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By John E. Latz

QUICKSAND far below the surface, stopped two attempts by the Potash Co. of America to sink a third shaft to a potash bed that lies 1000 ft below the southern New Mexico desert. Virtually all methods of grouting were employed in the two failures without any indication of consolidation of the flowing sand. Sinking the South Shaft at the Carlsbad potash mine seemed an almost insurmountable task, until freezing was employed as a final resort. This process that proved to be the answer may be defined as "the sinking of a shaft by freezing, consists of the formation, in the water-bearing strata, of a large block of frozen ground in which it is possible to sink a shaft without danger of an influx of water, providing the ice-wall between the water outside and the shaft itself is strong enough to resist the hydrostatic pressure." Freezing Method Used Extensively in Europe Successful frozen ground shaft sinking projects had been completed in Europe, and Russel G. Haworth, resident manager of the Potash Co. of America, went abroad in search of the know-how needed for the New Mexico undertaking. The freezing process, with a history of two failures at the time, was first successfully employed by Poetsch in 1885 at the Houssu Collieries near Haine St. Pierre, Belgium. Poetsch contracted to sink the remaining 64 ft of an uncompleted shaft through water laden strata from a depth of 190 ft to a depth of 254 ft. This work was in progress until 1887. The freezing and sinking consumed more than two years. As a result of early failures, the process was not favorably received until soon after the turn of the century. The accurate prediction of success in a given application was made possible by the concerted effort and study of a group of European engineers. Means of accurate deviation measurement and control were devised, the nature and properties of frozen water laden soil (the ice wall) were investigated, a thorough and rational basis of refrigeration load calculation developed, and concurrently the efficiency and dependability of refrigeration machinery was greatly advanced. Numerous shafts in Germany, Belgium, France, and England today testify to the reliability and economical surety of the freezing method. Applied to the South Shaft, which is circular in cross-section and 15-ft diam, the freezing method consisted of drilling holes 350-ft deep, through the water bearing strata into impervious ground-the freeze hole pattern being concentric with the shaft and 31-ft diam. The holes were cased with pipe closed on the bottom end. Smaller tubes were placed inside these casings and connected to a header supplying chilled brine from a refrigeration plant. The brine descended in the tubing to the bottom of the hole and ascended through the annular space between the two pipes to the top of the casing; flowed into the return header and back to the refrigeration plant. Under these conditions, each of the freeze hole casings became surrounded by a cylinder of ice

Jan 1, 1952

By FREDERICK W. BRADLEY

MINING is one of the world's oldest industries and has pioneered the civilization of all new lands. Today, mining is not only one of the essential and basic industries of the world, but it is constantly growing in magnitude and becoming more important. We think that the most of our mining is done in the western portion of this country, but in the old State of Pennsylvania mines and products derived from minerals account for about two-thirds of the entire productive wealth of the State. As our forests are denuded, mining furnishes substitutes for timber in the way of concrete, gypsum board, etc. ; and as civilization increases the wants of mankind, mining is producing metals and minerals of every kind in increasing quantities. For example: during the past ten years the per capita consumption of copper in the United States has increased 49 per cent, to 14.56 Ib.; that of lead has increased 35 per cent, to 12.24 lb.; and that of zinc has increased 70 per cent, to 9.57 Ib. The consumption in European countries is about one-half of this, and there are other countries with large populations where there is virtually no consumption; so when all other countries catch up in consumption with our country, you can see what an enormous demand there is going to be for the metals, even to the extent of having to find substitutes for copper, lead, and zinc.

Jan 1, 1929

By CHARLES SIMENSTAD

COAL preparation, or coal washing, is not a new subject to the Pacific Northwest. Most of the coals mined in this state smaller than lump, and nearly all such sizes mined on the Pacific slope of the Cascade mountains, require washing before marketing. A large proportion is being put through some washing process, but coal washing in this state, has not reached the efficiency it is practicable to obtain. In fields where the coal, as mined, contains less impurities, where working conditions make it practicable to eliminate some of these impurities under- ground, or where a large proportion of the run-of-mine coal is lump, coal preparation does not present the problem it does in our local field. Here the coal is associated with considerable impurities and the slack, or steam sizes, aggregate about 80 per cent. of the output. Therefore, approximately 80 per cent. of the coal mined must be washed to become a valuable fuel. Washing then becomes a major operation, as hand picking of the 20 per cent. of lump is a standard and comparatively simple operation. Some coal beds here are so interstratified with bone, of a more or less massive nature, that hand picking of lump is not economically efficient. In such cases the coal must be crushed fine enough for it to be freed from the bone, so that the two may be separated. Coal cleaning in this field, therefore, must receive skilled attention to purify this fuel and raise its stand- ard. Without greater efficiency in cleaning, the importation of coal from outside the state will be even greater than in the past.

Jan 1, 1926

Book Review MANAGEMENT AND MEN. By Meyer Bloomfield, Boston. The Century Co., New York, 1919, pp. 584, H.X. 5 1/2. $3.50. This hook is an exposition of English efforts to solve the problem of labor unrest in England. The first six chapters are reprinted from articles published in the Satur-day Evening Post, for whom the author went to England to study the problem at first hand. These articles deal with housing, increased production, eliminating the internal friction in the industrial machine and a chapter each devoted to the view-point of employer and employee. These chapters are written in the easily readable magazine style and give a complete general survey of the particular solution being tried. Perhaps their greatest., certainly not their least, worth lies in the fact that they form a vehicle for unusually voluminous appendices containing in full the famous Whitley Reports which are the basis of the new movement, together with various reports, which, except for this publication, would be largely inaccessible to those inter-ested in this country. The Whitley scheme considers each industry a unit and proposes to establish therein a Joint Standing Industrial Council composed of representatives of employers and employees to consider appropriate matters affecting the industry at large. There is to be a District Council for each industry which will, as its name implies, deal with the clatters pertaining to that interest in. the particular district. The third and last body in this scheme of Industrial Parliament is the Works Committee, which is com-posed of representatives of the management and of the workers employed in particu-lar plants or mines to act in close cooperation With the district quid national machinery. The Whitley or similar schemes have been tried in many communities in England and the book contains interesting comments on the result obtained, it being notable that most of the objections conic from plants which have not tried the scheme. Meyer Bloomfield, the author; is the specialist in industrial personnel problems who organized the industrial service activities of the United States Shipping Board, Emergency Fleet Corporation. P. E. B.

Jan 10, 1919

By Alton B. Cook, G. B. Spencer, F. P. Bobrowski

In estimating production gas/oil ratios and oil recoveries from reservoirs containing highly volatile oils it is highly important to include condensate that may be recovered from the gas produced from the reservoir. The volume of the hydrocarbon liquid condensed from the production of the solution gas that has been liberated. in some reservoirs may equal or even exceed the volume of recoverable stock-tank oil as estimated by present methods. The usual procedure1, 2, 3 in estimating future reservoir performance includes use of relative permeability data of the reservoir rock to gas and oil and includes material-balance calculations utilizing data on the volume of the reservoir fluids, oil and gas production and reservoir pressure decline, and data on the physical properties of the initial reservoir fluids. The inaccuracy in the procedure results from the false assumption that all of the free or liberated gas that enters the well bore of reservoirs containing highly volatile oils remains in the gaseous phase as it is produced. This paper presents a method for estimating future reservoir performance and oil recoveries based on special labora. tory analyses of reservoir-oil samples and recognition of the additional volume of hydrocarbon liquid that will be recovered at various stages of depletion from a solution.gas.drive reservoir. The method also includes calculations of the volume and composition of the hydrocarbon liquids that can be recovered by processing the produced gas in a natural-gasoline plant. The development of the method resulted from a study of laboratory analyses of reservoir samples and of field data obtained from two reservoirs containing oil of the highly velatile type. Relatively high pressures and temperatures prevail in oil reservoirs discovered at the greater depths of present-day drilling. The contained fluids may have high saturation -Dressures and large volumes of gas in solution. The oils and gases under these conditions may be almost identical in compositions and densities.4,5 Also, engineers have noted that, for a number of oil reservoirs and especially the deeper reservoirs, the API gravity of the stock-tank oil increaees as the production gas/oil ratios increase. They attributed this increase in API gravity of the stock-tank oil to the formation of condensate as the liberated gas in the reservoir is being produced. SOURCE OF DATA FOR CALCULATIONS Subsurface oil samples and well-test data were obtained from the E. Constantin-Lambert Well No. 1 in the Elk City Field, Okla., to demonstrate the need for and a method of calculating future reservoir performance when consideration is given to the recoverable hydrocarbon liquid from the production of solution gas that has been or will be liberated in a reservoir. The Lambert well is located in C, SW 1/4, SW 1/4, Set- 18, T-l0-N, R-20-W, Washita County, Okla. At the time of completion it was on the east edge of the development and Was producing from conglomerate through 30 perforations in the 5 1/2-in. casing at a depth of 9,859 to 9,864 ft. The well Was completed on July 9, 1949, and subsurface oil samples were obtained July 29 and August 1, 1949. Production gas/oil ratio data were obtained during the operation in series of two Separators at high and low-pressures of 314 and 44 psia, respectively, and at an average temperature of approximately 60°F. The flowing bottom-hole pressure at the time of sampling was 3,934 psis. The static bottom-hole pressure was not obtained at the time of sampling, as the well could not be shut in long enough for testing because gas produced from the well was used for fuel at an offset drilling well. However, the initial reservoir pressure was calculated to be 4,364 psia from knowledge of pressure gradients in other wells in the field and the depth of the casing perforations in the Lambert NO. 1 well.

Jan 1, 1951

By F. P. Bobrowski, G. B. Spencer, Alton B. Cook

In estimating production gas/oil ratios and oil recoveries from reservoirs containing highly volatile oils it is highly important to include condensate that may be recovered from the gas produced from the reservoir. The volume of the hydrocarbon liquid condensed from the production of the solution gas that has been liberated. in some reservoirs may equal or even exceed the volume of recoverable stock-tank oil as estimated by present methods. The usual procedure1, 2, 3 in estimating future reservoir performance includes use of relative permeability data of the reservoir rock to gas and oil and includes material-balance calculations utilizing data on the volume of the reservoir fluids, oil and gas production and reservoir pressure decline, and data on the physical properties of the initial reservoir fluids. The inaccuracy in the procedure results from the false assumption that all of the free or liberated gas that enters the well bore of reservoirs containing highly volatile oils remains in the gaseous phase as it is produced. This paper presents a method for estimating future reservoir performance and oil recoveries based on special labora. tory analyses of reservoir-oil samples and recognition of the additional volume of hydrocarbon liquid that will be recovered at various stages of depletion from a solution.gas.drive reservoir. The method also includes calculations of the volume and composition of the hydrocarbon liquids that can be recovered by processing the produced gas in a natural-gasoline plant. The development of the method resulted from a study of laboratory analyses of reservoir samples and of field data obtained from two reservoirs containing oil of the highly velatile type. Relatively high pressures and temperatures prevail in oil reservoirs discovered at the greater depths of present-day drilling. The contained fluids may have high saturation -Dressures and large volumes of gas in solution. The oils and gases under these conditions may be almost identical in compositions and densities.4,5 Also, engineers have noted that, for a number of oil reservoirs and especially the deeper reservoirs, the API gravity of the stock-tank oil increaees as the production gas/oil ratios increase. They attributed this increase in API gravity of the stock-tank oil to the formation of condensate as the liberated gas in the reservoir is being produced. SOURCE OF DATA FOR CALCULATIONS Subsurface oil samples and well-test data were obtained from the E. Constantin-Lambert Well No. 1 in the Elk City Field, Okla., to demonstrate the need for and a method of calculating future reservoir performance when consideration is given to the recoverable hydrocarbon liquid from the production of solution gas that has been or will be liberated in a reservoir. The Lambert well is located in C, SW 1/4, SW 1/4, Set- 18, T-l0-N, R-20-W, Washita County, Okla. At the time of completion it was on the east edge of the development and Was producing from conglomerate through 30 perforations in the 5 1/2-in. casing at a depth of 9,859 to 9,864 ft. The well Was completed on July 9, 1949, and subsurface oil samples were obtained July 29 and August 1, 1949. Production gas/oil ratio data were obtained during the operation in series of two Separators at high and low-pressures of 314 and 44 psia, respectively, and at an average temperature of approximately 60°F. The flowing bottom-hole pressure at the time of sampling was 3,934 psis. The static bottom-hole pressure was not obtained at the time of sampling, as the well could not be shut in long enough for testing because gas produced from the well was used for fuel at an offset drilling well. However, the initial reservoir pressure was calculated to be 4,364 psia from knowledge of pressure gradients in other wells in the field and the depth of the casing perforations in the Lambert NO. 1 well.

Jan 1, 1951

By R. D. Pehlke, J. V. Gluck

A study was made of the effect of small additions of metallic solutes on the thermodynamic activity of zinc in dilute solution with molten bismuth in the range 450o to 650°C. The experimental measurements were made in a multielectrode galvanic cell using. a fused LiCl-KCl electrolyte. The activity of zinc in binary solution exhibited a strong positive deviation from Raoult's law and obeyed Henry 's law to at least 0.050 mole fraction. The ternary addition of lead, gallium, or indium increased the activity of zinc. Cadmium or tin additions slightly decreased the zinc activity. Copper, mercury, silver, or antimony caused moderate decreases, while gold strongly decreased the zinc activity. The results are expressed in terms of Wagner's interaction parameter ejZn and a second-order cross-interaction parameter. The interactions for copper, gold, silver, and antimony showed a linear dependence with reciprocal absolute temperature, while the other interactions were essentially independent of temperature over the experimental range. Since tin and antimony decreased the zinc activity, the hypothesis of a purely periodic variation with atomic number was rejected. A semiquantitative explanation was possible with a free-electron model when relative electronegativities were used to express changes in the electron/atom ratio caused by the solute addition. Random solution and quasi-chemical models correctly predicted the majority of the interactions for which binary data were available to apply them. A knowledge of the thermodynamic interactions in liquid (and solid) metallic solutions is of considerable theoretical and experimental interest in the formulation of quantitative thermodynamic relations for metallurgical processes. The approaches to defining the interactions may be either phenomenological (i.e., "What mathematical function adequately describes observed behavior and permits extrapolation to new situations?") or theoretical, such as a specific model

Jan 1, 1968

By H. Wilhelm, E. L. Davis, W. A. Clark

MATHEMATICAL formulas for the analysis of the behavior of producing oil wells can be devised which will be correct for the assumed conditions. However, in an oil zone, variables always exist which are unknown, or to which. it is impractical to assign mathematical values. It seems apparent that one should reason back from observed facts to an analysis of causes, rather than start with a hypothetical reservoir with assumed properties and attempt to explain observed phenomena. In this paper we hope to throw some additional light on factors influencing production, especially edgewater behavior. OIL and gas are contained in reservoirs of either the sealed type or the edgewater type. In the former all the recoverable oil is produced by gas expansion only. In this type of reservoir, edgewater is not effective. This may be because of faulting or overlapping strata, or more often, probably, the edgewater pressure is ineffec¬tive on account of resistance or lack of head.

Jan 1, 1933

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members.) Members and guests who registered at Institute headquarters during January: A. Neustaedter, Jersey City, N. J. William Jones, Kent, England. A. J. Sweetser, Boston, Mass. Percy E. Barbour, Candor, N. C. Algernon Del Mar, Los Angeles, Cal. Herbert S. Kohlberg, El Paso, Texas. W. B. Cogswell, Syracuse, N. Y. I. N. Knapp, Ardmore, Pa. R. E. Chambers, New Glasgow, N. S.

Jan 2, 1914

By Zay Jeffries

Each generation accepts the developments of the preceding generations without full appreciation of the difficulties that had to be overcome or of the effect of any given development on society. Today, the production of pig iron is the yardstick with which general industrial health and progress are measured. So natural and logical does this seem to us, that it is difficult to picture conditions prior to the fourteenth century when pig iron was unknown. Not only was pig iron unknown but iron or steel could not be melted and poured into castings; all iron and steel articles were forged from sponge iron. All castings, as well as many worked articles, were made of non-ferrous metals or alloys. In many parts of the world, over long periods of time, not only was the annual exchange value of non-ferrous metals greater than that of iron and steel, but their combined tonnage was greater. At present, the value of the pig iron produced in a year is of the same order of magnitude as that of all non-ferrous metals combined; the tonnage of pig iron is, however, about twenty times that of all non-ferrous metals combined. Owing to lack of records, we will probably never know the relative importance of the various metals at all periods in historic times. A certain conclusion is that the iron and steel industry, since the discovery of pig iron and the cheap methods of converting it into steel, has grown at a much more rapid rate than the non-ferrous metal industries. Notwithstanding their fundamental fitness for man's needs, iron and steel owe their importance in no small degree to the low cost of production. The low cost was a result of increased knowledge of the production appliances and of the metallurgical processes. This increased knowledge is the key to our modern industrial civilization. It will remain for future generations to determine whether there is now going on a gradual change toward greater importance of the non-ferrous metals, as compared to iron and steel. The world's pig iron production in 1920 was slightly more than twice what it was in 1890, whereas the non-ferrous metals production in 1920 was about two and one-half times that in 1890. Every non-ferrous metal industry has shown marked growth during the last thirty years. During this period, the production of cop-

Jan 1, 1924

By J. L. Wyatt

THE smelting of ilmenite to produce a slag rich in titanium, with pig-iron as a byproduct, introduces new concepts in electric smelting metallurgy. Titanium slags are characterized by low electrical resistance, thereby requiring a different type of electric furnace operation, and power supply sources substantially different from those encountered in normal steel melting and siliceous ore smelting furnaces. This paper describes special apparatus for determining specific electrical resistivity of titanium slags, and reports the values obtained on slags encountered in the process of smelting ilmenite ores. In an induction furnace under conditions approximating normal furnacing operation, 25 general heats and 6 special standardization and comparison heats were run. Results indicate relatively low resistivity. Resistivity depends primarily on slag composition, and, to a lesser degree, on temperature. During the summer of 1947 a cooperative project between the National Lead Co. and the Bureau of Mines was conducted at Boulder City, Nevada, in the Electrometallurgical Laboratories of the Bureau. The project involved smelting of ilmenite ores in electric furnaces, and has been reported in detail.' The author participated as a member of the staff of the National Lead Co. during the entire campaign. One outstanding characteristic of the titaniferous slags, their apparently excellent and variable electrical conductivity, was considered sufficiently important to warrant further study. Although little electric smelting of iron ores has been done in the United States, a certain amount of information is available for comparative purposes. Personal experience in smelting siliceous iron ores in electric furnaces furnished further information for comparison. In general, silicate slags are relatively poor conductors of electricity. Current flow during smelting operations may be maintained through a floating layer of coke on top of the slag bath, or through a bath of molten iron, beneath the slag. Silicate slags are not sufficiently conductive to furnish a path for current passage when normal furnace voltages are used. Experimental smelting of a silicate iron ore was undertaken for comparative purposes. A fluid melt was not obtained until the FeO content was reduced to 15 pct. The resistivity increased as the FeO content decreased, FeO compounds being the most conductive of the various oxides in such a normal slag system. The converse appears to be true in slags containing large percentages of TiO2. It has been found that titanium slags become molten with FeO percentages in excess of 30 pct, and that the conductivity becomes generally better as the FeO con-tent of the slag diminishes. This phenomenon was demonstrated in the furnacing operations at Boulder City. During the initial smelting period furnace electrodes could be held immersed several inches in the slag, with tap selectors set for a no-load voltage of 70 v. As the FeO content decreased, the furnace electrodes would "walk up," until at one point in the process the tips would break the surface and arc on top of the slag. This was undesirable since direct arcing caused losses of important flux additions. The slag compositions under study at that time were such that losses due to surface arcing sometimes caused viscous slags to be formed. Forcing the electrodes into the slag bath by manual control to prevent surface arcing resulted in excessive power input and lack of control. Suitable low voltages were not available. Measurement of the electrical resistivity of titanium slags at various operating temperatures and slag compositions was undertaken. It was believed that this information would be of use in the design of electric furnaces suitable for smelting ilmenite, with voltages, electrode sizes, and electrode spacing adapted specifically to titanium slags.

Jan 1, 1951

PRESIDENT AND DIRECTOR DONALD B. GILLIES CLEVELAND, OHIO PAST PRESIDENTS AND DIRECTORS R. C. ALLEN CLEVELAND, OHIO D. C. TACKLING SAN FRANCISCO, CALIF. TREASURER AND DIRECTOR KARL EILERS NEW YORK, N. Y. VICE-PRESIDENTS AND DIRECTORS H. G. MOULTON NEW YORK, N. Y. HARVEY S. MUDD Los ANGELES, CALIF. PAUL -D. MERICA NEW YORK, N. Y. WILFRED SYKES CHICAGO, ILL. WILLIAM B. HEROY HOUSTON, TEXAS HENRY KRUMB NEW YORK, N. Y.

Jan 1, 1939

By M. Garfinkle, W. D. Klopp, W. R. Witzke

The tensile properties of binary W-Re alloys containing up to 33 at. pct Re were determined at temperatures from 78" to 3630°F. Elongations as high as 260 pct were observed in electron-beam-melted tungsten containing 23 at. pct Re when tensile-tested at 3630°F after a 1-hr anneal at 3090°F. All alloys tested under these conditions with rhenium contents between 20 and 28 at. pct exhibited elongations of at least 200 pct. These alloys also showed enhanced grain growth rates. The values of strain-rate sensitivity ranged between 0.2 and 0.3 for the alloys exhibiting high elongations. Houlezler, for swaged alloys tested just above the re-crystallization temperature, strain-rate sensitivities as high as 0.8 were observed. The high-temperature strengths of the high-rhenium-content alloys were also less than those of alloys with intermediate rhenium contents. ALLOYING with rhenium has two distinct effects on the mechanical properties of tungsten. One effect occurs in dilute solid solutions and is most clearly seen in the lowering of the hardness and of the ductile-brittle transition temperature at about 5 at. pct Re.1-3 The second effect occurs in the concentrated solid solution at about 25 at. pct Re, and is characterized by twinning and a larger decrease in the ductile-brittle transition temperature. An aspect of the high-rhenium-content alloy which has received little attention is the higher-than-usual tensile ductility at 3500°F.3 Anomalous high ductility has been observed in several other alloy systems. usually associated with a phase transformation or a solid-solubility limit.4'5 The phenomenon is now commonly termed superplasticity. High-strain-rate sensitivities6 and grain boundary sliding7 have been reported for materials that undergo superplastic deformation. Also, it has been found that superplastic materials usually have a very fine grain structure (less than 10 pm).8 and it has been proposedg that such a structure alone is sufficient for superplasticity. The purpose of the present study was to further characterize the high-temperature tensile properties of W-Re alloys to determine the conditions under which they might be superplastic. Tensile and selected strain-rate sensitivity tests were conducted on alloys containing 0 to 33.3 at. pct Re at temperatures from 78" to 3630°F. Grain-growth rates were also determined on most alloys at 3630°F. Fig. 1 indicates the compositions evaluated and their locations relative to the solvus line in the tungsten-rich end of the W-Re phase diagram. Twelve binary W-Re alloys containing up to 33.3 at pct Re were double electron-beam-melted and subsequently fabricated to 0.3-in. rod by extrusion and swaging. The starting materials were commercial powders of tungsten and rhenium with impurity levels as listed in Table I. The various blended W-Re compositions were hydrostatically pressed at 70 ksi. The pressed bars were drip-melted into 1.5-in.-diam ingots and then remelted into 2-in.-diam ingots at a chamber pressure of 10~5 torr. The ingots were canned in molybdenum and extruded to round bar at a reduction ratio of 6:l. The alloy extrusions were swaged to about an 80 pct reduction at 2100" to 2900°F. Buttonhead tensile specimens with a reduced section diameter of 0.16 in. and a gage length of 1.0 in. were centerless-ground from the swaged bars

Jan 1, 1970

By Homer F. Staley, C. P. Karr

The casting alloy 88 copper, 10 tin, 2 zinc, commonly known in England as Admiralty metal and in this country as Government bronze, gun metal, or Naval Department composition G, has, at its best, many valuable properties. However, its physical properties are known to vary widely with slight changes in method of manufacture of the castings, such as slight variations in composition, variation in pouring temperature, kind of mold used, method of pouring and gating of molds, size and shape of castings, amount and kind of heat treatment, and so forth.' The microstructure of castings made from this alloy is influenced by slight variations of composition, rate of cooling, and kind and length of heat treatment. This is best understood by reference to the equilibrium diagram. The part of the diagram in which we are interested and the effect of the thermal equilibrium relations on the physical properties of the alloy 88 copper, 10 tin, 2 zinc, have been discussed by Hoyt, Campbell, Primrose, and Rawdon.2 In Fig. 1 is given the equilibrium diagram of the copper-tin alloys. Briefly stated, the relations of composition and temperature changes are as follows. Compositions between A and a consist of but one constit ent—the a bronze, which is a solid solution of copper and tin, rich in copper. On cooling from the molten state these compositions gradually crystallize, at temperatures above 790°, into a mass of interwoven treelike crystals or dendrites. The cores of the dendrites are rich in copper and the percentage of tin gradually increases as the surfaces are approached. AS cooling progresses, after a11 the metal has crystallized, no further changes occur in the crystals other than diffusion within the crystals, which tends to erase the dendritic pattern and to render the structure more homogeneous. * Metallurgical Ceramist, U. S. Bureau of Standards, Associate Physicist, U. 8. Bureau of Standards. A. D. Flinn: Iron. Age (1915) 96, 1292-3. C. P. Karr: U. S. Bureau of Standards Tech. Paper 59, Pt. 1. S. L. Hoyt: Enging. (1913) 96, 667-7, 704-5. William Campbell: Trans. Am. Inst. Met. (1912) 6, 158-172. H. S. Primrose: Metal Ind. (1916) 14, 202-4. H. S. Rawdon: U. S. Bureau of Standards Tech. Paper 59, Pt. 11.

Jan 1, 1921

By T. G. Decker, A. F. Witt, A. M. Gaudin

The historical development of the concept of contact angle hysteresis is reviewed. The measurements of contact angles reported in literature have all been made under static conditions. For the measurement of dynamic advancing and receding contact angles, four methods are described together with an evaluation of their precision. Three of these methods were adapted from devices already used for the measurement of static contact angles. The fourth method uses a new principle and apparatus and is the most accurate. While the relationship between surface tensions and the contact angle was extablished as early as 1805 by T. Young,' it was only in 1890 that the existence of contact angle hysteresis was reported by Lord Rayleigh. His observations, however, remained almost unnoticed. With the invention of froth flotation, the contact angle and its behavior became the subject of investigation. In 1907, L. Sulman and collaborators investigated the cause of discrepancies between recorded values of contact angles. They found that certain variations existed in most cases, but that definite maximum and minimum values of contact angles are obtainable. The difference between the maximum and the minimum contact angle in a given system was termed "hysteresis" by Sulman. First attempts to explain hysteresis were made by E. Edser. In the following years extensive studies of contact angles in various three-phase systems

Jan 1, 1963

By W. O. Borcherdt

THE 650-ton underground mill of The Empire Zinc Company of Colorado (a subsidiary of The New Jersey Zinc Co.) serves the Eagle mine at Gilman in the Battle Mountain mining district of Colorado. The topography is rough, the mine and mill being under Battle Mountain and the alit entrance in the north wall of the canyon of the Eagle River, which is here a steel) gorge. The town of Gilman stands on a shoulder of the mountain at altitude 8975 ft., above sea level, along the Pike's Peak ocean to ocean highway and contains the company office and the usual facilities of a modern mining town. The railway contact is at Belden, altitude 8370 ft., at the bottom of the gorge directly below Gilman, where the westbound track of the Denver and Rio Grande Western Railroad is cut along the north bank and the eastbound track along the south bank of the river. A general description of the mine, mill and service facilities, with an account of the geology, character of the ore and methods of mining and milling having previously been published in a series of articles1, this paper will discuss with as little repetition as practicable the reasons for building the mill underground rather than as a conventional structure, the methods of construction employed and the experiences gained in what is apparently the pioneer plant of this type and extent.

Jan 1, 1937

By C. J. Rosa, W. C. Hagel

An attempt is made to determine the diffusion coefficients of oxygen ions in hypostoichiometric zirconium oxide. A phenomenological theory is developed for three-phase, unidirectional volume diffusion of a gaseous species from a planar source. Knowledge about oxygen diffusion in a and ß zirconium and experimentally measured rates of movements of interfaces permit the evaluation of oxygen ion diffusivi-ties in ZrO2-x. The results conform to the relationship: sq cm per sec, for the temperature range of 875" to 1050° C. DIFFUSION coefficients of oxygen ions in stoichio-metric oxides have been studied by many investigators. The obtained results not only supplement the knowledge about the lattice-defect structures of oxides and conduction mechanisms but also provide information of technological importance. Rate processes such as oxide sintering, high-temperature creep deformation, and oxidation of metals and their alloys are directly dependent on diffusion phenomena. Unfortunately, diffusion coefficients obtained from studies on stoichio-metric oxides cannot be treated without restraints when applied to oxidation kinetics, if precise evaluations of oxidation rates are desired. Oxides formed on metals are usually nonstoichiometric and exhibit nonuniform distribution of either cation or anion vacancies across their thicknesses. Debuigne and Lehr1 extended Danckwerts'2 mathematical analyses and furnished a semitheoretical treatment for evaluating oxygen diffusion coefficients in zirconium oxide in terms of weight gain measurements during oxidation of zirconium in the temperature range 400° to 850°C. Their calculations are based on theoretical partitioning3 of the total amount of oxygen between a zirconium and its oxide phase. An inherent discrepancy appears to continue throughout their calculations. The amount of oxygen confined to the oxide phase should be corrected by multiplying the calculated oxide thickness by the inverse of Pilling-Bedworth ratio, if expansion of zirconium dioxide is taken into account. The purpose of the present investigation is to provide a new semitheoretical treatment for evaluating diffusion coefficients of moving species in hypostoichiometric oxide. The analyses are relevant to unidirectional volume diffusion. Although the presented method is quite general, its applicability will be discussed in terms of kinetic measurements from oxidation of zirconium at temperatures above the a/ß transition, for reasons stated in the later part of this paper. EXPERIMENTAL Pure, 99.93 wt pct, zirconium samples of approximately 2 by 1 by 0.35 cm were exposed to oxygen for various times at four temperature levels: 875°, 950°, 1000°, and 1050°C. High-purity, better than 99.9 vol pct oxygen was passed through a cold trap and columns containing anhydrous CaSO4 to remove residual water vapor. Before exposing to oxygen at a pressure of 500 Torr, specimens were subjected to wet abrasion on 200- through 600-grit Sic papers and polished with 1—p diamond dust. Prior to oxidizing, all zirconium samples were vacuum-annealed at 10-6 mm Hg for about 15 min at the test temperature. The temperature variation across the uniform heat zone was ±2°C from the preset value. Final polishing, for phase thicknesses measurements, was performed by using 8- and 1-p diamond dust and followed by vibrator polishing with 0.05-µ ? Al2O3 solution. Measurements of phase thicknesses were made by projection on a metallographic viewing screen. Conventional powder X-ray analyses for the oxide were employed. RESULTS Fig. 1 is an example of the cross section of oxidized zirconium. Designations of phases given below this figure are the same as those used in the three-phase diffusion system represented by Fig. 5 in the following section. Zirconium oxidized for longer exposure times showed two types of oxides: white oxide at the surface and an underlaying layer of gray oxide. X-ray powder patterns of these oxides at room tern-

Jan 1, 1969

By C. R. King

Most of the acid volcanic glasses such as obsidian, perlite, pitchstone, pumice, and pumicite (volcanic ash) are susceptible to some expansion if suddenly subjected to a suitably high temperature in a properly designed furnace, and subsequently suddenly cooled. Expansion results from the action of chemically combined or dissolved water expanding as a vapor within the softened heated rock particles. This expansion forms countless minute bubbles within the pasty mass of the natural glass particles. If the particles are cooled before these bubbles can escape, the resulting products are cellular, more or less spherulitized glass froths or hollow glass spheres of many types. Chemically, they are essentially aluminum silicates containing about 70 to 75 pct silica, 10 to 16 pct alumina, and 2 to 7 pct sodium plus potassium oxides. They are relatively resistant to attack by acids or alkalies, are resistant to heat up to over 1000°F, and are completely inert to insect or fungus attack.

Jan 1, 1949

By H. H. Hausner, H. S. Kalish

IN recent years zirconium and beryllium have become of great interest because of their special properties. Zirconium is known for its remarkable ability to absorb the gases oxygen, nitrogen and hydrogen, has extensive use as a getter in electron tubes and has indeed become the primary metal in the manufacture of photoflash bulbs. Beryllium is of interest because it is light metal and as such could supplement aluminum and magnesium in light metal applications. The late development of zirconium ductile at room temperature produced by both the iodide and calcium reduction methods has stimulated frequent articles on this metal in the recent literature. Beryllium is so closely akin to zirconium crystall-ographically that some investigators are of the opinion that beryllium should be ductile at room temperature if it were pure enough. The crystallographic relationship of beryllium and zirconium, the interest created in Be-Zr alloys where the zirconium is believed to function as a remover of solid solution gas in beryllium and thus increase the ductility of the beryllium rich alloy, and the amenability of these metals to powder metallurgy methods stimulated this approach to an investigation of the system Be-Zr. Preliminary work showed that a zirconium compact melted when pressed in contact with a beryllium compact and sintered at 1250°C, without any apparent final bond between the two. A search of the literature revealed nothing pertinent about the Zr-Be system or about any zirconium - beryllium alloys. In 1936 Misch³ vaguely identified the compound ZrBe2 and reported that it has a deformed cubic structure. Two patents," , were issued to Mach-lett Laboratories in 1943 and in 1946 regarding the addition of small amounts of zirconium to beryllium in order to improve the ductility of beryllium so that it may better be used for X ray windows. In considering the alloy formation of beryllium with other metals Raynor thought it unlikely that zirconium would have any solid solubility in beryllium. From this indefinite information nothing could be ascertained about the possible use of Zr-Be alloys or the use of these metals intimately. A brief preliminary study of the system Zr-Be by powder metallurgy methods was undertaken to provide regions for more intense studies of Zr-Be alloys and as a guide to a formal phase diagram determination. The investigation described in the following pages was completed in less than three weeks. The usefulness of this rapid method to facilitate phase diagram studies and new alloy investigations will be shown. Materials and Procedure Zirconium powder was produced from crystal bar stock of high purity supplied by Foote Mineral Co. The crystal bar was converted to hydride at 730°C, crushed, and the hydride decomposed in purified argon at 850°C. 60 pct of the powder passed through a 325 mesh screen, 40 pct of the powder was —140 mesh, +325 mesh and the average particle size of the total was 8 to 12 microns. The beryllium powder was used as re-

Jan 1, 1951

By C. S. Barrett, O. R. Trautz

PREVIOUS investigations have shown that lithium is body-centered cubic from near its melting point to the temperature of liquid air1,2,3 Nevertheless there was an incentive to search again for a transformation at low temperatures: C. Zener4,5 has remarked that the low value of the elastic modulus (11 - C12)/2 of body-centered cubic metals and alloys implies a rapid increase in free energy with decreasing temperature, which would favor the occurrence of a transformation; also the shear movement to which this modulus applies is one that can transform a body-centered cubic structure into a slightly distorted face-centered cubic structure. It was confirmed that lithium does not transform spontaneously at liquid nitrogen temperature, but it was found that a transformation can be induced at this temperature by cold working the metal,6 and at slightly lower temperatures a different transformation occurs spontaneously. Transformations were also found in solid solutions of magnesium in lithium. THE NATURE OF THE TRANSFORMATIONS Before presenting a detailed treatment of the technique used and the specific data obtained, it would be well to give a brief survey of the general characteristics of the transformations. A new crystal structure begins to form spontaneously in a specimen when it is cooled below a critical temperature. In lithium the structure appears to be close-packed hexagonal; in the Li-Mg alloys most of the diffraction lines (but not all) are near those for hexagonal lithium. The transformation proceeds as the temperature is lowered and soon stops if the temperature is held constant or raised. The course of the transformation on cooling is indicated by the curve at the lower left of Fig I. This curve is drawn in stepped fashion because the transformation goes by discrete steps with audible clicks. Because of the similarity to the decomposition of austenite into martensite in steels, it seems appropriate to designate the beginning of the spontaneous transformation on cooling as the Ms point. On heating to room temperature after the low temperature treatment only the usual BCC structure is found. On heating, the low temperature modification begins to disappear at a temperature which will be designated as Ac. The transformation on heating is halted when the rise in temperature is halted. The temperature must be raised 40 to 50°C above Ac before the reversion is complete-an interval which is sensitive to the rate of heating and to the time of holding at temperatures above Ac. This behavior on heating thus has similarities also to the formation of martensite in the cooling of steels.

Jan 1, 1948