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By R. G. Brown

Tars paper will present a general description of the different mineral belts in the Butte City region (limited, however, to the copper and contiguous silver veins) such as may serve to give an intelligent idea of the distribution and characteristics of the deposits, forming thus a groundwork of information, which it is hoped will have value, when later writers enter into particularized detail.

Jan 1, 1895

By M. E. Straumanis, J. -P. Krumme

In basic ([KOH + KCl] with a total polarity of 2) or acidic (2N H2SO4) electrolytes and at anodic current densities of more thun 2 to 4 ma per sq cnz, n-type GaAs single crystals of lozo resistivity preferentially dissol~je forming etch tunnels with triangular or civc~ilay cross sections and of a width between 0.5 arid 5 p. These etch tunnels are oriented along any one of the four possible (111) directions of GaAs. However, their growth occurs only in one direction of a given (111) whick apparently is determined by the atomic sequence Ga —As (and not the rezlerse) in respect to an individual valence bridge in the crystal. It is concluded from comparison with the cubic lattice structure of GaAs that the etch tunnels represent macroscopic evidence for the tetrahedral bonds and their polar properties. If the anodic current density is increased the tunnel fomation results in the development of a fibrous surface layer consisting of GaAs. The latter separates frorn the substrate (in an anodic s~irface disintegration process) by the growth pressure of an As,0, filnz forming in the interior of the fibrous layer, 100 to 200 µ under the surface, at more than about 50 ma per sq cni. The fibrous GaAs film has the same crystallographic orientation as the substvate and represents a skeleton of the original crystal. Since the etch-tunnel density in a separated GaAs layer is about 108 c?n-', and the etch tunnels develop only along (111) in a given polar direction, it is assurraed tlmt the dislocations have no influence on the growth of these tunnels. ElECTROLYTIC treatment of smooth surfaces of poly- and single-crystalline GaAs at high anodic current densities causes the formation of porous surface layers.' This phenomenon suggests comparison with effects being observed with magnesium,' indium,, gallium,4 and aluminum5 and known as "anodic disintegration". The purpose of the present paper is to explore and to explain the reasons for the formation of such surface layers on GaAs and, in particular, to investigate the influence of the lattice polarity of this III-V compound semiconductor in the (111) direction on the anodic dissolution behavior. GaAs SINGLE CRYSTALS For the experiments described below GaAs single crystals from the Monsanto Co., St. Louis, Mo., were used. Their impurity levels were below 1 ppm and their dopant levels between 1 and 100 ppm. They were grown in (111) using the Czochralski or the gradient-freeze technique. The crystals had n-type conductivity and electric resistivities between 1 and 5 ohm-cm. EXPERIMENTAL The GaAs single-crystal rods were cut perpendicularly to (111) into wafers of about 1 mm thickness using a wire-blade crystal slicer and an aqueous slurry of Sic or a diamond saw. The orientation of the faces of these wafers were checked by Laue back-reflection patterns. If there was a deviation from (111) the faces were abraded under a certain angle using grinding paper and distilled water. The damaged surface layer was removed from each crystal by chemical etching with a mixture of 1HF:1HNO3: 1H20 or 2HF:1HNO3:2HAc (glacial). {110) faces were obtained by mechanical cleavage, producing surfaces which did not require a further treatment. The GaAs wafers were mounted using "alligator" clamps instead of soldered electrical contacts.' Only the bare crystal surfaces were dipped into the electrolyte. The clamps were coated with insulating wax to prevent any contact with the electrolyte. The experiments were carried out in aqueous 2 N H2so4,' or in an aqueous solution of KOH and KCl1 (1 mole KOH + 1 mole KCl in 1000 cu cm solution). Anodic current densities up to several hundred ma per sq cm were applied for periods between 30 sec and 2 hr. For the purpose of investigating the initial steps of disintegration the anodic current density applied never exceeded 20 ma per sq cm. The films which partially separated from the anodic surfaces under high-field conditions were treated with KOH to further their detachment by dissolving the As2O3 formed. The washed and dried films were pasted to strips of filter paper, and Laue pictures were made. The back-reflection patterns obtained were compared with those of the original anode surface before and after anodic dissolution. Furthermore, space reciprocal lattices7 were constructed from asymmetric rotation crystal patternsa which permitted the determination of the crystallographic orientation of the detached films of the corrugated anodic surfaces. The disintegration products were identified from assymmetric powder patterns.8 The polarity of the {111) faces was determined by chemical etching with mixtures of 1HF:1H2O2(30 pct): 2H2O or 1HNO3:2H2O. Different patterns on each of two inverse (111) sides appeared.'-l8 The correlation of these patterns to the Ga{111) or the As(111) side has already been established by the use of light figures,18-20 by X-ray diffraction near the absorption edges of gallium and arsenic,'lmZ4 and by LEED measurements.25 The geometric structure of these surfaces and the interior of the anodically attacked crystals were observed and photographed with a high-power microscope using oil immersion objectives up to magnification of X1720.

Jan 1, 1968

By W. H. Emmons

This paper is the second of a series treating the relations of ores of the metals to igneous rocks. In the first paper1 the general problem was outlined and the normal downward changes in metalliferous lodes were briefly stated, with references to earlier papers treating the relations of ores to depths of their formation. The present paper by a number of examples illustrates the relations treated in the first paper. These examples are chosen chiefly from the larger mining districts because their underground developments are more extensive, but the same relations are shown in maps of scores of undeveloped areas in which the main geological conditions are nearly similar. Ecology of Metalliferous Deposits Ore deposits are divided into three groups: 1, Those formed by sedimentary processes; 2, those deposited by meteoric waters; and, 3, those formed in connection with igneous processes. The last group is the most important. It includes the magmatic segregations, which are igneous rocks in the strict sense, and the veins and related deposits, which were formed by precipitation in channels from solutions originating in cooling intrusives. These deposits may be divided into two groups: 1. Those related to intrusives as basic as diorite; and, 2, those related to intrusives more acid than diorite. The second group probably includes more than 95 per cent. of all lode ores. Nearly all of the ores of this group are associated with granitic batholiths or are in positions where it is reasonable to suppose that such a batholith, not yet exposed by erosion, underlies the area containing the deposits. The batholiths are great masses of deep-seated igneous rocks. When they are intruded most of them are probably as basic as diorite and some

Jan 1, 1927

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 John R. Low

A number of cases of low-temperature, intergranu2ar brittle fracture of metals containing small amounts of certain impurities, have now been identified. Some degree of understanding of this phenomenon exists for the simpler binary systems of a metal and a single impurity, but the profound effects of other impurities and alloying elements in modifying this type of behavior remain unexplained. Current research in this area is reviewed and some of the newer techniques of investigation which should make possible a more quantitative study of the structure and composition of grain boundaries in impure metals are described. To indicate the subject matter of this lecture, we may begin by reviewing the experimental observations concerning low-temperature intergranular brittleness in impure metals, particularly those examples in which the embrittlement appears to result from what has been called "equilibrium grain boundary segregation."' These are the systems in which it has been impossible, at least up to now, to detect the presence of any second phase film at the brittle interfaces. When second phase films are present they are usually readily detectable by fractographic methods, often appearing as epitaxial films in geometric or dendritic patterns. An example is shown in Fig. 1 for the case grain boundary carbides in a sensitized stainless steel which failed by intergranular brittle fracture at 78?k2 In contrast to this type of embrittlement there are numerous examples of low-temperature intergranular embrittlement in which the fractographs are essentially featureless, for example, that of an oxygen-embrittled iron shown in Fig. 2. The only second phase particles visible are the small, widely separated, round oxide particles typical of the bulk material. The fracture surface is extremely smooth and the fracture path appears to follow the intergranular interface without deviation. This type of fractograph also implies that crack propagation has occurred without plastic deformation at the crack tip, since localized slip or twinning ahead of the crack would be expected to distort the interface and be readily visible in the fractograph. Such indications are occasionally seen in these fractographs, but are not characteristic. A second example of this type of fractograph is shown in Fig. 3, which is from a temper-embrittled, carbon-free, Fe-Cr-Ni alloy containing Sb, broken at 1OO?C.3 The similarity to the oxygen embrittled iron case will be apparent. In the case of the temper embrittled Cr-Ni ferrite containing antimony, it is possible to remove the embrittlement by suitable thermal treatment. The grain boundaries may then be examined by thin film transmission in the electron microscope for the material in both the nonembrittled condition and in the embrittled condition. Two boundaries are shown in dark-field transmission in Fig. 4, one in the nonembrittled

Jan 1, 1970

By M. J. Sheriff, D. H. Smith, W. Macdonald

The paper outlines the basic procedure used in electrical system planning and design. Consideration is given to the use of applicable codes and standards, development and use of a system One Line Diagram, power availability, load requirements and power factor. Also discussed are the factors influencing the selection of power supply and distribution arrangement, voltage levels, system grounding, distribution and utilization equipment such as switchgear, transformers, motor control, cable systems, motors. Short circuit calculation methods and system protection are discussed.

Jan 1, 1978

By George M. Bouton, Lawrence Ferguson

The experiments described in this publication were inspired by the Bell System's large interest in lead-alloy sheathed cables and by the wide range of fatigue and corroding conditions to which they are sometimes subjected in service. The first experiments consisted of operating specimens of lead + I per cent antimony telephone cable sheath alloy in a fatigue test while they were immersed in water taken from a manhole. Because of many published reports concerning corrosion-fatigue phenomena of various metals and alloys, a reduction in fatigue life was expected(1)2 Instead, however, the fatigue test ran on for many times the normal number of cycles an4 was finally stopped without failure. Because of this, the experiments were broadened to include the effect of many media on the fatigue properties of four lead alloys over a wide range of testing speeds and strains. One material, a viscous tacky polymerized isobutylene3 used in

Jan 1, 1945

By J. H. Klepinger, C. W. Goodale

I. Introduction....................567 II. Character oF the OrE................568 III. Old FluE System..................572 IV. Tests on Old FLUE System..............575 1. Aspiration Tests................. 575 2. Tests with Steel Settling Chamber........... 575 3. Test with Experimental Brick Flue........... 583 4. Testa on Blast Furnace Geses............. 591 V. Design of New FluE System.............. 597 VI. Main Dust Chamber................. 605 VII. Some DetailS of Construction ............. 609 VIII. THE Chimney.................... 616 IX. Operation of New FluE System............. 624 X. Temperatures and DraFTS............... 630 XI. Velocities and Volumes................ 632 XII. TeStS on the New FluE System............. 637 XIII. Conclusion..................... 643 I. Introduction. In the summer of 1909 the Boston & Montana reduction department of the Anaconda Copper Mining Co. completed a new flue system, at a cost of about $1,100,000, and as this includes the largest and highest chimney in the world, and some new features of flue construction, a description will be of interest. At the Spokane meeting of the Institute in September, 1909, a brief mention was made of this flue system, in discussing Mr. Brunton's presidential paper on the Progress of Metallurgy in the West, and a promise was given that when a long enough time had elapsed, so that operating results could be given, a paper would be offered. The smelting plant includes blast furnaces, MacDougall roasters, gas-fired reverberatories, and converters.

Jan 1, 1914

By G. Caetani, E. Burt

Jan 1, 1907

By Robert Mehl

METALLURGISTS are properly interested in papers dealing with subjects ranging from the theories of the metallic state to very practical details on the use of metals. A review of theoretical metallurgy naturally excludes papers concerned with the usefulness of metals and limits itself to those concerned purely with the science of metals. Even in this more limited field the reviewer is confronted with thousands of papers dealing with facts and theories of metallic behavior, from which he can select only a few hundred. The selection is necessarily highly arbitrary. Certain classes of papers definitely fall within the scope of this review. Thus, papers on the deformation of metals, on the structure of alloys, on recrystallization, to select only a few, are fully represented. Other subjects, which verge on what is generally accepted as the science of metals, such as the magnetic properties of metals, the less familiar electrical properties and theories, adsorption of gases by metal surfaces, and the like, are treated scantily. Particular attention is given to reviews of subjects that fall with in the groups chosen; in a summary such as this, which is largely in the nature of a progress report, capably written reviews are of importance, particularly since the monograph and text book literature is so meager in this field.

Jan 1, 1935

By H. A. Bright, H. C. Vacher, J. G. Thompson

The methods employed for the determination of oxides and oxygen in ferrous materials may be roughly classed in two groups, "wet" methods and "hot" methods, the first group including the iodine, electrolytic, mercuric chloride, hydrochloric acid, nitric acid, and chlorine methods; the second group including the vacuum-fusion and hydrogen-reduction methods. The wet methods depend upon preferential solubility in a selected medium to separate the metallic portion of the sample from the oxygen-containing constituents. Subsequent analysis of the insoluble residue permits the isolation and separate determination of individual oxides and compounds. The hot methods depend upon the reduction of the oxide constituents of the sample by means of carbon or hydrogen at elevated temperatures. With the exception of the recently developed fractional vacuum-fusion method, the hot methods do not identify individual oxides and compounds but yield only a single value representing the sum of the oxygen contents of several or all of the oxide constituents present. With such diversity in the principles and aims of the different groups, it is not surprising that concordance of results by different methods has usually been difficult to obtain. The present cooperative attempt to define more rigorously than has been possible heretofore the accuracy and limits of usefulness of the various methods, originated in correspondence between Dr. John Johnston, Director of Research of the United States Steel Corporation, and other interested metallurgists. The plan was, briefly, to submit identical samples to a number of laboratories for analysis by different methods and to collate the results of these analyses. The project was endorsed by the Iron and Steel Division of the American Institute of Mining and Metallurgical Engineers at the annual meeting in February, 1933, and has been conducted under the joint sponsorship of the Iron and Steel Division and the National Bureau of Standards. The latter organization undertook

Jan 1, 1937

By William Best

OIL burners, oil furnaces, and methods of installation, have been the subject of many articles, but information concerning oil-burning systems, based upon scientific principles, is still in great demand, especially in the manufacturing districts of our country. Fuel oil, as it is termed (this being the residuum from oil refineries), has for many years been of great service to our manufacturers, and has justified its popularity not only by producing a superior manufactured product, but by turning out approximately 50 per cent. more product than can be made with coal fuel under like conditions. To install a system requiring only an oil-storage tank, a small pump, and an oil-supply main with numerous laterals leading to the various burners, furnaces, boilers, etc., is a comparatively simple matter; and, because fuel oil is very volatile, it is not necessary to heat it, even during the winter months in a very cold climate. Furthermore, only a small amount of power is required to atomize fuel oil, this often being done by a positive pressure blower, or by a mechanical burner. An analysis of fuel oil, together with that of various other liquid fuels, is given in Table I.

Jan 2, 1914

By L. W. Legerwood

During the past three decades, the oil industry has expended increasing eflorts seeking improved drilling tools or systems to reduce drilling costs. The total cost of these efforts is unknown, but it certainly amounts 10 tens of millions of dollars. Most of the "new" system that past and present investigators have sought to develop actually are old public information. In seeking to implement new-systern concepts, investigators have tested the following: impact at frequencies ranging from 6 to 300 cycles per second; electrical, mechanical and hydraulic meam of actuating percussors; bit rotary speeds up to 2,000 rpm; electric and hydraulic bottom-hole means of rotating bits; bottom-hole machines with power outputs up to 400 hp; shock waves; explosives; high-velocity pellets; flame; arc; grinding wheels; abrasive jets; erosion by high-velocity gases; chemical attack; electric current; magnetic waves; retractable rock bits; reelable drill pipe; continuous coring with reverse circulation; and automation of drilling rigs. Table I shows how these investigations are grouped for discussion purposes in this paper. In spite of these efforts to discover new and improved systems, rotary drilling main;aim its economic leadership. Undoubtedly, rotary drilling costs will continue to be reduced by rigid application of the best available technology and by development of new rotary technology. In view of the extensive past development programs, however, significant long-range improvement appears to be a research, not a development problem. Research must postulate and prove theories and principles governing variour subsurface rock-failure processes pertinent to both rotary and new systems. Ah, research must produce physical and engineering data relative to these processes. When such information is available, earth boring will graduate from an art to a science. Major improvements in rotary drilling can then be expected, and the systematic evolution of an improved drilling method can be initiated—with a strong probability for success. Development of drilling methods other than rotary drilling has been one approach investigated by the industry as a means for reducing drilling costs. Major cost-reduction efforts, however, have been centered on engineering development work aimed at incremental improvements in rotary drilling. A relatively minor effort has been expended to establish basic physical principles and engineering data pertaining to the earth-boring process which can serve as a foundation for the development of cost-cutting drilling hardware. Current oil-industry economic trends have added impetus to the need for effective programs to reduce drilling costs. However, areas for expanded future efforts should be selected only after careful study of past investigations. It is the purpose of this paper to review past and Dresent industry efforts to develop new drilling tools or systems and to suggest areas where additional science is needed. Past reviews of drilling methods have been limited to a few processes prominent at the time the reviews were made. This paper seeks to present a concise, well organized review of all methods that have received actual development or test work. The preparation of a paper seeking to review all past developments is fraught with many difficulties, not the least of which are errors in or obsolesence of printed matter used as source material and the lack of data on industry developments which have not been published. Since de-

By H. S. Munroe

THE native copper of Lake Superior occurs in the form of fine grains and scales, disseminated in small percentage through the copper-bearing rock ; and in large and small masses, from a few pounds to several hundred tons in weight. Formerly the bulk of the copper came from the mines of Ontonagon and Keweenaw counties, producing mass copper. At present these mines furnish less than one-tenth of the total product, and fully one-half of this is from a single mine. The masses are usually found irregularly distributed in nearly vertical fissure veins, and require much dead work in sinking, drifting, and stoping for their development. The risk and expense attending the working of these mines have made them, with few exceptions, anything but profitable. * Read at the Montreal meeting, September, 1880.

Jan 1, 1880

By Adrien Berton

FOR nearly a century, the Corocoro deposit has been renowned among geologists from the fact that it shares with the Lake Superior deposits of the United States the distinction of being the only important copper districts where native copper is worked commercially. The Corocoro district, named after the city of Corocoro, the capital of the Province of Pacajes (Department of La Paz, Bolivia) is situated towards the western edge of the Bolivian high plateau, at an altitude of a little over 13,000 ft. The most interesting part of the district is that immediately surrounding the city of Corocoro, at a distance, by railway, of 65 miles from La Paz and 210 miles to the Chilean port of Arica on the Pacific Coast. The climate of the region is that of the semi-desert, dry and relatively cold, with big differences of temperature between day and night. The rainy season begins in December and ends in March. The cupriferous lodes of Corocoro have not attracted as much interest as the silver mines of Potosi but they have been known for a long time. In the precolonial period the Indians were using the charquis, or natural native copper sheets, to make small brass objects, and the beautiful pale green brochantite of the outcrops as a source of green pigments. During the colonial period, the oxidized ores of the outcrops were worked for copper, which was used by the mint at Potosi for making currency. The native copper ores were neglected because the Spanish miners were at a loss how to concentrate and smelt them. About 1830, work by rudimentary processes, which were improved little by little, was begun on the native copper ores. The total production of native copper in the following hundred years amounted to 100,000 tons. This native copper, which was remarkably pure, was much appreciated on the European markets before the introduction of electrolytic copper. It was useful for making special ornamental brass or bronze and the granular concentrates of native copper, called barrilla, containing 80 to 85 per cent copper were suitable for making copper sulfate by direct oxidation and subsequent leaching with sulfuric acid.

Jan 1, 1936

By H. O. McLeod, J. M. Campbell

This paper presents the results of the data obtained in the first stage of a long-range study at high pressures of the system, vapor-hydrate-water rich liquid-hydrocarbon rich liquid. The data presented are for the three-phase systems in which no hydrocarbon liquid exists. Tests were performed on 10 gases at pressures from 1,000 to 10,000 psia. One of these was substantially pure methane, and the remainder were binary mixtures of methane with ethane, propane, iso-butane and normal butane. Several conclusions may be drawn from the data. 1. Contrary to previous extrapolations, the hydrocarbon mixtures tested form straight lines in the range of 6,000 to 10,000 psia which are parallel to the curves for pure methane, when the log of pressure is plotted vs hydrate formation temperature. 2. The hydrate formation temperature may be predicted accurately at pressures from 6,000 to 10,000 psia by using a modified form of the Clapeyron equation. The total hydrate curve may be predicted by using the vapor-solid equilibrium constants of Carson and Katz' to 4,000 psia and joining the two segments with a smooth continuous curve between 4,000 and 6,000 psia. 3. The use of gas specific gravity as a parameter in hydrate correlations is unsatisfactory at elevated pressures. 4. The hydrate crystal lattice is pressure sensitive at elevated pressures. INTRODUCTION Prior to 1950 many studies had been made of the hydrate forming conditions for typical natural gases to pressures of 4,000 psia.""'"'"" Most of these attempted to correlate the log of system pressure vs hydrate formation temperature, with gas specific gravity as a parameter. One of the more promising correlations was made by Katz, et al, which utilized vapor-solid equilibrium constants. The only published data above 4,000 psia are those of Kobayashi and Katz7 for pure methane to a pressure of 11,240 psia. In the intervening years, most published charts for the high-pressure range have represented nothing more than extrapolations of the low-pressure data, with the methane line serving as a general guide. The reliability of these charts has become increasingly doubtful (and critical) in our present technology as we handle more high-pressure systems. The portion of our high-pressure hydrate research program reported here was designed to: (1) investigate the reliability of existing charts; (2) obtain actual data on gas mixtures to 10,000 psia; and (3.) develop a simple hydrate correlation that was more reliable than those which simply used specific gravity as a parameter. Binary mixtures of methane and ethane, propane normal butane, or iso-butane were injected into a high-pressure visual cell containing an excess of distilled water. Hydrates were formed and then melted to observe the decomposition temperature of the hydrates at pressures from 1,000 to 10,000 psia. EQUIPMENT The equipment consisted of a Jerguson 10,000-lb high-pressure visual cell, a 10,000-1b high-pressure blind cell and a Ruska 25,000-1b pressure mercury pump. The visual cell was placed in a constant-temperature water bath controlled by a refrigeration unit and an electric filament heater. A Beckman GC-2 gas chromatograph was used in analyzing the gas mixtures after each run was completed. EXPERIMENTAL PROCEDURE After evacuating the gas system, the heavier hydrocarbon was injected into the high-pressure mixing cell to that pressure necessary to give the desired composition. This cell then was pressured to 1,100 to 1,200 psia by methane from a high-pressure cylinder. The mixing cell holding the gas contained a steel flapper plate and was shaken intermittently over a period of 15 minutes. After mixing, the valve to the high-pressure visual cell containing excess distilled water was opened, and the gas mixture was allowed to flow into the cell. The temperature in the water bath was lowered 10" to 15'F below the estimated hydrate decomposition point. As a first check, the temperature was increased at a rate of 1°F every six minutes to find the approximate point of decomposition. It was again lowered 1.5° to 5°F to form hydrates. The temperature was raised to within l° of the estimated decomposition point and then increased 0.2F every 10 to 15 minutes until the hydrates decomposed. This procedure was repeated at various pressures to obtain 7 to 13 points for each mixture between 1,000 and 10,000 psia. After completion of the hydrate decomposition tests, the gas mixture composition was analyzed with a calibrated gas chromatograph. These gas analyses have an estimated error of ± .1 per cent.

By W. Rostoker, D. W. Levinson, A. Yamamoto

The influence of carbon on tensile strength, tensile ductility, transformation kinetics, and grain growth characteristics of selected Ti-Mo base alloys was studied. No systematic influence of carbon in tensile strength or significant deleterious effect on tensile ductility was observed. There was a marked increase in transformation rate due to carbon. Dispersed carbides exert a marked inhibiting effect on grain boundary migration, and thus effectively prevent grain coarsening during solution treatment in the ß phase field. AS part of a research program directed toward the illumination of factors governing modes of transformation, transformation kinetics, and mechanical properties obtainable through these transformations by heat treatment, Ti-Mo base alloys were selected for study. The binary system is a characteristic phase diagram type which has been studied in some detail', ' in relation to transformation kinetics and mechanical properties. Although carbon bearing alloys have acquired a bad reputation, the possibilities of melting titanium under conditions which occasion some carbon pickup are very attractive. It is therefore of considerable importance to know whether carbon, present as a dispersed carbide phase, is actually deleterious when all other detrimental factors are minimized. Basic alloy compositions containing nominally 3, 5, 7, and 11 pet Mo were prepared with systematic carbon addition up to 1 pet by weight. Various of these alloys were subjected to a series of critical and definitive experiments to delineate the effect of carbon on the transformation behavior and associated mechanical properties. Experimental Procedure Alloys were prepared from 115 Bhn magnesium-reduced sponge titanium. This sponge analyzed ap- proximately 0.05 pet C. Ti-Mo and Ti-C master alloys were made by arc-melting the sponge with high purity (99.9 + pet) molybdenum and spectro-scopic grade graphite, respectively. Alloys were then prepared from the master alloys and sponge by double are-melting. One kg ingots were prepared by melting in a nonconsumable electrode furnace. These ingots were forged at 1000°C to '/z in. rods, and cleaned and processed into electrodes for the second melting operation. The final ingots were ground to remove surface defects, then forged again to 1/2 in. or 3/8 in. diam rods for processing to test samples. It is significant that all of the alloys at all carbon levels forged satisfactorily. For convenience, the alloys will be referred to throughout the text by their nominal analyses. Samples for the study of transformation rates were prepared from 1/2 in. diam round stock. They were then solution treated in a helium filled tube furnace at 1000°C for 30 min prior to the isothermal transformation treatments in lead bath furnaces. Temperature control in both cases was within ±3oC. Following the isothermal transformation treatments the samples were water quenched. These experiments were carried out before the general adoption of the resistometric procedure for kinetic studies. The data were therefore obtained entirely by metal-lographic analysis. M, temperature was also determined by the metallographic method. Shoulder-type tensile test pieces were machined from heat treated, 1/2 in. diam slugs to provide a 0.252 in. test diam and a 1 in. gage length. The isothermal-type heat treatments were chosen from previous data' to provide three levels of strength and ductility.

Jan 1, 1957

By B. Russell, J. R. Tuffley

The stability regions of the normal sulfate and the various basic sulfates of lead in 02-SO2 and PhS-SO2 gas atmospheres were calculated from available thermodynamic data over the temperature range 600o to 1200oC. Roasting experiments were carried out on samples of synthetic lead sulfide at various temperatures and for various roasting times. Compounds in the oxidized surface layers were identified by X-my techniques. The order in which the various reactions occurred was determined by considering the experimental results in conjunction with the thermodynamic calculations. The results of these investigations were applied to the sintering of lead sulfide concentrates, and the extent to which each of the various reactions occurred in a sinter bed was determined. PRODUCTS which may be formed during the roasting of PbS are PbS04, PbSO4. PbO, PbSO4 . 2PbO, PbSO4 . 4PbO, PbO, and Pb.1, 2 The formation of some sulfates has been studied by a number of investigators3-' whose experiments have mostly been confined to the temperature range between 500" and 850°C. Culver, Gray, and spooner3 were able to isolate the reactions which formed PbSO4 and PbSO4. PbO by carefully controlling the compositions of the roasting gases. The kinetics of these reactions were studied within the temperature range 673" to 807°C. Gardner4 and Merrick5 also studied the kinetics of oxidation of PbS. Gardner disregarded the existence of basic sulfates and, as a result, misinterpreted some of his experimental data. Merrick recognized that most of the products of oxidation were mixtures of basic sulfates, but was unable to identify the individual components. Hoschek6 oxidized PbS in air at temperatures up to 800°C. The products were analyzed after roasting had proceeded for some minutes, but no attempt was made to follow the reactions in the initial stages. Consequently, no roasting mechanism was derived. He also showed that PbSO4 and PbSO4 - 4PbO decomposed slowly in air at temperatures in the region of 800°C. The stability regions of sulfates in the temperature range 500" to 850°C have been only partially determined, while practically no information is available for higher temperatures. In the lead sintering process, PbS concentrates are roasted at temperatures within the range 1000o to 1200°C. In order to investigate sulfate formation, it is necessary to determine the effects of temperature and gas composition upon the various oxidation reactions and upon the regions of stability of the various lead sulfates. Kellogg and Basu2 introduced an equilibrium diagram similar to those in Figs. 1 to 3 which provides a convenient medium for represent-

Jan 1, 1964

Jan 4, 1951

By J. Rourke, F. S. Minshall, E. G. Zukas, C. M. Fowler, O&apos

The Hugoniot curves were determined for Fe-Si alloys containing up to 7 wt pct (13 at. pct) Si. The pressure of the transition increased as the silicon content of the alloy increased. Single crystals of 2.9 wt pct Si-Fe were also studied. The pressure of the transition was not dependent on crystallo-graphic orientation. All of the Neumann bands (mechanical twins) were attributable to (112) planes but not all of the {112} planes showed twin markings. A thorough study of the iron Hugoniot (the relationship between specific volume and pressure) under plane wave shock loading revealed a pressure transition at about 130 kbar shock pressure. The results of this investigation were reported by Bancroft, Peterson, and inshall1 in 1956. At the time of this discovery, it was felt that this was probably the a, to y transition normally found in iron and many of its alloys. Subsequently a number of iron alloy systems were surveyed in which the alloying element has a considerable effect on the normal a, to y transformation. The influence of carbon and nickel and/or chromium have already been reported.2,3 At the present time, there appears to be some doubt that this pressure transition is the usual a, to y transition In this study, Fe-Si alloys containing up to 7 wt pct (13 at. pct) Si were chosen for several reasons. To the present, the transition has been found only in iron-base alloys which were originally in the a, phase (bcc). Secondly, the y loop at atmospheric pressure extends to only about 2.5 wt pct Si. If the transition were a, to y, then one might expect a rather drastic pressure effect for alloys containing more than 2.5 wt pct Si. Finally, single crystals of Fe-Si alloys large enough for shock loading studies are readily available thereby making it quite easy to determine the effect of crystal orientation on the transition pressure and on the twinning behavior of the alloy. EXPERIMENTAL PROCEDURE Fe-Si alloys containing up to 7 wt pct Si were produced by normal vacuum casting procedures. Single crystals of Fe-2.9 wt pct Si were purchased from Monocrystals Co., Cleveland, Ohio. The orientations of these crystals were determined and samples cut so that the shock wave would be parallel (to within 1.5 deg) to either the (loo), (Ill), or (112) principal orientations. Three distinct experimental testing techniques were used. First, the pin technique, described elsewhere,4 was used to determine the transition pressure for the polycrystalline alloys as well as for the (111) and (112) orientations of the 2.9 wt pct Si single crystals. Secondly, the recovery studies, described in detail in an earlier paper,2 were used for determining the effect of alloy composition and crystal orientation on the plastic II compression-plastic I rarefaction interaction zone for several specific shock pressures. Finally, measurements of pressures above the two-wave threshold were made on the polycrystalline alloys so that more complete Hugoniot curves could be constructed for this alloy system. The optical techniques described by Rice et al.5 were used to measure the shock and free surface velocities of the samples from which the Hugoniot data were obtained. This method is applicable only in the single wave region, since velocities are obtained from the measured total transit times of the disturbances through measured sample thicknesses.

Jan 1, 1963