oxidation reaction on rod specimens and found a cubic rate law to fit the data.

Jan 1, 1958

By H. J. Gluiskoter

The chlorine content of the coals in the Illinois Basin ranges from 0.00% to more than 0.60%. The chlorine content of the Herrin (No. 6) Coal has been mapped on a regional scale and, in general, increases with the depth of the coal. The depth-chlorine correlation exists because the coal is in apparent equilibrium with the composition of the ground water associated with it, and the salinity of the ground water generally increases with depth. At least part of the chlorine can be easily removed from the coal in the laboratory. In a natural weathering experiment, chlorine values decreased markedly during an 8-week period. Results to date indicate that none of the coals studied has a sufficiently high chlorine content to make it unusable in high-temperature steam boilers, although special steps may be necessary in the preparation or utilization of some of the highest chlorine coals. Investigations into the occurrence and distribution of chlorine in Illinois coals have been in progress at the Illinois State Geological Survey for over 35 years. Since 1948, chlorine analyses of face channel samples and of drill core samples of coal have been made routinely. The increased interest in chlorine and alkalies in coal in the U.S. followed that in Europe, where power plants during World War II were called upon to produce at higher levels than previously and with less down time for maintenance. Higher steam temperatures were reached, resulting in increases in the amount of fouling of external heating surfaces and in corrosion of boiler tubes when high chlorine coals were used. Early studies of the problem showed that coals with high chlorine content were more likely than those low in chlorine to cause difficulties in installations fired with powdered fuel. Crossleyl reported that the first rule of thumb developed for British coals was that coals considered to be high in chlorine (more than 0.30%) caused the most trouble, those intermediate in chlorine content (0.15% to 0.30%) were less likely to cause difficulties and those low in chlorine (less than 0.15%) generally were not associated with alkali bonded deposits and corrosion. However, this relatively simple picture was not adequate to characterize the difficulties that could be expected during the utilization of a large number of coals and Crossley1 developed another scheme for assessing the chances of superheater corrosion. This scheme took into consideration the observation that coals high in sulfur as well as chlorine are more likely to cause corrosion and fouling than coals low in sulfur and high in chlorine. Crossley also considered the ash content. When two coals had the same chlorine and sulfur contents, the one with the greater amount of ash would be the less likely to cause difficulties. Knowing only the amount of chlorine in a coal obviously will not give all the answers. Indeed, the significance of the chlorine content has been much discussed and it has been suggested that perhaps the total alkalies are a better indicator of possible troubles. The observation that the deposits that form

Jan 1, 1968