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By A. Schild

The effect of heating a producing well on the rate of oil recovery has been analyzed in the simple case of a well producing oil by a radial drive and in the steady state. Differences of production rates with and without borehole heating have been calculated and plotted; these measure some of the benefits of the thermal recovery process. A striking feature is that the production increase tends rapidly to a constant value for large production rates. Some concrete examples, including a rough comparison with field data. are discussed. Heating requirements have been calculated and plotted on the assumption that the heaters used are 100 per cent efficient. Heating has been thought of as applying only to low volume wells producing heavy oils. However, the calculations suggest that the thermal process considered might be profitable even for some wells producing large quantities of light oil, especially in unconsolidated formations where fracturing is not possible. In the case of wells producing other fluids with the oil or of wells producing partly or wholly by gravity drainage, the theory developed does not apply in detail. It can be expected, however, that any general qualitative be-havior will remain valid. Under normal temperature conditions, high viscosity emulsions sometimes form around the wellbore, lowering the permeability in the vicinity of the well and impeding the production of oil. Borehole heating often prevents such emulsification. This important effect is not easily amenable to mathematical analysis and has not been included in the theory presented here. It should therefore be kept in mind that the benefits due to borehole heating may in fact exceed the values given by the following calculations. INTRODUCTION The recovery of viscous, low gravity oils can often be stimulated by applying heat to the production zone. The higher temperature lowers the viscosity of the oil, increasing its mobility, and therefore its rate of production. One thermal method of recovery 1,2,3,4. consists in operating a heater inside a producing well and, at the same time, producing oil from the well. In this paper a simple theoretical model is analyzed to study the effect of such heating on the recovery of oil. The reservoir mechanics of the process is the only aspect of the problem which is considered here. The details of the heating system are ignored, and it is simply assumed that the heater raises the temperature in the immediate vicinity of the producing well to a pre-assigned temperature T w. Although heating requirements are calculated, these refer only to the heat supplied to the formation and to the oil being produced; they do not include heat losses due to the inefficiency of the heater. A short outline of the theory follows: The heat supplied to the producing well flows out into the formation by means of thermal conduction. At the same time, the flow of oil carries heat by convection from the formation towards the producing well. After sufficient time has elapsed, a steady-state is reached where the temperature, the velocity of the oil, etc., no longer vary with time but are functions of position only. In the steady state the temperature decays like an inverse power from the high value Tw at the wellbore to the original reservoir temperature T. at some distance away from the well. The effect of the high temperature and low oil viscosity near the producing well is the same as if the oil were produced at reservoir temperature To but through a producing well of a larger radius. From this point of view, the energy and money being expended to provide heat

Jan 1, 1958

By Samuel S. Adams

Potash, the generic term for a variety of potassium-bearing minerals, ores, and refined products (Table I), owes its importance as an industrial mineral to the potassium requirement of growing plants. The term "potash" originally referred to potassium carbonate produced by the leaching of wood ashes. This process, for which the first U.S. patent was issued in 1790, was the basis for the largest United States chemical industry in the early nineteenth century. The agricultural use of potash soon eclipsed the chemical applications following the German discovery in 1840 that potassium is essential to plant growth. The initial discoveries of large deposits of soluble potassium minerals, essential for agriculture applications, were made in 1857 in Germany and in 1914 in the United States. More than 90% of the 20.4 million short tons K2O produced in the world in 1970 (Eilertsen, 1971 ) was derived from marine evaporite deposits and approximately 90% was used in fertilizers. The potassium content of an ore, mineral, or product is customarily expressed as % K,O, a unit of measure which is neither a natural nor synthetic compound of potassium (1 .O% K is equivalent to 1.2046% K,O) . Geology Potassium, the seventh most abundant element in the earth's crust, is present in silicate minerals in igneous, sedimentary and meta- morphic rocks. Potassium is also a major constituent of many surface and subsurface brines (Table 2). Economic potash deposits are essentially restricted, however, to widespread, thick accumulations of marine chloride evaporite deposits. These deposits yield high grade, large tonnage ore bodies, many of which are amenable to low cost mining and beneficiation. The products from these deposits are, moreover, ideal for use in fertilizer because of the high relative solubility of the potassium chloride and sulfate evaporite minerals. World potash production and reserves for such de- posits so vastly overshadow other sources of potassium that the following discussion will be limited largely to potash deposits in marine evaporites with brief reference to certain potash-rich brines. Approximately 85% of current domestic production is from bedded salt deposits and much of the balance is from brines. Marine evaporite deposits are accumulations of salt minerals deposited in structural sedimentary basins through the evaporation of sea-water or mixtures of seawater and other brines. The salt minerals are precipitated in assemblages and sequences of assemblages as determined by the compositions of the brines and the solubility relations in the salt systems (D'Ans, 1933). The evaporation of seawater normally yields carbonate minerals as the first precipitates (Table 3). Further evaporation and concentration of the brine leads to the precipitation, in succession, of sulfate, chloride, and supersaline mineral assemblages including the salts of potassium and magnesium. The common minerals, ores, and products of potassium deposits are listed in [Table 1]. Many potash deposits contain accessory evaporite minerals together with a variety of detrital and authigenic silicates (Braitsch, 1971).

Jan 1, 1975

By John L. Lamont, Walter Craft

Adequate hardenability has long been recognized as one of the first requirements for producing desired mechanical properties in a heat-treated steel. Since the introduction of the Jominy end-quench test' and the development of correlative information to expand its use, industry has had an effective measure of hardenability. Prediction and control of the hardenability have been made possible by Grossmann's principle2 for calculating hardenability from chemical composition; and Field's conversiona from depth of half-martensite hardening to Rockwell C hardness has made the relation more quantitative. These developments have facilitated the design of new steels and the control of standard grades to the extent that it has been possible to establish tentative hardenability bands for some of the more commonly used alloy steels.4 As the depth of hardening of the Jominy test specimen is usually measured by Rockwell C hardness, it was considered that it should be possible to predict the hardness by a more direct calculation. It has been found that this can be accomplished by the addition of Rockwell C units proportional to the carbon and alloy content, grain size, and position in the Jominy test specimen. The calculation has been found to be fairly accurate, and because of its additive character is relatively simple to use. In principle the method of calculation is somewhat similar to the expressions developed by Herty, McBride, and Hollen-back,5 Burns, Moore, and Archer,= and Burns and Riege1.l The calculation is started from a base that includes the effects of carbon content and position in the Jominy test speimen. Rockwell C units are added to the base in proportion to the alloy content and grain size. This sum represents the Rockwell C hardness up to the level at which a disproportionate increase of hardness is caused by the formation of martensite, and above this level an increment for martensite hardening is added. The effects of alloys are directly proportional to the amounts present and are independent of each other, the carbon content, and the position in the specimen. Furthermore, the factors for determining the martensite increment are dependcnt only on carbon content and are independent of cooling rate and alloy content. It is this absence of interrelation between the different factors that makes it possible to calculate the hardness and makes the method of calculation consistent with the principle that the character of the hardening reaction is governed primarily by carbon and that alloys exert their effect chiefly through control of the critical cooling rate. The principle of the calculation, and the effects of alloys on the critical cooling rate,

Jan 1, 1947

By G. W. White

Over the past several years, the steady progress of gas lift from a mysterious art into a developing science has been traceable through the many fine papers that have appeared in Journal of Petroleum Technology. Consequently, this magazine has rightly become a standard for the serious students of gas lift all over the world. The following discussion is offered in a sincere attempt to accurately present certain topics covered in the subject paper in the light of acknowledged state of the art procedures. INSTALLATION DESIGN The first point to be questioned is the author's installation design, beginning with Eq. 6. The use of 1,200 psi in the spacing equation instead of the 1,275 psi noted as available seems, at first glance, to be a simple arithmetic error. Upon further examination, it appears evident that both this 75 psi plus the 100-psi safety factor must be subtracted from available kickoff pressure because of conditions imposed by the characteristics of the ASC valve (see Fig. B-1). Pressure-charged valve design is incorrectly penalized by spacing the first valve using only 1,100 psi. The use of such a high back-pressure makes it appear that a typical ASC installation would require no more valves than a comparable conventional valve installation. Using a value of 100-psi tree pressure, the well could be valved to 11,000 ft very conservatively with seven pressure-operated valves, but would still require 11 ASC valves. The use of 400-B/D spacing gradient for a 140-B/D rate is not an accepted practice using precharged valves. The author would have done well to note the advantages to be gained by reducing the 500-psi tree pressure, which is clearly explained by Beadle, Harlan and Brown.' In Step 1 of Part III of the continuous flow discussion, the author incorrectly applies the Poettmann and Carpenter curves.2 Item 2 is an incorrect statement. An excellent reference on this point is the paper by Baxen-dell and Thomas.' VALVE MECHANICS The next topic relates to the mechanics of precharged valves. Eq. 2 for the ASC valve can be used to describe the condition of equilibrium, wherein the valve is closed with opening pending. When this equation is used to determine relative values of casing, dome and tubing pressure with conditions approaching the transition value, some strange results are obtained. The following uses the author's symbols and values given on page 689. Fig. B-1 shows the condition that exists at the moment an ASC valve has been uncovered during the unloading process (Condition I). The obvious result is a locked condition. The basis for the curve is shown on the figure which includes 1,000 psig casing pressure to uncover the valve. If injection gas is not bled off the casing until the pressure is decreased by an amount exceeding the stabilizer discharging valve pressure, upward adjustment of the casing pressure is mandatory for the valve to open and unloading operations to continue. In Condition I the dome pressure exceeds the casing pressure by 20 psi, and the tubing pressure required to open the valve is 1,212 psig. This tubing pressure would not exist under the assumed conditions. In Condition I1 the casing pressure is increased to the dome pressure, and the tubing pressure required to open the valve is 1,102 psig. It is apparent that the casing pressure must be increased to a value exceeding the dome pressure before unloading operations could continue. In Condition I11 a maximum casing pressure of 100 psi (stabilizer charging valve set pressure) above the dome pressure is reached, and the tubing pressure required to open the valve is 549 psig. The author's statement after Eq. 5 that "the minimum tubing pressure required to open an ASC valve is equal to the casing pressure at depth less the transition pressure of the valve" is incorrect except for Condition I11 only. Otherwise, the equation is invalid.

Jan 1, 1965

By R. F. Stewart, A. W. Hall

A method has been developed for continuously measuring the moisture content of coal. The method is based on the thermalization of fast neutrons by hydrogen in the coal. Neutrons from a small radio-isotope source penetrate the coal, are scattered by hydrogen, and measured by a thermal neutron detector. The number of thermal neutrons counted can be directly correlated with the moisture content of coal. In a pilot-scale system, moisture was measured continuously within 0.2% in coal moving at rates up to 20 tph. The method is adaptable in industry for continuously measuring the moisture content of coal at high tonnage flow rates. Such an application would permit continuous recording of moisture in coal without sampling and facilitate quality control. An automatic and continuous method of measuring the moisture content of coal is needed by the coal industry. Automatic control of the coal quality would reduce the cost of coal preparation, improve the product, and thus indirectly increase the use of coal. Moisture in coal can be determined by several methods, but the time required to obtain samples and analyze them by existing methods makes it difficult, if not impossible, to control the quality of the product. Both producers and consumers need a method for continuous and instantaneous measurement of moisture content without sampling in order to regulate process equipment and keep the moisture content of coal within specifications. At the Morgantown, W. Va., Coal Research Center we are developing a nuclear method for continuous measurement of moisture in coal. This method is based on the thermalization of fast neutrons by hydrogen in the water and organic matter of coal. Neutrons from a small radioisotope source penetrate the coal, are scattered by hydrogen, and are measured by a thermal neutron detector. The number of thermal neutrons counted can be directly correlated with the moisture content of coal. Design of a moisture meter based on neutron thermalization depends on many variables, any or all of which can affect the sensitivity of the meter. These factors include those related to the nuclear aspect; type and size of neutron flux and source, type of detecting device, and background count; and those related to the coal being tested: rank, particle size, and ash content. A survey was initiated to eliminate the relatively insignificant factors and to ascertain the magnitude of the major effects. Such information was necessary to fully evaluate the technique and to establish design criteria. Coal contains a relatively large amount of hydrogen in the organic coal substance and the water of hy-dration of the shaly material as well as in the moisture. To apply this concept of moisture measurement to coal requires that the organic substance in coal from any one seam of a particular mine be uniform in hydrogen content. The difference in total hydrogen content of wet and dry coal is relatively small, so that a moisture measurement based on this concept requires a measurement between two large numbers to a high degree of precision. Thus, it was necessary to develop a highly precise instrumentation system for continuous measurement and to obtain a physical arrangement permitting measurement of moving coal with a minimum effect from density variation. EXPERIMENT WITH TRAYS OF COAL Tests were conducted with metal trays containing SO to 100 lbs of coal to develop an instrument system of high precision. A scaling system with a maximum instrument error of 0.2% was used to test different types of thermal neutron detectors. The most suitable type of detector was a boron-10-lined proportional counter tube. While this type of detector showed satisfactory stability, extensive testing disclosed a long-term count reduction probably due to some type of deterioration in the detector. However, development of an electronic system using dual detectors eliminated this deterioration as a serious problem. (The second detector would be used to measure a reference drum of dry coal — the difference in count rate between the wet coal and dry reference coal being a direct measure of moisture content.) Table I, column 1, shows typical results with a 1-curie plutonium-beryllium neutron source and a thermal neutron detector beneath a tray of coal and illustrates the precision of measurement. Consecutive measurements (indicated in Table 1, columns 2-5) of thermal neutrons at various times and positions be-

Jan 1, 1968

By C. E. Birchenall, C L. McCabe

IN attempting to extend vapor pressure measurements of the type previously reported by Schadel and Birchenall1 for silver and by Schadel, Derge, and Birchenall' for silver-silicon to other systems, it was observed that the materials melted at indicated temperatures 10" to 15" below their accepted melting points. Further investigation revealed that the thermocouple readings were in error due to appreciable conduction losses along the reference thermocouple wires. If the wire diameter of the reference couple inserted into the Knudsen cell was reduced, the correction for the indicating couple changed in a manner tending to explain the melting behavior. When extrapolated to zero wire diameter from measurements with several reference thermocouples of different wire thickness, the melting point of silver then agreed with the indicated temperature at which silver chips were observed to coalesce into a sphere. Approximately the same calibration was given by observing the melting of small wires of silver or gold in the Knudsen cell connected in series with an ammeter, where the leads into the cell were very fine in order to minimize heat conduction. Unfortunately neither of these methods seemed to yield a sufficiently precise temperature calibration to match the apparent precision of the other aspects of the vapor pressure measurement. It was decided. therefore, to redetermine the vapor pressure of silver in another setup under conditions permitting precise temperature measurement. The vapor pressure of pure silver could then be used as an internal calibration of temperature in the older unit in making runs on alloys. This has been done; the present report is a correction to ref. 1. Experimental Procedure The apparatus, shown in Fig. 1, was very similar to that employed by Harteck,3 except that the orifice sizes were smaller and the residual pressure in the vacuum system was probably much lower. A small, sharp-edged hole, nearly circular in shape, was ground into the rounded end of a quartz tube. The orifice area was then measured by tracing the image at known magnification on graph paper and counting the squares enclosed. The silver specimen was sealed into the tube to make a Knudsen cell. A tantalum jacket surrounding the cell served to increase the uniformity of temperature. This assembly was placed in the bottom of a long quartz tube with an inside diameter of about 1 in., which was connected to the vacuum system through a ground joint sealed with picein wax well removed from the furnace. A thermocouple tube inserted through the top of the vacuum line reached into the tantalum jacket so that the thermocouple junction was immediately adjacent to the Knudsen cell except for the protection tube wall. A resistance furnace could be raised to cover the end of the quartz tube containing the cell in such a way that the cell was in the uniform temperature zone 13 in. from the end of the furnace. An ionization gage was included in the vacuum system in the cold lines of wide diameter, immediately beyond the ground joint. The vacuum system consisted of a mercury one-stage diffusion pump, backed by a Welch duo-seal mechanical pump. The pumps were separated from the reactor chamber by a dry ice trap. The ionization gage always read less than 10-5 mm Hg after initial outgassing and before each run was started. Each newly filled Knudsen cell was evacuated at high temperature overnight before the first weighing was made. The cell was returned to the system, heated for a measured time at constant temperature, cooled, and reweighed. The heating and cooling times were quite short since the hot furnace was raised to receive the reactor at the beginning of the run and removed again at the end. The tube heated or cooled quickly. The total mass loss was attributed entirely to effusion of silver vapor from the quartz cell, since empty quartz cells maintained constant mass through similar heating cycles. The vaporized silver condensed on the cold walls of the quartz tube extending above the furnace. Earlier studies in the induction heated unit had shown that the same vapor pressure was found for silver, whether the silver was in contact with the tantalum metal cell or with porcelain or quartz liners. The Pt-Pt-10 pct Rh thermocouple was calibrated against a secondary standard of the same material and found to agree with the published tables. Always operating in air at temperatures below 100O°C,

Jan 1, 1954

By Didyk M. Marko, Vásquez Ñ. Gregorio

INTRODUCTION The Salvador Division of Codelco Chile is an important copper molybdenum production center, located 1,200 km north of Santiago and 124 km east of the Pacific Ocean, in the foothills of the Andes Range. El Salvador Mine produces by block caving 8,600,000 t of ore with a content of 1 .l0% Cu and 0.02% Mo, from a copper porphyry ore body. The geology of the ore body shows a great heterogeneity as to rocks, grade distribution, ore height and undercutting levels. This has resulted in a variety of designs for the productive units (blocks) and in the mineral handling systems. Up to now, 4 systems have been employed: grizzly and intermediate haulage; slusher drifts with intermediate ore pass and haulage; slusher drifts with scraper loading directly into trains; and, LHD. On the other hand there is a marked dispersion in the final results from each block mined out. We report here the conclusions reached after analyzing the data gathered on the mining of 163 depleted blocks, representing a total production of 102,000,000 t, with an undercut area of 340,000 sq m. The final results of each block, characterized in terms of tonnage and fine cop- per recovery, were studied as a function of a number of design, geological, and operational parameters. BASIC CONCEPTS Indices of Efficiency In order to evaluate the final result of each block, or group of blocks, the following indices of efficiency were defined : Tonnage Recovery (TR) . It is the ratio between the ore tonnage extracted and the in situ tonnage estimate for each block or group of blocks. Grade efficiency (E) . It is the ratio between the Cu mill feed grade and the in situ Cu grade estimate for each block or group of blocks. Grade efficiency is numerically equal to the ratio between fine copper recovery (FR) and tonnage recovery (TR) . Figure 1 shows the final results for 163 mined out blocks, in terms of tonnage and fine copper recovery. Different grade efficiencies are also indicated. The marked dispersion in the final results of mined out blocks must be stressed since it greatly incides in mine planning. It must be kept in mind that an eventual concentration of low overall efficiency in the blocks during a given period (e.g., one year) will make it necessary to bring into production new blocks over the standard development schedule. It is worth noting that the final results in the 163 mined out blocks corresponding to a production of 102,000,000 t of ore with a mill feed grade of 1.445% were obtained from an ore estimate of 93,000,000 t and a grade of 1.671% Cu, which represents 110% tonnage recovery and 86% grade efficiency. Parameters Studied The following parameters are considered in this study: Geological Parameters. These parameters depend exclusively on the geological and geotechnical features of the ore body. IN SITU GRADE: The initial estimate of the block grade. Four copper grade categories were considered : (a) lower than 1.3% ; (b) 1.3 to 1.6%; (c) 1.6 to 2.0%; (d) higher than 2.0%. The overall initial in situ estimate of the ore body was 1.6% Cu. IN SITU TONNAGE: Initial tonnage estimate of the block. Four categories are considered: (a) below 500,000 t; (b) 500,000 to 1,000,000 t (c) 1,000,000 to 1,500,000 t; (d) over 1,500,000 t. CONTACTS SLOPE: Since up to 4 rock types can be found in a block, resulting in a corresponding number of contacts, a horizontal con- tact was defined as that which forms an angle of less than 45" with the horizontal and a vertical contact that which forms an angle of more than 45" with the horizontal. GRADE DISTRIBUTION: As in rock types, horizontal and vertical grades were defined. ORE HEIGHT: The distance measured between the undercut level and the top of ore. Four categories are considered: (a) less than 60 m; (b) 60 to 100 m; (c) 100 to 150 m; (d)over 150 m

Jan 1, 1981

By W. N. Lacey, B. H. Sage

The growing background of experimental information concerning the volumetric and phase behavior of binary and ternary hydrocarbon systems is used as the basis for a comparison of these systems with naturally occurring hydrocarbon mixtures under conditions representative of underground petroleum reservoirs. The qualitative and semiquantitative similarities and differences between the two types of systems are considered in reference to the possibilities and limitations of using experimental data on binary and ternary systems for predicting the volumetric and phase behavior of naturally occurring hydrocarbon mixtures of low molecular weight. The possible influence on such phase behavior of water, hydrogen sulphide, nitrogen, and components of relatively high molecular weight is discussed. INTRODUCTION During the past two decades much effort has been devoted to the study of the volumetric and phase behavior of pure paraffin hydrocarbons and of binary and ternary mixtures of these compounds. Many of these studies were carried out with the direct objective of utilizing a knowledge of the detailed characteristics of binary and ternary mixtures of the lighter paraffin hydrocarbons for predicting the behavior of more complex mixtures. The ability to make such predictions with accuracy would be of great value in petroleum production and refining. Although the behavior of the methane-propane system' served at one time as a qualitative illustration of the probable characteristics of the more complex hydrocarbon mixtures found in nature, it' fell far short of requirements for quantitative predictions. The present paper endeavors to indicate the relation of the more recently accumulated information concerning the behavior of binary and ternary hydrocarbons to this problem. In discussing binary and ternary systems as examples pointing toward the behavior of multi-component systems no effort is made to present new methods of predicting the characteristics of natural hydrocarbon mixtures. Preliminary proposals have been made elsewhere for the prediction of volumetric phase equilibrium and thermodynamic data for multicomponent mixtures, utilizing as a basis the behavior of binary and ternary systems. Numerous other proposals have been made. That based upon the concept of a pseudo-critical state" has proved to be of value to the petroleum industry. Concurrently with this study of binary and ternary systems investigations have been made of natural hydrocarbon systems. Of the many publications reporting such experimental information only a few examples will be mentioned. A number of studies of black oil and natural gas have been made and much attention has been directed to extended and detailed investigations of the behavior of fluids in condensate fieldS 16,17,18,19,20. This work has been supplemented by some studies of the separation of bitumen from natural hydrocarbon liquids The over-all behavior of such systems has been used in predicting the volumetric and phase behavior of naturally occurring mixtures This background of experimental and correlated information concerning the behavior of multicomponent hydrocarbon systems also permits a direct comparison of the characteristics of binary and ternary aliphatic systems with those materials produced from underground reservoirs. PRESENTATION OF DATA The primary limitation encountered in using binary and ternary aliphatic hydrocarbon mixtures as examples of the characteristics of the fluids encountered in underground reservoirs lies in the existing lack of knowledge of the quantitative effect upon behavior of the presence of several important constituents, notably hydrocarbons of high molecular weight, water, carbon dioxide, hydrogen sulphide, and nitrogen. The presence of substantial quantities of hydrocarbons of fairly high molecular weight serves to increase the complexity of the phase behavior of natural systems. No simple systems yet studied give adequate guidance in this regard. The influence of such materials of high molecular weight was indicated earlier",?' to an extent which serves to show that definite limitations now exist in the correlation of simple and complex systems. However, significant progress is being made in filling gaps in the information. For example, similarities in the behavior of fluids in condensate fields with that of binary and ternary systems are becoming more systematically evident. A few studies of the behavior of water in paraffin hydrocarbon systems have been made Results of investigations of mixtures of carbon dioxide and the lighter hydrocarbons also are available Limited work has been reported con-

Jan 1, 1949

By V. C. Allison

Large-scale testing of the explosibility of coal dust as conducted by the Bureau of Mines in its Experimental Mine involves a large initial investment, and a high charge for maintenance and conduct of the test; in addition the work is necessarily slow because of the time required for the preparntion of the tests and the cleaning and repairing of the mine after each test. These tests have been made along practical mining lines that admit of a range of mixtures of dust varying from 5 to 10 per cent. and with gas as low as 0.5 per cent. increments. Because of the time and expense involved, efforts have been made to devise a type of gallery for laboratory use in which the results obtained in the Experimental Mine may be correlated as an aid in a study of dusts, the explosibility of which might be approximately determined quickly and at a minimum of expense. The explosibility of coal dust has been studied by a number of European investors, using small laboratory devices; among these may be mentioned the experiments conducted by Galloway, Vital, Hall and Clark, Abel, Mallard and Chatelier, Thorpe, Bedson and Widdas, Engler, Holwartz and Meyer, and Taffanel, results of whose experiments have becn reviewed by the Bureau of Mines.' The Bureau has conducted many tests with the Frazer-Cle1ncnt5 apparattus, which gives the pressures set up when the dust cloud within is ignited with a platinum coil or tube, heated to different temperatures, but for these tests the sample must be especially prepared as to size (200 mesh) and must be dry. Need for a Dust-testing Apparatus An attempt has been made to design an apparatus that may be used for checking and correlating the expcrimental tests. The first design was a wooden gallery, 8 by 10 in., inside cross section, and 12 ft. long, and having a number of strips along each side for creation of turbulence. The wooden gallery did not get beyond its period of calibration; it mas difficult to make the gallery sufficiently tight, for it was necessary that the top be removable in order that the gallery could be cleaned. In the use of the wooden gallery, however, sufficient operating data were obtained to be a guide in the design of a steel gallery having a circular cross-section. One of the features was a flap valve, at the closed end of the gallery, that would open inwardly thus preventing a reduced pressure within, caused by the cooling of the gases of combustion, and the explosions propagated much better than when the valve was not used; another feature was the determining of the best method for getting a cloud of dust simultaneously in all parts of the gallery, which was accomplished by the use of the concussion wave of a small quantity of powder or by the use of compressed air.

Jan 1, 1927

By L. E. Snow, L. F. Pett

AT the Utah Copper Pit of Kennecott Copper Corp. a versatile mobile drill unit has been developed and tested. Through increased drilling speed and additional available drilling time, an improvement of 233 pct in drill performance has been realized. Operators using drill power can quickly and easily convert the unit from a vertical to a toe hole drill. Drilling is done with the machine in line with the unit or at right angles to it. Table I covers the 1950 drill record at the mine, showing the types of machines used and the footage obtained. [ ] Development of the new units was prompted by a desire for solution of the following problems: 1-The ever-expanding operations within the Utah Pit, requiring some 65 miles of transmission pipe lines radiating from a central compressed air plant, have now taxed this compressor plant beyond capacity. While 100 lb per sq in. pressure is maintained at compressors, transmission losses from innumerable small leaks result in low terminal pressure at the drills. Fig. 1 illustrates that while terminal pressure varies according to size of air hose and fittings used, the average drill is operating on air pressures within the 60 to 70-lb range. The compressor plant is operated primarily for air rock drills. All drilling is done on day shift, but it is necessary to run two of the three 3720 cu ft capacity compressors during night shift in order to prevent drastic loss of pressure through leaks. On day shift all three compressor units are operated at capacity, so that there is no reserve safeguard available for extensive repairs to any compressor. The calculated volume of compressed air required for operation of 25 drills is but 33 pet of three day-shift compressors. While compressed air is being used to a minor extent for purposes other than drilling, it is felt that satisfactory substitute facilities could be provided in the event that air lines were no longer available. 2-Drill performance has increased beyond the capacity of present 3 ½ -in. drifter machines. 3-The installation, maintenance, and moving of air lines in routine mining is a growing problem. The 2-in. level lines are placed outside electrification towers and must be moved to new location upon completion of each shovel cut. In addition to these moves it is often necessary to dismantle level lines so that excessive shovel spillage, or material covering track following a blast, can be pushed in the clear with bulldozers. Where level room is limited, it is often necessary to remove air lines in giving bulldozers room to prepare grades for wagon drills. In spite of precautions taken, many level lines become buried, twisted, and constricted, with excessive air loss resulting. Excessive back break in blasting often leaves several sections of air line suspended in mid-air. Occasionally air lines come in contact with defective electric transmission towers, so that holes are burned through pipe. 4-Rail-handling of drilling equipment such as wagon drills from one location to another requires considerable locomotive crane crew time. Any new unit developed should travel under its own power. 5-Present practice requires accessory material including hose, water pressure tanks, water barrels, drill steel, and bits to be transported by means of push cars when drill locations are changed on any level. 6-In order to supply numerous drill locations with material, many stock piles of new drill rods, drill bits, and other essentials must be left at strategic points, usually in the vicinity of powder magazines. This practice makes for poor housekeeping and contributes to the loss of supplies. Planning the Unit It was felt that a mobile drill unit which would rectify the foregoing problems should meet certain demands: 1-It must furnish compressed air to operate a 4-in. rock drill at a pressure of 90 to 100 lb.

Jan 1, 1952

By F. H. Buttner, H. Udin, J. Wulff

Using a modified Udin, Shaler, and Wulff technique, the surface tension of gold Udin, purified helium was found to be 1400 ± 65 dynes per cm for the temperature range 1017° to 1042°C. IN the original Udin, Shaler, and Wulff technique for measuring the surface tension of copper: variously weighted wires were allowed to extend or contract in a copper cell held at elevated temperatures in vacuum. By plotting stress vs. strain for a wire array in one test, the stress at zero strain is obtained. This is the point where the contractile forces resulting from surface tension are balanced by the applied load, according to the expression: y = e=o r [1] where y is the surface tension in dynes per cm; a,,,, the stress at zero strain in dynes per cm; and T, the radius of the wire in cm. The assumption that the wires deform viscously permits the drawing of a straight line through the points on the stress-strain plot. Justification of the assumption has received further experimental support recently.'-' The presence of grain boundaries in the wires requires a correction to the original expression used." Thus: y = d4=T [l- (dl) (ar)Y1 [2] where, n/l is the number of grain boundaries per unit length, and a, the ratio of grain boundary tension to free surface tension. Alexander, Kuczynski, and Dawson in studying the creep of gold wire in vacuum were unable to obtain reproducible values of the surface tension of gold. In plotting stress vs. strain for progressively longer times, they found that the stress at zero strain drifted with time from positive stress values to negative values. Similarly, for the surface tension of silver, reproducible values were obtained only when a purified helium atmosphere was substituted.' Evidently the evaporation rate of silver in vacuum is too high at the temperatures employed to obtain solid-gas equilibrium even in a similar metal enclosure. Thus reproducibility of results is lost. Experimental Procedure The experimental procedure was much the same as that originally developed by Udin, Shaler, and Wulff with a few modifications and improvements. For greater accuracy in strain measurements, knots gave way to cut gage marks as shown in Fig. 1. These were made with a hand-driven lathe in which razor blades serv'ed as cutting tools. Also a more precise cathetometer with a screw accurate to 0.00015 cm was used. The tests were conducted in an atmosphere of purified .helium rather than in vacuum in order to avoid possible evaporation difficulties. Five mil wire of high purity gold (99.98 pct) was used. After cutting in the gage marks, each wire of a series of about 12 was differently loaded by welding a gold ball to one end. This was done by dipping the end of the wire in a cooling gold droplet, previously melted on a charcoal block with a No. 2 acetylene torch. The other end of the wire was strung through a hole in a gold lid and twisted over the edge to hold the wires fixed and in suspension from the lid. The lid and mounted wires were then dipped in pure ethyl alcohol to dissolve any skin oils and dirt on the surface of the wires due to handling. Finally the lid was put in place on an alundum crucible lined with gold so that the wires hung freely within the gold-lined chamber. This whole assembly was next heated in a quartz nichrome wound tube furnace and heated for a few minutes at 600°C to soften the wires. After this anneal the wires were easily straightened with tweezers. The wire assembly was finally annealed 10" to 25°C above the subsequent test temperature for 2 hr. This treatment allowed the grains to grow to equilibrium size and shape. After the anneal, the lid was mounted in front of the cathetometer. The gage length was measured by sighting the 40 power microscope on the upper lip of the lower gage mark for the first reading, then traveling up to the lower lip of the upper gage mark for the final reading. This procedure was repeated four times to give an average gage length value. In this manner the annealed gage length and the final gage length could be measured to determine the strains. During all measurements, grain counts were made.

Jan 1, 1952

By Henry F. Hebley

In preparing this paper it has been the aim of the writer to keep the problems of both producers and consumers in mind. Until now, no attempt has been made to familiarize each group with the other's practice and limitations. This paper is an effort to acquaint the readers with some of the factors pertaining to the problem and cost of mining and preparing steam coal, and also to the economics of producing steam with such coal. In recent years all lines of endeavor have turned to intensive mechanization in order to lower the unit cost of production. The average fuel consumption in steam electric generating stations has dropped in 20 years from 4.0 lb. to 1.4 lb. per kilowatt-hour; while the modern power station can generate 1 kw-hr. on a fraction under 1 lb., or 13,000 B.t.u. coal. Also, the amount produced per man has in that same period risen from 3.8 to 8.2 tons, owing to the use of modernized equipment below ground for coal cutting, drilling, shooting, loading, hauling and hoisting. Unfortunately, the rapid speed of 5 tons per minute of operation at which the coal is loaded mechanically precludes any appreciable removal of impurities at the coal face, so that the raw coal is hoisted containing a markedly higher percentage of impurities than the hand-loaded coal, which was subjected to the scrutiny of the miner during loading. Also, during the past 20 years, certain seams of coal lying close to the surface have been made economically available by the improved design of electrically operated shovels and draglines for the removal of overburden running as high as 56 ft. This strip coal frequently contains so much ash in the raw state (Table 1) that it would have no sales value. Therefore, coal preparation must be adopted to beneficiate the raw product. Some seams in the United States have a decreasing ash content with decreasing size, owing, in all probability, to the fact that the coal is friable while the impurities are hard, causing a concentration of the low-ash material in the fine sizes. Illinois No. 6 coal being rather hard, naturally the reverse is true.

Jan 1, 1938

By W. D. Ludemann, J. E. Dor, L. A. Shepard

Recovery of the creep resistance of 99.99 pct pure Al was studied at temperatures 540°, 573°, 600°, and 611°K. Poly-crystalline specimens crept under a stress of 950 psi to a strain of 5.5 pct were allowed to recover for periods of from 1 min to 16 days under a residual stress of 4.4 psi. Increased creep rates upon reapplication of the 950 psi stress evidenced softening of the material. The activation energy for the recovery process was found to be 64,000 cal-per mol. THREE major observations have clearly revealed that the creep of polycrystalline aluminum above about 510°K is controlled by the rate of climb of jogged edge components of dislocations past the barriers impeding their motion: 1) Extensive polygonization, characteristic of climb, takes place during creep.'9' 2) The activation energy for creep equals the estimated activation for self-diffusion. 3) The stress law for creep coincides with theoretical predictions based on the climb mechanism.4,5 The decreasing rate during the primary stage of creep must be ascribed to the introduction of additional barriers to the glide of dislocations. During secondary creep the density of barriers must remain constant, the rate at which new barriers are formed being equal to the rate at which they recover. For this reason the nature of the barriers, and their rates of formation and recovery, are significant to a complete understanding of creep. It is proposed here to study the kinetics of the recovery of barriers to creep of high-purity polycrystalline aluminum in the climb range. The technique will consist of creeping a series of tensile specimens under a prescribed stress to given state following which the specimens will be recovered for various times and temperatures under approximately zero stress. The amount of recovery will be determined by comparing creep curves following the recovery. EXPERIMENTAL PROCEDURE The material used for this investigation was a 99.99 pct pure Al supplied by the Aluminum Co. of America in sheets of 0.001-in. thickness having an H-18 temper. The spectroscopic analysis of impurities gave Cu-0.004 wt pct, Fe-0.002 pct, Si-0.001 pct, others-0.000 pct. Creep specimens were machined with their tensile axes in the rolling direction of the sheets. Annealing in a molten potassium nitrate-potassium nitrite bath for 1 hr at 686K, followed by air-cooling, resulted in a grain diameter of from 0.22 to 0.27 mm. Creep machines were equipped with constant stress lever arms of the type suggested by Fullman, Carreker, and Fishher,' which maintained the applied stress to within 0.04 pct of the reported value of 950 psi. Creep strains were calculated from extensions over a 6-in. gage section to the nearest 3 X 10"5. The temperatures of testing, 540°, 573", 600°, and 611°K, were obtained by immersing the specimen and extensometer assembly in a molten KNO2-KNO3 bath. Temperatures during the periods of creeping could be maintained constant to within better than ± 1°K. Correlation of creep data at different temperatures of testing demanded the use of an appropriate temperature-compensated time 8. Previous investigations have shown that the creep of pure metals at temperatures above about 0.55 of their melting temperatures can be correlated by the functional relationship3" e=f(0), s= const. [1] where e = total plastic strain during creep f = a function that depends on stress a = stress 6 = te-Q/RT = a temperature-compensated time t = time under test Q = 35,500 cal per mol = activation energy for creep R = gas constant, and T = absolute temperature In the present series of tests all of the creep was conducted under the same stress of 950 psi. To provide identical initial conditions for the recovery all specimens were first crept to a temperature-compensated time of = 47 X 10-14 min which resulted in a creep strain of 0.055 + 0.005 regardless of the creep temperature. During recovery, a small stress (4.4 psi) was permitted to remain upon the specimens to maintain tautness in the pulling assembly and to prevent mechanical damage to the soft specimen. After each recovery period, the full stress was reapplied and

Jan 1, 1961

By E. R. Borcherdt

METHODS and equipment are subject to study in the Butte district at all times in order that advantage may be taken of any new developments that might serve to increase efficiency and lower costs. Detailed time studies of each operation involved in the entire mining process have been of invaluable assistance in analyzing the individual operation for possible improvement. In other words, the fact that a practice has been in vogue for many years does not exempt it from change provided an easier and cheaper method can be found. EXPLORATION Ore occurs in the Butte district in such manner that structures must be drifted on, no matter how small or unimportant they appear when intersected by a crosscut. Parallel structures also add to the crosscut requirements. This prospecting work, which formerly was done entirely by drifting and crosscutting, is now being supplemented by diamond drilling, to aid in greatly decreasing the amount of waste. In long-shot prospecting, or in second or third class prospecting, where the chances of developing commercial ore are not very great, diamond drilling is of particular value. In prospecting where chances of encountering commercial ore are certain or where crosscuts can be used later for haulage or ventilation, drilling obviously is not applicable. Improvement in drilling machines and bits has contributed greatly to the present success of diamond drilling. STOPING For many years square-set filled stoping was the principal mining method used in the Butte district. Later timbered and untimbered rill stopes were used, also some horizontal cut-and-fill stoping where both ore and walls were particularly strong. Because of the amount of timber required for square-set stoping, and the relatively low production per stope unit, experiments with horizontal cut-and-fill stopes were begun in ore bodies of which many had fairly weak walls. It was felt that increase in the speed of the stoping operation, followed closely by filling, to avoid weight being produced by permitting ore and walls to remain insufficiently supported over comparatively long periods, would maintain the walls and backs in safe condition without the use of timber and without ore dilution from wall slough. Cycles of drilling, scraping ore, and filling were devised, which have materially increased stope production and decreased timber consumption, so that both stope labor and supply costs were lowered appreciably without materially affecting grade control. In the larger mines of the district, where wide veins favor this stoping method, half of the total production is now being mined by horizontal cut-and-fill stopes (Fig. I). The increase of the filling rate demanded by the increased stoping rate was the greatest obstacle encountered in the accelerated stoping operations. Finally this problem was solved by replacing the time-honored method of transferring filling waste by small cars, which were hoisted or lowered in the auxiliary shaft, by a transfer

Jan 1, 1941

By D. W. Mitchell

INE operators have a choice of several classi- fications of mechanical loaders. Within each classification there are many types and makes available. Table I lists loaders on which manufacturing data as to operating characteristics are available. This paper discusses the conditions met in a mine as they affect these characteristics. It is assumed that management will provide satisfactory engineering, supervision, power, maintenance, loader service within a concentration of workings, and a balanced working cycle served by balanced production equipment. These are factors which affect the optimum operational efficiency of a loader. The conditions which determine loader choice are: Height of Vein—The main limitation to the use of a loading machine is the height to which the vein is mined; i.e. a loader cannot be higher than the place in which it is to work unless rock is taken. Since there are several low vein loaders being developed and successfully applied, this does not appear to be a requisite of an efficient mining operation. The maximum useable height of a loader should be equal to the working seam thickness less a working clearance for travel and operation. A—Working seam thickness = B—Artificial roof support thickness = C—Safe headroom below support = (generally about 6 in.) D—Height of roadway = E—Total of B + C f D =_______________________ A—E = maximum loader height F—Distance from top of roadway to bottom of roof support = G—-Height of loader's coal or ore line (see Table I) = H—Difference between F and G = Size of largest broken particle + a safety factor of 2 to 3 in. H is a loadability factor and is important because the clearance over the top of the conveyor chain to the roof or roof support must be greater than the largest broken particle or else the particle and/or the conveyor chain may be broken. From this standpoint it might be desirable to use a lower height machine even though it may have a smaller capacity, though this is warranted only when increased lump realization offsets lower man-day and machine pro- duction rates. Ivan Given has stated, "Loading should not be handicapped by securing lump only to grind it in the breaker." Width of Working Place—The width of a working place is the greatest width a place may be safely driven. The working place includes not only the face but the roads the loader must tram when mucking out more than one face. The width is limited by the system of placing props with sufficient room between them for the machine runner (about 2 ft). Maximum width of place in which the loader will operate at maximum efficiency is determined by the type of mounting. With track-mounted loaders, maximum width of place is determined by maximum angular swing of the loading head and proximity of track to the face. The use of double track leads to added expense and operational complexities. Several mines that have used double-track systems have found that a substantial saving is made by the use of machines that load out wider places. Trackless loaders may work in rooms of any maximum width. Minimum width of place in which a loader will operate is determined by width of the loader plus a safe movement area for the operator. Often a barodynamic study of the mine will show that either an increase in room width and/or a change in the system of propping may be made by using roof bolting, full or part-width room timbers, removable aluminum I-beams at the face, etc. Increasing the width of a working place will, in general, increase loader operating efficiency by providing more material per fall and by decreasing the preparation and moving time per ton. A change in the system of propping that would increase the minimum width might permit the use of a higher capacity loader with safer working conditions. Proper face tirnbering is necessary to insure safety from roof falls and because the speed of preparation and loading generally increases since the men work with greater assurance and there is less chance of kicking out posts. Maximum Room Length—With the exception of the scraper and the duckbill, the limit to room

Jan 1, 1952

By J. T. Norton, A. L. Mowry

The monocarbides of the A subgroup elements in the fourth and fifth group of the periodic table in addition to being hard and refractory are of special interest in that they are isomorphous in crystalline structure. They are cubic with a sodium chloride type structure in which the metal atoms are essentially close packed in a face-centered cubic arrangement with the carbon atoms placed in the interstices between. Interstitial structures of this close packed type were first investigated systematically by Egg1 and he gave the rule for their formation, stating that the radius ratio of the nonmetal to the metal atom should not exceed the value of 0.59. The carbides of interest are those of titanium and zirconium of the fourth group and vanadium, columbium and tantalum of the fifth group. Table 1 shows the radius ratio using the Goldschmidt radii for 12 coordination for the metal atoms and the diamond radius for the carbon atom. It will be noted that while there is considerable variation in the size of the metal atom, in all cases the ratio is smaller than the limit of 0.59 placed by Hägg. It has been known for some time that these cubic carbides are soluble in one another, at least to some extent or, in other words, the metal atoms can be replaced, one by another without destroying the stability of the structure. Since the stability of these close packed interstitial substances appears to depend more upon geometry than upon the exact chemical nature of the atoms involved, it is of interest to examine the possibilities of replacement in these carbides in some detail. Hume-Rothery2 has pointed out the importance of the difference in size of solute and solvent atom as a factor in limiting the solubility in simple binary solid solutions. Largely on an empirical basis, he states that if the difference in size between solvent and solute atom is more than 14-15 pct of the solvent atom, the range of solubility is very restricted. The atom size was based on the distance of closest approach in the elements involved. While there is some question as to how one should calculate the size of the metal atom in the carbide structures, reference to Table 1 will show that zirconium is the largest and vanadium the smallest of the group and that the difference is about 15 pct. The Ti-Zr difference is about 9 pct and the others are smaller. Thus one would predict that if the size factor controls the solubility, all of the pairs except VC-ZrC would have wide or complete solubility whereas this latter pair is on the border line and might have restricted solubility. The purpose of the present investi- gation was to examine the solubility of the several pairs of carbides by heating them together until equilibrium was established and then examining the product by X rays. Previous Work Agte3 and his associates prepared various transition metal carbides and determined the melting points of binary mixtures. He concluded from the shapes of the melting point curves that there was extensive solubility in the case of the cubic carbides. Umanskii and his colleagues made an investigation of a number of pairs of the cubic carbides, using X rays and plotted lattice parameter vs. composition curves for the systems TaC-Tic, CbC-Tic, TaC-ZrC and CbC-ZrC. All pairs showed a continuous series of solid solutions. The first two pairs gave a linear relation while the latter two showed a negative deviation from Vegard's law. Kiefer and Nowotny, in a paper which became available after the present work was well advanced, investigated the binary pairs of the five cubic carbides by means of X rays. Relatively few points were obtained and results indicated that in some cases, at least, equilibrium was not reached at the temperatures used. The results indicated that solubility in the VC-ZrC system was not complete. All of the results of previous investigations indicated the desirability of a more detailed study. Materials The raw materials used were mono-carbides of titanium, zirconium, vanadium, columbium and tantalum and were the purest which could readily be obtained commercially. Spectrographic qualitative analysis showed that the CbC and TaC contained less than 1 pct

Jan 1, 1950

By James O. Lewis

Gravity drainage is the self-propulsion of oil downward in the reservoir rock. Under favorable natural and operational conditions, it has been found to effect recoveries comparable to water displacement. With modern technical knowledge, the operator can often make a choice between dissolved gas drive, water drive and gravity drainage as the principal recovery agent in a reservoir. It is desirable that the opeator be able to determine which of the three agents will be most effective under each set of conditions. So far, gravity drainage has received less consideration than the other two. In this paper. an endeavor is made to set forth some of the principles of gravity drainage, to point out the types of reservoirs favorable for it, and to show how it may be applied in them. Field examples are described and discussed. Introduction Since early in the history of the oil industry, it has been recognized that gravity is one of the three important natural forces for expelling oil from the reservoir rock. As knowledge of the technology of oil recovery progressed, ideas changed with respect to the relative importance of the three forces and with respect to the manners in which they functioned. For a time, disproportionate emphasis was placed on the importance and function of gas and the need for conserving gas pressures. More recently, disproportionate emphasis has been placed on encroaching edge water. Only lately has there been evidence that the function and importance of gravity was to receive due consideration. Study of this neglected phase of oil recovery is needed to round out our knowledge of reservoir behaviors and to gain a balanced viewpoint of the interplay of forces that may operate in varying importance in reservoirs. The purpose of this paper is to discuss mainly in a qualitative way, the functions of gravity, to present some concrete instances where it has been important and to raise some questions that should be investigated further. Oil-recovery Agents The important natural agents for effecting oil recovery that may be originally available in a reservoir are gas, both dissolved in the oil and free in gas caps, encroaching edge water and gravity. Each of these agents can act in a dual capacity—physically to overcome the surface energies that hold the oil within the pores and mechanically to overcome viscous . resistance and to propel the oil through the porous reservoir rock to the wells. Advancing edge water displaces the oil from the pores and lifts it updip to structurally lower wells. Gravity drains the oil from the pores and flows it downdip to the wells. Gas displaces oil from the pores, entrains it in the gas stream and flows it to the wells, but gas in solution also affects the physical properties of the oil and thus can influence oil recovery by the other agents, whether or not the mechanical energy in the gas is utilized. Of the two functions of these agents, the more important is the ability to dis-

Jan 1, 1944

By Carl Altstetter, Roy Adams

Measurements of enthalpy changes and transformation temperatures me reported for the fcc -hcp marten-sitic transformation in pure cobalt single and multi-variant crystals andpolycrystalline specimens. From these measurements the free-energy difference between the two phases was calculated for both heating and cooling and for repeated cycles through the transformation. For heating of single crystals the average value of enthalpy change was 113 cal per mole but on cooling it was 84 cal per mole. This difference is interpreted in terms of lattice imperfections which are introduced during transformation. A calorimeter suitable for measurement of enthalpy changes of athertnal transformations is described. COBALT exhibits an allotropic phase transformation at around 417°C' where an hcp phase (a = 2.507, c = 4.0686, c/a = 1.6228)~ stable at low temperatures transforms to an fcc phase stable up to 1495°C. The transformation has a hysteresis of about 30°C— the exact magnitude of the hysteresis depending on the number of transformation cycles, grain size, impurity content, and prior treatment.'-6 The athermal character of the transformation and surface relief due to transformation shear indicate that the transformation is martensitic. Pole mechanisms for the transformation have been discussed by Sebilleau and Bibrin, Bilby, Seeger,' and Basinski and Christian. These authors have proposed that the cooling transformation is effected by rotation of a Shockley partial dislocation around a pole dislocation with a screw component of 2a/3(111). Such a rotation would change the stacking of close-packed planes from the abcabc fcc stacking to the ababab hcp stacking sequence. This mechanism would predict a lattice correspondence of {111}fcc~~(0002~cp, have been observed. One would expect the heating transformation to occur similarly, involving dislocation movements on the (0002)hcp. However, a high density of pole dislocations and high dislocation ve- locity are required to account for microscopic observations. Furthermore, the high back stress developed on the Shockley partial dislocation as it rotates toward the sessile dislocation associated with it makes it doubtful that this is in fact the transformation mechanism. A mechanism for spontaneous nucleation of partial dislocations1*l2 seems more reasonable. If a single crystal of cobalt is cycled through the transformation but never heated above 600°C, it will remain single."13 However, if the specimen is heated through the transformation and held for a short time at or above 1000°C before cooling, the cooling transformation usually involves all four {lll}fcc habits, resulting in neighboring orientations of hcp differing by 70.5 deg. This condition is termed multivariance and has been observed by Bibring and sebilleau5 and Nelson and ~ltstetter.' The latter authors used single crystals of cobalt grown in an electron beam zone refiner. They proposed that the strongly directional cooling caused the initial cooling transformation to occur on the {lll)fcc most nearly perpendicular to the temperature gradient. Transformation shear on one set of {lll}fcc planes immobilized dislocations on the other {lll}fcc planes involved in the initial transformation. Since there is only one (0002)hcp plane orientation, the product of subsequent heating transformations could have no more than two variants—the original fcc orientation or its twin. If, however, the specimen was annealed at a high temperature, such as 1000°C, there would be relaxation of dislocations into low-energy configurations, and in the absence of a sharp temperature gradient transformation on all four (111 Ifcc planes could occur. If a dislocation mechanism is responsible for the transformation, the perfection of the lattice should affect the reversibility of the transformation. Mutual constraints of neighboring grains in polycrystalline material would inhibit dislocation movement resulting in increasingly sluggish transformation. Indeed, Nelson and Altstetter found the M, to decrease and the A, to increase in going from single crystals to multi-variant specimens to polycrystals. The effect is enhanced by decreasing the grain size of a solid specimen or a powder.6'14 Data on the free-energy difference necessary to initiate the transformation gives information about the driving force of the transformation. This is an important consideration in the understanding of the transformation mechanism. The free-energy change associated with the transformation of the hcp phase to the fcc phase at some temperature T different from the equi-

Jan 1, 1969

By G. H. Kessler

ALTHOUGH considerable attention has been devoted to reaction mechanisms and equilibria of a number of endothermic reactions through which metals or their refractory compounds can be formed upon heated surfaces, only a comparatively small amount of work has been done to develop rate information for these systems. The interestin and very worthwhile work of Holden and Kopelman, Runnalls and Pidgeon,Dijring and Moliere, and Herrick and ICrieble4 is to be noted; however, their work was done under very specific conditions and the rate information which they have developed is not applicable to many systems which have been studied experimentally. That a more generalized approach is needed is shown by the diversity of these systems and of the experimental conditions which they require. These include the preparation of titanium, zirconium, tungsten, molybdenum, chromium, co-lumbium, aluminum, and silicon by decomposition or disproportionation of their halides, in some instances through hydrogen reduction; the preparation of nickel and iron by decomposition of their car-bonyls; and the preparation of copper by decomposition of the acetylacetonate. They may be carried out at temperatures ranging from 100" to over 2000°C and at pressures of from less than one mm Hg to superatmospheric. The physical mechanism of the overall process can be broken down into several steps, any one of which may be rate-determining; and the rate associated with each of these basic physical processes can be predicted. Consequently, by proper application of the present technology of rate processes, it is possible to arrive at a rate of metal deposition in the system of interest and to reach an understanding of the influence of' each major variable upon the deposition rate. It is the purpose of this paper to illustrate how this can be done and to present experimental results for a specific system for comparison with theory. The overall process of deposition of metal upon a heated surface which is immersed in vapors of a compound of the metal can be broken down into the following steps: 1) Transport of the reactant vapors to the surface. 2) Decomposition of the reactant in the immediate vicinity of the surface to a) establish chemical equilibrium if reaction rates are high; or to b) establish a dynamic equilibrium in accordance with the several reaction rates. 3) Diffusion of reaction products away from the vicinity of the surface, with or without simultaneous recombinations to form still other products. The overall process is said to be diffusion controlled if Step 1, or the equivalent Step 3, is slow; it is reaction-rate controlled if Step 2b is slow. When experimental evidence shows the reaction rate to be controlling, the well-known theories of Eyring' and others can be used as a basis for correlating and extrapolating the experimental data. Although these theories give only approximate estimates of reaction rates, they are of considerably greater value in correlating experimental data. Most deposition systems operate at surface temperatures sufficiently high that reaction rates near the surface are very high. Mass-transport rates then become controlling; and it is this regime of diffusion controlled rates which is most often of concern and Which will be considered here. When the system pressure is very low, i.e., in the micron range, then the transport processes are those of molecular movement, and the results of kinetic theory can be applied to specify a rate of arrival of reactant molecules at the heated surface. If the condensation coefficient can be estimated, then the deposition rate will be given by the product (rate of arrival) x (condensation coefficient), Conversely, experimental data can be used to determine a condensation coefficient, as was done by Holden and Kopelman' for the decomposition of zirconium tetraiodide upon a heated molybdenum surface, who found the coefficient for zirconium on molybdenum to be 1.0 at temperatures of 1382°C and above. In this pressure range, the geometry of the system. and in particular the distance between the source of reactant molecules and the heated surface, can exert a considerable effect upon the deposition rate;

Jan 1, 1961

By J. H. Scaff, H. C. Theurer, E. E. Schumacher

The microwave region of the radio spectrum was effectively utilized in radar designs during the recent war and it has become of increasing interest in the field of communications. Work in this field has led to an important use for silicon—that of the point contact rectifiers†1 in the frequency converter of microwave (radar or radio) receivers—and has stimulated considerable interest in the electrical properties and preparation of silicon and its alloys. Silicon is an electronic semiconductor. Its conductivity at room temperature results principally from the presence of certain impurities. While for metals an increase in impurity content increases the resistivity, for semiconductors such as silicon the opposite occurs and, in general, the addition of impurities lowers the resistivity. Silicon materials may be classified into one of two groups depending upon the manner in which the impurities contribute to electrical properties. These have been termed for convenience p-type or n-type. P-type silicon develops a very large positive thermal emf against metals, has a Hall coefficient of positive sign and a low resistance direction in point contact rectification with the silicon positive with respect to the point. N-type silicon, on the other hand, develops a negative thermal emf against metals, has a Hall coefficient of negative sign and a low resistance direction in rectification with the silicon negative with respect to the point. Impurities which produce n-type silicon are called donors inasmuch as these elements contribute to electrical conductivity by donating electrons to an unfilled energy band in the silicon. On the other hand, elements which produce p-type silicon are known as acceptors as these impurities contribute to the electrical conductivity by accepting electrons from a filled energy band permitting what is known as conductivity by "holes" in which the sign of the carriers appears to be positive. A general treatment of the mechanism of conduction in semiconductors from the viewpoint of modern band theory has been given recently by Pearson,2 by Becker, Green and Pearson,3 and by Torrey and Whitmer.4 In this investigation boron and aluminum have been found to be acceptors, and phosphorus, arsenic, and antimony to be donors in silicon. Data on the effect of boron and phosphorus on the electrical properties, when present singly and in combination, have been acquired. These data are discussed in the present paper. Raw Materials Used and Methods for Adding Seeond Constituents Silicon from two sources was used in this work and these will be referred to as A and B respectively. Silicon A is a material of high purity supplied by the Electro Metallurgical Co. It is prepared by chemical purification of "commercial" silicon obtained from the arc furnace reduction of SiO2. It contains 99.8 pct silicon, minimum, with small amounts of calcium, iron, aluminum, boron, and phosphorus as the principal impurities. This material was extensively employed in these studies as well as in the commercial preparation of rectifier materials. Silicon B is a material of high purity from the du-Pont Co. It is prepared by a pyrolytic reduction of Sicl4 and is free of analytically detectable amounts of boron and phosphorus. Its use permitted study of the effect of boron and phosphorus individually on the properties. This material contains, however, spec-troscopic traees of a number of metals, some of which affect electrical and rectification properties. Typical analyses for the two grades of silicon are given in Table 1. To make controlled additions of boron to the charge it was necessary to employ a low boron content master alloy since the quantity of boron to be added was usually only a few thousandths of one percent. The alloy containing nominally one percent boron was prepared by melting chemically pure boron with silicon A using the melting techniques for 320 g silicon

Jan 1, 1950