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By W. A. Walker, G. W. Ostroot

An increase in the number of deep wells being drilled where extreme bottom-hole temperatures are encountered, and the anticipated drilling of wells where temperatures in the range of 500°F or higher may occur, has brought about a comprehensive investigation of cementing materials and of the techniques involved in their proper usage at these elevated temperatures. Included are developments in cements, retarders, weighting materials and other cement additives which make it possible to formulate a variety of compositions to help resolve the cementing problems of these extreme well conditions. The problems associated with the selection and testing of cements are discussed, and a resume of field results is included. Previous studies on strength retrogression indicate that caution should be exercised in the selection of a cementing composition for use in high-temperature wells. It now appears that, by the addition of silica flour as a stabilizing additive to certain cements, compositions covering a wide range of slurry densities can be designed to meet extreme well conditions without strength retrogression. Improvements in cement retarders make it possible to produce a four-hour thickening time at static temperatures up to 500°F. This temperature is considerably higher than conditions presently being encountered in drilling and completion work. Inert weighting materials, used to produce 20-lb/gal or heavier cement slurries, are reviewed. INTRODUCTION As the search for oil continues, the number of wells being drilled to depths of 10,000 ft or below has continued to increase over the past decade. During 1959, there were 50,893 wells drilled in the United States for a total of 209 million ft of hole. Of this total, approximately 4.45 per cent were drilled below 10,000 ft and 0.30 per cent below 15,000 ft, with a record depth of 25,340 ft recorded (Table 1). With the drilling of this record-shattering hole comes the question, "How deep can wells be drilled?".' Limitations with respect to equipment (surface and subsurface), cementing materials and techniques would cause some concern; however, a panel of experts have agreed that the U. S. oil industry has the equipment and know-how to drill a 50,000-ft hole. The greatest deterrent would be the 700°F temperature they would anticipate encountering at this depth. Although the number of wells drilled under what is generally considered hot-hole conditions (230°F and higher) has been relatively high, each well often presents distinctly individual problems and requires separate consideration and selection of special materials, techniques and equipment. At the present time there are over 30 additives and special cements available for use in "tailoring" a cementing composition for a specific well. It is not uncommon to use three or four different additives with the basic cement to produce the desired slurry characteristics. A generally accepted procedure is to make laboratory tests on selected cementing compositions prior to pumping them into wells deeper than 12,000 ft, or where static temperatures are in the range of 260°F or higher. In some instances, it is recommended that laboratory tests be made where less severe well conditions are encountered. Prior to selecting a cementing composition for a particular well, key personnel representing the operator, drilling contractor and service company should meet to determine that each individual is acquainted with every detail which might influence cementing results and to discuss the execution of the job. For cementing hot-holes, a number of factors must be evaluated before proceeding with the operation. Consideration must be given to the following. 1. Thickening time—The slurry must remain fluid for a sufficient length of time to allow displacement down the casing and up the annular space in a primary cementing job or, in squeeze-cementing, adequate thickening time for both the build-up of a satisfactory squeeze pressure and the reversing out of excess cement. The thickening time of standard retarded cements will often be too short under extreme temperature conditions, thus involving special formulations and requiring laboratory tests to determine the proper amount of additional retarder to obtain the desired pumpability.

By A. E. Jenkins, A. Jostsons

Isothermal sections of the Ti-0-H phase diagvam at 600°, 700°, and 800°C have been constructed from equilibrium hydrogen pressure measurements over a range of Ti-0-H alloys containing up to 34 at. pct 0. Oxygen reduces the hydrogen solubility at fixed hydrogen pressure but increases the terminal solubility in the a solid solutions at the a/(a + P) phase boundary. Metal-lographic studies of alloys annealed below the eutectoid temperature show that oxygen also increases the ter-ninal solubility of hydrogen in the a solid solution in equilibrium with the hydride phase. The effect of oxygen on hydrogen solubility is discussed in terms of the electronic and geometric structure of interstitial solid solutions. THE isothermal solubility of hydrogen in a Ti-0 alloys at 800°C has been measured by Hepworth and ~chuhmann' who subsequently used ternary Gibbs-Duhem integrations to calculate oxygen activities in binary Ti-0 alloys. The present study aims to extend Hepworth and Schuhmann's measurements to alloys richer in oxygen and to a range of temperatures. This paper presents the results of hydrogen equilibrium pressure/concentration measurements in Ti-0 alloys as well as observations on the effect of oxygen on the terminal solubility of hydrogen in a titanium. The thermodynamic properties of binary Ti-0 alloys, derived from these measurements, will be published separately.' EXPERIMENTAL METHODS Specimen Preparation. Ti-0 alloys were prepared from iodide-refined titanium and titanium dioxide obtained by hydrolysis of redistilled titanium tetrachlo- ride. Specimens containing up to 16 at. pct 0 were prepared by electromagnetic levitation3 whereas a conventional tungsten arc furnace with a water-cooled copper hearth was used to melt oxygen-rich alloys. The specimen homogeneity was indicated by the constancy of lattice parameters of samples from various parts of the ingot as well as by the sharpness of the reflections on X-ray powder patterns. Oxygen-rich specimens in the composition range (20 to 34 at. pct), where ordering has been ~bserved,~ were annealed for 300 hr at 600°C prior to use in hydrogen solubility measurements. Apparatus. The hydrogen pressure/concentration measurements were made with a modified Sieverts apparatus shown diagrammatically in Fig. 1. Specimens were placed in a clear silica tube and impurity pickup by direct reaction with silica was prevented by lining the heated end of the silica tube with thin molybdenum sheet. A double silica tube was required to eliminate loss of hydrogen by diffusion through silica at high temperatures and high hydrogen pressures, the space between the tubes being maintained at a hydrogen pressure equal to that above the specimen. Hydrogen was purified by diffusion through a Ag-Pd tube.= Hydrogen pressures were measured with a mercury McLeod gage in the range 0.001 to 4 Torr

Jan 1, 1968

By A. G. H. Andersen

A FEW years ago, while the writers worked on the constitution of ternary and quaternary alloys consisting mainly of iron, chromium and silicon1,2 some information on microstructures and hardness, not incor-porated in the published work, was obtained. It has not been possible to do any further work on the properties of the alloys. The information possessed is hereby presented for the interest it. may have in connection with the constitution of the alloys.

Jan 1, 1937

By W. A. Straw

IN the manufacture of telephone apparatus a number of nonferrous sheet metals are blanked and formed to produce a wide variety of parts, which are generally small in size because of space and weight requirements. Many are given sharp bends in forming, so that they may be assembled into compact units. This study covered sheet metal of the alloys of brass, phosphor bronze and nickel silver that are most extensively used by our company. In general, the sheets range from 0.005 to 0.100 in. in thickness and from 1/4 hard to extra spring temper in hardness. As many parts function as flat springs, and others require the maximum stiffness for structural reasons, a large percentage of the metal is used in the hard and spring tempers. So, because of the necessity for the minimum radius of bend consistent with the maximum in hardness, there has been a need for information as to the forming characteristics of these sheet metals in the various alloys, tempers and thicknesses. The literature yields relatively little regarding such forming characteristics, so that designers of apparatus and tools have been largely dependent upon past experience or tool tryouts for guidance. In presenting tabular data intended as a basis for selecting the temper of the metal and radius of the bend, we recognize the influence of many other factors which are not covered in this study. For example, the angle of the bend and conditions of the metal, such as grain size and presence of impurities, as well as conditions of the fabricating process, such as rate of forming and adjustment of the tools, may all affect the result. In addition, a bumping operation subsequent to forming, which is frequently used to set the bend, increases the strain on the metal. We wish to emphasize the fact that this is not considered a scientific investigation of the formability of materials or an attempt to correlate forming, characteristics with various other properties of the metals, except in so far as such properties are controlled by commercial limits on composition and temper.

Jan 1, 1931

By D. W. Fuerstenau, G. D. Gumtz

Use of the discretized batch-grinding model for the simulation of locked-cycle grinding tests from batch-grinding data is illustrated. The simulated results were compared with actual locked-cycle experimental data for the dry grinding of dolomite. To illustrate the utility of this simulation method, a number of relationships between operating and performance parameters were generated, including relations between batch grinding and the Bond test, the production rate and the circulating load, and the production rate and the product size. A large amount of testing is done each year in the mineral industry for use with grinding unit cperations, and much of the experimental test data is obtained by the tedious locked-cycle testing procedure. In addition to being experimentally complex and requiring large amounts of sample, the very nature of the locked-cycle experiment yields results that cannot readily be interpreted. The attempts that have been made to model comminution systems during the last few years may provide a better and simpler way to obtain and analyze grinding test data; these models involve elements of both fitting to "model equations" and deterministic representations.1-1 The traditional engineering design techniques for comminution systems have relied mainly upon large amounts of industrial operating data that have been correlated with locked-cycle grinding data.',' Bond's empirical mill-design procedure involving locked cycle testing remains the most generally available method to this day. The purpose of the present paper is to show how much more useful data can be obtained from a simple batch-grinding experiment that provides information which subsequently can be utilized with population balance models of the grinding process to simulate locked-cycle behavior. These simulation results can, of course, be used in Bond's general design scheme. However, the combination of batch-grinding tests and the population balance model allows many more conditions to be considered than do single laboratory tests under specific locked-cycle conditions. The use of these simulation techniques for prediction of locked-cycle behavior represents one of the first practical applications for the simulation method in comminution.

Jan 1, 1971

By M. G. Driessen

For a number of years the cyclone, familiar to Americans as a dust collector, has been used as a thickener of suspensions at one of the coal-preparation plants of the Netherland State Mines in Limburg. The plant treats nut-size coal at 120 tons an hour in a heavy-medium washer. The diluted medium from the rinsing screens is thickened in cyclones. More recently the cyclone has been adapted to act as a coal cleaner. The principle of the cyclone thickener is the same as that of the cyclones used in industry for catching dust or fine particles suspended in the air or in gases. Generally the latter are more efficient in this respect—the smallest particles that can be caught with reasonable efficiency are considerably smaller than with the cyclone thickeners. The reason is obvious; the ratio of specific gravities between the dust particles in a gas and the gas itself is about 800 times larger than the ratio between, for instance, the specific gravities of shale particles and water. The ratio of the velocities of fall of shale particles (? = 2.5)† in air and in water is as follows: In the range of Stokes: ?air = 93?water In the range of Allen: Wair = 49Wwater In the range of Newton-Rittinger: ?air = 36.6?water The same ratios apply for the velocities in the centrifugal field, from which it follows that it is especially difficult to catch the very fine suspension particles in a liquid. The efficiency of a cyclone thickener depends mainly on the circumferential velocity of the liquid at its innermost radius, because here the centrifugal forces are the highest. However, these velocities cannot easily be calculated, as the flow is three-dimensional, and thus the axial components cannot be neglected .(p. 252, condition 3). We believe that at first a spiral tangential motion along the cyclone wall is created, which causes the inner vortex ascending from the apex of the cyclone (Fig I). At the same time the inner vortex is strengthened by the individual vortices in horizontal planes, and thus a part of the total flow can find another and perhaps quicker way to the outlet. In any case, the exact motion, not only of the fluid but especially of the suspended particles, is so difficult that we have to refer to the experiments to find the exact behavior of this kind of apparatus. Method of Judging PerforMance of Coal Washer Geologists, rather than mechanical en-gineers, would be able to describe the separating or stratifying effect in nature, but even a bather on the shore lying on the soft sand near the sea wonders why all the small sand grains have approximately the same size. A child playing on the border of the river could easily

Jan 1, 1949

By W. R. Atkins

THE Negaunee mine is at the east end of the Marquette Range, in the city of Negaunee, on the Upper Peninsula of Michigan. Iron ore was first discovered on this property in 1883 by diamond drilling. A shaft was sunk soon afterward, and the mine has been worked continuously ever since. The total shipments from 1887 to' Jan. 1, 1945, were 20,417,587 long tons. The mine was taken over by the present operators, The Cleveland-Cliffs Iron Co., in 1903. During the past four years, 1941 to 1944 inclusive, the property has produced an average of nearly a million tons a year, and has employed more than 400 men. GEOLOGY The ore body at the Negaunee mine lies in a large syncline dipping about 15° to the west, the ore coming to ledge at the east end of the trough. The ore occurs in the Negaunee formation of the middle Huronian age, which consists of ferruginous cherts and slates through which intrusions of diorite have occurred. Although these intrusions of diorite have an important bearing on the formation of ore on the range, they are not important in this ore body. Some faulting has taken place along the diorite intrusions, or dikes as they are called locally, and also other faults are known to exist across the formation. These faults do not complicate either mining or development of the ore body. The footwall consists of jasper underlain with Siamo slate; the hanging wall is jasper and ferruginous chert. Fig. I shows a typical cross section of the ore body. The ore body is quite regular, about 120 ft. thick in the middle of the syncline and thinning out toward both sides of the fold. Its width ranges from 400 to 800 ft., the average being about 600 ft. The footwall is uniform in dip and strike, but irregular lenses of ore often extend 50 to 75 ft. up into the overlying jasper capping. METHOD OF MINING Ore in the Negaunee mine has been mined by top slicing almost exclusively since 1903. This method of mining has been employed because it is especially adapted to the size and shape of the Negaunee ore body, and to the soft, sticky nature of the ore as well as the generally soft, broken jasper capping. Development The ore body has been developed from six different levels with intervals varying between l00 and 125 ft. On the average, the dip causes a horizontal offset of 350 ft. per level, and under these circumstances it has been necessary to carry on considerable development in rock to make available the ore lying along the north and east footwalls. This is not as disadvantageous as might be supposed, because of reduced pressure and the accompanying saving in maintenance costs. The development of the

Jan 1, 1946

By P. Somasundaran, H. S. Hanna

The separation of minerals such as apatite and scheelite by flotation from other salt-type minerals such as calcite is extremely complex owing to the close similarity between their physicochemical properties. In this paper, properties relevant to flotation such as crystal structure, solubility, surface charge and adsorption behavior of important salt-type minerals are examined along with the role of inorganic modifying agents such as silicates and polyphosphates and organic modifying agents such as starch and tannin. Flotation characteristics of these minerals are then reviewed and selected separation problems involving salt-type minerals are discussed.

Jan 1, 1976

By F. G. Miller, T. D. Mueller, L. B. Davidson

A mathematical model of reservoir behavior during one cycle of the intermittent steam injection process is presented in this paper. A cycle of the process is considered to be composed of three stages: injection, condensation and production. The model concentrates on behavior during the production stage. The influence of several parameters on production improvement is described, using the results obtained with a numerical equivalent of the model. Reservoir system parameters considered are thickness, reservoir thermal conductivity, oil viscosity, solution gas-oil ratio and the change in oil effective permeability with temperature. Operating parameters investigated are heat injection rate, steam temperature and cumulative injection time. In the face of considerable uncertainty, the model appears to give a fair prediction of the behavior observed during an actual test. This makes the model a useful means of selecting projects. It is shown that the model may also be utilized to select an optimum set of operating conditions for a particular project. Results of this study show the extent to which production improvement depends on each of the parameters investigated and give an indication of the range of system conditions within which the process would be effective. INTRODUCTION In recent years the intermittent steam injection or steam soak process of oil recovery has become a popular method of improving recovery in reservoirs bearing high-viscosity hydrocarbons. Production improvement due to the process results from heating the reservoir near the wellbore. The process is applied on an individual well basis and is executed in a series of cycles, each consisting of three stages: injection, condensation (the soaking period) and production. During the injection stage, high-pressure steam is injected into the reservoir surrounding the well-bore. This study assumes that injection is carried out over the entire vertical section of the reservoir rock that can be exposed to fluid injection. The condition of steam entering the reservoir is considered to fall within the following limits: (1) steam pressures less than 1,000 psig, (2) steam temperatures between 300 and 700F and (3) steam quality less than 90 percent. The last restriction is due to equipment limitations. Normally, injection re maintained for less than 3 weeks. After termination of injection, the condensation stage begins. The well is shut in for several days, supposedly to make certain that the injected steam condenses. This condensation would insure the retention of injected heat. The production stage is initiated when the well is opened again. Reservoir response during this stage determines the effectiveness of the process (response is defined as the oil production rates, the water production rates and the wellbore temperatures observed during the entire production stage). The immediate response of the reservoir is sometimes quite good. Sets of case histories by Longl and by Owens and Suter2 give some typical figures for response. Duration of the production stage is equal to the time needed for the oil production rate to decline to some predetermined value. This usually requires 4 to 6 months. Termination of the production stage coincides with the start of the next cycle. The process is continued, cycle by cycle, until it becomes unprofitable to continue. One simple model2 and two more sophisticated models3,4 of the process have been presented. These are based on fundamentally different assumptions than those used in this investigation. Although the three models might be modified to fit the assumptions used in this study, it is felt that greater rigor would result by developing a

By J. A. Scott, F. R. Hensel

The paper deals with the investigation of two types of coreless induction furnaces, one of 60 cycles, the other of 5000 cycles. Nickel was used as test material and the absorption of oxygen by molten nickel was chosen for determining the influence of the frequency on the metallurgical characteristics of the furnaces. Dr. Herty's aluminum method, slightly modified, was found suitable for determining the nickel oxide content in nickel. Also an electrolytic method for determining alumina in nickel was worked out. The solubility-temperature relations for nickel oxide in molten nickel were determined approximately. It was found that the solubility of nickel oxide increases with the temperature. Comparative tests on the rate of oxygen absorption made in a 60 and a 5000-cycle furnace showed that the absorption of nickel oxide in nickel is an increasing function of turbulence, time and temperature. The rate of oxygen pickup in the 60-cycle furnace is about three times as great as in the 5000-cycle furnace. In the 60-cycle furnace the maximum oxygen content of the melt comes close to the saturation limit. Melting under an oxygen-free atmosphere prevents oxidation in both types of furnaces. DISCUSSION (Iloward Scott presiding) H. Scott, East Pittsburgh, Pa.—When Professor Desch was in Pittsburgh recently he mentioned that the induction furnace has practically replaced the crucible furnace in Sheffield except for the carbon tool steels. Dr. Hensel is to be congratulated on the development of analytical methods for determining inclusions and for getting two different methods to agree. F. R. Hesnsel—Recently the purification of molten metals with hydrogen or other suitable gases has become an important issue and a number of patents have been taken out covering gaseous treatments of molten metals. In this connection I wish to call

Jan 1, 1933

By Thomas L. Kesler

Present Raw Materials The lithium industry has had exceptional growth since publication of the last edition of this volume, and the present scale of mining and consumption of raw materials is a great many times that of 1949. The materials of present economic importance consist of four pegmatite minerals and lithium-bearing brine. Spodumene, a lithium pyroxene, occurs in greatest abundance, and is the chief source. It has the formula LiAlSi2O6 and theoretically may contain 8.03 pct Li2O, but in the more important deposits the content is 6.5 to 7.5 pct. The hardness is 6.5, the specific gravity 3.1 to 3.2, and the color mostly pale green to white although deep green, lilac, and yellow varieties exist. The crystals are prisms with strongly developed longitudinal cleavages, and crushing characteristically produces lath-shaped particles. Giant crystals up to 47 ft long are known, but in most occurrences the predominant size range is 0.5 to 12 in. long and 0.1 to 2 in. wide. Hypogene* alteration has formed lithia-bearing sericite and coarser muscovite and rarely eucryptite, while supergene* alteration yields kaolinite and hydrous mica. Lepidolite, of second importance, is a mica of varying composition approximating K2Li3-A14Si7O21(OH,F)3. It has lamellate cleavage, book structure, and a specific gravity of 2.8 to 3. The books range in size from microscopic to a diameter of several inches. The color is mostly violet, but other colors include pink, gray, yellow, and white. Most commercial lepidolite contains 3 to 4 pct Li20 and chemically is in the higher grade range of a series of lithium micas that includes polylithionite, zinnwaldite, and protolithionite. In this series, the content of Li2O is exceptionally as high as 7 pct. Petalite and amblygonite are also of economic importance, but are used in smaller amounts. Petalite has the formula LiA1Si4O10 and is white, gray, or pink. The hardness is 6, the specific gravity 2.4, the cleavage in two planes 114° apart, and the Li2O content commonly 3 to 4.7 pct with a maximum of 4.88. Amblygonite has the formula LiA1FPO4 in which OH may substitute for F to form montebrasite. It is white and has polysynthetic twinning in two directions at 90°. Amblygonite superficially resembles potash feldspar, but has a bluish or grayish tint unlike the cream or salmon tint of the feldspar.[t] The hardness is 6 and the specific gravity 3 to 3.1, and the content of Li2O is the highest among lithium minerals that occur in significant quantity, ranging mostly from 7.5 to 9 pct with a maximum of 10.2. The brine of Searles Lake in California30 has been a commercial source of lithium since 1938. See Chap. 7, p. 108. The "lake" is a saline evaporite deposit, and the exposed part has an area of 12 sq mi. To an average depth of 71 ft, this part of the deposit consists of crystalline salts with 50 pct interstitial voids. The voids are filled with brine that contains mainly sodium and potassium compounds, but the brine also contains 0.015 pct Li2O, which is recovered as dilithium sodium phosphate containing 21 pct Li20. This deposit overlies a

Jan 1, 1960

By Walter P. Jenny

I. The Reducing Action of Carbon and of Hydrocarbons,. .. 445 11. Protective Action of Carbon and of Hydrocarbons,. 451 111. Contributory Action of Carbonic Acid Gas,..452 IV. The Stability of Carbonic Acid and of Water,..453 V. Occurrence of Carbon and the Carbon-Compounds,. 455 VI. The Occurrence of Carbon, Alone,.... VII. The Occurrence of Carbon Combined with Hydrogen,. .. 460 VIII. The Relative Reducing Power of Minerals,..487 I. The Reducing Action of Carbon and of Hydrocarbons. Carbon has long been recognized as one of the most powerful reducing agents in the deposition of ores. Investigations, made by myself, of the zinc- and lead-deposits in Southwest Missouri, in the region centering about Joplin, where the formation of the metallic sulphides has been due to the action of bitumen, carbonaceous shales and bituminous coal, have afforded abundant evidence that the solid oxygenated hydrocarbons, particularly when in fine powder and in suspension in the waters circulating through the ore-bodies, are the most energetic and powerful reducing agents known. Bitumen, liberated by the decomposition of the ore-bearing limestone, is found in the Joplin mines in all degrees of fluidity and hardness, dependent on the amount of oxidation it has undergone. From semi-fluid maltha it grades into partly oxidized mineral-pitch, which, by further oxidation, changes to hard asphalt, finally breaking up, from continued absorption of oxygen, into a fine powder resembling in appearance powdered coal. In this condition oxidized bitumen, from its light gravity, is transported readily in suspension in the underground circulating-waters. Bituminous coal and black carbonaceous clays and shales occur as surface formations, often in intimate association with

Jan 1, 1903

By G. F. Loughlin, C. H. Behre

THE DEVELOPMENT OF CLASSIFICATION WHAT is the use of a classification of mineral deposits? From the days of Agricola, the founder of the science of ore deposits, successive authors on the subject have attempted classifications, none of which have attained unanimous indorsement of miners, engineers, or geologists. The miner and engineer naturally have little regard for a classification that does not help them to find ore. Mining geologists may share this feeling, and deplore the overemphasis that may be placed on classification by their academic brothers. Apparent effects of such overemphasis may be reflected by students or new graduates who have grown to think that each deposit must fit perfectly into some pigeonhole of the more or less arbitrary scheme that has been drilled into them. Diversity in mineral deposits as in other natural phenomena, however, is too great to be fully expressed in the usual tabular classification, and experience is essential for the appreciation of the value or usefulness of a classification. The succession of classifications has closely followed the growth of the science of mineral deposits and reflects that growth, as well perhaps as the limited or comprehensive viewpoint of each proponent. The earliest classifications were based on metal content, and were superseded by those based mainly on form of deposit. Source of materials also became a basis, and was followed by physical and chemical conditions and processes. In spite of this development it is interesting to note that in many of the latest reports on mining regions the authors adopt special classifications suited for their particular districts. Some of these, like the earliest classifications, are based primarily on metal content, and others are most conveniently based on form, and it may be convenient to modify these by reference to source of material or temperature of deposition. Some, including the writers, after noting these different usages, have refused to worry much over classification as an ultimate objective, but,

Jan 1, 1933

By Lyall Zickrick

Experiments of previous investigations have indicated that calcium-copper alloy, when used as a deoxidizer for molten copper, results in a sound copper casting of good physical and electrical properties. Braden-berg and Wiensl have obtained successful results in casting sound copper using calcium for deoxidizing. Masing2 has obtained deoxidized copper of high density and high conductivity by use of calcium. Pratt,3 in 1907, patented the use of calcium for the deoxidation and degasification of copper. Schumacher, Ellis and Eckel,l in 1929, conducted a series of experiments on deoxidizing copper with calcium. They concluded that so long as there is only a small percentage of residual calcium the mechanical and electrical properties of the copper deoxidized are not impaired, and the deoxidation is thorough. For this investigation, a copper-calcium alloy high in calcium and 10 variously deoxidized copper ingots were prepared. The investigation concerns itself with the casting properties and structure of these variously deoxidized ingots, their working and annealing characteristics, and the resulting physical and electrical properties of the worked materials. Preparation of Special Copper-calcium Alloy and Experimental Ingots For use as a deoxidizing agent, an alloy of copper and calcium with fairly high calcium content was prepared, by melting pure electrolytic copper in a graphite crucible in an ordinary gas-fired pot furnace. The molten copper was kept well covered with calcium chloride slag. Small chunks of calcium were wrapped in thin copper sheet, placed on the end of a graphite rod and plunged down into the molten copper and thoroughly stirred. Upon completion of the calcium additions the crucible content was poured out into a cake about one inch thick. Analysis of this alloy gave 4.4 per cent calcium. The alloy was brittle and easily broken into small chunks. Some calcium was lost during the addition, owing to

Jan 1, 1933

By Frederick M. Becket, Russell Franks

WideSpread experimentation has been conducted in recent years to devise a means of preventing intergranular corrosion in austenitic chromium-nickel steels of the 18 per cent chromium-8 per cent nickel type. Additions of titanium to these steels have been used commercially to overcome this dificulty, as advocated by Krupp of Germany, and the latest literature reference concerning improved details of this method is the article by Bain, Aborn and Rutherford.' Extensive work by the present authors has shown columbium also to be a particularly valuable agent for inhibiting intergranular corrosion. This paper does not deal with steels that are largely or wholly austenitic; it is limited to a discussion of the results obtained through the use of titanium and columbium in plain high-chromium steels. For many years titanium has been used commercially by some steelmakers as a cleanser, and to a lesser extent as a hardener, but then in greater percentages. The results of the work to be described disclose that titanium and columbium in proper Proportions act as effective softeners in the high-chromium steels. It is well known that chromium intensifies the hardening effect of carbon in steel; it imparts pronounced air-hardening properties within a rather wide range of chromium content; it provides increased ductility in steels of given strength and hardness; and it enhances resistance to corrosion and oxidation at elevated temperatures to a marked degree. However, in applications requiring a combination of some of these valuable properties great hardness is frequently a detriment rather than a merit. When the objective is a soft and ductile steel having optimurn corrosion resistance, the producer strives for a carbon content as low as commercially practicable. Despite these efforts some of the commercial high-chromium steels low in carbon present considerable difficulties during production, owing to their air-hardening properties, and in consequence the economic result is not favorable. A good example is found in the 5 to 6 per cent chromium steels employed chiefly in the oil-cracking industry. Sleels

Jan 1, 1934

By L. R. Duncan, O. M. Wicken

Magnesium, the eighth most abundant element in the earth's crust, is found widely distributed in a variety of minerals. Among the more commercially important ones are magnesite (MgCO,), brucite (Mg[OH],) , dolomite (CaMg[CO,],), and the salts magnesium sulfate and chloride often found in natural brines. Among other commercially important magnesium-containing minerals are olivine ([MgFe],- SiO,) , talc (H,Mg,[SiO,],) , and serpentine (H,Mg,Si,O,) . These are valuable because of desirable characteristics given them by the magnesium content and its placement in the particular crystal structure. These minerals are the raw materials for a host of products including magnesium metal and several grades of magnesia or magnesia- containing materials for refractories, fluxes, fillers, insulation, cements, decolorants, fertilizers, and chemicals. Considering only those minerals valued for their magnesia or magnesium content, over 85% of the material tonnages are processed to be used as refractories. Dolomite, which is used in enormous tonnages for its physical properties in construction, has an important use as a refractory raw material in its own right and, after calcination, as a precipitant for magnesium hydroxide, which is an intermediate for the production of magnesia or magnesium metal. Magnesia from the reaction of calcined dolomite (or limestone) with sea-water or magnesium-containing brines has supplanted much of the production of magnesia from mined magnesite, particularly in the United States. The best known of the minerals directly and widely exploited for magnesia content is magnesite, one of the calcite group of rhombo- hedral carbonates which includes calcite (Ca- CO,) , siderite (FeCO,) , and rhodocrosite (MnCO,) among others. The members of this group enter into a wide range of substitutional solid solutions when the positive ions have similar radii. The radii of magnesium and iron ions are within 6% of each other; hence, magnesite and siderite form a complete series of which breunnerite (ferroan magnesite) is a well-known end member. However, the radius of calcium ion is 36% larger than that of magnesium ion, and only limited substitution exists at each end of the MgC0,-Cam, series. Dolomite is not a member of the calcite group, but results when calcium and magnesium ions alternate in equal number in an ordered structure among carbonate ions. The result of these relationships is that calcite and dolomite, often found intermixed with magnesite, occur commonly as identifiable crystal entities which can often be separated to a varying degree from the magnesite by various beneficiation techniques. Magnesite, when pure, contains 47.8% MgO and 52.2% CO,. The pure mineral is sometimes, but rarely, found as transparent crystals resembling calcite, but, preponderantly, magnesite contains variable amounts of the carbonates, oxides, and silicates of iron, calcium, manganese, and aluminum. Magnesite may be either crystalline or "amorphous" (cryptocrystalline). The crystalline form has a hardness of 3.5 to 4.0. The color may range from white to black with shades of yellqw, blue, red, or gray. The color is not a fundamentally significant indicator of purity, but in a given deposit, an experienced person can often roughly grade magnesite by assessing color and crystallinity. The crystalline form of magnesite occurs in

Jan 1, 1975

By B. F. Decker, D. Harker

The recrystallization reaction in OFHC and spectroscopically pure copper has been followed by X ray diffraction determinations of the amount of material with the cold-worked and recrystallized textures in specimens which had been given various heat treatments. The heats of activation for recrystallization are found to be: 29.9 kcal per rnol for OFHC copper and 22.4 kcal per rnol for spectroscopic copper. A reliable and speedy method for measuring the amount of recrystallized material in a piece of rolled metal, together with a new scheme for low temperature heat treatment, have made possible a determination of the activation energy for recrystallization in rolled copper. This method for studying recrystallization rates is different from others reported in the literature.' Oxygen free, high conductivity copper—OFHC copper—of purity 99.98 pct gave an activation energy for recrystallization of 29.9 kcal per mol with recrystallization data taken in the temperature range 208-245°C. Copper of purity 99.999 pct from the American Smelting & Refining Co. gave an activation energy for recrystallization of 22.4 kcal per mol with recrystallization data taken in the temperature range 43-135°C. The great change in activation energy for recrystallization as the small amount of impurity in the metal is decreased suggests that the motion of grain boundaries is conditioned by the impurities which must be concentrated in them. Thus the OFHC copper recrystallizes with an activation energy of the order of magnitude to be expected for the diffusion of the kind of impurities likely to be present. The high purity copper, on the other hand, recrystallizes with a much lower activation energy, in accord with the notion that the grain boundaries need not wait for the impurities to diffuse with them. Copper when strongly cold-rolled has a well-defined crystallite texture which can be described by saying that the [111] direction of the face- centered cubic crystals is aligned approximately in the cross-rolling direction and that faces of the form {110} lie approximately in the rolling plane. When such rolled copper is completely annealed the crystallite texture is quite different: the [loo] direction is in the cross-rolling direction and faces of the form (100) are in the rolling plane. At intermediate stages of annealing, the copper contains both textures. If a Geiger counter X ray diffraction spectrometer is set up so as to measure the intensity of the (200) Bragg reflection from the rolled surface of a piece of copper strip, this intensity increases from a very small value in the cold-worked state to a maximum as the specimen is annealed. The same would be true for (200) reflections from planes normal to the rolling or cross-rolling directions. In view of this fact, the amount of material in the copper which has recrystallized can be measured by comparing the intensities of one of these reflections just mentioned with the intensity from a similar specimen after complete annealing. In much the same way the intensity of (111) reflections from planes normal to the cross-rolling direction could be used to measure the amount of unrecrystallized material in the specimen. In the work to be described here the amounts of recrystallized and unrecrystallized material in partly annealed rolled copper specimens were determined in this way. Experimental Procedure Samples of oxygen free high conductivity (OFHC) copper, cold-rolled 99.7 pct to 0.002 in. thickness, were subjected to heat treatments for various chosen times at four different temperatures, and high purity copper samples, cold-rolled 98.0 pct to 0.0015 in. thickness, at six different temperatures. Each sample, after treatment, was placed in an orientation sample holder for use with a Geiger counter X ray spectrometer and a reading was taken of the intensity of the (200) reflection from planes perpendicular to

Jan 1, 1951

By N. C. Fick, R. L. Rickett

Despite the large volume of literature on alloys of iron and silicon,' there is little published information dealing specifically with the constitution, at various temperatures, of the alloys containing less than 0.10 per cent carl~on and from 0.5 to 4.5 per cent silicon that are used extensively in the electrical industry. Because such information was needed by those engaged in the production of these alloys in sheet and strip form, the constitution nas determined of a series of commercial silicon steels containing 0.05 to 0.08 per cent carbon and 0.20 to 4.1 per cent silicon, over the temperature range 1300° to 1500°F. These alloys were all from regular production heats and of commercial quality. The results of the tests are given in Fig. I and for comparison the constitution diagram of iron-silicon alloys with 0.01 to 0.02 per cent carbon, taken from the literature, is also presented Material and Procedure All steels were hot-rolled to a thickness of 0.060 to 0.080 in. and used in this condition. Their chemical compositions, including over-all check analysis, and "center" analysis for carbon and silicon, are given in Table I. The so-called center analysis was determined on samples pickled to remove the outer surface and leave only the center third of the gauge thickness—the portion of the sample on which metallographic ratings were based. In most, but not all, of the alloys, slightly higher carbon was found at the center than when the whole strip was sampled; the two methods of sampling show relatively little difference in silicon. Two of the steels, A and E, contain relatively high phosphorus, while I and K are somewhat higher in manganese than the others. The procedure consisted essentially of heating specimens (about 1/16 by 3/8 by 3/4 in.), protected from oxidation or change in carbon content, at a temperature in the desired range and for a selected period, after which they were quenched in iced brine; the degree of transformation that had then occurred was determined by metallographic examination. The soaking periods were selected after preliminary investigation had shown that a con-

Jan 1, 1947

By H. A. Wriedt

A method of calculating activities in binary systems having miscibility gaps is described. The method, which applies only to the phase in which the gap occurs, is exact when the function defined by the equation varies linearly with composition. Analytical and numerical solutions (as a function of the conjugate phase compositions) are presented for two coefficients A and B from which the thermodynamic activities can be calculated. Deviations from Henry's law, calculable by the method presented, are shown graphically for the particula~ case of the component i at the edge of the miscibility gap more remote .from pure component i. For symmetrical gaps, the deviation from Henry's law at this gap edge becomes smaller as the gap becomes wider, The interrelation of gap location, the direction of departures from Henry's law and the occurrence of maxima and minzma in these departures is discussed in some detail. Values for a and for activity calculated from phase diagrams show fair to excellent agreement with corresponding experimental values in the Al-Zn and CaO-SiO2 systems. WHEN structurally similar phases, B and 6, lie at the sides of a two-phase region in a constitution diagram, it can be assumed that, stably or metast-ably, they will become completely miscible at a higher temperature. The B and 6 phases are particular composition ranges of a single B6 phase region with a miscibility gap. Below, as above, the critical solution temperature, the free energy of formation of the 06 phase is a continuous function of composition through the range of the miscibility gap. It is the purpose of this paper to use this continuous free-energy function in order to develop a simple method for computing the thermodynamic activities in the B6 solution of a binary system. To make these calculations it is assumed that the function ai, familiar from Gibbs-Duhem integrations and defined by the equation

Jan 1, 1962

By E. Hoek

INTRODUCTION Rock slope stability research has been in progress for the past four years at the Royal School of Mines in London under the sponsorship of a consortium of 23 companies* with interests in open pit mining. This paper reviews the principal aims and achievements of this research project. In order to assist the reader in following these details, the basic philosophy underlying the formulation and direction of this research project is discussed. DISTRIBUTION OF RESPONSIBILITY In open pit mining, the economic necessity of keeping waste rock removal to a minimum generally means that the mine slopes have to be excavated to the steepest possible slope angle. On the other hand, excessive steepening of these slopes can induce failures, which may negate the economic benefits that have been aimed at and which may also result in loss of life and damage to equipment. Consequently, where slope failures are likely to prove to be a problem, an evaluation of the stability of the slopes to be created should be included as part of the overall pit design. How is the stability of a rock slope evaluated? When this question was examined, during discussions on the research policy to be followed at the Royal School of Mines, it was clear that relatively few satisfactory techniques were available in a form that would be comprehensible and therefore useful to the practical mining engineer. It was recognised that the research project must be directed towards two distinct aims: a) The evaluation of existing techniques for rock slope stability analysis and the provision of new techniques where these existing methods were found to be inadequate and b) The presentation of the results of this evaluation and research in a form that would be useful to engineers without specialist training in rock mechanics. It was soon realized that a university based research team, however large and efficient, could not achieve these aims without the co-operation and assistance of mining engineers,

Jan 1, 1972