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By S. J. Swainson

"It appears to me that the chief progress in milling operations in America have been made in the steady improvement of existing practice through both higher extractions and increased efficiencies of operations rather than by the development of new processes. The recent rapid development of sink-float, or heavy-medium separation, however, is an exception, and is becoming increasingly used to permit the economic treatment of certain low-grade ores that otherwise could not profitably be mined. The use of spirals and of small cyclones, both of which employ the principle of centrifugal force, show promise of increasing adoption through their application and efficiency in special cases." So did our distinguished colleague, O. A. E. Jackson, consulting metallurgist for the Union Corporation and president of the Chemical, Metallurgical and Mining Society of South Africa, summarize his impressions of a recent tour which he made of various metallurgical and milling plants in North America. I believe that all mineral dressers will agree with Dr. Jackson's concise conclusions.

Jan 1, 1950

By L. F. Mondolfo

An investigation of the relationship between properties of the elements and type of binary diagram formed was conducted. It was found that, for each type of equilibrium diagram, the factors for the size, valence, electronegativity, period, melting point, entropies of fusion, and sublimation calculated for each pair of elements cover a range of values. However, these factors show sufficient relationship to the equilibrium diagram so that the correlation of several of them can be used to predict the type of diagram formed, or at least limit the choice to only a few types. ThE goal of the metallurgist concerned with alloy development has always been to find a method that predicts the properties that can be obtained when a certain metal is added to another one. In most cases a qualitative predictiton of properties can be made if the equilibrium diagram is known. However, this means that for new metals the alloy development has to start with the experimental determination of the equilibrium diagrams. Because this determination is at least as complicated and time-consuming as the determination of the properties themselves, most alloy development has taken place by trial and error, and the study of the equilibrium diagrams has followed rather than preceded the creation of new alloys. Alloy structures and properties depend on the interaction between electrons and a complete knowledge of these interactions would permit prediction of structure and properties of alloys. Unfortunately direct measurement of these interactions is extremely difficult and somewhat doubtful and only properties that depend on them can be measured easily and with certainty. Study of the relationship between properties of the elements and equilibrium diagrams is not new. Besides the well known Hume-Rothery rule of the necessity of an atomic diameter fit within 15 pct for extensive miscibility in the solid, and the wide knowledge of the effect of such factors as size, electronegativity, electron-atom ratio on solid state features,"' work relating to liquid state and liquid-solid reactions can be found in the literature. Of particular interest is the work by Axon,3 who investigated the effect of size and melting point on a selected number of eutectic and monotectic dia-

Jan 1, 1962

By Leon W. Dupuy

Many articles have been written describing peculiar and particular types of drilling. Little correlation has been made between the character of ground to be drilled and sampled and the type of drilling most desirable for procuring satisfactory samples. In development work, the engineer and metallurgist often desire the recovery of a sample in as physically natural a condition as possible, particularly when the sample must provide material for process tests as well as chemical and physical analyses. This paper describes the results of experimentation in drilling unconsolidated materials carrying titanium minerals in the Magnet Cove area, Ark. The drilling was most difficult in that the ground varied much in consistency, and it was vitally necessary to recover a physically natural sample. Ordinary churn drilling recovered a sample that could be analyzed chemically, but the sample was not in its natural state. The problem was successfully solved by utilizing and further developing methods used in the oil and clay industries.

Jan 1, 1949

By John H. Hollomon

The interpretation of notched-bar impact results has been a matter of controversy since the introduction of more or less standard tests by Fremont,' Charpy2 and others at the turn of the century. Many investigators3-l1 have contributed to the understanding of the significance of such tests. Several symposiums12,13 have been held with the express purpose of discussing the significance and interpretation of the impact tests. It is not the purpose of this paper to review all these contributions to the development of the knowledge on this subject, but rather to present an interpretation of notched-bar impact tests that appears to be in agreement with the available published data. Fundamentally, the interpretation discussed in this paper of the brittle failure of some steels in notched-bar impact test is similar to the qualitative analysis presented by Ludwik3 in the I92o's. Essentially, Ludwik stated that the function of the notch was to increase the tensile stress necessary for yielding, and that brittle failure occurred when the stress necessary for yielding exceeded the normal stress required for fracture (with no plastic deformation). Ludwik, however, had no means of measuring this normal stress necessary for failure of a plastically* undeformed metal, therefore he could not extend his interpretation beyond the qualitative stage. Kuntze14 and recently Mc-Adam15 attempted to determine the effect of deformation on the stress necessary for fracture by testing, in tension, specimens notched to various depths and angles. Because of the uncertainties in Kuntze's (and McAdam's) analysis of the stresses (which have been pointed out by Sachs16) and the inherent nonuniformity in the stress distribution in notched bars, the results of such investigations are difficult to interpret. A more direct method of measuring the effect of deformation on the fracture stress was suggested in previous papers"-18 and has been utilized in the present investigation. The present paper concerns itself primarily with the behavior of notched impact specimens. The effects of strain rate, temperature, and stress distribution, which are discussed with reference to the impact specimen, apply just as well to the behavior of metal at the bases of notches in any engineering structure. All that is necessary is to determine the stress distribution in the structure at the base of the notches.

Jan 1, 1944

By John H. Hollomon

The interpretation of notched-bar impact results has been a matter of controversy since the introduction of more or less standard tests by Fremont,' Charpy2 and others at the turn of the century. Many investigators3-l1 have contributed to the understanding of the significance of such tests. Several symposiums12,13 have been held with the express purpose of discussing the significance and interpretation of the impact tests. It is not the purpose of this paper to review all these contributions to the development of the knowledge on this subject, but rather to present an interpretation of notched-bar impact tests that appears to be in agreement with the available published data. Fundamentally, the interpretation discussed in this paper of the brittle failure of some steels in notched-bar impact test is similar to the qualitative analysis presented by Ludwik3 in the I92o's. Essentially, Ludwik stated that the function of the notch was to increase the tensile stress necessary for yielding, and that brittle failure occurred when the stress necessary for yielding exceeded the normal stress required for fracture (with no plastic deformation). Ludwik, however, had no means of measuring this normal stress necessary for failure of a plastically* undeformed metal, therefore he could not extend his interpretation beyond the qualitative stage. Kuntze14 and recently Mc-Adam15 attempted to determine the effect of deformation on the stress necessary for fracture by testing, in tension, specimens notched to various depths and angles. Because of the uncertainties in Kuntze's (and McAdam's) analysis of the stresses (which have been pointed out by Sachs16) and the inherent nonuniformity in the stress distribution in notched bars, the results of such investigations are difficult to interpret. A more direct method of measuring the effect of deformation on the fracture stress was suggested in previous papers"-18 and has been utilized in the present investigation. The present paper concerns itself primarily with the behavior of notched impact specimens. The effects of strain rate, temperature, and stress distribution, which are discussed with reference to the impact specimen, apply just as well to the behavior of metal at the bases of notches in any engineering structure. All that is necessary is to determine the stress distribution in the structure at the base of the notches.

Jan 1, 1944

By W. C. Hagel, J. H. Westbrook

Usittg a sectioning technique with Agl10 as the tracer, the diffusion of silver in silver-excess (45.8 at. pct Mg), near-stoichiometric (49.8 at. pct Mg), and magnesium-excess (52.0 at. pct Mg) cylinders of CsCl-type AgMg was determined from 500" to 700°C. Diffusion coefficients conform to the expression D = Do exp (-q/RT) where the respective Do values are 1.53, 0.280, and 0.134 sq cm sec-I and the Q values are 41.3, 40.6, and 38.0 kcal g-atom-'. Lnttice-parameter and density measurements were performed on a more numerous assortment and wider range of compositions. Substitutional defects were found on both sides of stoichiometry. Activation energies for other rate processes in these alloys show related trends with changing composition, although silver may not be the rate-detemining species. KNOWLEDGE of diffusion coefficients is necessary for a quantitative understanding of the many rate processes (e.g., grain growth, precipitation, sintering, oxidation, or mechanical deformation) occurring in solids. Although these data are available for most metals and common alloys, they are quite limited for intermetallic compounds—a group of materials whose unique physical and mechanical properties are presently attracting great interest. From a fundamental viewpoint, diffusion in intermetallic compounds also offers several engaging aspects owing to: their ordering, the possibility of introducing large, stable concentrations of lattice defects, and the variety of bonding types and crystal structures which can be found. In the case of CsC1-type compounds, some previous work has been directed at examining the role of vacancy defects by changing their concentration compositionally. The diffusion of Co60 was measured in 0 NiAl1- and in P COA., Except for the results of Smoluchowski and Burgess, isothermal diffusion coefficients were found to pass through a minimum at the stoichiometric composi- they decreased sharply on what was reported by Bradley and co-wrkers' to be the vacancy-rich (aluminum excess) side of stoichiometry. This investigation of the diffusion of Agl110 in AgMg was undertaken both as an adjunct to a concurrent study of its deformation behavior and for the purpose of obtaining information on the influence of lattice defects and temperature on diffusion in another CsC1-type intermetallic compound. Bcc AgMg remains ordered up to and melts congruently at 820°C. Solubility limits at 300°C are about 41 at. pct Mg and 53 at. pct Mg. It is one of the Hume-Rothery electron compounds with a 3/2 electron-atom ratio. Previous investigations of its properties include hardress,' tenile,'-' electrical reistivity, and thermodyna-mic1',14 studies. Indications of a high bonding strength may be found in the large heat of mixing1' and in the 6-pct vol contraction on compound formaticp, as calculated using atomic radii of l.40 and l.55a for Ag and Mg. EXPERIMENTAL PROCEDURE Alloys were prepared by the induction melting of selected fine silver (99.95) and low-iron magnesium (99.95) in magnesia crucibles under 1 atm of A. Supplied by the Handy and Harmon and Dow Chemical Cos., respectivelv. Melts were poured under argon into graphite molds providing 1 1/8-in.-diarn. by 4-in.-long ingots. These were homogenized in evacuated and argon-filled fused-silica capsules by heating for 16 hr at 750'. Three 1 in.-diam. by 3/4-in.-long cylinders were machined from the mid-portion of each ingot for diffusion measurements. Three alloys, analyzing 45.8, 49.8, and 52.0 at. pct Mg were taken as representing the extremes of interest, with 49.8 at. pct Mg being very close to the stoichiometric composition of 50.0 at. pct Mg.

Jan 1, 1962

By G. D. Cody, D. S. Beers, B. Abeles

The thermal diffusivity (thermal conductivity divided by specific heat) of Armco iron has been measured over the temperature range 30º to 1025ºC. The results are in good agreement with the thermal diffusivity computed from published values of thermal conductivity and specific heat, except near the Curie point and at the a to y phase transition, where the measured diffusivity undergoes rabid variations. The differences observed are ascribed to a rapid variation in the electronic thermal conductivity near the Curie point, and a decrease in the lattice thermal conductivity, at the a to ? phase transition. A major difficulty in measuring the thermal conductivity of materials at high temperatures is the determination and elimination of radiation losses. It has been shown, however, that in measuring thermal diffusivity D (thermal conductivity/specific heat) radiation losses can be taken into account exactly.' In order to test the performance of a newly designed apparatus for measuring thermal diffusivity of solids,' we measured Armco iron to an accuracy of 2 pct in the temperature range 30" to 1025°C. This material was selected since both the thermal conductivity,3'4 k, and specific heat,5 C, are known accurately in this temperature range and thus the measured values of D could be compared with D computed from the pub-

Jan 1, 1962

By Waldemar Lindgren

No one would maintain that all ore deposits or all deposits of useful minerals have been formed by the same processes. Generally they have originated by special processes of concentration but these may be of many different kinds. Some deposits have their origin in chemical or biochemical processes of concentration in rivers, lakes or seas, others developed on land by means of chemical reactions of surface waters on various forms of rocks. Certain insoluble substances remained behind; others were dissolved and precipitated in favorable places. This action proceeded in the realm of the oxidizing surface waters or in the deeper zones to which the waters from the surface could find their way. Examples of the latter kind may be found in the extensive copper and vanadium deposits of some sedimentary beds or in the lead and zinc deposits of certain broad limestone strata. In these instances the evidence for any other mode of origin would seem to be very weak indeed.' Nor does it seem possible to deny that circulating waters may form deposits of the more common metals along fissures after having dissolved many constituents from paths traversed. Another very large class has been formed by magnetic processes of concentration. The last 40 years have been a period of intense activity in the investigation and description of a vast number of deposits; all modern methods have been employed and the result is an accumulation of data, difficult or impossible to master. It has been a period similar to that in petrography. The generalizations, the able deductions, have lagged behind. Evidently several geologists have become weary of this "infinite detail" and a mistrust of the microscope seems to have arisen. Although this feeling of being swamped in microscopic detail is a painful experience, nevertheless only through the detail in combination with the large features, and only by utilizing all the related sciences shall we

Jan 1, 1927

By Roy A. Lindgren

SINCE the year 1643, when the first blast furnace in America for treating iron ore was built at Saugus, Mass., out of mica schist quarried in the neighboring district, the procurement of a suitable refractory for furnace lining has been a problem of concern to the operators of furnaces. The stacks built of mica schist continued to smelt iron ore until about 1836, when, according to F. H. Norton, the first firebrick were produced', at Queens Run, Pa. Other writers speak of brick having been molded and burned in Massachusetts about the year 1834. In 1841, Andrew Russell began to produce medium refractory plastic clay brick near East Liverpool, Ohio, that were used for lining blast furnaces'. The well-known Kentucky clay-producing district was not opened up until the year 1871, but since then it has produced a large percentage of the linings for iron blast furnaces. While some strides have been made by the refractories industry during the 100 years that have passed since the first firebrick were produced, it has been only during the last two decades that any real progress has been made towards bettering the product, even though the method of production had improved. Perhaps the fault lies with the user of the brick rather than with the producer, for not sooner demanding a supe¬rior product. During the past 15 years the tonnage produced per lining has increased from 500,000 gross tons to 1,000,000 gross tons, and now some furnaces are producing 1,600,000 gross tons and better on a single lining. It is true that enlarged capacity of furnaces and improved practice have accounted for some of this increase in tonnage, nevertheless better quality in firebrick must be given credit for its share. However, we are not yet ready to say that we have reached a maximum life of furnace lining. We believe that a better product can be produced and that the refractories industries of America will, through their extensive research depart-

Jan 1, 1937

By Harry L. Washburn, Robert L. Llewellyn, W. J. Halvorsen

Many of the problems that occur in the preparation plant originate from practices in the mine. Impurities in raw coal can be in the seam itself or from extraneous material taken in mining from the roof or bottom. In the case of underground mines, the choice of mining equipment will affect the size consist and the amount of extraneous material included with the coal. Also, governmental regulations concerning the degree of rock dusting, gobbing underground, and cleanup have increased the dirt in raw coal. Sulfur dioxide emission standards, on the other hand, are pressuring the coal industry to clean coal more thoroughly. Coal supplied for coking purposes is nearly all upgraded by washing, while for the largest market, electric power generation, a high proportion is shipped as a raw product with processing, in whole or in part, only necessary when excess impurities are mined with the coal. This chapter will deal primarily with plants that process or wash coal to some extent (Fig. 1) and only incidentally with mines shipping raw run-of-mine coal crushed to a top size of, usually, 51 to 102 mm (2 to 4 in.), with little, if any, other treatment. JUSTIFICATION FOR COAL PREPARATION During the past decade, major changes have occurred affecting the market, profit, and long-range planning of the coal industry. Mining companies have become "partners" with consumers at many new and some old mines, both for steam and metallurgical coals. Coal properties have become "assigned" tonnages at mutually agreed upon conditions and prices. Lower unit-train tariffs have been instrumental in helping coal markets to compete against oil and nuclear energy. Coal prices for power plants are still on a Btu (British thermal unit)

Jan 1, 1981

By G. F. Comstock

In the literature of metallography there is a large amount of material describing the various non-metallic inclusions found in iron and steel, and the appearance of sulfides, silicates, oxides, or alumina in steel under the microscope is fairly well known. The inclusions found in non-ferrous metals are, however, not so well known, at least judging from published writings, and the author has been interested in examining small castings of copper, brass, or bronze with certain inclusions purposely mixed with the metal, to see what was the characteristic appearance of each kind of inclusion, and if they could be readily distinguished from one another. The method employed in most cases consisted in overheating and oxidizing a small charge of copper, then cooling it somewhat, and adding a suitable amount of the element whose oxide it was desired to observe. This element was stirred in well and given time to react with the oxygen in the copper, then the melt was poured in a sand mold in the form of a cylinder about 21/2 in. (63 mm.) in each dimension, with a sprue about 11/2 in. (38 mm.) in diameter and 3 in. (76 mm.) high on top of the cylinder, the sprue forming the only riser. Samples for examination were cut sometimes from the center of the casting, and sometimes from the sprue or riser. A few of these samples were cast in chill molds. The appearance of sulfides was studied in an alloy containing 10 per cent, each of tin and lead, with which a flux of plaster of Paris was used. The appearance of foundry sand was studied in several alloys, one of them having sand stirred into the metal intentionally, and others having cut into the molds badly when poured, so that the castings were spoiled by included sand. As all this work was done on alloys having copper as the chief ingredient, the natural starting point was copper oxide, the appearance of which in a micro-section is well known. Cuprous oxide is soluble in molten copper, but separates out in freezing and forms a eutectic containing 3.5 per cent. Cu20, or 0.39 per cent. oxygen. If there is less

Jan 1, 1919

By V. H. Wilhelm

In contrast with the previous year's activity, the California oil industry for 1938 showed a decrease in drilling, market demand, and discovery of new oil reserves, although there was an increase in oil production. Although additions to reserves from new fields and extensions were less than withdrawals during the year, reappraisals of discoveries in 1937 added to new discoreries during 1938 amounted to over 300,000,000 bbl. The following comparative statement shows the important changes in various phases of the industry: Throughout the year the storage situation became progressively more acute, owing principally to less Pacific foreign demand, and increased potential from drilling the newly discovered fields and pools (Fig. 1). California storage increased approximately 32,000,000 bbl. during 1938, most of which (approximately 18,000,000 bbl.) was heavy crude and residuum. The market demand for the year was around 600,000 bbl. per day. Because of the trend toward Diesel power for heavy transportation, the non-gasoline-bearing crudes arc fast becoming a drug on the market. New discoveries were instrumental in increasing the potential production of the state from 1,076,000 bbl. per day in January to an all-time high of 1,420,000 bbl. per day at the close of the year; although the indicated reserves of these new discoveries were not equal to the yearly withdrawal of 249,000,000 bbl. As of the end of 1938, the state was voluntarily curtailed about 58 per cent. As a result of prospecting during the year, six new fields were discovered, three fields were extended, and deeper zones were reached in five of the older fields.

Jan 1, 1939

By V. H. Wilhelm

In contrast with the previous year's activity, the California oil industry for 1938 showed a decrease in drilling, market demand, and discovery of new oil reserves, although there was an increase in oil production. Although additions to reserves from new fields and extensions were less than withdrawals during the year, reappraisals of discoveries in 1937 added to new discoreries during 1938 amounted to over 300,000,000 bbl. The following comparative statement shows the important changes in various phases of the industry: Throughout the year the storage situation became progressively more acute, owing principally to less Pacific foreign demand, and increased potential from drilling the newly discovered fields and pools (Fig. 1). California storage increased approximately 32,000,000 bbl. during 1938, most of which (approximately 18,000,000 bbl.) was heavy crude and residuum. The market demand for the year was around 600,000 bbl. per day. Because of the trend toward Diesel power for heavy transportation, the non-gasoline-bearing crudes arc fast becoming a drug on the market. New discoveries were instrumental in increasing the potential production of the state from 1,076,000 bbl. per day in January to an all-time high of 1,420,000 bbl. per day at the close of the year; although the indicated reserves of these new discoveries were not equal to the yearly withdrawal of 249,000,000 bbl. As of the end of 1938, the state was voluntarily curtailed about 58 per cent. As a result of prospecting during the year, six new fields were discovered, three fields were extended, and deeper zones were reached in five of the older fields.

Jan 1, 1939

By Edward Jeffrey

THE use of coke in metallurgy, to any important degree, dates from the middle of the 18th century. Its utilization came most opportunely for European civilization. The forests of Europe, except in the most remote and inaccessible regions, had been largely fed, in the form of charcoal, into the smelting furnaces. For a hundred years-the middle of the 17th to the middle of the 18th century-there was a stationary condition of population corresponding to the exhaustion of European forests. This situation, which was particularly evident in Great Britain, was due to the fact that the forests had been depleted and the practical utilization of coke had not begun. The coking industry is essential for our metallurgical industries, which in turn are basal to healthy economic progress. But coke is of great importance, not only on its own account, but for its byproducts, which enter fundamentally into all the arts of peace and war. The dyestuff industry and the manufacture of explosives are intimately connected with one another, as was shown by the recent war. The subject of coking coal, therefore, is well worthy the serious attention both of practical industry and the scientific investigator. The most valuable coking coals, from the metallurgical standpoint, are derived from the coals of highest ranks. Coals, for example, that have a carbon ratio of from 70 to 80 per cent. yield the most valuable coke for the blast furnace. The difficulty of investigating these coals, however, is great, for they are rather friable and delicate and possess a high carbon content, which makes them difficult to manipulate. They present, on account of their high carbon content, a considerable degree of opacity when examined, in thin sections, under the microscope. The tenderness of structure and blackness of such high-grade coking coals as those of Connellsville and the Pocahontas region make them extremely difficult to investigate.

Jan 1, 1925

FRIENDS of the late Charles F. Rand presented in 1930 a sum of money from which the income is available to support various phases of the work of the Institute in which Mr. Rand was so deeply interested. At present the fund amounts to $10,400. The specific terms of the deed of gift are as follows: "The fund collected to establish a memorial to the late Charles F. Rand shall be placed in the custody of the Board of Directors of the American Institute of Mining and Metallurgical Engineers, to be set up as a trust to be known as the `Charles F. Rand Foundation,' the income of which shall each year be applied to a distinct purpose to be decided upon in that year by vote of the Board of Directors. This purpose shall be such as to promote the general welfare of the Institute and to constitute a permanent memorial of the usefulness of Mr. Rand, who for many years gave unstintingly of his time and talents in its service. "It shall be within the discretion of the Board of Directors to establish a medal to be known as the Charles F. Rand Memorial Medal to be awarded at such a time and under such rules as may be determined by the Board of Directors, for Distinguished Achievement in Mining Administration." The establishment of this medal was announced at the annual meeting in February, 1932, the term "mining" being defined in its broad sense to include metallurgy and petroleum. Robert Linton is chairman of the Charles F. Rand Foundation Award Committee.

Jan 1, 1943

By G. Das, S. V. Radcliffe

The substructural features developed in tungsten as a function of annealing temperature (up to 2200°C) and type of material [undoped and doped powder metallurgy (PM) tungsten and electron beam melted tungsten] have been investigated by transmission electron microscopy. For doped PM tungsten wires, characteristic "par-ticulate" substructural features developed rapidly with increase in annealing temperature above 700°C. The features consisted of parallel rows of elongated or circular shapes (500 to 1000A diam) lying along the direction of the wire axis and were identified as internal voids by diffraction contrast experiments. In recrystallized doped PM rod, larger voids were observed and were identified by precision dark field analysis to be cubic in shape and bounded by (100) planes. In marked contrast with both the doped PM materials, recrystallized undoped PM rod exhibited only very occasional and randomly arranged voids. Furthermore, no voids were observed in either material after electron beam melting. The high concentration of voids in the doped PM materials is attributed primarily to vaporization of doping additions or their pvoducts situated at the original grain boundaries , whereas the few voids in undoped material are considered to be traces of microporosity which were not eliminated during sintering. A tentative mechanism is suggested for the dezlelopment of the voids in relation to the processing sequences (sintering and working) and to the subsequent annealing. In recent years, a characteristic substructural feature consisting of rows of small elongated or circular regions of light contrast lying along the direction of working has been seen in thin foil electron microscopy studies of annealed sheet, wire, and rod tungsten. These features were present in the published micrographs of sheet by Weissmann et al.1 and of wire by Meieran and Thomas2, although the authors did not draw attention to them. Wronski and Fourdeux3 observed similar features in sintered rod tungsten (it was not specified whether or not the material was doped*) and interpreted them on the basis of their ap- particles, based on extraction replica evidence from the fracture surface of the initial hot-rolled slab material from which the sheet was prepared. No diffraction contrast experiments on the features were reported in any of these studies. The present investigation was undertaken with the primary objectives of: a) identifying the nature of these substructural features in tungsten by electron diffraction contrast experiments, since the contrast for voids can be expected to differ from that for crystalline or glassy particles, and b) elucidating the origin of the features and their development. For the latter purpose, doped and undoped powder metallurgy tungsten was obtained as rod and wire to represent different stages of reduction during final processing. These materials were examined both in the as-processed condition and after annealing to successively higher temperatures. In addition, the same doped and undoped materials were examined after vacuum melting in rod form. I) MATERIALS AND PROCEDURE Doped powder metallurgy (PM) tungsten wire (commercial purity 99.9 pct W) was obtained in the as-drawn and surface ground condition (0.030 in. diam "ground seal rod"). Doped and undoped tungsten rod (0.075 in. diam) representing an earlier stage of final processing was obtained from the same commercial source (Refractory Metals Division, General Electric Co.). Lengths of both the doped and undoped rod materials were single-pass melted in an electron-beam zone refiner to examine the effect of vacuum melting on the substructure. Annealing was carried out in a tungsten crucible in a tantalum strip resistance furnace under a vacuum of l0-15 mm Hg. Longitudinal sections of the wire and rod materials were examined by light and electron microscopy. The preparation of thin foils suitable for electron transmission from 0.030 in. diam tungsten wire and the rod specimens was carried out by means of a high-precision microjet technique developed to provide lack of jet stability and precise control of the area thinned. The method is described in detail elsewhere.' The foils were examined in a JEM 6A electron microscope using a goniometer stage (±20 deg tilt, 360 deg rotation) and operated at 100 kV. To minimize contamination problems a 200 µ condenser aperture was used in conjunction with a useful beam current of 50 µA. II) RESULTS AND DISCUSSION A) Diffraction Contrast Analysis. In order to determine the optimum conditions for the development of the substructural feature, a series of isochronal 30 min annealing experiments were carried out on specimens of the doped PM tungsten wire. The transmission electron microscopy analysis showed that the as-drawn wire, Fig. 1(a), consists of 'fibers' whose long axis is closely parallel to the wire axis of (110). The fiber width averages some 0.5 µ. Dense disloca-

Jan 1, 1969

By C. B. Alcock, M. G. Hocking

The kinetics of the growth of sulfate layers on blocks of Cu20 has been studied between 688" and 800°C. At 788c the over-all weight increases followed the parabolic rate law, with k = 216 30 sq mg per cm4 min, using a 1:1 entering gas mixture of SO2:02. At 757 after an initial linear period the parabolic rate law was followed, with k = 57.8 10 sq mg per cm4 min. The gas mixture required a platinum catalyst to produce the maximum SOs pressure. The sulfation rate at 757' and 788c was high until all the CUZO had changed into a core of CuO, when it became very much lower. At 757°C marker experiments showed that the sulfates (CuO. CuS04 and CuSO4) grow outwards from the oxide surface, but CuO. CuS04 mixed with CuO was found beneath the markers. At 688 markers were found at the CuO. CuS04/CuS04 interface. Visual observations at 757 showed a liquid eutectic moving beneath the sulfate surface. causing very rapid sulfation and extruding to solidify as thick 'needles" up to 8 mm long. Marker experiments have shown conclusi.cely that CuO grows on Cu20 in air by the outward migration of copper. ThermODYNAMIC measurements on the sulfate and basic sulfate of copper, reported recently,' are followed here by measurements of the rates of formation of these sulfates on cuprous oxide, in order to provide a background for the understanding of roasting processes. peretti2 and McCabe and Morgan3 have shown that the phase Cu20 lies next to Cu2S when the sulfide is roasted under conditions where sulfates will be formed. Since this would present too complex a system for kinetic study, the present work4 has been based on the kinetics of sulfation of the oxide phase. The results of a study of the kinetics and mechanism of the sulfation of cobaltous oxide have recently been reported.4,5 Results on the sulfation of cuprous oxide have also appeared,6 but are at variance with those to be reported here. This seems to be because the previous workers6 did not obtain constant SO3 pressures from the SO2/O2 sulfating gas mixtures used, as will be discussed later. Wadsworth, Leiter, Porter, and Lewis found that the sulfates produced when SO2/O2 mixtures are passed over Cu20 at red heats are CuS04 and the basic sulfate CuO.CuSO4. When the decomposition of CuS04 was followed' by differential thermal analysis, a stage corresponding to CuO .CuS04 was reached before decomposition into the oxide occurred. APPARATUS The vertical furnace used for quantitative studies was a conventional resistance-heated and propor- tionately controlled furnace with an even zone (1 deg) which was 4 cm long. The gas mixtures of SO2 and 02 were made by mixing measured flows from capillary flowmeters and drying over phosphorous pentoxide before passing them into the Pyrex top-piece of the furnace assembly. A mullite tube of bore 2% cm was used as reaction vessel and at the bottom of this tube was a trap for SO3, which condensed as a colorless liquid. The residual gas was led into a fume cupboard for ventilation to the atmosphere. The furnace used for visual observations of needle growth and other phenomena consisted of a transparent silica reaction tube of bore 3 cm, having an optically flat silica window sealed into its wall. The reaction tube was clamped vertically, inside a mullite tube of bore 4 cm and length 42 cm which was heated by Kanthal windings. The window in the silica reaction tube was arranged opposite a hole 3 cm wide and 2 cm tall which had been cut in the wall of the mullite winding tube 19 cm from its top end. A binocular microscope was used to look through the window, illumination being provided by a focusing microscope-lamp offset sideways and downwards. The oxide block to be sulfated was suspended from the removable Pyrex top-piece to the reaction tube, by means of which it was inserted at the start of the experiment, and through which entered the S02/02 gas mixture. The variation of the temperature inside the reaction tube with horizontal and vertical displacement from the window was investigated, and, while it can be said that the temperature was constant 1 deg, its value at a given position was known only to 12 deg. In both furnaces, the oxide block to be sulfated was suspended from a small silica hook immediately downstream from a platinum thimble used as catalyst, which was held on a long silica rod from a Pyrex spring attached to the removable Pyrex top-piece of the furnace. The spring was only included in the quantitative sulfating furnace; its sensitivity was 1.4 cm per g and it was found to be free from creep in a 16-hr test when carrying the working load. The extensions were followed by a cathetometer which could be read to 0.001 cm, corresponding to i0.7 mg. Extensions of the spring were measured on adding weights between 5 and 500 mg to the working load (thimble + oxide block), and Hooke's law was closely obeyed. SAMPLES Cuprous oxide blocks were prepared by oxidizing Johnson Matthey "Specpure" copper sheet of 1 mm thickness (impurities: iron at 3 ppm, silver at 2 ppm, lead, nickel, sodium, and silicon each at 1 ppm, calcium, chromium, magnesium, and manganese each at less than 1 ppm) for 6 days in air at 1000°C in a re-crystallized alumina boat. It has been reported7 that when Cu20 is prepared by heating copper sheet for 1 day the central plane of the blocks produced consists

Jan 1, 1967

By C. Scala, M. Gondouin

Published laboratory data have established that very significant streaming potentials can exist across mud cakes subjected to pressure differentials such as exist between a mud column and formation fluids. Since shale is similar in kind and in properties to a well-formed mud cake, it appeared possible that streaming potentials might also arise across shales. A practical consequence would be that the streaming potential contribution to the SP would be smaller than might otherwise be assumed since the SP is measured with respect to the "shale bare line". The resultant contribution would be the difference between the streaming potential across the shale and that across the mud cake. In order to investigate this possibility, a laboratory apparatus was devised for measuring streaming potentials under pressure conditions normally encountered in wells. Reported data on streaming potentids across mud cakes were verified. More important, appreciable streaming potentials were found across shale samples. As in the case of mud cakes, the shale potentials varied with the concentration and nature of the impregnating electrolyte. Dependence on pressure was In a different rela-tion than that for mud cakes, possibly because of the lower compressibility of shales. The differences in streaming potentials between the shales md mud cakes were generally small, although they might vary considerably in practice depending on the relative electro-kinetic properties of the particular shale-mud cuke combination. A "poorly eflective" shale with a "very eflec-tive mud cake" would produce the largest negative addition to the electrochemical component of the SP. Results of field experiments with pressurized wells were considered in the light of the laboratory results. INTRODUCTION Field experiments wherein the pressure of the mud column in a borehole was varied have often indicated the presence of a streaming potential, but its magnitude was not easily predictable and its sign sometimes changed from one formation to another in the same well.' In the interpretation of SP logs from standard surveys, nevertheless, the correct value of R,, is very frequently obtained, within the limits of field accuracy, using only the simple electrochemical expression of the SP provided that proper corrections are made for bed thickness, ion activity, etc.' Accordingly, it was apparent that the streaming potential component of the SP in a borehole was considerably more complex than commonly assumed and clarification was indeed necessary The close similarity in nature and constitution of a shale to a well-compacted mud cake suggested that a streaming potential might also exist across shales as pointed out by M. P. Tixier in 1953 and as recently emphasized by Wyllie." e practical consequence would be that the streaming potential across the mud cake would be canceled, at least in part, on electrical logs since the SP is recorded with respect to the shale potential as a base line. This appeared to be a plausible explanation for many of the effects observed but no supporting data were available. In 1955 preliminary experiments at low pressures were conducted in our laboratories which supported the hypothesis of the shale streaming potential and formed the basis for later studies at borehole pressures.* EARLY LOW PRESSURE EXPERIMENTS The early experiments were conducted primarily to determine the possibility of a streaming potential across shales. The shale used was a compact type designated as No. 7 from Reagan County, Tex. (Permian). Cut samples were saturated for over one month in .2 to 2.0-N NaCl solutions. In order to eliminate all electrode polarization effects, a dynamic method was used. A transient pressure of about 1 atm was applied across

By F. S. Young, K. E. Gray

Drilling tests with a 11/4-in. diameter roller bit were performed on Berea and Bandera sandstones and Leuders limestone using water and two conventional drilling muds as circulating fluids to evaluate the influence of dynamic filtration on penetration rate. The muds possessed widely differing API fluid-loss properties. Mud filtrate was constrained to flow beneath the bit; no filtrate flowed radially through the borehole wall. Rock pore pressure at three different locations ahead of the bit, cumulative filtrate volume, borehole pressure and bit location were monitored during drilling. The rock samples, cored in three orientations with respect to bedding planes, possessed a wide range of liquid permeabilities. and were drilled at borehole-to-formation pressure differentials of 0, 250, 500 and 1,000 psig. The effect on penetration rate of API fluid loss, borehole pressure and rock permeability was studied. Rock permeability damage and pore pressure gradients beneath the bit were evaluated. The importance of borehole-to-formation pressure differential was illustrated for each drilling fluid and rock permeability combination. Penetration rates decreased with increased borehole pressure and reduced fluid loss. The observed penetration rate reduction due to changing fluid Ioss was attributed to decreased filtrate flow and improved mud cake plastering hy the low fluid-loss mud. The reduction in filtrate flow could not be related to spurt-loss phenomena. Rock permeability influences penetration rate through particle invasion ahead of the hit, which damage leads to high pressure gradients. Penetration rate variance with sample orientation was evident for water-drZled samples but less obvious for mud-drilled rocks. Permeability damage beneath the bit ranged from 1 to 3 cm. Maximum damage occurred in the first 0.1 cm. Pressure gradients varied with API fluid 10.s.s and could be correlated with penetration rate. The pressure gradient was found to influence penetration rare in rocks of all permeabilities tested. INTRODUCTION Early microbit and small-scale drilling experiments proved to be invaluable contributions to understanding the mechanics of drilling at depth. For example, the effect of borehole-to-pore pressure differential on drilling rate was demonstrated conclusively by Murray and Cunningham', Eckel' and others .' However, the effects of various drilling fluid properties on drilling rate, particularly filtration, have not been studied extensively on a laboratory basis. Microbit correlations of penetration rate with different viscosity and API fluid-loss muds led EckelV o conclude that viscosity and density. more than API fluid loss, were the most important fluid properties in controlling drill bit penetration rates. Ferguson and Klotz6 studied filtration beneath the bit and stated that the maximum amount of filtrate which could conceivably flow beneath a drilling bit could be described by a potential function associated with flow from a moving disc source. and be characterized by a depth-of-filtrate invasion. Invasion depth is a function of penetration rate, formation porosity and permeability, flooding efficiency, pressure difference between borehole and formation and borehole radius, assuming that no filtrate flows through the borehole walls. Electric analog and experimental measurements were obtained, assuming no plugging of the formation pores. Theoretically, filtrate invasion was predicted to extend from 1- to 15-hole radii beneath the cutting surface; experimental results indicated that the extent of invasion was only Y2 in. Comparing these data with results of core-plugging experiments by Norwak and Krueger' led Ferguson and Klotz to state that the drilling operation apparently contributes to higher filtration rates than are observed in nondrilling core filtration tests in which the core face is jetted and scraped. Glenn and Slusser: in describing a linear filtering system in which a rotating bit continuously scraped mud cake from the surface but did not penetrate Alundum cores, stated that mud-solids invasion and permeability damage of the cores were most severe in the first 2 to 3 cm. The filtrate flow rate through the core was found to stabilize after sufficient time had elapsed for the formation of an internal mud cake whose effective permeability was estimated to be 50 to 300 times as high as that of bulk filter cake. Krueger and Vogel reported core permeability damage depths up to 12 in. during a 5-day exposure period in which filter cake buildup was prevented. Havenaar pointed out that the discrepancy between reported and calculated values of filtrate volume obtained in the experiments of Ferguson and Klotz was due, among other things, to failure of the reported API fluid loss to truly represent filtration beneath the bit. Williams," Pro-koplz and others"" have shown that dynamic filtration tests (where a flow of fluid parallel to the filter surface continually erodes the deposited filter cake until a dynamic equilibrium between wall-shearing forces and normally directed compaction forces is attained) yield higher filtration rates than do static tests. Cunningham and Goinss reported results of drilling tests in impermeable shales. They found that by reducing

By M. L. Fuller

MOST commercial alloys undergo changes in phase composition after casting. This is a natural result of the fact that the alloys are not in a state of phase equilibrium as cast and phase changes will therefore take place, with more or less rapidity, in an attempt to attain equilibrium. The practical aspect of aging in zinc-alloy die castings concerns the changes in physical properties and in dimensions that may accompany aging phase changes. Harmful alterations have been reduced to a minimum and zinc-alloy die castings are being produced today that are so stable with respect to dimensions and physical properties that they are entirely suitable for most practical purposes1. In the first paper2 of this series, and in this paper, aging phase changes of zinc alloy die castings have been investigated and the possible influence of these changes on dimensional changes of the castings has been evalu-ated and compared with the dimensional changes actually experienced. The change of dimensions has been selected for practical comparison in these papers because the effect of phase changes on the dimensions of a casting is directly calculable; from X-ray crystal-analysis data of the phase structure. The die-casting alloys considered contain, in addition to zinc, 4 per cent of aluminum, about 0:03 per cent magnesium, and from 0 to 3 per cent of copper. It was shown in the former paper that the eutectoidal decomposition of the beta aluminum-zinc phase, while intrinsically capable of causing a considerable shrinkage, can have very little effect on the observed shrinkage of die castings because it takes place within a few days of aging, whereas the observed shrinkage continues for five weeks. It was therefore concluded that the other existing phase change,

Jan 1, 1935