Search Documents

By R. G. Schaal

The Magma Mine at Superior, Arizona had an unimpressive beginning as a. worked out silver mine that was purchased in 1910 for $130,000 and then incorporated into the Magma Copper Company which has been continuously mining the deposit since 1915. Copper is the principal metal produced. However, zinc, gold, silver and iron have also contributed to the total metal product. Prior to 1973, the production rate of 1500 tons per day was maintained by hoisting 4 and 5 ton pay-loads at speeds up to 1100 FPM through four small hoisting shafts. The hoists used included 8' and 7' diameter double drum, double clutched doc. and a.c. motor driven geared units built as early as 1917. One old timer that did yoeman's service for many years was an 8' Bollen Pulley with a.c. geared drive that utilized an endless rope system with mechanical grip and release mechanism built into the pulley's throat. Primary power for all of these old production hoists was 25 Hertz. Exploration that was completed in 1967 developed a reserve of 10 Million tons of 5 per cent copper which was sufficient to justify new capital expenditures for enlargement of productive facilities to 3300 tons per day. To reach the new reserves a 22' I.D. concrete lined vertical shaft was sunk to an initial depth of 48431. A 12 ½ diameter adit was bored from the mill side of the mountain to intercept the shaft at a point about 1100' below the collar. This 9200' long adit provides the right-of-way for the mine to mill railway and egress for heavy supplies from rail head as well as a conduit for potable water, electric power, compressed air and mine drainage. Mine operating levels begin 3582' below collar and thereafter have been cut at 100' vertical intervals. Skip loading stations have been installed 4282' and 46821 below collar with an in-shaft skip dump station located 800' below collar. This provides for 4500 tons of storage above the mine to mill train loading station located 1100' below collar. Ore and waste are moved horizontally from stope chutes and drift headings by rail haulage to transfer raises which channel all material to the two mentioned skip loading stations. The 22' diameter shaft crossection is arranged with the two skip compartments on the south side separated from the manway and utility compartments by the cage compartment. The cage counterweight operates in a portion of the southwest quadrant of the shaft. The hoisting plant consists of two conventional Nordberg double drum, single clutch, geared, d.c. motor driven units that are identical except for the drives and automatic controls. The drums are 15' diameter x 105" face with LeBus grooving for 2-1/8" diameter wire rope wound in three layers. Mechanical design emp1o::ed is the same as has been used for the past twenty- five years. One drum is attached to the main shaft by 2 large bolted integral shaft flenge. The loose drum is engaged by a 4-arm positive tooth clutch meshing with radially cut teeth of the clutch ring which is bolted to the drum. The drums are one-piece steel plate weldments having a finished weight of 60 tons each and are mounted upon a 36" diameter shaft that also weighs 60 tons. With the addition of brake rings, clutch, bull gear and rope, the total dead weight adds up to nearly 250 tons that is supported by just three double row spherical roller pillow block bearings. There is no bearing between the drums. All pinion shafts as veil as all head sheave journals are supported in the same type of antifriction bearings.

Jan 1, 1975

By W. R. Kanne, P. R. Strutt, R. A. Dodd

A study has been made of the creep behavior of ß-NiAl of stoichiometric composition in the temperature range 475" to 775°C. Single crystal tensile specimens were deformed under a constant applied load. From slip line studies and tensile axis rotations it was concluded that the crystals deformed by pencil-glide on (100) and (110) planes with a (100) slip direction. Electron microscope thin-film studies showed evidence for profuse cross-slip, and the dislocation Burgers vector was determined to be (100). There was no tendency for the dislocations to lie in definite slip planes, although a strong alignment of segments of edge dislocations was frequently seen. The activation energy for creep in the temperature range 475" and 775°C was judged to be much lower than that for creep at temperatures above 775°C. It is possible that the rate-controlling process is the thermally activated cross-slip of screw dislocations. In recent years considerable interest has developed in the possible use of high-melting-point intermediate phases for high-temperature applications necessitating good creep resistance. Ordered alloys such as Ni3A1, modified by alloying additions, have received particular attention, culminating in the recent development by Pratt and Whitney of single crystal turbine blades.' The intermediate phase NiAl has considerable theoretical interest from a creep standpoint because not only is it ordered up to the melting point (-1650°C at stoichiometry) but it contains a high concentration of structural vacancies on the aluminum-rich side of stoichiometry. These vacancies are known to exert a strengthening effect under some conditions,' but in addition they might be expected to affect high-temperature creep rates through dislocation climb. The present paper deals with the slip line and dislocation structures developed during creep of stoichiometric NiAl between 475" and 775C, and with possible attendant creep mechanisms. MATERIALS AND TEST TECHNIQUES NiAl ingots of stoichiometric composition were prepared by induction melting 99.996 pct A1 and 99.98 pct Ni (kindly provided by the Kaiser Aluminum Co. and the International Nickel Co., respectively) in 100 cc pure alumina crucibles in a helium atmosphere. No chemical melting flux was used in order to avoid con- tamination of the alloy. Each ingot was slowly direc-tionally solidified to avoid porosity and to produce very large grains up to 2 in. in length. In this way, ingots were obtained which were suitable for sectioning into single crystal creep specimens. Chemical analysis indicated that all alloys were within the range 49.6 0.3 at. pct Ni. For the present investigation, identical rectangular single crystal blanks were cut vertically from one particularly large crystal in an ingot using a series of three diamond cut-off wheels with appropriate spacers. Thus, all sliced crystals had the same orientation with the tensile axis parallel to the long side of the rectangle; the initial orientation of the tensile axis is shown as S, in Fig. 1. The blanks were homogenized at 1250 to 1300°C for 48 hr and subsequently cooled slowly to room temperature. A gage length of rectangular cross section and about 0.75 in. in length was prepared on each specimen using an electrolytic lathe and a dilute nitric/phosphoric acid electrolyte. The gage length cross section was 0.250 0.0005 in. by 0.040 ± 0.0005 in. Holes to accommodate tensile grips were electrolytically machined using a rotating acid jet. After creep testing, this same technique was used to cut discs for transmission electron microscopy. Thus, all shaping was done electrolytically, the only exception being that (122) sections were spark-machined from some speci-

Jan 1, 1970

By N. H. Harrison, J. K. Rodgers, S. Regier

This paper presents comparisons of data obtained from a laboratory reservoir study and from a calculated behavior prediction with the actual production history of a condensate reservoir. A small non-commercial discovery was depleted under closely controlled conditions and the well fluids were sampled at frequent intervals. Data on the reservoir and production variables were accumulated on a fixed schedule. A laboratory reservoir study war made using the initial well fluid samples as charging stock. The production procedures and operating conditions were held constant throughout the study wherever possible and in general paralleled the field work. The well fluid compositions and the cumulative recoveries ar a function of the reservoir pressure were also calculated using conventional flash vaporization procedures and equilibrium constants. Comparisons based on the composition of the well fluid show good agreement, the laboratory study agreeing within experimental accuracy with the field work and the calculated data comparing equally well. The gas-oil ratios are also in good agreement, but with somewhat greater deviations at the higher pressures. In the overall picture, it is believed that a model st,~tiy can predict within experimental accuracy the production history of a condensate reservoir. Better equilibrium constants for the heavier hydrocarbons are needed in order to attain improved composition accuracy by calculation. INTRODUCTION In Aug., 1955, a gas condensate well was completed in San Juan County, Utah, that was initially thought capable of good commercial production. These conclusions were derived principally from core data and electric logs, which indicated good permeability, porosity and gas content. However, after the usual series of potential tests it was found that the reservoir pressure had declined some 22 per cent, and it was obvious that the zone tapped was but a small pocket or trap. It became apparent that, with a controlled depletion of a small reservoir, a unique opportunity was available to compare laboratory and calculated studies with an actual field depletion and to further the present knowledge of condensate reservoirs. FIELD WORK The Coalbed Canyon Well No. 1 was conventionally completed in the Paradox limestone formation to a total depth of 5,912 ft. The producing zone from 5,762 to 5,806 ft was perforated with four jet shots per ft. The wellhead and field equipment were also conventional, the major items consisting of a two-pass indirect fired line heater, a high- and a low-pressure separator with the necessary controls and accessories, gas meters, back-pressure regulators, flare stacks and condensate stock tanks. The initial testing of this well con-sisted of a series of flow potential and pressure build-up tests during which some 30 MMcf of gas was produced. The reservoir pressure declined from an estimated 2,300 to 1,782 psig during this period, from which it was concluded that the reservoir was very small. In order to approach steady-state conditions in the reservoir and so provide optimum conditions for making comparisons, the field depletion was programmed to approach, if possible, constant production conditions. Bi-hourly readings were taken of the tubing pressure, the pressure and temperature of the separators, oil and gas rates, and other pertinent operating data. The gas rate, as indicated by the orifice meter, was held constant by the adjustment of the choke in the line heater. The temperature of the first stage separator was held constant by adjustment of the line heater jacket temperature. Practical considerations of production made the maintenance oi a constant gas rate impossible. The test started with a gas rate of 4 MMcf/D and a separator pressure of 250 psig. This rate was maintained until the choke was fully opened. The gas rate then declined with the falling tubing pressure and production was continued until the rate was about 2

By J. C. Trantham, J. W. Marx

From 1955 to 1958 the Phillips Petroleum Co. conducted a series of small scale counterflow combustion field tests in a tar sand about 60-ft deep and 6 to 12-ft thick near Bellamy, Mo. A total of seven different well patterns, including conventional five-spots and seven-spots plus a 15-well line drive pattern and a 10-well radial pattern, were employed. Electric heaters, gas burners and wellbore fuel packs were tested as counterflow ignition devices. Direct drive ignition followed by reversal to counterflow operation was not possible in this case because of formation plugging by the semi-solid tar during the direct drive phase. Sustained counterflow burning was achieved with wellbore fuel packs under conirolled conditions which permitted close correlation of fire front velocity, air velocity, air-oil ratios and yields for a wide variation in process parameters. The tar in place was about 10' APl with a reservoir viscosity greater than 500,000 cp. The composite oil prodlcct was 26' API with a viscosity in the range of 5 to 15 cp. Vertical sweep efficiency in the line drive pattern was essentially 100 per cent, with no evidence of gravity segregation. Original tar in place ranged between 800 and 1,000 bbllacre-ft, specific rock permeability averaged about 800 md before burning and effective air pemeability with residual oil and water in place (at the time of ignition) averaged 250 md. The volume of oil recovered during stabilized line drive counterflow burning represented about 67 per cent of the volume of tar originally in place in the burned out zones. A minimum was found when air-oil ratios were plotted against formation air velocities, and a limiting air velocity existed below which the counterflow fire front reversed and burned back over its own trajectory, using the residual coke left behind. INTRODUCTION Early in 1955 the Phillips Petroleum Co. began preparations to field test counterflow underground combustion as a method for producing oil from high viscosity hydrocarbon deposits, such as bituminous (tar) sands. At that time all published information on the use of underground burning io increase oil recovery was based on the direct drive process, in which the fire front moved through the formatim in the same direction as the injected air stream. Such direct burning is not applicable to many heavy oil sands or to most tar sands because the heat-thinned native hydrocarbon congeals in the cold rock ahead of the fire front forming a gas permeability block which smothers the combustion. Laboratory experiments first demonstrated that this permeability blocking would not occur if the fire front and the air stream moved in opposite directions. In this counterflow (reverse) burning process the heated heavy oil or tar is driven back through the combustion zone. Here thermal cracking produces relatively light hydrocarbon products which pass through the heated rock behind the fire front (largely in the vapor phase) and are incapable of causing a gas permeability block.' Exploratory wring revealed that consolidated bituminous sandstones with a combination of tar saturation, permeability, thickness and depth favorable for experimental field testing existed at several points in western Missouri. By the fall of 1955, a test site for determining technical feasibility of the counterflow process under field conditions had been selected near Bellamy, Vernon County, Mo. — about fifty miles north of Joplin. The pay zone was too thin and too shallow to constitute a commercial prospect, but these same factors permitted controlled experimental operation with a small compressor installation and with a large number of monitor wells. These were needed for adequate observation of the underground phenomena at reasonable cost. RESERVOIR CHARACTERISTICS The reservoir chosen for the experimental field tests was a 124 thick section of tar sand extending from 49 to 61 ft subsurface, with shale and siltstone laminations sealing the top and bottom. This section was part of a larger 30-ft thick tar sand deposit which extended both above and below the test zone. Core analyses showed that the 12-ft sand was effectively subdivided into two approximately equal sections, with the lower zone being consistently more permeable than the upper zone. The most significant laboratory core data are summarized in Table 1. The line drive test which is the principal subject of this report utilized only the lower 6-ft thick zone, with the upper zone regarded as part of the 55-ft overburden. WELL PATTERNS The over-all field test program involved a total of seven different well patterns, including conventional five-spots and seven-spots plus a 15-well line drive pattern and a 10-well radial pattern. In some of the tests the full 12-ft zone was employed; in other cases only the more perme-

Jan 1, 1967

By Langtry E. Lynd

The predominant tonnage use of titanium is as a white pigment, in the form of rutile or anatase, which are allotropic modifications of titanium dioxide. Because of its whiteness, high refractive index and resulting light scattering ability, titanium dioxide is unequaled as a white pigment for paints, paper, rubber, and a wide variety of other materials. Consumption of titanium dioxide pigments for these uses has been rising steadily for many years, United States consumption in 1956 amounting to about 486,000 tons, worth $250,000,000. Production was off a little in 1957 and 1958. An outstanding development in the titanium field in recent years is the expansion of titanium metal production. Virtually nonexistent before 1948, United States production of pure titanium metal sponge reached a high in 1957 of about 17,200 tons, worth about $77,000,000. United States titanium sponge metal production in 1958 was cut back to about 4,600 tons because of reductions in military requirements. Another major use of titanium, in the form of the mineral, rutile, is for welding rod coatings. United States consumption of rutile for this purpose in 1958 amounted to about 11,000 tons, worth $1,100,000. Titanium-Bearing Minerals Although several minerals contain titanium as a major constituent, only a few of these occur in sufficient quantities and concentrations to be of commercial importance. These are ilmenite (FeTiO3), rutile (TiO2), and alteration products of ilmenite which have been referred to as weathered ilmenite, leucoxene, or arizonite. The other polymorphs of titanium dioxide, brookite and anatase, occur in a few deposits, of which only one has been of even minor importance. Considerable concentrations of titanite or sphene (CaTiSiO5) and perovskite (CaTiO3) are known, but do not compete with ilmenite and rutile deposits in grade or size. Rutile is very widely distributed as an accessory mineral in most rocks, but large deposits of commercial importance are rare. A few rock deposits have been worked for rutile but only one, in Virginia, is in operation (1959). Development of one in Mexico was discontinued recently. At present, the main sources of rutile are the beach and dune sands of Australia and Florida. A major use of rutile is for the manufacture of titanium tetrachloride, which is the intermediate compound universally used in titanium metal manufacture. Another main use of rutile is for welding rod coatings. Although the whiteness and brightness of titanium dioxide pigment is due to the high refractive index of rutile or anatase, natural rutile is too impure to be used directly as a white pigment, is too expensive to use for manufacturing pure oxide pigment, and is too scarce to provide the required tonnages. Instead, the cheaper, more abundant, mixed oxide of iron and titanium, ilmenite, which is readily decomposed by sulfuric acid, is used for manufacture of rutile and anatase pigments. Ilmenite is mined from both rock and sand deposits. Rock deposits contain ilmenite in massive or heavily disseminated form along with magnetite or hematite and are almost invariably associated with anorthositic and gabbroic rocks. Ilmenite also occurs as an accessory mineral in a great many igneous and metamorphic rock types. Concentrations of

Jan 1, 1960

By John J. Gilman

BECAUSE of their layerlike structure, zinc crystals exhibit strong anisotropies for almost all physical and chemical properties. This should, and indeed does, greatly influence the plasticity of zinc for various crystal orientations. At low temperatures, the investigator of this plastic anisotropy is plagued by the great variety of deformation modes that operate. However, at high temperatures (250° to 419°C) only two deformation modes predominate: basal (0001) and prismatic (1010) glide. Furthermore, since strain hardening is virtually absent at high temperatures, the plasticity for these two modes of deformation can be very simply described by means of two equations of state. It is the purpose of this paper to describe the experimental behavior of basal and prismatic glide in zinc crystals, and to interpret this behavior in terms of other physical properties (in particular, the thermal expansion coefficients and the elastic constants) using the theory of dislocations. Fig. 1 defines the two planes of the zinc structure that will be discussed. Glide occurs very readily on the basal planes at all temperatures, and there is a very large literature on this subject. Much of the literature has been reviewed by Schmid and Boas;' it will not be reviewed here. Kolesnikovl was the first to show that if basal glide is circumvented by stressing a zinc crystal parallel to the basal planes (giving zero shear-stress on the basal planes) then, at temperatures above about 320°C, glide on the first-order prism planes occurs. His results have recently been confirmed by Cahn, Bear, and Bell." These previous workers have established the existence and crystallographic elements of prismatic glide; the present paper is concerned with the stress, strain rate, and temperature relations of prismatic glide as contrasted with basal glide. Experimental Methods The crystals were square ones, 6x6 mm, that had been grown in precision Pyrex tubes by a method that is described in detail elsewhere.' Most of the crystals were 99.999+ pct Zn (New Jersey Zinc Co. CP grade). Some were alloyed with 0.1 -+-0.005 atomic pct Cd, and chemical analysis showed that almost all of the added cadmium persisted through the crystal-growing process. For measurements of nonbasal glide, crystals were oriented with their basal planes parallel to both the rod axis and one of the flat faces of the square cross section. However, the orientation of the close-packed directions [1210] with respect to the rod-axis was variable. For basal glide measurements, the angle between the basal plane and the specimen axis was 35". The orientations were measured by the Gren-inger back-reflection X-ray method. The problem of finding a suitable method of gripping the crystals was the most serious experimental obstacle that arose. Because of the large plastic anisotropy of zinc, the usual gripping methods were unsatisfactory. Some methods that were tried were: high melting-point solder, making heads on the ends by locally melting a crystal, and electroplating nickel on the ends to form enlarged portions. For all these methods, the regions of the grips were weaker than the crystals themselves. Finally, two methods were decided upon: bend tests and direct machining of tensile specimens. In the bend tests, specimens were loaded as simple beams so that gripping was not a problem. The beams were 1 in. long and the axis of bending was parallel to the hexagonal axis of the crystals. For the crystals that were machined into tensile specimens, brass bars with slots in them were used to support the crystals, and thereby minimize the distortions due to machining. The crystals were glued into the brass bars with plastic cement which was later dissolved away with acetone. See Fig. 2, left. No clamps were used near the crystals and the machining was done using a milling machine with a fly-cutter. The tool bit was very sharply pointed to minimize burnishing. The feed was less than 1 mil per cut. The depth of cut was 2 mil for roughing cuts, and % mil for the finishing cuts. This machining method produced surface layers of tiny recrys-tallized grains only 2 to 3 mil deep, and the bodies of the crystals were not measurably disturbed. After the crystals had been machined and removed from the brass holders, they were chemically polished until about 5 mil had been removed from all their surfaces. The polishing reagent consisted of equal parts of concentrated HNO,, 30 pct H3O and ethyl alcohol; it is described in detail elsewhere." A typical crystal is shown in Fig. 2, right. The I-shaped faces are normal to the hexagonal axis of the crystal; otherwise the projections at the ends would simply shear off when the crystal was loaded. The cross section in the 2?-in. gage length is 0.215x0.115 in. It was found that the polished

Jan 1, 1957

By Juanito C. Fernandez

INTRODUCTION The Philippines is endowed with mineral resources, much of which still remains unexploited. The country's known reserves, at least for the major mineral commodities, have increased every decade since the first major discoveries more than 80 years ago. Mining, therefore, naturally evolved as one of the pioneer industries and has ever since been a major factor in economic development. The Philippines has entered a new era in mineral resources development and management. One significant feature of this era is the degree to which the government is involved with the industry. In recent years, the state has increasingly encouraged the private sector to carry out detailed exploration aided by governmental contributions through extensive geological and geophysical surveys, fundamental researches and even indirect financial assistance in some specific areas. Significant changes in mineral resources development policies were brought about with the promulgation of Presidential Decree 463 or the Mineral Resources Development Decree of 1974. The Decree provides for a more rational system of administration and disposition of mineral lands to promote mineral resource exploration and exploitation. Various forms of incentives are provided. Foreign entities are allowed to participate in development through service contracts with leaseholders or with the government in the case of reserved areas. The thrust in mineral resources development has been focused on the base metals which as envisioned would provide the foundation for sound economic development. In recent years, however, major strides have been made to promote the exploitation of the non-traditionally produced commodities especially the non-metals. Development likewise point to the growing determination of the government and the private sector to expand benefits from mining. This is evident in efforts to promote downstream processing operations and to encourage investments in exploration, exploitation and mineral processing ventures. The integrated mineral resources development plan, therefore, proposes the vertical integration of mining extraction activities with the processing requirements of the metal-based manufacturing industries. While mining activities shall continue to be carved out by the private sector, the government shall influence the industry's direction by establishing legitimate goals to maximize benefits through an integrated approach giving due consideration to environmental protection and resource needs of future generations. STATUS OF MINERAL RESOURCES DEVELOPMENT Extent of Exploration Application of modem exploration tools and concepts complemented by intense infusion of foreign technology and rapid development of indigenous expertise have enabled the government jointly with the private sector to geologically explore vast grounds and to expand the country's known mineral resources. Approximately 93% of the country's total land area of 30 million hectares have been geologically mapped on at least 1:250,000 scale. Of the 93% total coverage, roughly 37.54% or 11.07 million hectares have been done on scales of 1:10,000 to 1:50,000 as shown in Figure I. Only 3.07% of the total coverage have been surveyed in detail. Land gravity surveys have been undertaken on over 45% of the total, while some 77,300 line km. of aeromagnetic surveys have been flown over 110,000 sq. km. of land area. Processing of data is almost complete. Total magnetic intensity and IGRF-corrected maps are available. Geological interpretation utilizing Landsat MSS imagery and low altitude aerial photography augmented by ground truthing have been undertaken in several large areas with very encouraging results. Beach and offshore mineral surveys were initiated in 1977 and have covered substantial areas in northwest and southeast Luzon and northeastern Mindanao. Highly promising areas for detrital magnetite, chromite, gold and some heavy minerals including ilmenite and titanium have been identified. In the petroleum sector, two offshore oilfields are currently producing from Miocene limestone reefs in Northwestern Palawan. Another field from the same area will be on stream in mid-1982.

Jan 1, 1982

By G. L. F. Powell, L. M. Hogan

Samples of silver and Ag-O alloy, 0.12 wl pet, have been undercooled to a maximum of 250°C by melting in a slag of commercial soda-lime glass. Grain refinement occurred in undercooled silver samples whet the degree of undercooling exceeded a critical value which varied from 153° to 175°C, depending on the melting conditions. In under cooled Ag-0 samples, the grain structure was fine and equiaxed at degrees of undercooling larger than 50oC. The grain refinement in both silver and Ag-0 alloy samples was the result of recrystallization during or immediately following freezing. When the oxygen content was increased, the degree of undercooling at which recrys-tallization occurred decreased. INVESTIGATIONS of the grain structure of strongly undercooled melts of nickel and cobalt1-4 have revealed a change in room-temperature grain size as a function of undercooling. At large degrees of undercooling the grain size was fine, but samples undercooled by smaller amounts exhibited a much coarser grain structure. The reported undercooling at which this grain size transition occurred in nickel varied between 140° and 175'C undercooling. Walker1 attributed this grain size change to an enhanced nuclea-tion rate. Cavitation at a melt-solid interface was con sidered to generate a high-pressure wave. This, in turn, produced nucleation in the liquid as a result of an elevated freezing point increasing the undercooling in the melt. A similar grain size transition was observed in undercooled silver between 133° and 153°C undercooling.5 The grain size transition in undercooled silver was found to be dependent on oxygen con tent. More recently, the authors5 showed that a simila transition occurred in an undercooled Cu-O alloy, =0.08 pet, but not in oxygen-free copper undercooled more than 200°C. The transition was attributed to recrystallization of the solidified grains after freezing; the greater the degree of undercooling, the more complete the recrystallization. In view of this effect of oxygen content on grain size transition, additional undercooling experiments were carried out with silver. This paper reports the results of these studies on silver and Ag-O alloys undercooled more than 50°C EXPERIMENTAL 1) Materials. The silver was supplied by Matthey Garrett Pty., Ltd., as fine granulate, silver mini' mum 99.9 pet, and contained the trace impurities shown in Table I. The silver originated from two different refineries resulting in the difference in impurity content shown in Table I. However, the variation in composition had no discernible effect on the undercooling behavior. Samples of the silver were melted in an open-ended, vertical, cylindrical resistance furnace, wound with Kantha] wire, the temperature of which was adjusted by means of a variable transformer, 2) Melting and Undercooling. Bulk samples of silver were undercooled by preoxidation and removal of oxidized impurities in a glass slag, as previously described,5 but special precautions were necessary to allow comparison between oxygen-free silver and a Ag-O alloy. Samples free of oxygen were prepared by first melting weights of granulate varying from 200 to 400 g in clean vitreous silica crucibles in air for approximately 15 min. A sample was frozen and a complete glass cover formed over the top surface by adding granulated glass rod. The sample was then melted and frozen several times until no oxygen bubbles appeared in the glass slag. Subsequent thermal analysis indicated that the oxygen content was negligible. The glass acted as an efficient barrier to absorption of oxygen from the air. Ag-O alloys were prepared by melting silver in silica crucibles with only a partial cover of glass, so that the top surface of the melt was in contact with air. The silver was held molten in air for several hours at 1000° to 1050°C, in the expectation that the oxygen in solution would reach equilibrium with atmospheric oxygen. At T - 1000°C the equilibrium oxygen content was calculated as 0.12 wt pet O, using Sieverts law and Eq, [l], derived by Mizikar et a!.7 from the data of Sieverts and Hagenacker8 for 1 atm of oxygen:

Jan 1, 1970

By C. D. Hall, F. E. Dollarhide

Fluid Ioss agent.s for crude oil and for water have been studied in dynamic tests. A treatment using a spearhead with a fluid loss agent followed by plain fluid appears feas ible in crude oil, but not in water. An equation for spearhead depletion shows that spurt loss relative to fracture width must be low, if the portion of spearhead fluid in the treatment is to be small. The presence of colloidal matter in crude oils aids the fluid Ioss agent. Unlike in kerosene, where flow limited the agent deposition, in crude oils the filter cake continually formed and leak-off declined. The volume-time relation varied somewhat for different crudes, but was best described by a square root of time function. Spurt loss was inversely proportional to agent concentration. After the fluid loss agent initiated the filter cake, the crude oil colloids built on it effectively. A 2-minute or a 5-minute spearhead with double the normal agent concentration gave the same fluid Ioss curve as the same concentration did for a 30-minute test. The agents tested in water gave fluid Ioss plots on which, for the first few minutes, volume was proportional to the square root of time, but later became proportional to time. For fracture area calculation the customary square root of time function is a satisfactory approximation. Leak-off rates and spurt losses were higher in water systems than in oils. The spurt Ioss tended to be inversely proportional to concentration. In spearhead tests, the filter cakes were not eroded by water flow. However, the rather high spurt loss values make spearhead treatments impractical for water-based fluids. Introduction The effects of dynamic testing conditions on the performance of fluid loss agents in kerosene have been studied previously.' We have extended the work to include crude-oil- and water-based fracturing fluids. An understanding has been gained of the mechanisms of formation and functioning of the filter cakes of fluid loss agents. The practical aspects of evaluating performance of agents in relation to fracture area calculations also are considered. The feasibility of using the fluid loss agent in a spearhead stage of the treatment is examined further for both types of fluids. Experimental Procedure The dynamic fluid loss tests were performed in an apparatus similar to the high-pressure apparatus described in a previous publication.' A fracturing fluid was circulated over a rock surface located in a closed pressurized loop. The fluid flowed axially over the cylindrical surface of a core 2 in. in diameter X 3.5 in. long, mounted (with the flat ends sealed off) in a pipe, with 0.117 in. annular clearance. The filtrate was collected in a central hole in the core and led through valves to graduated cylinders. Provision was made for changing quickly the circulating fluid during the test (spearhead runs) without interrupting the filtration pressure. The only modifications were to add heating tapes and water jackets for the tests with crude oils, all conducted at ISOF, and to change all parts exposed to the test fluid to stainless steel for the tests with water-based fluids. The latter tests were made at room temperature, 80F. Three crude oils were tested. A mixed crude, obtained from a local refinery, contained a considerable amount of light ends. For safety reasons, it was stripped to 250F vapor temperature before use in the fluid loss tests. The other two oils were used as obtained from lease tanks. One was a greenish-brown, 37" API paraffinic crude, and the other was a black, 32" API asphaltic crude. The fluid loss agent for oil, here designated for brevity as Agent A, was Adomite@ Mark II*, a granular solid commercial agent, the same as previously tested in kerosene.' Three different compositions of fluid loss agents were tested in Tulsa tap water. Agent B was adomit& Aqua*, a solid commercial fluid loss agent, comprising clays and hydrophilic gums principally derived from starch. Agent C was a mixture of three parts of Agent B with two parts of silica flour. Agent D was Dowel1 J137, a mixture of guar gum and silica flour. The test cores were cut from contiguous blocks of Berea or Bandera sandstones. For the oil tests, the cores were oven dried, evacuated, saturated with kerosene, and the kerosene permeability was measured. The cores used with the water-based fluids were pretreated by saturating with 3 percent calcium &loride solution to minimize pemeability damage by the fresh water due to clay migration. The

Jan 1, 1969

By Charles F. Hickey, Eric B. Kula

Thermomechanical treatments applied to the maraging steels include a) cold working in the austenitic condition at 650°F, followed by transformation to martensite and aging, b) cold working in the murtensitic condition and aging, and c) cold working in the aged condition with and without subsequent reaging. The strength increases in these steels are very small compared to the increases observed in conventional carbon and alloy steels. The changes that are observed are compatible with the strengthening mechanisms operative during thermomechanical treatment of conventional steels, however. Differences are caused by the absence of a carbide precipitate and the low work-hardening rate in both the solution-treated and the aged conditions. ThE 18 pct Ni maraging steels represent a class of steels which are finding great interest for high-strength applications.1~2 They are essentially carbon-free, and contain 7 to 9 pct Co, 3 to 5 pct Mo, and 0.2 to 0.8 pct Ti. Although austenitic at elevated temperatures, they can be air-cooled to room temperature to form a martensite, which because of the absence of carbon is relatively soft. On subsequent reheating age hardening occurs and strength levels of 250 to 300 ksi yield strength can be attained. These steels appear to be particularly suitable for studying the response to various thermome-chanical treatments for additional reasons other than the obvious one of attempting to improve their already attractive properties. Thermomechanical treatments can be defined as treatments whereby plastic deformation, generally below the recrystal-lization temperature, is introduced into the heat-treatment cycle of a steel in order to improve the properties. With an absence of intermediate transformation products on air cooling the maraging steels have good hardenability and hence can readily be cold-worked in the austenitic condition prior to transformation to martensite. Further, they can be worked in the martensitic condition prior to aging, and even can be deformed in the fully aged condition. Finally, it is of interest to compare their re- sponse to that of the more conventional alloy and carbon steels, where the role of carbides is important in the strength increase by thermomechani-cal treatments. The thermomechanical treatment of conventional steels has been the subject of a recent review.' I) MATERIALS AND PROCEDURE The steel used in this investigation was a commercially produced vacuum-melt heat, which had been rolled to 0.090 in. and mill-annealed. The composition of the alloy was as follows: 0.02 C, 0.08 Mn, 0.10 Si, 0.009 P, 0.009 S, 18.96 Ni, 7.34 Co, 5.04 Mo, 0.29 Ti, 0.05 Al, 0.004 B, 0.01 Zr, and 0.05 Ca. Unless otherwise stated the heat treatments used were the standai-d solution treatment at 1500°F for 1 hr, air cool, followed by a 900°F, 3 hr age. In this condition, the material exhibited 232 ksi yield strength and 239 ksi tensile strength. Mechanical properties were determined by Vicker's hardness measurement (20 kg) and by tensile tests on standard 1/2-in.-wide, 2-in.-gage-length sheet tensile specimens. Notch tensile tests were run using the 1-in.-wide NASA type, edge-notched specimen.4 Fracture-toughness determinations were made on 3-in.-wide, center-notched, fatigue-cracked specimens, following the recommendations of the ASTM Committee on Fracture-Toughness Testing.4 An electric-potential technique was used for measuring the crack size at the onset of rapid crack propagation5 which is necessary for calculations of Kc, the critical stress-intensity factor under plane-stress conditions. The critical stress-intensity factor under plane-strain conditions KI, was also calculated, using the stress at which the first observable crack growth occurred. 11) RESULTS A) Cold-Worked in the Austenitic Condition. The reported M, temperature for the 18 pct Ni maraging steel is about 310°F.1 Therefore, a temperature of 650°F was selected as suitable for rolling in the austenitic condition. Specimens were solution-treated at 1500°F for 1 hr, air-cooled to 650°F, and rolled varying percentages from 0 to 60 pct, at 20 pct reduction per pass. Tensile and hardness properties after aging at 900°F for 3 hr are shown in Fig. 1. The tensile strength increases from 253 to 271 ksi and the yield strength from 247 to 265 ksi as a result of a reduc-

Jan 1, 1964

By Frank Doxey

AT Dominion Steel & Coal Corp. it has long been recognized that continued mechanization of mine operations is necessary in the Pictou, Cumberland, and Sidney coal fields of Nova Scotia. The varied physical conditions in these fields call for special consideration of individual cases before planning is finalized. Because standard equipment cannot be procured which would operate successfully, many experiments have been necessary over the years to keep pace with the progress made in other countries. There are two mines, producing 2000 tpd, located in the Pictou coal field. The field is badly distorted and crossed by many faults. Seams are highly inclined and irregular and vary in thickness from 5 to 40 ft. Entries are difficult to maintain because of squeezing of the coal. ribs and movement of the roof and pavement. Output from the three operating mines in the Cumberland field is 3000 tpd. The field is highly inclined, inclination varying from 12° to 32°. Overlying beds consist of shales and massive sandstone lenses of extreme toughness and are responsible for bumps when the stresses are relieved by extraction. At greatest depth these are among the deepest coal workings in the world. Depth of cover ranges from 2300 to 4000 ft. This prohibits room-and-pillar working and necessitates longwall operation. Working of contiguous seams concurrently to maintain output increases the already difficult conditions. The Sydney field, with a frontage of about 30 miles, is the most important of the Nova Scotia coal fields. With the exception of one small area it is now wholly submarine. Output is approximately 21,000 tpd. Seams are 21/2 to 8 ft thick, and cover in the areas varies from 600 to 2300 ft, with an average of 1500 ft from sea bottom to the top of the seam. The seams dip in a seaward direction, pitches ranging from 6" to 4.0". The shoreline is the last place of entry to the seams and distance from the bank to the working faces is generally over 3½ miles, in some cases as much as 6½ miles. Ventilation is a problem and requires the construction of large permanent airways. Getting and Loading Coal: In 1925, in view of heavy pressures exerted by thickness of cover overlying the seams, roadways and pillars of the room-and-pillar system being worked began to break up and coal was lost. It was decided that a change in the method of extraction in areas with heavy cover was necessary, and experiments were made with many short walls and longwalls varying between 90 and 250 ft. Trial and error proved that the best operating length was between 400 and 500 ft, delivering all coal to the dip, with roadways to the face following a level course. The change-over was gradual, and the technique of roof control developed with the system, so that falls to the face are now very infrequent. An advantage of longwall mining is that it yields 95 pct extraction, especially important in coal seams of high quality or in seams where faults or disturbances restrict the workable areas. This percentage of extraction is based on the fact that the longwall advancing system takes development faces where pitch permits instead of driving headings and leaving roadway pillars. This system yields high tonnage during development and limits loss in extraction to duff left during operations. Accompanying disadvantages, on the other hand, are the heavy construction cost of main roadways and the necessity of driving all new flank face roadways through the gob. If the main roadways are driven through the solid, and large enough pillars are left on each side for protection against flank face weights, then the width of solid coal is approximately 1700 ft. This represents 10.6 pct of the coal available, or 89.4 pct extraction of the whole. These pillars, however, are of such size that they provide a useful pillar drawing area as a final operation of the mine. It may be that although the seam cannot be generally mined by the room-and-pillar method, it can be adapted to

Jan 1, 1955

By R. B. Burt, James A. Barr, I. S. Tillotson

THE pumping of solids in water suspension is an important part of many metallurgical and mining operations. In most cases, it is still in the rule of thumb category for which no universal formula has been developed, and much research is needed. Because of the limited and incomplete data available, this article may be classed as an experience paper, which is presented with the hope that some contribution will be made toward the development of the so-called universal formula. This formula, if and when developed, may be evolved from several factors, many of which are not now available for general application. The designing engineer is interested in obtaining accurate forecasts on: 1-the minimum velocities needed to prevent choke-ups in the pipeline, which in turn dictates pipe sizes, 2-power required for pumping, 3-pump selection. The basic factors for a given problem will include: 1-weight per unit of time of solids to be handled, 2-specific gravity of solids, for calculation of volume, friction and power, 3-screen analysis of solids with the colloidal acting, i.e., the slime fraction, a very important factor, 4-shape of particle or some means of determining a friction constant, 5-effects of percentage of solids, 6-development of a viscosity factor to be used in the overall calculations, 7-calculation of the lower limits of pipeline velocities permissible, 8-calculation of total head, pump horsepower, and 9-setting up of pump specifications. In certain limited cases horsepower and total heads and minimum velocities may be computed and a suitable pump selected from basic data, but in many cases, as in mining of Florida pebble, phosphate, experience rather than a hydraulic formula still should be used as a basis of selection. Pumping Florida Pebble Matrix Pumping at the Noralyn mine of International Minerals and Chemical Corp. will be used as an example. Other areas will vary as to the characteristics of the matrix, especially the slime content. A typical screen analysis of this matrix is: +14 mesh, pebble size,* 2.1 pct; -14 +35 mesh, 11.4 pct; -35 +150 mesh, 60.5 pct; -150 mesh, 25.0; total, 100 pct; moisture in bank, 20.0 pct; weight per cu ft in bank, 120 lb. The -150 mesh fraction may increase to as much as 35 pct in adjacent areas. When thoroughly elutriated, the matrix has a relatively slow settling rate, which is an important factor in permitting lower pipeline velocities without choke-ups. Exact data is not available to evaluate settling rates. For a factor of 100 a suspension of clean building sand in water is suggested. When pumping long distances, a quick settling matrix allows the coarser solids to settle out along the bottom of the pipeline, causing drag, turbulence, and increased friction. With a slow settling matrix as at Noralyn, turbulence acts to keep the solids in suspension at a lower friction head, regardless of the pumping distance. When the pebble, content of the matrix, i.e., the +14 mesh fraction, is in excess of 10 pct of the total solids, trouble may be expected from settling out even in normal pumping distances. To prevent choke-ups and maintain tonnage, an additional pump must be added in the long runs, where one pump would otherwise be satisfactory. A typical pulp handled is: total volume, 7800 gpm; water, 4500; solids pumped per hr, 4200 lb; sp gr pulp, 1.4; percent solids in pulp, 46.; pipe size, 16-in. ID; pulp velocity, 12.85 fps; probable critical velocity, 10 fps, as below this minimum -velocity choke-ups would be numerous. In calculating friction heads the Armco handbook is used where a roughness factor based on 15-year-old pipe is set up. Because the pipe used in pumping matrix is, smooth and- polished because of the scouring, action of the phosphate and its silica content, the head losses in the Armco table for water are practically the same as in pumping the Noralyn matrix through smooth pipe, plus the fact that conditions vary widely over short periods, making accurate determinations difficult to obtain. New pumps and pump, changes are being tested continuously and a wealth of data built up. This has resulted in a substantial improvement and lower relative costs in pumping matrix. The Florida phosphate industry is constantly seeking to offset higher wage and material costs with improved technique. Until a few years ago a 12-in. discharge pump was commonly used, with heads as low as 80 ft. Sizes have gradually increased and heads more than doubled. For example, the following pump was placed under test at the Noralyn mine: make, Georgia Iron Works; size, suction 16 in., discharge 14 in.; impeller, 39-in. diam; motor, 600 hp, slip ring; full load speed, 514 rpm. The results were increased head, higher capacity than the older design, with fewer pumps in the line from mine to washer.

Jan 1, 1952

By Northcutt Ely, Charles F. Wheatley

This chapter deals with the systems of laws by which governments regulate the exploration for and production of the minerals within their jurisdictions. It is a summary, restricted by necessary space limitations, of material assembled by the author for a forthcoming publication of the United States Bureau of Mines, "Summary of Mining and Petroleum Laws of the World." (Information Circular, 1959.) The present study is organized in three parts, dealing with (1) the historical background of these legal systems, (2) laws of the United States, and (3) laws of other countries of the world. The reader's attention is invited to the acknowledgments at the end of the chapter, which inadequately express the appreciation due those who have assisted in the collection of this material. Part I. Historical Development of Major Western Systems of Land Tenancy with Respect to the Ownership and Control of Minerals The use of metals in primitive societies was largely confined to the manufacture of weapons for self-preservation. The ruler's control over copper, then brass, then iron, was essential to maintenance of his own ascendancy at home and his group's position against neighbors who had access to similar metals. Ancient societies were thus characterized by the ruling group's ownership of minerals and metals. The Egyptian civilization, which emerged in the fourth millenium B.C. upon the agricultural subjugation of the lower valley of the Nile, was responsible for extensive development of the upper valley as a source of mineral wealth. The production of gold during the height of that civilization has been estimated at $30,000,000 per year, thus equaling the early placers of California and Australia. The mines of Egypt were the property of the Pharaohs and were controlled at their direction. Greek mining developed a different scheme of land tenancy which more closely resembled modem concepts. Development of mineral resources was

Jan 1, 1959

By A. L. Mincher, W. F. Sheely

Mechanical properties of columbium have been studied over the temperature range of -196 to 1093oC. The decreased strengthening influence of cold-work at temperatures below ambient has been interpreted in terms of the Peierls-Nabarro effect. Maxima in the rate of strain hardening observed during tensile testing in the range 250-600°C. have been correlated with interstitial impurities to indicate the temperature ranges at which carbon, oxygen, and nitrogen, respectively, are responsible for strain aging. THE growing need for structural materials for use above the useful service temperatures of the iron-, nickel-, or cobalt-base alloys has caused the refractory metals to be considered as potential engineering materials. These metals, which include columbium, tantalum, molybdenum, and tungsten, are called refractory because the lowest melting point among them,that of columbium, is about 1000°C higher than the average melting temperatures of conventional high-temperature alloys. They are all body-centered cubic transition metals and, as such, their mechanical properties have basic characteristics which distinguish them from the face-centered cubic metals. For example, all show a much steeper rise in strength with decreasing temperature below room temperature than do the face-centered cubic metals, and their mechanical properties are strongly influenced by interstitially dissolved impurities. In order that these new metals may be used efficiently, it is necessary that their characteristics of behavior be fully known. In this paper, the mechanical properties of columbium will be examined over a wide range of temperatures. In particular, the influences of cold-work and individual species of interstitial impurity atoms on mechanical properties will be described, and basic mechanisms which may control the observed characteristics will be explored. EXPERIMENTAL The material used in this investigation was Union Carbide Metals Co. columbium roundels consolidated to four 4-in. diam ingots, three by consumable-electrode arc melting and one ingot by electron beam melting. Impurity contents of the ingots and methods of ingot conversion and treatment are summarized in Table I. The only metallic impurity occurring in any significant quantity was tantalum at about 0.1 pct. Iron, silicon, titanium, and zirconium were each less than 0.015 pct; boron was 1 ppm or less. This should have no appreciable influence on properties. The electron beam melted material, being the purest, will be used as the basis for comparison in the discussions to follow. Tensile tests were conducted from-196 to 1093oC, on both cold-worked and fully recrystallized arc-melted and electron-beam melted columbium using standard 1/4-in. diam, 1-in. long gage length test specimens. A strain-rate of 0.005 in. per in. per min was employed until the 0.2 pct yield strength was achieved and then the strain-rate was increased to 0.05 in. per in. per min for the balance of the test. Samples were protected in an inert atmosphere at tests above 300°C. The tensile properties obtained on the electron-beam melted columbium, E, in both the cold-swaged and recrystallized conditions are given in Fig. 1. The yield strength data of Dyson, et al.,' obtained on recrystallized electron beam melted columbium and the tensile strength data reported by Tottle2 on powder metallurgy columbium are included in Fig. 1. The material used by Tottle had been purified by vacuum sintering. There is excellent agreement between Dyson's data and those obtained in the present investigation. The tensile strengths obtained by Tottle were slightly greater than those obtained in this investigation on electron-beam melted columbium but varied with temperature in a similar manner. Tottle's data showed a maximum in tensile strength near 500°C, as did our data on electron-beam melted material, and also showed a small maximum at 300°C. The significance of these maxima will become evident later in the discussion. The tensile properties of cold-swaged and recrys-tallized arc melted columbium are plotted in Fig. 2. It was found that the properties of the recrystallized arc-melted columbium from all three heats showed very close agreement except at temperatures between about 500" and 800°C. A reason for this range of disagreement will be suggested in the discussion. The generally good agreement, however, attests to the ability of cold-working and subsequent recrystal-lization to erase the effects of the three different primary breakdown procedures and to produce nearly equivalent structures in the samples derived from the three different heats. wesse13 reported tensile data on columbium having interstitial impurity contents between those of the

Jan 1, 1962

By William M. Boorstein, Robert D. Pehlke

The rates of solution (of hydrogen in liquid pure iron and in several liquid binary iron alloys were meas-ured using a constant volume technique. The rates of absorption and desorption were found to be equal un-der all experimental conditions. increasing concen-trations of S, Si, or Te decrease the rate of hydrogen uptake but additions of Al, B, Cr, Cu, or Ni have no measurable effect up to concentrations normally en-countered in steelmaking practice. No relation ship was found between the effect of an alloying element on the equilibrium solubility of hydrogen in liquid iron and its effect on the solution rate constant. Mathe-rnatical analysis of the data indicates that under the present experimental conditions the rate of reaction of hydrogen with liquid iron is controlled by transport of gas solute atoms in the metal phase. Comparison of the present resuts with data on nitrogen taken un der similar conditions establishes that the hydrody-nurnic conditions which exist near the surface of a metal bath are best approximated mathematically by a surface renewal model for the case of rapid in-ductive stirring and by a boundary layer model for more quiescent melts. HYDROGEN has long been recognized as being a detrimental constituent in steel. If dissolved in the molten metal in excess of its solid solubility, hydro-gen can be evolved during solidification and cause bleeding or porosity in ingots and castings. In the solid metal, lesser amounts play a definite role in causing other defects such as hairline cracks, blisters, and embrittlement. For significant refinements to be made in metallurgical procedures designed to control or eliminate hydrogen from liquid iron or steel dur-ing processing, available equilibrium solubility data must be supplemented with reliable fundamental in-formation pertaining to the kinetic factors involved in the transfer of hydrogen to or from the metal. The scarcity of such information in the literature prompted the present investigation. PREVIOUS RESEARCH Whereas much of the existing data on the solution kinetics of gases such as nitrogen were obtained during the course of thermodynamic investigations, the solu-tion rate of hydrogen has been found too rapid to be accurately determined by conventional solubility meas-urement techniques. Consequently, little work on hy-drogen solution kinetics has been reported in the lit-erature. Carney, Chipman, and crant1 attempted to study the rate of solution and evolution of hydrogen from liquid iron by employing a newly devised sampling method. Although no significant quantitative data could be obtained, it was observed that the rate of solution was approximately equal to the rate of evolution of hy-drogen from the melt. Karnaukov and Morozov2 stud-ied the rate of absorption and Knuppel and Oeters3 the rate of desorption of hydrogen from molten iron by measuring pressure changes with time in a constant volume system. Karnaukov and Morozov determined the hydrogen pressures over their inductively stirred melts with the aid of a McLeod gage and therefore, were forced to work at pressures not in excess of 40 mm of Hg. Their experimental data conformed to a mathematical correlation based on diffusion control: and the rate coefficients calculated on this basis were shown to be independent of the initial absorption pres-sure. These authors reported the solution rate of hy-drogen to be eight-to-ten times higher than they had found for nitrogen in a previous study. They also re-ported that under identical conditions, hydrogen dis-solves somewhat more slowly in iron-columbium alloys than in pure iron. Knuppel and Oeters found that the desorption of hydrogen from pure iron at 1600°C was controlled in all cases investigated by diffusion in the metal bath as long as bubble formation was sup-pressed. This was substantiated by Levin, Kurochkin, and umrikhin4 who studied the kinetics of hydrogen evolution from liquid (technical) iron while applying a vacuum. Salter5 measured the rate of hydrogen ab-sorbed by iron buttons, arc-melted by direct current, as a function of hydrogen partial pressure in a hy-drogen-argon atmosphere. A carrier gas technique was used for analysis of the hydrogen absorbed. The initial rate of absorption was found to increase di-rectly with the square root of the partial pressure of hydrogen. EXPERIMENTAL METHOD Because of the rapid uptake and evolution of hydro-gen by iron-base melts, a constant volume technique was devised in order to obtain meaningful kinetic data over the entire course of the solution process. Apparatus. A schematic view of the experimental apparatus is given in Fig. 1. The hydrogen-liquid iron reaction system consisted of a gas storage bulb con-nected to a meltcontaining reaction chamber through a normally-closed solenoid valve. The gas storage bulb, an inverted 250 ml round-bottomed Pyrex flask was joined to the inlet port of the solenoid valve by a glass-to-metal seal. A more detailed illustration of the reaction chamber is shown in Fig. 2. The design of the Vycor reaction bulb was essentially that de-scribed by Weinstein and Elliott6 with the exception of a shorter, larger diameter gas inlet for this kinetic study. In position, the reaction bulb was closely by an eight-turn coil of water-cooled copper tubing which, when energized by a 400-kc oscillator, provided the inductive heating source. The walls of the bulb were maintained relatively cool by circulating cold water along their outer surface, thus preventing

Jan 1, 1970

By Paul A. Farrar, Harold Margolin

The system Ti-Cr has been re investigated From 40 to 100 pct Cr. The high-temperature modification of TiCr, was found to exist in the temperature range from 1365 where it terminates in the eutectoid reaction TiCr,(TI)* — HE chromium-rich region of the Ti-Cr system was investigated by Vogel and Wenderott,' Mc Quillan,' Van Thyne et dl.,' and Cuff Duwez and Taylor determined the crystal structure of the low-temeperature modification of TiCr, to be fcc a = 6.943A and Levinger' discovered the existence of a second (high-temperature) modification of TiCr, and determited its crystal structure to be hexagonal a = 4.932A, c/a = 1.617i. No information was obtained as to the temperature range over which each modification of TiCr? existed; therefore the present investigation was initiated. I) Experimental Techniques Alloys employed for the delination of this system were prepared from iodide titanium and high-purity chromium. The purity of these materials is as follows: Iodide titanium: purity 99.99 pct; major impurities—carbon 0.0001 pct; oxygen 0 to 0.002 pct; nitrogen 0 to 0.002 pct; silicon 0 to 0.005 pct; manganese 0.001 pct; copper 0.001 pct (Foote Mineral Co., Lot 609-29). Chromium #1: metallic purity 99.997 min.; interstitial content—oxygen 0.27 to 0.46 pct; hydrogen 0.028 to 0.038 pct; nitrogen 0.0002 pct (Ave-quipo Inc.). Chromium #2: purity 99.9 pct; major impurities—carbon 0.01 pct; oxygen 0.013 pct; nitrogen 0.02 pct; silicon 0.01 pct; sulfur 0.03 pct; iron 0.01 pct (Fulmer Research Institute Ltd.). A total of sixteen alloys of thirteen different compositions was prepared in the range from 40 to 95' *All percentages are given in weight percent. pct Cr. The compositions of the alloys prepared were as follows: Ti-40, 45, 50, 60, 62, 64, 66, 68, 70, 80, 85, 90, and 95 pct Cr. Two buttons were prepared of the 66, 90, and 95 pct Cr alloys. The 40 pct Cr and one of the 66 pct Cr alloys were prepared from the chromium # 2. All the other alloys were prepared from chromium #1. The alloys were arc-melted as 25-g buttons in a copper-hearth glass-walled furnace7 under an inert atmosphere of high-purity helium. The alloys were sintered at 250 amp and melted twice at 350 amp for 30 sec with the buttons being turned over between melts. Weight losses during melting were determined and in the range 45 to 68 pct Cr they were found, in all cases, to be less than 1.25 pct of the total alloy weight. A number of the high-chromium alloys shattered during cooling from either the first or second melt, which made the weight loss considerably larger than usual. The 70 and 80 pct alloys lost approximately 5.7 pct of their total weight, the 85 pct alloys 1.5 pct, the 90 pct alloy 2 pct, and the 95 pct alloy 3 pct. However, it is felt that the actual composition of the alloys in this region is probably within approximately 1 pct of the intended composition, as a large portion of the material lost was that due to shattering after melting. Nominal compositions were therefore used in plotting data and referring to the alloys. The alloys were cut into specimens, wrapped in molybdenum sheet, and encapsuled in argon-filled quartz or Vycor tubes for heat treatment. The heat-treatment times and temperatures are given in Table I. The specimens were quenched in iced brine (I.B.Q.) following heat treatment. The standard techniques of grinding, polishing., and etching were used in preparing the specimens for metallo-graphic examination. For alloys below 68 pct Cr

Jan 1, 1963

By A. K. Mukherjee, John E. Dorn

The effects of strain rate and temperature on the critical resolved shear stress for (321)[111] slip were determined for the silver-rich CsCl type of intermetallic compound AgMg. The flow stress increased only slightly as the test temperature was first decreased below room temperature; a rapid increase in the flow stress was obtained with yet further decrease in temperature from about 250' to 4OK. The effect of both the temperature and strain rate on the flow stress over the low-temperature range could be rationalized satisfactorily in terms of the Peiwls mechanism when the deformation was controlled by rate of nucleation of pairs of kinks. IN spite of the well-documented interest of metallurgists and engineers concerning the mechanical behavior of intermediate phases and intermetallic compounds, very little definitive information is available on this important subject. As recently summarized by westbrook,1 only limited and modest progress has been made thus far in elucidating the details of the mechanism of plastic deformation for the intermetallic compounds; the available information largely concerns phenom-enological descriptions of empirical observations and experimental facts, principally with reference to poly crystalline aggregates. The present report on the elucidation of the rate-controlling mechanism for slip in the bcc structure of AgMg is part of the comprehensive program of a systematic investigation on the mechanical behavior of intermetallic compounds. The intermetallic compound AgMg has a CsCl type of lattice structureZ and is completely ordered up to its melting point of 820c3 This material was selected for our present investigation because of its simple crystal structure, moderate and congruent melting point, ordered structure persisting up to the melting point, and some solubilities of the constituent elements, which could be expected to help in the growing of single-crystal specimens. Whereas previous investigations on the properties of AgMg include hardness,*"6 slip systems,7 tensile flow stress of polycrystalline specimens,' and electrical resistivity,4 the current investigation will be directed principally at elucidating the rate-controlling dislocation mechanism responsible for slip in single crystals at low temperatures. It will be shown that the strain rate is consistent with a model involving the rate of nucleation of pairs of kinks by the Peierls mechanism for plastic deformation. EXPERIMENTAL TECHNIQUES Single-crystal specimens of the AgMg intermetallic compound were prepared and tested as follows: 1) A master alloy ingot of AgMg was produced by melting and chill casting the high-purity silver (99.995 wt pct) and high-purity magnesium (99.997 wt pct) in an induction furnace under a helium atmosphere. 2) Sections of the above-mentioned ingot were placed in a graphite mold containing a spherical cavity in which a single-crystal sphere of 1 in. diam was grown under helium by the Bridgman technique. 3) The operative slip systems were investigated at room temperature on a singlecrystal of AgMg, from measurements of the angles made by the slip traces on the two surfaces of the specimen, which were at 90 deg to each other. The investigation confirmed that the AgMg compound undergoes slip primarily in the (321) plane and in the [Ill] direction, but a small amount of secondary slip was also noticed in the (112) (111) system. No slip was observed in the (110) planes. 4) The single-crystal sphere, mentioned earlier, was oriented in a graphite mold containing a cylindrical cavity of 3/8 in. diam above the spherical receptable to give the angle xo = 45 deg between the axis of the cylindrical bar and the normal to the slip plane (321), and the angle AO = 45 deg between the slip direction [Ill] and the axis of the bar. Oriented single-crystal bar seeds were produced by melting, under a helium atmosphere, a polycrystalline bar in the cylindrical cavity above the oriented spherical seed and by growing an oriented single-crystal bar from the seed. 5) Finally, oriented single-crystal specimens were grown from these cylindrical seeds. 6) The cylindrical specimens were machined in a High-Tension Spark Cutting unit to give a 2-in. gage length. The spark-machined gage section was elec-tropolished in a bath containing 200 ml of H3PO4,

Jan 1, 1964

By H. R. Gardner

The heat treatmmt of plutonium was studied using the Jominy end-quenching technique commonly used for determining the hardenability of steel. Plutonium specimens were end-guenched from temperatures in each of the ß, y, d, d') and E phases. One series of specimens with a low-iron content, 165 pprn Fe, and another gvoup with a high-iron content, 678 pprn Fe, were used in order to study the effect of a Pu-Pu,Fe eutectic network on the hardness and micro-structure. Hardness traverses indicated no significant variations in hardness with either cooling rate or quench temperature. Metallographic studies indicated major effects on microstructure. Grain size was found to vary markedly with quenching temperature and cooling rate. It was determined that the Pu-PueFe eutectic network could be modified extensively by heat treatment, including spheroi -dization in the y phase and 6 phase below 413°C. An unidentified spheroidal inclusion was observed to go into solution in the delta and higher temperature phases. 1 HE element plutonium is unique among metals in that it has six allotropic forms in the solid state.' These have been designated' as the a, ß, y, d, d', and phases. The respective phase transformations occur at approximate temperatures of 122", 210°, 319°, 450°, and 480°C with a melting point at 640°C. With this number of phase transformations it becomes pertinent to consider the effect of heat treatment and cooling rate in the various phases on the microstructure and hardness of plutonium. To determine; the effect of a wide range of cooling rates, the Jominy end-quenching technique was applied to cylindrical plutonium specimens. In addition, since the presence of iron in amounts greater than 500 pprn is common in plutonium and results in a network of the Pu-Pu6Fe eutectic, it was decided to study heat treatment effects on two bomb reduced plutonium buttons with different iron contents. A low iron button containing 165 ppm Fe and a high iron button containing 678 ppm Fe were selected for this comparison. EXPERIMENTAL PROCEDURE Experimental Material. The cylindrical bars for Jominy quenching were cast from button stock in vacuo in MgO coated graphite molds. Metal pouring temperature was approximately 950°C and the molds were preheated to 300°C. The castings were machined to 0.5 in. diam. by 2.5 in. long cylinders. Chemical analysis and density data for the two groups of Jominy specimens containing different iron contents are presented in Table I. Except for iron, heats 19-12-1 and 20-2-1 are comparable within the limits of analytical accuracy. Representative specimens from the low-iron and high-iron bars were taken for metallographic examination. The low iron specimen was found to have extensive microcracking, Fig. 1. In addition, numerous unidentified spheroidal inclusions were present, Fig. 17. The average grain size of the low-iron plutonium is 0.068 mm, Fig. 4. In the high-iron plutonium, a Pu-Pu6Fe eutectic network is prominent, Fig. 7. The average size of the network is 0.100 mm. Unidentified spheroidal inclusions were also common in the high-iron plutonium. The average grain size of the high-iron plutonium is 0.036 mm. Experimental Technique. A Jominy end-quenching fixture was fabricated for glove box use. A 2.5 in. water height was used with an orifice of 0.250 in. ID. The orifice to specimen distance was maintained at 0.5 in. Annealing temperatures of 160°, 265°, 400°, 465°, and 535°c were chosen for the study of the effect of quenching from ß, y, d, d', and e phases on microstructure and hardness. During quenching, cooling curves were obtained from the Jominy specimens at distances from the quenched end of 1/16, 1/8, 3/8, 3/4, 1-1/4, and 2 in. Cooling rate calculations were made from the cooling curves for temperature intervals of 100° to 110° 160" to 170°, 330" to 340°, 420° to 430°, and 490° to 500°c. These temperature intervals were chosen

Jan 1, 1962

By W. M. Parris, P. D. Frost, H. A. Robinson

The effects of hydrogen content and strain rate on the static tensile and notch-rupture properties of the Ti-3Mn-complex alloy heat-treated to differed strength levels were investigated. The extent of embriulement was found to be proportional to the amount of hydrogen present and the strength to which the specimens were heat-treated. The research suggests the possible necessity of specifying lower hydrogen limits than are now allowed when titanium alloys are heat-treated to higher strengths than are presently used. The research also supports a hypothesis advanced earlier for a mechanism of hydrogen embrittlement. MUCH attention has been focused on the effects of hydrogen in in Most of the published in- formation has dealt with the effects of hydrogen on alloys in the annealed or lowest-strength condition. The work of Kotfila and Erbin3 is one of the few exceptions. In view of the fact that heat-treatments are now being used to produce high strength in titanium alloys,' it is necessary that more attention be given to the effects of hydrogen on these alloys in the heat-treated condition. Research was initiated to establish the effects of hydrogen on the properties of the Ti-3Mn-complex alloy at various strength levels. This research, which supplemented that of Kotfila and Erbin, was started because it was found that high-strength tensile specimens of this alloy were strain-rate sensitive. The essential results of the research are summarized in this paper. MATERIALS AND EXPERIMENTAL PROCEDURES Material for this investigation was a 41/2-in.-diam bar forged from a single commercial heat of the Ti-3Mn-complex alloy having the composition given in Table I. The as-received forging was reduced further by forging at 1750°F to 3/4-in. square bars. About one fourth of this material was vacuum annealed at 1400°F for 24 hr to obtain a base hydrogen content of 25 ppm. The remaining bars were hydrogenated to levels of 90, 140, and 260 ppm in a large Sievert's apparatus in the following manner: Four 3/4-in. square bars, 5 in. long, were placed in the reaction chambzr. The chamber was evacuated, heated to 1400°F, and a measured amount of hydrogen was introduced. When absorbtion was complete, as indicated by the drop in pressure, the reaction tube was cooled and the bars removed. Each batch of bars was then sealed in individual evacuated Vycor containers and heated for 24 hr at 1400°F in order to distribute the hydrogen homogeneously. After vacuum-annealing or hydroge nation, the bars were rolled at a temperature (1400°F) below the ß-transus to 1/2 - in. - diam rounds. Groups of the rolled specimens representing each of the hydrogen levels were given the following heat-treatments: 1) One hr at 1300°F, water-quenched. 2) One hr at 1300°F, water-quenched, and aged 8 hr at 1100°F. 3) One hr at 1300°F, water-quenched, and aged 4 hr at 1000°F. 4) One hr at 1300°F, water-quenched, and aged 48hr at 800°F. Heat-treated bars were machined into standard 0.250-in.-diam tensile specimens having 1-in. gage lengths. Throughout the processing and testing of this material, hydrogen analyses were made by vacuum-fusion methods to check for accuracy of hydrogen additions, homogeneity, and possible losses during processing. A summary of these analyses is given in Table II It may be seen that the actual hydrogen contents were reasonably close to the desired levels. In addition, it was noted that the variation in hydrogen content within any one bar did not exceed

Jan 1, 1959

By Y. A. Chang

Phase relationships in the system Cr-Si have been established based on the melting point, X-ray, metallo-graphic, and DTA studies. The three intermediate phases, Cr3Si, Cr5Si,, and CrSi,, melt congruently at 177V ± I@,Cr3Si, 1680"i 20°, and 1490" *20°C, respectively, while the fourth intermediate phase CrSi, melts peritectically at 1413" i 5°C to Cr5Si3 and a melt containing 51 at. pct Si. The temperatures and compositions of the four eutectic isotherms occurring in this system are given below: DTA and metallographic evidences indicate that Cr5Si, undergoes a phase transformation at 1505" i20°C. The high-temperature form of this phase could not be retained by the quenching techniques used in this study. TECHNOLOGICAL interest in the developing of composite systems, consisting of Sic on the one hand as a fiber-reinforced material and metallic substances such as chromium, nickel, or Cr-Ni alloys as a binding agent on the other hand, stimulated the present investigation of phase relationships in the binary system Cr-Si. Earlier works concerning this system have been evaluated and summarized by ansen and Anderko.' Their phase diagram was based mainly on the works of Kieffer, Benesovsky, and schroth2 and Kurnakov.~ According to these authors, the three intermediate phases Cr3Si, CrSi, and CrSi, all melt congruently at approximately 1730°, 1600°, and 1550°C. However, they did not agree on the compositional stability of the fourth intermediate phase between Cr3Si and CrSi. Later Parthe, Nowotny, and schmid4 determined the structure of this phase to be tetragonal T-1 type using the single-crystal method, and concluded that this phase had a formula of Cr5Si3. Since the compilation of Hansen and Anderko,' a new phase diagram for the system Cr-Si has been proposed by Elliott5 based on the works of Goldschmidt and rand,' Guseva and ~vechkin,~ and Trusova, Kuzev, and Ormont8 and the earlier works quoted by Hansen and Anderko.' According to this proposed phase diagram, all four intermediate phases have large ranges of homogeneity and all melt congruently. More recently, Svechnikov, Kocherzhinskii, and yupkog studied the system Cr-Si by the DTA-method. According to their findings, the three intermediate phases, Cr3Si, Cr5Si3, and CrSi,, melt congruently at 1700°, 1720°, and 1475"C, respectively, while the fourth intermediate phase, CrSi, melts peritectically at 1475°C to Cr5Si3 and a melt containing 50 at. pct Si. The temperatures and compositions of the four eutectic isotherms were found to be: In view of the discrepancies existing in the literature concerning the system Cr-Si, it was decided to rein-vestigate the phase relationships in this system. EXPERIMENTAL a) Starting Materials. Chromium disilicide and chromium or silicon powders were used in the present study to prepare the melting point and DTA samples. CrSi, was obtained by directly reacting cold-pressed elemental powders in an atmosphere of Hz at a temperature of about 1250°C. Chromium powder, purchased from Stark Chemical Co., had the following impurities in ppm: Fe, 200; Mg, 1000; and 0, 250; while silicon powder, purchased from the Welded Carbide Co., had the following impurities in ppm: Ca, 700; and Fe, 3500. b) Melting-Point Determination and Differential Thermal Analysis. Cylindrical melting-point samples of approximately 13 mm in diam and 30 mm in length with a rectangular groove in the center were prepared by hot-pressing of well-mixed powder mixtures in graphite dies. Before the melting-point determination, the hot-pressed samples were ground on a sand paper to remove any minute surface contamination of graphite. A small hole of 1 mm in diam, drilled on the center portion of the samples, served as a blackbody cavity for the temperature measurements. DTA samples approximately 13 mm in diam and 15 mm in length were prepared in a manner similar to the melting-point samples. Melting points were determined using the Pirani technique under a helium atmosphere of 40 psi. The design, performance, and operation of this apparatus have been described in detail by Rudy and ~ro~ulski.'~ The temperature measurements were carried out with a calibrated disappearing-filament-type micro-pyrometer. The measured temperature was corrected for losses from the quartz window of the melting-point furnace and for deviations from blackbody conditions of the observation hole. The procedure for temperature correction has also been previously described." The DTA method of Heetderks, Rudy and Eckertl' was also used to check any phase transformations of selected alloys in the system Cr-Si. It was not possible to make remated runs on the same sample once melt-

Jan 1, 1969