Search Documents

By Ralph Arnold

While much geological work and drilling have been done in Venezuela, the incompleteness of geological evidence obtainable and the restricted areas in which drilling has been done make any estimates of oil resources extremely speculative. Nevertheless, it is felt that the data given are justified, in the belief that the ideas of a geologist familiar with the region are better than those of a promoter. The oldest beds of interest to oil men are those of the Cretaceous, which are well developed in eastern Venezuela and about parts of Lake Mara-caibo. In both cases, a hard massive limestone is overlain by a great thickness, most of which is shale. In the west, in places this shale is more than 2000 ft. (610 m.) thick, while in the east it-mag attain 3500 ft. (1067 m.). The limestone and parts of the shale are oil producing. In the east, the Tertiary where present is almost entirely covered by the Quarternary, but in the west it is well developed. In probable unconformity over the Cretaceous shales is found a series of sandstones and shales, which may be called the lower coal series. It is well developed southwest of the lake, where it is the oil container, and is probably the lowest series exposed east of the lake. Above this is the Pauji shale, which is probably the point of origin of all the oil east of Lake Maracaibo and in the State of Falcon. It has a thickness of about 3000 ft. (914 m.) in the Mene Grande region. The upper coal series is developed as a great thickness of sands, shales, and clays, with some partly consolidated limestone. Its thickness may be as great as 10,000 ft. It is the oil container of the Falcon-El Mene region and a probable location for oil in some of the area about the lake. It may or may not include the so-called Maracaibo series in which the oil is found at Mene Grande. Over much of Venezuela, the Quarternary is present in unknown thickness, which probably is not great. It obscures oil structure in all cases and presents the greatest hazard of oil exploration for the fields which probably exist below.

Jan 1, 1923

By Ralph Arnold

While much geological work and drilling have been done in Venezuela, the incompleteness of geological evidence obtainable and the restricted areas in which drilling has been done make any estimates of oil resources extremely speculative. Nevertheless, it is felt that the data given are justified, in the belief that the ideas of a geologist familiar with the region are better than those of a promoter. The oldest beds of interest to oil men are those of the Cretaceous, which are well developed in eastern Venezuela and about parts of Lake Mara-caibo. In both cases, a hard massive limestone is overlain by a great thickness, most of which is shale. In the west, in places this shale is more than 2000 ft. (610 m.) thick, while in the east it-mag attain 3500 ft. (1067 m.). The limestone and parts of the shale are oil producing. In the east, the Tertiary where present is almost entirely covered by the Quarternary, but in the west it is well developed. In probable unconformity over the Cretaceous shales is found a series of sandstones and shales, which may be called the lower coal series. It is well developed southwest of the lake, where it is the oil container, and is probably the lowest series exposed east of the lake. Above this is the Pauji shale, which is probably the point of origin of all the oil east of Lake Maracaibo and in the State of Falcon. It has a thickness of about 3000 ft. (914 m.) in the Mene Grande region. The upper coal series is developed as a great thickness of sands, shales, and clays, with some partly consolidated limestone. Its thickness may be as great as 10,000 ft. It is the oil container of the Falcon-El Mene region and a probable location for oil in some of the area about the lake. It may or may not include the so-called Maracaibo series in which the oil is found at Mene Grande. Over much of Venezuela, the Quarternary is present in unknown thickness, which probably is not great. It obscures oil structure in all cases and presents the greatest hazard of oil exploration for the fields which probably exist below.

Jan 1, 1923

By M. J. Buerger

Possibly the most puzzling features observed during a single-crystal deformation test are the appearance of slip striae on the surface of the crystal and the strengthening of the specimen.' While the first phenomenon is mainly of theoretical interest, the latter is fundamental to all strain-hardening and cold-working processes in which the deformation occurs by translation. The plastic deformation of crystals has received considerable discussion2 and need not be reviewed here in any great detail. It has been observed, essentially, that after a certain amount of. initial stress is applied, the surface of the crystal becomes covered with sets of parallel striae or rings which appear to divide it into thin slabs or slip blocks.3 The striae are the traces of rational crystallographic planes along which shearing movements are localized, these movements providing the strain which accompanies stress applied beyond pure elasticity. As deformation under the applied stress proceeds the slip blocks shear past one another, although the essentially single-crystal character of the specimen is unimpaired. All of the shearing apparently takes place in the immediate vicinity of the original slip striae without the appearance of new planes of movement.4 Since each increment of strain is attended by an increased stress requirement to continue the deformation, the crystal strengthens during the process.

During the war, American chemists were puzzled as to the scource of the enormous amount of sulfuric acid the Germans were able to secure. Information now in the hands of the Bureau of Mines shows. that at no time during the war was there any particular stringency in Germany's supply of this acid. During the early months of the war, before conventions could be made with neutral countries, very large shipments of pyrites were made to Germany; in fact, the importation of pyrites into Germany continued in some volume throughout the war. This reserve built up at the beginning of the war gave Germany time to find new resources of sulfuric acid. A noteworthy development of the Meggen pyrites took place and other pyrite beds were opened in Germany and Hungary. Considerable sulfur was also obtained from Asia Minor. In addition, Germany made important use of its rich beds of blende and galena. Means was found promptly to eliminate the lead dust, which has been a source of trouble in the contact process of manufacture. Kaiserite and plaster of Paris also were sources of sulfuric acid; some sulfur was also obtained by purifying gas at coke plants. As a matter of fact, sulfuric acid was so plentiful in Germany near the close of the war that restrictions on its use by industries were rapidly being lifted.

Jan 6, 1919

By Howard Eavenson

ONE who has been trained in belief in the law of supply and demand and its effect upon prices finds it difficult to adjust himself to the minute regulations imposed by the New Deal, and also to the bewildering changes of government policy as expressed within a short period of time between the antitrust laws and the N.R.A., and later by the Bituminous Coal Conservation Act of 1935. A survey of the coal industry since the World War, both in this country and Great Britain, however, shows that regula-tion of some sort is needed if any stabilization is to be achieved and if the Wage structure and economic welfare of the many communities dependent solely upon coal are to be maintained. Let us look at what has happened to the industry since 1920, which can be considered as the end of the period affected by the war influence. This discussion will be confined solely to bituminous coal, although many of the general conditions are equally applicable to anthracite, the position of which now is at least as bad as that of the softer variety. Since 1920-to the end of 1934-the production of coal has decreased from 568.7 million to 358.4 million tons, or 37 per cent; the number of mines from 14,766 to 6,258, or 58 per cent; the average annual production per mine has changed from 38,512 to 57,425 tons, or 50 per cent. The number of large mines has increased considerably, and the number of men employed has decreased from 639,547 to 458,011, a reduction of 28 per cent, while the average output per employee has changed from 4.0 to 4.4 tons, or an increase of 10 per cent. The average price per ton of coal at the mine has varied from $3.75 to $1.75. During that time wages decreased largely until 1933 and since that time have increased, until now the rates paid are- considerably above those in other occupations, although the actual yearly earnings are low, because of part-time work. From 1920 to the signing of the Jacksonville wage agreement in 1924, about two-thirds of the men were union members and practically all of the nonunion mines were south of the Ohio River; with the fixing., of the high wage scale of that agreement, which soon proved to be an uneco-nomic one, many of the mines found that they could not retain their business, so gradually changed to nonunion. By 1928 the proportion

Jan 1, 1936

By F. C. Clapp

Although many oil fields have been, and still are being, discovered in Oklahoma, the geology and structure of most of them have not become familiar to the general public because of the delay in securing government geological surveys and the reluctance of oil companies and other intercsted parties to give out their "inside information " Therefore, until official surveys are available, it behooves us to publish geological results as soon as possible. Fortunately the writer has been authorized by the Cement Field Oil Co. to publish his data on the Cement field, Caddo County, at this time. Locality and Description The Cement field is situated in the part of Oklahoma known generally until recently, as "Healdton fields," and lies 60 mi. (96 km.) northwest of the Healdton field proper. Like the Healdton field, it forms an approximate ellipse, trending northwest and southeast through the village of Cement on the St. LouisSan Francisco Railroad, on which it is reached in 21/2 hours from Oklahoma City. In its geological structure, the field constitutes an anticline over 13 mi. (21 km.) long and from 1 to 3 mi. wide; the point of greatest width being not far from its intersection by the above-named railroad. The major axis trends north 75' west from the village of Cement; but eastward appears deflected (if field interpretations are correct) to about south 45" east. About 5 mi. south lies an approximately parall el syncline, which may be conveniently called the Cyril syncline, the south and west boundaries of which may be distant many miles, but forming a closed basin south of the Cement anticfine. The positjon of the offsetting synclinal axis, which is believed to lie north and east of-Cement, has not been discovered. TOPOGKAFHY In the southwest part of the state, nearly all maps of Oklahoma show two mountain areas—Arbuckle and Wichita—which are conspicuous geological and topographic landmarks. In addition, some maps show a third, and smaller, range, named the Keechi Hills, in the vicinity of Cement. These hills also form a conspicuous feature in the landscape; but for some reason they have been neglected by geologists, and the

Jan 1, 1921

Taking advantage of the lessons in administrative organizations which were taught by the war, Director Van H. Manning has put into effect a new form of organization in the Bureau of Mines. The Bureau is divided into two branches, one the investigations branch and the other the operations branch. F. G. Cottrell, who has been chief metallurgist of the Bureau, has been promoted to the position of assistant director and will be in charge of the investigations branch. F. J. Bailey, who has been chief clerk of the Bureau, has been placed in charge of the operations branch with the title of, assistant to the director. All research and technical control will be exercised through the investigations branch, while the non-technical work, administrative duties, and dissemination of the results of the Bureau's activities will be handled by the operations branch. Under the investigations branch comes the division of mineral technology, in charge of Dr. C. E. Parsons; the division of fuels, under the chief mechanical engineer, 0. P. Hood; the division of mining, under the direction of George S. Rice, the chief mining engineer; the division of petroleum and natural gas, under the direction of J. 0. Lewis, the chief petroleum technologist; and the division of experiment stations, under the direction of D. A. Lyon.

Jan 9, 1919

By Pedro Beltrán

DURING the war South America attained a very important position in the production of metals and minerals, brought about by her strategic location near the "Arsenal of Democracy" and the loyalty of her peoples to the cause of freedom This seemingly miraculous achievement in the wartime delivery of the all-essential metals-copper, tin, lead, zinc and tungsten -as well as 35 other war-important minerals and metals, was not the simple result of orders received and of routine production It was the end result of pioneering, prospecting, developing, planning and plodding throughout the lifetime of your organization It was the introduction of new engineering principles, mining techniques, smelting procedures and refining practices, which presaged the entrance of the vast amount of venture capital essential to carry these promising mineral potentials through the dangerous stages of early development Many of those attending the meeting must in the past, as young engineers, have braved the untold hardships and discouragements that beset them at every turn Only they can really appreciate the true meaning of the overwhelming wartime demand on the mineral production of every one of the South American countries No one country has all of everything necessary to produce armaments on a scale imperative during an emergency Not even the United States, with its wealth of natural resources, could hope to meet the unprecedented de-

Jan 1, 1947

By A. N. Mitinsky

Discussion of the paper of A. N. MITINSKY, presented at the San Francisco meeting, September, 1915, and at the New York meeting, February, 1916, and printed in Bulletin No. 104, August, 1915, pp. 1697 to 1705. ALBERT SAUVEUR, Cambridge, Mass.-The author expresses the belief that steel will not fail under fatigue when subjected to ultimate stresses unless the stresses exceed the elastic limit or the limit of proportionality. I think this statement is contrary to the evidence. It is conceivable, however, that a stress ever so small does produce a permanent set, although so slight that we cannot detect it with the instruments at our disposal. Nevertheless the repetition of this small stress a great many times will finally break the piece and the nearer, we approach what we call the elastic limit, the quicker will the piece break under fatigue. J. W. RICHARDS, So. Bethlehem, Pa.-I would like to ask Professor Sauveur whether there is a similar indefiniteness about the limit of .proportionality as there is about the elastic limit. ALBERT SAUVEUR.-Yes; I believe it also depends upon the delicacy of our instruments. J. W. RICHARDS.-If that is so then we are as badly off by adopting the limit of proportionality as a criterion as we are by adopting the elastic limit.

Jan 5, 1916

By L. P. Davidson

THE new electrolytic zinc plant of the American Zinc Company of Illinois commenced operation in April 1941. The simple flowsheet using the standard current density and the economic reasons that dictated it are given herewith. The Evans-Wallower Zinc Co. built an electrolytic zinc plant at Monsanto, Ill., in 1929 and operated it for about two years. The plant stood idle from 1932 and was purchased by the American Zinc Co. in 1940. Because of the condition of the equipment, excepting the motor generator set, a complete rebuilding was necessary. The Fairmont City plant of the American Zinc Co. could treat the leach residues, the purification cake and the skimmings from the melting furnace in its various plants. This possibility permitted a simple flowsheet with good economic results. The flowsheet is shown in Fig. I. The calcined concentrates are leached in mechanically agitated tanks with spent electrolyte and such ferric iron solution as necessary. When the acid has been neutralized and the iron coagulated, the fluid is discharged to settling tanks. The underflow from these thickeners is filtered on a Moore filter; the filter cake leaves the plant for retreatment and the filtrate joins the thickener overflow. Zinc dust is added to this solution until the copper and cadmium are precipitated. The pulp is filtered through Shriver presses, which deliver the purified solution to storage tanks, and the copper-cadmium-zinc cake is shipped for retreatment and recovery of these three metals. The purified solution is electrolyzed; the regenerated acid is returned for use in the leaching plant and the cathode zinc, after stripping, goes to the melting furnace, from which it is cast in slabs. The skimmings from the melting furnace are shipped to the Fairmont City plant for reduction to metal in the retort furnaces. The choice of this simple flowsheet was made possible only because of the facilities of the Fairmont City plant. The long leaching period, with high acid content and high temperature which characterize the high-density process, gives a higher zinc extraction but also dissolves more impurities, which must be removed. The same is true to a lesser degree of the multi-step leaching of the western low-density plants. By the sacrifice of some initial extraction, solutions can be obtained that are relatively easy to purify and give good ampere efficiency. This loss in initial extraction is made up in the retreatment of the residues in the Waelz plant. The impurities that accompany the zinc thus extracted are inconsequential when the Waelz product is treated in a distillation plant. It was recognized that this flowsheet would require a somewhat greater amount of sulphuric acid-either as acid or as sulphate sulphur in the calcine-because of poorer washing. The sulphuric acid plant at Fairmont City could deliver 60° Bé. acid to compensate for the sulphate loss and the cost would be less than the cost of more intensive washing.

Jan 1, 1942

By Joachim J. Hauser

Experiments on latent hardening were peyformed by compressing single crystals along a direction perpendicular to the tension axis. The slope and length of easy glide in the tension test were found to depend only on prior deformation in the same slip plane. Prior deformation on a different slip plane changes the stress level of the resulting stress-strain curve. The yield points appearing upon reloading after prior extension and unloading were related to the end of easy glide. SEVERAL researchers have studied the latent hardening due to deformation of a crystal by slip on a slip System after prior deformation. These experiments can be divided into those in which the prior deformation was on the same plane as the subsequent and those in which the two deformation processes were in different planes. In the former category are the experiments of Buckley and Entwistle,1 Parker and washburn,2 and Haasen and Kelly.3 The latter case has not been studied systematically; it was the main purpose of this investigation to produce this type of latent hardening and explain the results in terms of the existing theories of work hardening. In general, tension producing slip on a certain slip system can be preceded by tension, transverse compression or longitudinal compression, each with predictable dislocation movement and intersection. The intersection of dislocations can lead to glissile or sessile jogs, Cottrell-Lomer locks and other sessile dislocations. The effect on the stress-strain curve could depend on which combination of the former mechanisms is operating. Haasen and Kelly3 have studied the yield points which occur in aluminum and nickel single crystals upon reloading after prior unloading in a tension experiment. They attributed this effect to the anchoring of dislocations occurring during unloading. As Cottrell and stokes4 have shown that dislocations cutting through the "forest" could only lead to reversible changes, they attributed the anchoring to the formation of sessile dislocations during unloading. However, different kinds of sessile dislocations could be formed during unloading, and it was the purpose of this experiment to determine whether Cottrell-Lomer locks are responsible for the yield effect and for the end of easy glide. The case where a longitudinal compression is followed by tension along the same axis is commonly referred to as a Bauschinger test. This type of effect was studied by Buckley and Entwistle1 on aluminum single crystals and by Parker and washburn2 on zinc single crystals. In such a test, the tension and the compression activate the same slip plane with opposite slip directions. The use of sideways compression in the present experiments permits the activation of different types of slip systems and the study of their effect on the easy glide region and on the transition between the elastic and easy glide region. The theory of seeger5 for the flow stress in fee materials is applied to explain the latent hardening. EXPERTMENTAL PROCEDURE All the single crystals used in this investigation had an axial orientation close to <210>, called the "0.5" orientation. This is the orientation for which the tensile axis is 45 deg from both the slip plane and the slip direction. The single crystals were grown from the melt under a helium atmosphere using milled graphite boats,=at a rate of 8.6 mm per min. The silver used in the experiment was 99.98 pct pure. The single crystals had a square cross section about 0.9 by 0.9 cm and a length of 14 cm. The orientation of the specimen was determined within ±2 deg by the Laue back-reflection method. The specimens were annealed at 940&apos; ± 2°C in a helium atmosphere for 24 hr and then furnace cooled over a period of 7 hr. The specimens were electropolished in a solution of 9 pct KCN in water. The specimens were tested in a soft-type tensile machine (the load is prescribed) up to 3 pct strain. The stress was increased continuously at approximately 30 g per mm2 per min. The strain was measured over a 5 cm gage length with a mechanical extensometer employing an optical lever. The strain and stress were measured with accuracies of i 2 X 10-5 and ± 2 g per mm2, respectively. The remainder of the stress-strain curve up to 20 pct strain was obtained in a hard-type tensile machine (the strain rate is prescribed). The strain and the stress were measured in that machine with an accuracy of ±2 pct. The compression tests were performed in the hard-type machine using accurately machined steel blocks without lubrication. The blocks were used so as to apply a uniform compression over a length of 13 cm. The strains were measured on the hard-type machine and with a micrometer.

Jan 1, 1962

By R. S. Hoch, Roy A. Bobo

Maintenance of desirable plastic flow properties of weighted drilling muds may be greatly simplified by use of centrifugal classification to control the drilled solids content. The new application of a decanting type centrifuge to separate and reject the low density solids from the weighting material results in a drilling mud of greatly improved quality with lower values of yield and rigidity. Its practicality and economy has been proven in field operation. The degree of separation of light and heavy solids is not limited by the machine, but by the particle size distribution of the solids in the mud. Removal of the low density component of drilling mud that makes chemical treatment necessary permits a marked reduction in chemicals. The main uses of the centrifugal process are the treatment of muds while drilling, the reclaiming of discorded muds, cleaning up of workover muds, and the reduction in lime content of mud for completion. INTRODUCTION Drilling mud in any circulatory system is made viscous and difficult to pump by gradual accumulation of drilled solids which pass through the shale shaker and are continually reground. In a weighted mud containing a large proportion of barite by volume, the amount of drilled solids that may be tolerated is greatly reduced. Much effort has been expended to control by chemical treatment the effects of such solids. Though chemical treatment is quite effective, the time eventually comes at deeper depths after enough drilled solids have entered the system when a portion of the mud must be discarded and replaced with water and more weighting material. Once begun, this process is generally continued at frequent intervals with resultant high maintenance costs. At the termination of drilling, mud highly contaminated with light solids and spent chemicals is poorly suited for completion operations.&apos; It is likewise limited in utility for other drilling operations. This investigation was conducted for the primary purpose of determining an acceptable mechanical means of removing the lightweight solids from weighted drilling muds in order to maintain viscosity at a minimum. A decanting type of centrifuge was selected from the various possible methods of mechanical separation. The centrifugal process has been employed in this country for this purpose in central mud reclamation systems in California in earlier years. It also was used for treatment of weighted muds on the Gulf Coast.&apos; In more recent years only sporadic attempts have been made to employ it in the field on weighted muds. DISCUSSION OF PROCESS Selection of Apparatus Two factors favor mechanical procedure for the separation and removal of drilled solids or clays from the mud circulatory system. First, the greater specific gravity, 4.1 to 4.3, of the barite would promote more rapid settling than the clays whose specific gravity range is from 2.5 to 2.7. Second, the relative coarseness of the barite particles also facilitate faster settling of this phase. A decanting type of centrifuge was preferred for this process over other possible methods for these reasons: 1. Requires no costly additives or excess dilution. 2. Centrifugal force affords greatly accelerated separation as compared to gravity.

Jan 1, 1955

By Arnulf Muan, Klaus Schwerdtfeger

Equilibrium ratios C02/C0 of a gas phase coexisting with selected phase assemblages of the system Fe-Mn-0 have been determined in the temperature range 1000" to 1300°C. The oxygen pressure for the "hfnO" +hfn30, equilibrium and for the "(Fe,hTn)O" + (Fe,Mnh 0* equilibrium at high manganese contents has been determined by electromotive force measurements using stabilized zirconia as a solid electrolyte. The notstoichometry 01&apos; "hTnO" and of "(Fe, iM1z)O" solid solutions has been determined by ther-mog-/avi?netry and by wet-chemical analysis. The data obtained are used to derive activity-composition relations in "(Fe,hfn)O" and (Fe,Mn),O4 solid solutions. WUSTITE "FeO" and manganosite "MnO" form a continuous series of solid solution at high temperatures,&apos; and so do magnetite Fe304 and the high-temperature, cubic modification of Mn304 (Ref. 2) (high hausmannite, -1170). The oxides "FeO" and "MnO" are cation-deficient phases.495 The nonstoi-chiometry of "(Fe,Mn)O" solid solutions has been studied by Engell and ~ohl&apos; at two selected C02/C0 ratios at 1250°C. The two oxide end members of the spinel solid solution, FesO4 and Mn,04, however, are known to be close to stoichiometric under the experimental conditions used in the present investigation.&apos;&apos;&apos; The oxygen pressures of "(Fe,Mn)07&apos; solid solutions in equilibrium with iron have been determined by Schenck and coworkers,8 by Foster and welch," and by ~n~e1l.l&apos; The two former groups equilibrated the condensed phases in C02-CO atmospheres of lmown compositions, whereas Engell" used a galvanic cell with stabilized zirconia as a solid electrolyte. The results of these investigators are not in good agreement. Activities of FeO in manganowiistite as calculated from the results of Foster and Welch show ideal behavior, those of Engell yield a pronounced positive deviation, and those of Schenck et 01. show a moderate positive deviation from ideality. In the present work oxygen pressures for the iron + manganowiistite and manganowustite + spinel equilibria and the nonstoichiometry of manganowiistites have been measured. The data were used to calculate activities in the manganowiistite and spinel solid solutions. EXPERIMENTAL METHODS The COz/CO ratios at which manganowustite and iron are in equilibrium were determined by thermo-gravimetric and quenching methods. Experimental details are described in a previous publication.&apos;2 In the thermogravimetric technique, incipient reduction of manganowiistite pellets to metallic iron was observed as a break in the weight vs log COZ/CO curve. In the quenching technique, manganowiistite samples were partially reduced to metallic iron, or the metallic iron of manganowustite + metallic iron mixtures was partially oxidized to manganowustite, in atmospheres of constant C02/CO ratios. After quenching the composition of the oxide phase was determined by X-ray lattice parameter measurements and comparison with a standard curve obtained from oxide solid solutions of known compositions. The nonstoichiometry of "MnO" and "(Fe,Mn)07&apos; solid solutions was determined by chemical analysis of samples equilibrated in C02-CO atmospheres and quenched to room temperature, as well as thermo-gravimetrically by reducing (Fe,Mn),04 or Mn304 to manganowiistite or manganosite. The equilibrium between manganowiistite and (Fe,Mn),04 was measured thermogravimetrically by reducing (Fe,Mn),04 solid solutions having composition in the range of %„ l(NFe +NM) from 0 to 0.63. No experiments could be performed with this technique at higher manganese contents, because the equilibrium C02/C0 ratios are too large for accurate control. An additional difficulty arises at the higher manganese contents due to the strong increase in oxygen content of the manganowustite phase with increasing log Py near the manganowiistite-spinel boundary. Consequently a sharp break in the weight loss vs log C02/CO curve cannot be observed at the phase boundary. At high manganese contents of the manganowiistite, e.g., (NMn/(NF~ + NMn) > 0.9, electromotive force measurements with stabilized zirconia as a solid electrolyte were made to determine the equilibrium oxygen partial pressure. Experimental details are described in a previous paper.* Mixtures of "(Fe,Mn)O" and (Fe,Mn),04 were pressed to pellets, and the oxygen pressure of the equilibrated samples was compared to that of Ni + NiO mixtures in the cell The composition of the manganowiistite in the equilibrated two-phase mixture was determined by lattice parameter measurements and comparison with known standards. The oxygen pressure for the Ni + NiO equilibrium was taken from available data.l3~l4 No reliable results were obtained with the electromotive force technique on iron-rich oxides. The electromotive force drifted strongly with time in this composition range. An additional difficulty arises from the partial de-

Jan 1, 1968

By D. H. Thompson, A. W. Tracy

Season-cracking is a type of failure of brass that results from the simultaneous effect of stress and certain corrodants. The object of this paper is to present data that will aid in a more complete understanding of the mechanism of season-cracking and related phenomena. Results presented show that certain high copper alloys are susceptible to season-cracking or stress-corrosion cracking, and possible explanations are discussed. Starting at least as far back as 1906, many papers have been devoted to this subject but the symposium1 held in Philadelphia in 1944 is the richest source of information. In order to study season-cracking, several of the many variables were held constant so as to learn the effects of others. Season-cracking is generally understood to refer to the corrosion cracking of brass having internal stresses;²,³ it is a special case of the general stress-corrosion cracking. Inasmuch as applied stresses are more readily produced and controlled, they were used exclusively in this research and the resulting phenomenon must he called stress-corrosion cracking.²,³ Only constant tensile stresses were used. The agents believed to be most frequently responsible for season-cracking are ammonia. amines and compounds containing then]. Both moisture and oxygen also appear to he necessary. Therefore, an atmosphere containing ammonia, water-vapor and air was selected for these tests. Briefly, the work consisted of exposing sheet metal specimens, having a reduced section ¼ by 0.050 in., of copper-base alloys to the effect of static tensile stresses between 5,000 and 20,000 psi and simultaneous contact with a. continuously renewed atmosphere containing 80 pct air, 16 pct ammonia and 4 pct water vapor at 35°C. The gas mixture and the speci- mens were maintained above the dew-point. The time-to-failure in minutes was the primary measure of results. In order to limit the experiment to finite time, it was considered that a specimen which had neither failed nor undergone microscopically detectable cracking in 40,000 min. (4 weeks) while under a stress of 10,000 psi or more could be considered immune to cracking. This is merely a convenient limit and is not to be considered proof of immunity. Supplementary tests in the absence of stress using weight loss or microscopical appearance as measures of attack were made. Apparatus The apparatus used in this research is shown in Fig 1. To facilitate the description it may conveniently be divided into six parts: stress-producing units, test chamber, gas train, electrical controls, timers and gas analysis device. A stress-producing unit is shown in an exploded view at the left in Fig 2. At the right is an assembled unit with a specimen in place in the lower portion; it is this part that remains in the ammonia atmosphere during a test. The upper part contains a spring, a central threaded rod, a large nut and necessary washers, pins, and so forth. Stress is produced in the specimen by screwing down the top nut against the spring, thus putting a tensile load on the central rod and so on the specimen. The wrench that turns the nut by extending through the upper cap, is seen at the upper right of the figure. The magnitude of the load is gauged by measuring from the pin that extends through the side of the tube, to a fixed point on the large flange. Measurement is made with a vernier beam caliper, shown at the right of the figure. The necessary spring compression to give a desired stress is calculated from the calibration curve of the spring and the dimensions of the specimen. The test chamber, center Fig 1, consists of a thermally insulated steel box 32 in. long by 10 in. high by 7 in. wide. A horizontal baffle reaching nearly to each end divides the chamber equally. Below this baffle are inlets for air and ammonia, a heating coil and a fan. Thus the gases are warmed and mixed in the lower level and flow past the specimens in the upper level. A thermo-regulator and thermometer project into the upper space. The top is pierced by 12 ports flanked by 3/8 in. threaded studs. A test starts when a port is opened and a unit containing a stressed specimen is thrust through it and bolted down against a neoprene gasket. The test chamber is held at 35°C. The gas train, right rear Fig 1, carries ammonia and air continuously to the test chamber. Tank ammonia passes through two reducing valves, a needle valve, a flow meter and into the test chamber. The air from either the plant compressor or a small laboratory compressor passes through wool towers and flow controls to the flow-meter. It then bubbles through water at 34°C and through a heated line to the test chamber. Electrical controls, left rear, Fig 1, provide rectifiers and mercury relays for the test-chamber and humidifier-heating-control circuits and outlets for

Jan 1, 1950

By F. H. Froes, D. H. Warrington

Electron microscope evidence which indicates that TaC may precipitate at random sites in the matrix is presented. Initially the particles are almost spherical and coherent with the matrix. However, as they grow in conditions in which there are insufficient vacancies to relieve lattice strain, the particles rapidly lose coherency in two directions and continue to grow as plates with approximately the full lattice mismatch strain present perpendicular to the plane of the plate. The necessary relief of strain comes from dislocations loops which do not become visible until the later stages of aging. The rapid decrease of apparent strain to low values of appoximately 1 pct at small particle sizes arises not from a complete incoherency but from applying a model wrong for the particle shape and strain distribution. PREVIOUS work has shown that MC-type carbides may precipitate intragranularly in austenitic stainless steel on dislocations,1&apos;2 in association with stacking faults,3&apos;4 and randomly through the matrix,5-7 In investigations of the matrix precipitate by thin-foil electron microscopy, considerable lattice strain has been found to occur around the precipitating phase.7&apos;8 Attempts have been made to evaluate the amount of lattice strain by using the methods developed by Ashby and brown.9,10 Values of the linear strain, much less than the 17 pct theoretical mismatch (for TaC), have been reported; it has been suggested that this is due to either a loss of coherency1&apos; or vacancy absorption which occurs during either the initial nucleation or growth of the precipitate." This report is an extension of earlier work7 that dealt with the precipitation of TaC from an 18Cr/12Ni/ 2Ta/O.lC alloy after it had been quenched from 1300°C and aged between 600" and 840°C. In particular, the shape of the precipitate particles and the amount of strain in the matrix, due to the precipitate, have been studied. The work described here is part of a wider investigation of factors that affect carbide precipitation in austenitic stainless steel," details of which are to appear elsewhere. RESULTS The present investigation can be conveniently split into two aspects of the strain-fields surrounding the matrix particles: 1) information derived from the strain-field which indicates the shape and habit plane of the precipitate particles and 2) the magnitude and sign of the strain-field. The Shape and Habit Plane of the TaC Precipitate. In the early stages of aging twin lobes (normally black F. H. FROES, formerly at the University of Sheffield, Sheffield, England, is Staff Scientist, Colt Industries, Crucible Materials Research Center, Pittsburgh, Pa. D. H. WARRINGTON is Lecturer, Department of Metallurgy, University of Sheffield. Manuscript submitted November 1, 1968. IMD on white background, i.e., for the deviation parameter, S > 0) that indicate the strained region of the matrix define the position of the particles by bright field transmission electron microscopy. The actual particles were not detected until they were approximately 120Å diam; below this size they were too small to be imaged in the electron microscope. This meant that particle growth that had occurred before this stage had to be inferred from the matrix strain-field contrast. In all cases when diffraction effects were observed from the precipitate particles, a cube-cube orientation relationship (i.e., (llO)ppt Il<llO>matrix and {1ll }ppt {III} matrix) existed between the precipitate and the matrix. From the matrix precipitate particles lying along edge-on {111} planes (e.g., at A, Fig. I), the precipitates are seen to be plate-like with their diameter being roughly 18 times their thickness after 5000 hr at 650°C. However, the exact shape of the particles cannot be determined because of the masking effect of the strain-field contrast. If a dark-field micrograph, using a precipitate reflection, is studied, Fig. 2, a number of the projected images of the TaC particles [on the (110) foil surface] apear to have straight edges parallel to projected f111) planes. Thus, it appears that in the later stages of aging the TaC particles are plate-like with some tendency for the edges of the plate to be bounded by the matrix close-packed {ill} planes (though the general shape of the particles in the plane of the plate is circular and thus the "diameter" of the particles has a real physical significance). It should be noted that the bands of fine discrete particles observed in Figs. 1 and 2 are not the matrix precipitate discussed in this paper but are precipitates associated with extrinsic stacking faults3j4 occurring on (111) matrix planes. **£** ****** \ *x 23 Fig. 1—18/12/2~a/0.1~ alloy. Solution treated at 1300°C for 1 hr, water quenched, and aged 5000 hr at 650°C. The (112) directions shown are the traces of the e&e-on (111) planes. Foil normal [110]; operating reflection (331); bright field micrograph.

Jan 1, 1970

Jan 1, 1905

By A. Ghosh, T. B. King

The kinetics of the discharge reaction: 20&apos;- (in silicate melt) = O,(g) + 4e- at a platinum anode in lithium silicate melts have been studied al 1350°C by galvanostatic methods. Plots of the sleady-state overpotential, q, as a function of the logarithm of the current density, i, showed injlections and were linear only at high current densities. The value of the overpotential was influenced by bubbling gas through the electrolyte. The ocer potential was also studied as a function of time. The rise and decay of overpotential were very slow processes. At low current densities transport is the likely rate-controlling process but at high current densities passivation of the electrode, Presumably by an oxide film on the surface, seems to be a contributory functor. IT is well-established that molten silicates behave as electrolytes&apos;5 and, except in a few cases,6 conduction is entirely ionic. Moreover, it is supposed that a possible, and perhaps predominant, mechanism for phase boundary reactions between metals and slags is similar to that in corrosion whereby anodic and cathodic processes occur at unrelated sites, the metal serving to conduct electrons.1&apos;8 Thus electrochemical studies of some slag-metal reactions would seem to be a useful way to diagnose the rate-controlling steps in the overall reaction. The electrochemical method is, in principle, a better diagnostic tool than the direct chemical method for the following reasons: 1) The partial electrochemical reactions, which are simpler than the overall reaction, may be studied individually. 2) The rate of reaction can be controlled at will and independently of the concentrations of reactants. 3) Fast reactions can be studied by relaxation methods.&apos; Esin and his coworkers5&apos;10"12 have pioneered such studies in silicates and have deviloped some ingenious techniques. Not all of their findings, however. can be accepted without a good deal of further work. In this investigation, the kinetics of the oxygen discharge reaction: 202- (in silicate melt) = Oz(g) + 4e- [I] at a platinum electrode were studied by both steady-state and transient galvanostatic techniques. Interest in this reaction was first developed as a result of the findings of Fulton and chipman13 that the reduction of silica, in a silicate slag, by carbon, dissolved in liquid iron, is a very slow reaction. Subsequent work, for example, by Rawling and ~lliott,&apos;~ has demonstrated that the reaction under these conditions must be slow, because the rate is limited by diffusion of oxygen in the iron to the metal-crucible phase boundary at which a CO bubble may be nucleated. Further work by Tarassof,&apos;~ in which the reduction of silica by aluminum dissolved in copper was studied, has shown that under these conditions, where carbon monoxide evolution is not involved, control of the reaction rate resides in diffusion of silica in the slag phase. However, there is no practical way of inducing sufficient convection in the system to make it clear that the phase boundary reaction is indeed fast. The overall reaction of silica reduction involves the discharge of silicon ions at cathodic sites and oxygen ions at anodic sites. In the examples cited, the discharged ions are dissolved in a liquid metal. In the present study of oxygen ion discharge, gaseous oxygen may be evolved at high current densities or oxygen may simply dissolve, possibly as oxygen molecules, in the silicate at very low current densities. The discharge of an oxygen ion at an anode must, in silicates less basic than the orthosilicate composition, be preceded by a reaction in the vicinity of the electrode, such as: which makes oxygen ions available. Platinum was chosen as the working electrode since it is comparatively inert to oxygen and is, therefore, expected to come rapidly into equilibrium with the electrolyte and with gaseous oxygen. Minenko, Petrov, and Ivanova16 have measured the electromotive force at a platinum electrode in molten silicates as a function of the partial pressure of oxygen in the atmosphere, the concentration of oxide ions in the melt, and the temperature. They found platinum to behave as a reversible oxygen electrode. At two different oxygen pressures, Po2 (I) and Pq (11). the electromotive force is given by: where F is the Faraday constant, equal to 23,060 cal per v equivalent, indicating that the electrode reaction is as written in Eq. [I.]. Platinum has been similarly used in molten silicates by other inve~ti~ators. "&apos;~~ In this investigation platinum was used only as an anode, since a current deposits other elements on its surface and changes its characteristics.

Jan 1, 1970

By L. I. Hewes, Joseph W. Roe

A graphic solution of Kutter&apos;s formula for the flow of water has been worked out by Dr. L. I. Hewes in connection with his course in Graphic Computations, given in the Sheffield Scientific School, Yale University, which may be of interest to those who deal with canals, flumes and streams. 1.811 0.002811 , 41.66+ -n+-S- I Kutter&apos;s formula, V= - n 0 .00281 78- 1+(41.66 + 0.00281)7B781 is probably the most accurate of those proposed determining the flow of water. But it is extremely cumbersome, and if many calculations are to be made their solution becomes drudgery. The purpose of this chart, Fig. 1, is to furnish a rapid solution, sufficiently accurate to be well within the limits of the observed data. The chart consists essentially of three parallel scales, one for the mean velocity, V, one for the hydraulic radius, R, and one for the slope; a diagonal line, not graduated ; and a set of curves for the various values of n, the factor which involves the na-

Jan 1, 1910

By R. M. Waterstrat

The phases occurring in the V-Mn system were studied by means of X-yay diffraction and metallo-paphic techniques, using are-melted alloy specimens annealed in the temperature range 800° to 1150°C and quenched. The bcc solid solution extends at 1250°C all the way from vanadium to 6-manganese. Below 1050°C the a-phase is formed, and the terminal a-manganese phase is stabilized up to about 900°C by vanadium in solid solution. IN the only previous general survey of the V-Mn system Cornelius, Bungardt and Schiedtl reported the existence of three intermediate phases corresponding to the approximate compositions VMn,, VMn, and V5Mn. The phase VMn8 has recently been identified as a o phase2 but the alloy VMn was found to have a bcc structure2 corresponding apparently to the vanadium solid solution rather than to the large cubic unit cell reported by Cornelius et al. 1 Subsequent work by Rostoker and Yamamoto3 has shown that the vanadium-base bcc solid solution extends to at least 15 pct Mn at 900°C. An alloy corresponding to the composition VMn, was examined by Elliott,4 who reported that the as-cast sample as well as samples annealed at 1200o and 1300°C had bcc structures, but that annealing at 1000°, 800") and 600°C produced two phases. One of these phases was apparently the bcc solid solution and the other resembled the o phase structure. Hellawell and Hume-Rothery5 established the phase relationships in manganese-rich alloys above 1000°C, and showed that the o phase in this system is replaced by the 6 Mn (bcc) solid solution at temperatures above 1050°C. These results suggest that a continuous bcc solid solution may exist above 1050°C between vanadium and 6 Mn. The present investigation was undertaken in order to develop more complete information in regard to this system. EXPERIMENTAL METHODS The alloys used in the present work were prepared by arc-melting electrolytic manganese having a minimum purity of 99.9 pct and vanadium lumps with a purity of 99.7 pct. The major impurities present in these metals were carbon, nitrogen, and oxygen and this would account for the small percentage of nonmetallic inclusions observed metal-lographically. The arc-melting was at first performed under a helium atmosphere and it was necessary to keep the melting times as short as possible in order to minimize the loss of manganese by vaporization. It was later found that the evaporation of manganese was considerably reduced when the melting was done under argon atmosphere. The final composition of each alloy was calculated by assuming that the total weight loss during melting was due to evaporation of manganese. Compositions which were calculated in this manner agreed reasonably well with the results of chemical analysis, as shown in Table I. Spectrographic analysis revealed the presence of contamination by tungsten, but in no case was the percentage of tungsten greater then 0.4 at. pct. The specimens were in each case broken in half and the fractured section was examined visually and microscopically for evidence of inhomogeneity. Each specimen was homogenized at temperatures near l100°C, as shown in Table I. After this treatment most specimens consisted of large columnar grains of the bcc vanadium solid solution. The etchant used in most of the metallographic work consisted of 20 pct nitric acid, 20 pct hydro-flouric acid, and 60 pct glycerine. It was found that this etchant would clearly delineate the phases present in these alloys although it does not produce any striking contrast between the phases. For certain manganese-rich alloys, a 1 pct aqueous solution of nitric acid was used. This etchant gave a brown color to the a-manganese phase, whereas the o phase was virtually unattacked and appeared very light as shown in Fig. 1. The etchants used by Cornelius et a1.l were found to produce spurious effects in some of these alloys. In particular, the vanadium-rich alloys etched in hot sulfuric acid often appeared to consist of two phases when both X-ray diffraction and etching with the glycerine-acid mixture indicated the presence of single phase bcc solid solution. A few percent of what appears to be an oxide or nitride phase was found at the grain boundaries and in the interior of the grains, especially in the vanadium-rich alloys. All alloys were annealed in sealed silica tubes containing 1 atm of pure argon and these tubes were then quenched in cold water. Although some manganese loss occurred during annealing, the loss seemed to be confined to the surface of the speci-

Jan 1, 1962

By David D. Rabb

Leaching or solution mining, a relatively simple and economical process for beneficiating metallic ores, is likely to find increasing application in the treatment of low-grade ores that are impractical to mine by any other means. This process may be carried out in two different ways: 1) dump leaching, where the ore is moved from its original location to be leached at another site; and 2) In-situ leaching, where the ore is leached in place by introducing the leach solution at the top, letting it flow down through the ore under gravity, and then recovering it plus the dissolved metals it contains. Whichever leaching method is used, it is almost always necessary to break up the ore before leaching. In this paper a study is reported which indicates that rock broken by an explosion-in particular, an underground nuclear explosion-is significantly more amenable to leaching then is rock broken by other methods. These results suggest that the leaching speed and efficiency could be increased by nuclear fracturing of the ore. Not only would the leach time be shortened, but the resulting increase in strength or richness of the solutions would decrease plant installation expense as well as reduce pumping and processing costs. A considerable fund of experience has been accumulated in the course of several hundred experimental underground nuclear explosions, so that the gross results of any given nuclear explosion can now be predicted with a fair degree of confidence.&apos; From this knowledge it seems clear that, under the proper conditions, large ore bodies can be fractured much more economically-macroscopically speaking-by nuclear explosions than by other methods. The present study concentrates on smaller scale effects that is, the cracks in the chunks of rock broken by the explosion-and shows that here too, in the microscopic domain, there are important advantages to nuclear fracturing. The intense shock produced by the very fast acting, high-brisance nuclear explosive fractures the rock in a way that should significantly improve its leachability. Experimental Procedure This study compared rocks broken by nuclear explosives with rocks produced by conventional mining, quarrying, or core drilling. The test samples, granite chunks 6 to 8 in. on a side, plus core sections, came from the area of the Hardhat*2 nuclear explosion and were taken both before and after the explosion. For comparison, several samples of quarried granite were obtained from a local gravestone monument company. The general procedure was to soak the test samples in leaching solution and then determine the extent of penetration. A standard commercial copper leaching solution was used (10 gpl Cu, 10 gpl H2SO4, 5 gpl ferric Fe, 15 gpl total Fe, pH about 1.5), to which a water-soluble penetrant dye, Zyglo 1-c, had been added. Details of the procedure were as follows: 1) Sample leached in solution containing Zyglo penetrant dye. 2) Washed with water. 3) Air-dried. 4) Cut with granite wire saw. 5) One face polished with granite monument polish. 6) Sent directly to be photographed, or heated at 110°C for 2 hr and then sent to be photographed. 7) Photographed under ultraviolet light to show crack patterns. Results After 10 days of leaching at 70-75°F, the samples were removed from the solution, washed, dried, and cut in half with a granite wire saw to study the penetration of the leach solution. Since the Zyglo dye in the leach is visible under ultraviolet light, the degree of penetration of the leach (and hence the cracks in the samples) can be studied on photographs of the crosscut samples made under ultraviolet light. The photos in [Fig. 1] show how the leach solution penetrated various representative samples. Of the 71 rock samples examined, fractures were most frequent and prominent in samples from the rubble produced by the nuclear explosion [(Fig. 1D)]. Fracturing was less apparent in shaft-mined rock [(Fig. 1B)], still less evident in drift-mined rock [(Fig. 1C)], and practically nonexistent in cored or quarried specimens [(Fig. 1A)]. The samples in [Fig. lA-C] were from the same general area as the nuclear explosion, but they were obtained before the explosion. Results of the crack studies are summarized in [Table 1]. The Zyglo-treated leach solution penetrated the test samples at the rate of about 1/2 mm during the first hour, 1 mm by the end of 4 hr, 2 to 3 mm in 12 hr, and 4 to 6 mm in 10 days, showing a progressively slower rate with time.

Jan 1, 1972