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By A. W. Ambrose

The underground losses of oil exceed by hundreds of thousands of barrels all the oil that has been lost in storage, transportation, or refining. The quantity lost is, of course, indeterminate; but when it is considered that the contents of an entire oil field have been excluded from recovery by invading waters, some idea of the amount wasted may be gained. Similarly, enormous quantities of gas have been lost underground. Conservation of the oil, therefore, should start before it is brought to the surface rather than after it is placed in storage tanks. Water is one of the most important causes for underground losses and the operator should give as serious consideration to an underground flood of water as he would to a destructive surface flood. The best insurance, of course, is to have the wells drilled in such a manner that water has no access to the productive oil and gas horizons, and on abandonment the wells should be properly plugged. The encroachment of edge water and the occurrence of waterin;the base of an oil sand present a very serious problem to an oil company sooner or later these waters are bound to cause considerable damage, if they do not entirely destroy the possibilities of further production. Too often, however, a field has been considered to be in a hopeless condition, whereas wells in as bad a condition in other areas have been repaired and the life of the field appreciably lengthened. The corrections are very often suggested by technical study. Very successful results have been accomplished by detailed underground work in the California oil fields, in Cushing, Oklahoma, and in other areas. The purpose of this paper is to outline briefly1 general methods of analyzing oil-field water problems in a producing or in a producing and developing oil field, with a view to suggesting repair work on offending wells. Reference is continually made to producing oil wells; the same general method of procedure, however, should be adopted in a gas field.

Jan 1, 1921

By Walter J. Karplus, Otto J. M. Smith

The transient response of earth formations may be tlcter.171ined by means of four electrodes mounted coli-rienrly on n sonde. Exponentially decaying current pules are applied to one pair of electrodes and the re.rrrlting voltage transient at the other pair is recorded. It is shown by theoreticol analysis and verified by laboratory experiments that this arrangement readily yields the direct resistivity of the formation and provides valrrable additional information as well. INTRODUCTION Although electrical transients have been employed with moderate success in geophysical prospecting, their application to well logging has received virtually no attention in technical literature. In the conventional direct resistivity logging methods only the zero frequency impedance of the formation under study is measured, and no information is obtained regarding its reactive characteristics. Since the use of certain transients appears to offer some advantages in this respect, experiments were performed on a laboratory scale to investigate this possibility. This investigation was limited to a study of a four-electrode array where both the receiving and transmitting electrode pairs are mounted on a logging sonde, and decaying exponential pulses are applied to the transmitting electrodes. THEORY Given an electrode configuration as shown in Fig. I, located in a homogenous medium of resistivity p, if each electrode has an effective radius, r, which is small compared to the spacing, s and a, it is easy to show by integrating the volume resistivity that the input resistance, Rrw, of the transmitting electrodes is Rxw=p/2pr If a capacitor of capacity C, charged to a voltage Em, is suddenly connected to these electrodes, the resulting current, I(t), will then be The voltage transient, E(t), at the receiving electrodes may then be found by substracting the resulting potential at electrode Y from that appearing at electrode Z. and by inserting Eqs. 1 and 2 Integrating Eq. 4 with respect to tim

Jan 1, 1957

By D. Harrington

Efficient ventilation of metal mines consists in having such complete control of air currents that there is always supplied at placcs where men work sufficient moving air to allow working at maximum capacity without injury to health; and in case of underground fire or of surface fire in the vicinity of mine openings, underground air currents may be quickly reversed if desired, or air may be sent into or excluded from any region and fire fumes confined to only part of the mine workings, instead of penetrating practically the entire mine. Health and safety of workers in mines as well as proper safeguarding and operating efficiency of mining properties are so intimately associated with proper ventilation of mines (both coal and metal) that they are inseparable, yet ventilation is only too frequently neglected, especial1y in metal mines. The metalliferous operator, generally not confronted with inflammable gas or explosive dust which so frequently force ventilation of coal mines, usually disregards air supply altogether except such as may be obtained from compressed air; and generally, even when attention is given to metal-mine ventilation, the air currents rarely are found where they are needed, namely, the working places, especially the working faces. After several years' study of miners' consumption, the writer is convinced that long continued breathing of air impregnated with large quantities of any kind of finely divided dust, such as is found in a large number of the working places of our mines, will ultimately produce some respiratory disease, whether it be asthma, bronchitis, or phthisis; and the progress of these diseases is hastened if there are also present high temperatures, high humidities, or harmful gases or if there is present (and allowed to remain to be breathed) large quantities of the finely divided dust when air temperatures are low, hence favorable to maximum performance of work with accompanied maximum breathing into the respiratory passages of the harmful material. It is generally accepted

Jan 1, 1923

By D. Harrington

Efficient ventilation of metal mines consists in having such complete control of air currents that there is always supplied at placcs where men work sufficient moving air to allow working at maximum capacity without injury to health; and in case of underground fire or of surface fire in the vicinity of mine openings, underground air currents may be quickly reversed if desired, or air may be sent into or excluded from any region and fire fumes confined to only part of the mine workings, instead of penetrating practically the entire mine. Health and safety of workers in mines as well as proper safeguarding and operating efficiency of mining properties are so intimately associated with proper ventilation of mines (both coal and metal) that they are inseparable, yet ventilation is only too frequently neglected, especial1y in metal mines. The metalliferous operator, generally not confronted with inflammable gas or explosive dust which so frequently force ventilation of coal mines, usually disregards air supply altogether except such as may be obtained from compressed air; and generally, even when attention is given to metal-mine ventilation, the air currents rarely are found where they are needed, namely, the working places, especially the working faces. After several years' study of miners' consumption, the writer is convinced that long continued breathing of air impregnated with large quantities of any kind of finely divided dust, such as is found in a large number of the working places of our mines, will ultimately produce some respiratory disease, whether it be asthma, bronchitis, or phthisis; and the progress of these diseases is hastened if there are also present high temperatures, high humidities, or harmful gases or if there is present (and allowed to remain to be breathed) large quantities of the finely divided dust when air temperatures are low, hence favorable to maximum performance of work with accompanied maximum breathing into the respiratory passages of the harmful material. It is generally accepted

Jan 1, 1923

By Richard Henry Lee

Since the economies in the blast furnace resulting from enriching iron ores are so great, much attention has been paid during the past few years to the various methods of concentrating lean ores, and, as the concentrated ore is usually of extreme fineness, various methods of agglomeration and sintering, of more or less value, have been put into operation. The resulting agglomerated concentrates are generally obtained in the form of briquettes or nodules. The briquettes naturally divide themselves into two classes: (1) those made by the mixture of some binding agent, and then formed into briquettes under great pressure; and (2) those made by sintering the concentrates, the latter either being formed into bricks before exposure to heat or the sintered mass broken into fragments afterward. Of the first class I will not speak, as they are not used on an extensive scale in this country. The second class of briquettes, or those made by sintering, are simply masses of melted or fused silicate and oxide of iron mingled with more or less silicates of aluminum, lime, and magnesia. The fact that the material in a briquette is sintered is proof positive that there are no pores in the material. There are, however, quite a number of holes of greater or less diameter through the gubstance of the briquette. They are not pores in the common acceptance of that term as applied to ores by furnacemen, as the ides of the holes and channels are fused. In reality the material is simply mill cinder. It is practically untouched by the gases in the upper part of the furnace, and the iron has to be reduced by solid carbon in the boshes and hearth. Briquettes sometimes show a little saving in fuel in the furnace over an ore mixture of large lumps, but that saving is made simply because, owing to the numerous holes and channels through the mass, the briquette is practically composed of numerous small or fine lumps, and, as is well known, the finer the

Jan 1, 1914

By R. E. Zimmerman

WITH coal-preparation plants becoming more complex and containing widely diversified types of equipment and processes, it is necessary that considerable control be exercised in their operation. Rising mine costs make it imperative that close check be made of plant efficiencies to assure a minimum loss of coal to the refuse bank. Further, much of the coal sold today is sold on a competitive specification basis, and this makes it necessary to provide frequent analyses and inspections. Many ' plants are required to operate on a two or three-shift basis, and as a con- sequence an efficient organization is required to eliminate down time and provide for smooth low-cost operation. ORGANIZATION Probably the most important item for successful operation of a preparation plant is a capable, properly organized staff, with the individual workers properly informed and well trained for their particular jobs, clear-cut lines of authority among the supervisors and in general a standard operating procedure for most conceivable conditions that may occur. The idea of placing the older, partially disabled and generally incompetent coal miner in the cleaning plant, as was the practice on the earlier tipples, is entirely inadequate in a modern complex cleaning plant. The new plants require intelligent, alert, and reasonably educated men. With perhaps millions of dollars invested in an installation, it is poor business to use other than a well organized, well trained, and properly supervised force. Organizations naturally must vary with the size of the plant and local conditions; whether it is a central cleaning plant at a distance from the mine organization or one of several cleaning plants operated by the company. Smaller operations can be operated by a washery foreman, under the supervision of the mine superintendent or perhaps the "outside" superintendent. Large installations should have a plant superintendent either responsible to the mine superintendent or preferably, where possible, responsible to a preparation manager or engineer. A typical organization chart for companies operating in the anthracite region of Pennsylvania is shown in Fig. 1. Breaker (preparation plant)

Jan 1, 1950

By J. W. Stewart

That our American civilization will have extensive postwar problems in such fields as economics, unemployment, and social adjustment is now well understood by all readers of the press and listeners to the radio. But precious little is heard from these sources regarding the impact of the war on education, though education is one of the fields where the effect of the war is going to be felt most-for youth is fighting the war. Unquestionably, serious educational problems will ;rise in the postwar period, challenging the best efforts of our educators. Most acute will be the problems at the college level of education, for it is this age group that will have had its educational process most thoroughly disrupted. The return of these students to our college and university campuses wiI1 bring about a new set of conditions which we might as well try to foresee and begin to prepare for now. To begin with, the average returning college student who has had his education interrupted by war service will certainly be more mature in both years and mental outlook, and possibly married. As a result he will want to finish his college education as quickly as possible. His natural action will be to shop around among the various schools of the country to see where he can get the most credit for work he has done or thinks he has done. It is just possible that what might impolitely be termed "dark - market" schools may arise to cater to his needs. These schools will not think of them- selves in this light, of course, but will be conscious only of a keen sympathy for the veteran student and an urgent desire to help him solve his pressing problems. A considerable number of American colleges are going to be pretty well impoverished before this present war is ended and unless some professional organization takes it upon itself to place this possible situation under supervision and regulation, we may well suffer a serious setback to the

Jan 1, 1944

By F. E. Wood

This paper is written primarily as a discussion of Dr. W. P. Hase-man's paper on "A Theory of Well Spacing"' and presents briefly the production records, and intensity and rate of development in a large portion of the two principal producing sands in the Salt Creek field, Wyoming. The study includes 1350 wells, 160,000,000 bbl. production, well spacings varying from two to seven wells per 40 acres and early and late development. The general conclusions to be derived from this study are: 1. It is impossible to formulate a mathematical rule to apply to well spacing in the Salt Creek field. 2. Each tract is a separate problem. 3. Tracts first drilled produce the most oil, with many exceptions. 4. Initial production is not a reliable index to the relationship between past, current, or future production. 5. Wells which have produced the most oil in the past are not necessarily yielding the greatest current production nor will they yield the greatest future production. In fact, wells which have yielded the greatest past production will, in at least one-half the cases, make less oil currently or in the future than wells which have produced a smaller quantity of oil in the past. 6. The following is a safe rule to apply in well spacing in the Salt Creek field: (a) If the drilling of an additional well on a tract results in a sustained increased production, with prospects of making a profit, the tract is not overdeveloped and additional wells might be drilled. (b) If the drilling of an additional well does not effect a sustained increase in the production of a tract, the tract is fully developed. Second Wall Creek Sand The Second Wall Creek sand, covering 20,000 producing acres, is the principal producing horizon in the Salt Creek field; 1610 wells are producing at this time from this sand. This paper deals with hut a portion of the entire field including 10,680 of the more productive acres,

Jan 1, 1930

By Richard Lee

SINCE the economics in the blast furnace resulting from enriching iron ores are so great, much attention, has been paid during the past few years to the various methods of concentrating lean ores, and, as the concentrated ore is usually of extreme fineness, various methods . of agglomeration and sintering, of more or less value, have been put 'into operation. The resulting agglomerated concentrates are generally obtained in the form of briquettes or nodules. The briquettes naturally divide themselves into two classes: (1) those made by the mixture of some binding agent, and then formed into briquettes under great pressure; and (2) those made by sintering the concentrates, the latter either being formed into bricks before exposure to heat or the sintered mass broken into fragments afterward. Of the first class I will not speak, as they are not used on an extensive scale in this country. The second class of briquettes, or those made by sintering, are simply masses of melted or fused silicate and oxide of iron mingled with more or less silicates of aluminum, lime, and magnesia. The fact that the material in a briquette is sintered is proof positive that there are no pores in the material. There are, however, quite a number of holes of greater or less diameter through the substance of the briquette. They are not pores in the common acceptance of that term as applied to ores by furnacemen, as the sides of the holes and channels are fused. In reality the material is simply mill cinder. It is practically untouched by the gases in the upper part of the furnace, and the iron has to be reduced by solid carbon in the boshes and hearth. Briquettes sometimes show a little saving in fuel in the furnace over an ore mixture of large lumps, but that saving is made simply because, owing to the numerous holes and channels through the mass, the briquette is practically composed of numerous small or fine lumps, and, as is well known, the finer the

Jan 10, 1913

By Henry A. Stiff, Lawrence E. Davis

A graphic method was developed which can be used to predict the tendency of oil field waters to precipitate calcium Sulfate under a variety of conditions. Application of this method is made to the prediction of sulfate scale formation in heater treaters. boilers. oil wells. cooling systems and water injection wells. INTRODUCTION A solution may be said to be in equilibrium with respect to a given salt when the concentration of that silt in equal to its solubility. If for any reason the concentration of the salt is increased or its solubility decreased. the equilibrium is upset and precipitation of the salt takes place. Thus, if the concentration of a salt in a particular solution is known and its solubility can be calculated for a given set of conditions, the tendency of this salt to form a precipitate under these conditions can be predicted. Based on these principles a method has been developed for determining the tendency of oil field waters to form calcium Sulfate precipitates under various conditions. THE SOLUBILITY DIAGRAM Calcium sulfate precipitation most frequently occurs when two waters are mixed: one containing calcium ions. and the other sulfate ions. As one of these waters is added to the other a point may be reached where the concentration of calcium Sulfate is greater than its solubility. thus causing the formation of a precipitate. The solubility diagram is a graphic device for determining the location of such points, thereby making possible a prediction of the tendency of such a system to deposit sulfate scale. A similar diagram can be used to solve many other problems involving the precipitation of calcium sulfate. Fig. 1 shows a solubility diagram representing the mixing of two waters. Water "A" contains a high concentration of odium, magnesium, and sulfate ions together with a small amount of calcium. Water "B" contains a high concentration of calcium ions together with sodium, magnesium and a small amount of sulfate ions. The percentage mixture of these waters is plotted along the abscissa of a system of rectangular coordi-

Jan 1, 1952

By R. Agarwal, S. Boshkov, M. T. Wane

The majority of the work done in the field of rock mechanics uses as a basis for analysis the classical linear theory of elasticity. Most workers in rock mechanics realize that removing the assumptions of homogeneity and isotropicity will bring the analysis of stress-strain relationships for geologic materials closer to reality. However, the algebra involved in reducing these restrictions is usually heavy. It is the purpose of this paper to relax the condition of isotropicity to that of orthotropicity and examine the sensitivity of this change for some simple geometries. In addition some necessary relationships between stress and strain for orthotropic materials will be developed. The recent years have seen an increasing interest in the field of rock mechanics. This is amply demonstrated by the number of articles appearing in the technical literature. The majority of these articles use as a basis for analysis the classical linear theory of elasticity. In addition, the assumptions that the material under consideration is elastically homogeneous and isotropic reduce the number of constants necessary to write an analytical relationship between stress and strain to two, e.g., Young's modulus and Poisson's ratio. Most workers in the area of rock mechanics realize that removing the conditions of homogeneity and isotropicity will bring the analysis of stress-strain relationship for geologic materials closer to reality. However, the algebra involved in analysis without imposing these restrictions is usually heavy. It is the purpose of this paper to relax the condition of isotropicity to that of orthotropicity and examine the sensitivity of this change on stress concentration for some simple geometries. In addition, it is shown that the expression for maximum stress concentration for some simple geometries considered can be further simplified if further assumptions are made. The maximum stress concentration, under these additional simplifying assumptions, is shown graphical1y. In the linear theory of elasticity, generalized Hooke's law assumes the following form

Jan 1, 1965

By Robert H. Dickson

Limestone replacement and contact metamorphic orebodies are 80 irregular that sampling and estimating are far less. exact than in more regular types of deposits; both the mineralized masses and the lenses of ore within them are extremely irregular. So much development work is required to find the ore that the expense of blocking out great tonnages is prohibitive; furthermore, the rock near these orebodies is so heavy that drifts or raises cannot be kept open for many years without excessive repairs. As a result, few mines in limestone have more than three years supply of ore in sight. As most of the ore, is developed by stoping— not by drifting, raising, or drilling—estimates of ore developed do not indicate the total amount of ore that may be expected; they simply indicate the relative condition of the mines. But even if they are to do this, they must be made according to a fixed plan, intelligently carried out. The estimates of ore in the Calumet & Arizona Copper mines, Warren District, Ariz., have been of much value to those who plan the mining and development work. This paper describes the methods of sampling and estimating used in these mines. Sampling Samples are taken in various ways and depend on the condition of the working and the purpose for which the sample is to be used. Drifts, crosscuts, and raises are sampled by channels or by taking a grab off each mine car as it is filled. Stopes are usually sampled by drill holes or by taking a representative sample off each mine car; the latter, or chute, sample is by far the best sample. All workings are studied periodically by an engineer, who makes graphic and detail notes of the geologic structure, as shown in Fig. 1. The daily car tally and assay of each particular working is added to the same sheet opposite the material it represents. These sheets make a permanent record, showing the exact boundaries as well as the grade of ore in all workings.

Jan 1, 1925

By J. J. Kramer, K. Foster

The orientation distribution of surface-energy -induced secondary recrystallized grains was determined. This work was conducted on thin sheets of a 3 pct Si-Fe alloy annealed under environmental conditions that furor grouth of grains with a (100) plane in the surface of the sheet. The texture was found to be extremely sharp and almost independent of sheet thickness. The distribution varied exponentially with the angular deviation from the {100} plane. It was possible to relate the distribution to the nu-cleation rate of the secondary rains as influenced by the surface-energy difference. THE role of surface energy in the secondary grain growth of cube-oriented grains (grains with a (100) plane in the plane of the sheet) in thin Si-Fe sheets has been previously discussed.1-4 In high-purity sheet material normal grain growth usually occurs until the grains have extended through the sheet. Further grain growth is inhibited by the thermal grooving of the boundaries at the sheet surface. However, additional growth of cube grains can occur by a secondary grain growth process under conditions where the (100) plane has a lower surface energy than other orientations. Apparently for these alloys, cusps exist in the polar plot5 of surface free energy with the lowest cusp energy occurring at the (100) orientations. This has been reported to be the result of preferential adsorption of sulfur on the (100) planes.6 As a result of this process, a distribution of orientations could arise from two possible mechanisms. First, when a cusp is present in the polar plot of surface free energy, there are orientations inside the cusp that have a lower surface energy than elsewhere on the polar plot. Also, at sufficiently high temperatures, flat surfaces whose orientations are inside or just outside the cusp (depending on its shape) can often thermally etch, yielding a microscopically stepped surface of even lower surface energy. As a result, grains oriented close to cube would also have a lower surface free energy, either because of the cusp shape or by thermal etching, and could possibly grow as secondary grains by the surface-energy phenomenon. One should thus observe a distribution in the surface orientation of the cube grains comprising the secondary structure. It is the purpose of this paper to investigate this orientation distribution experimentally and to discuss the factors involved in its formation. For this purpose, the surface orientations of a large number of secondary grains in various sheet thickness were determined by means of the Laue back-reflection X-ray technique. PROCEDURE A vacuum-melted 3 pct Si-Fe alloy containing a nominal impurity content of 0.005 wt pct was processed into strip. A single cold-rolling step of 90 pct reduction was used for each strip regardless of the final sheet thickness. Final strip thicknesses of 0.60, 0.30, 0.15, and 0.075 mm were used. Care was taken to insure that the final strip surface was smooth and flat. All strips of a given thickness were annealed together at 1200°C in dry hydrogen (dew point -70°C) to develop the desired secondary structure and to insure identical environmental annealing conditions. The annealing time was selected to develop a complete secondary structure in the thinner sheets but to permit the thicker sheets (0.60 mm) to have residual primary grains remaining. This was necessary to determine whether growth impingement could lead to one secondary grain consuming another at a greater angular deviation. For the X-ray determination of the surface orientation of the secondary grains, a special specimen holder was used. The camera and holder arrangement could be aligned by X-raying a grain in three positions rotated 180 deg to each other. Thus, with a small beam X-ray focus (1 mm), the surface orientation of any grain could be determined to within one-half a degree. The surface orientations of one hundred cube secondary grains were determined for each sheet thickness. The criteria of a secondary grain were its size relative to the sheet thickness and the number of sides of the grain observed in the sheet surface. (A primary recrystallized grain extending through a sheet will generally have six edges visible in the plane of the sheet, whereas a secondary grain will have many more when growing entirely into primary grains.) Grains were selected as randomly as possible by X-raying every secondary grain found along a line drawn on the strip. No attempt was made to determine the exact orientation of the planes of the surface, as many strips from randomly selected sheets were used. On1y the angular deviation of the surface plane from {100} was measured. In order to assess the volume distribution in the

Jan 1, 1965

By J. F. Smith, J. E. Davison

The heat capacity of CaMg2 was measured over the temperature interval, 4.8° to 287°K, by the technique of low-temperature adiabatic calorimetry. Heat content measurements were performed with a drop calorimeter over the temperature interval, 273" to 673°K. From these data the thermodynamic functions, (FT - H0)/T, ST - So, and & - Ho, were evaluated. A third-Law calculation of the standard entropy of formation of CaMg2 yields a value of -0.25 * 0.06 cal per (°K g-atom) , and the free-energy function derived from this study when combined with existing equilibria data yields a value for the standard enthalpy of formation which is in agreement with direct calorimetric enthalpy measurements. The accompanying paper' shows that the enthalpy of formation of CaMg2 has been determined with good precision by three different calorimetric techniques.'-= TWO independent determinations of the Gibbs free energy of formation of CaMg2 have also been made; both determinations were based on vapor pressure measurements, being in one case hydrogen vapor pressures over ternary Ca-Mg-H alloys4 and in the other case magnesium vapor pressures over binary Ca-Mg alloys.5 The present determination of heat capacity of CaMg2 below room temperature and of the heat content of CaMg2 above room temperature was undertaken to provide supplementary data. These data are useful in their own right but can in addition be used to evaluate an entropy of formation for CaMg2 which, because of the interrelation of free energy, enthalpy, and entropy, can be used as a check of the self-consistency of the composite of the presently available information. LOW-TEMPERATURE HEAT CAPACITY The heat capacity of CaMg2 was measured over the temperature interval 4.87° to 286.64°K in an adiabatic calorimeter. The physical details of the calorimeter and the experimental procedure for measuring the heat capacity of a specimen have been adequately described by Gerstein et a1.6 The source and purity of the calcium and magnesium are described together with the methods of sample preparation and chemical analyses in the accompanying paper.' Results of chemical analyses of the material which was used in the present investigation are shown in Table I. These analyses show that, on the basis of the published phase diagram,7 the heat capacity sample contained a slight excess of a calcium while the heat content sample contained a slight excess of magnesium. However, in both cases the excess was small, and X-ray diffraction patterns showed reflections which were without exception attributable to CaMg2. The sample which was used for heat capacity measurements weighed 69 g while the sample container and addenda weighed 132 g. The sample was in the form of annealed powder, 50 to 60 mesh, and was sealed into the sample container under 0.1 atm of helium. Copper fins inside the sample container facilitated thermal equilibrium of the powdered Sample. Time intervals of the order of 10 min were required for thermal equilibration, and such times are normal for this calorimeter regardless of the form of the sample. The observed heat capacities were corrected for the small excess of a calcium through use of the heat capacity values tabulated by Hultgren et a1.8 The corrected heat capacities are tabulated as a function of temperature in Table II. The free-energy function and the absolute entropy of CaMg2, which were calculated from the experimental heat capacity data, are listed in Table 111. A smooth curve was fitted to a plot of the experimental values of the heat capacity and in only two instances above 30°K did the plotted points deviate from the curve by more than 0.2 pct. Below 10°K the deviation of several of the points was as much as 50 pct. These large percentage deviations were attributed to the small value of the heat capacity and to the low sensitivity of the platinum resistance thermometer in this temperature range. The deviations in the region of 10°to 30°K were less than 5 pct. Although the percentage deviations of some of the low-temperature measurements are large, the actual value of these deviations is small since the magnitude of the heat capacity in that temperature range is small. The error in the value of the third-law entropy at 298.15°K was estimated to be less than 0.01 cal per (°K g-atom). A value of -0.25 ±0.06 cal per (°K g-atom) was obtained for the standard entropy of formation at 298.15°K from the relation:

Jan 1, 1969

By Fred Wise

THE Getchell mine, a comparatively recent gold discovery, is in the old Potosi mining district, Humboldt County, Nevada. All ore is mined from open pits using Diesel shovels and gasoline trucks. Two types of ore are mined, oxide and sulphide. Oxide ores are siliceous or shaly; sulphide ores either gougy, siliceous or shaly. In mining, the sulphide ore is segregated into hard and gougy ore, because the gouge must be dried before it can be crushed, The oxide ore is not segregated. GENERAL METALLURGY The oxide ore is the leached outcrop that overlies the sulphide ore body. All of the iron and arsenic sulphides found in the sulphide ores have been thoroughly oxi-dized, The sulphur and arsenic have been leached out while the iron is present as hematite and limonite. The oxide ore is amenable to direct cyanidation, and although no visible free gold is present it is released at a comparatively coarse grind. The sulphide ore is more refractory, since the gold is all of micron size and some of it is locked in fine sulphides. It has been established microscopically that the free gold is coated with an impervious shell, which is probably some form of iron compound. The sulphide ores contain from 1.5 to 2 per cent of arsenic, which is present as orpiment and realgar with minor amounts of arsenopyrite. The orpiment and realgar are of a later mineralization than the gold and are barren. Roasting and washing of the sulphide ore prior to cyanidation is necessary to eliminate the arsenic, to alter the gold coating from an insoluble form to a soluble form, and to release the gold associated with the fine sulphides. Washing the ground calcine in weak sulphuric acid, trona, or hot water are beneficial in the order named, but to date the water is the best from an economic standpoint. Metallurgical tests as well as plant practice indicate that a certain amount of gold cannot be recovered even by going beyond economic practices, On this basis metallurgical results are viewed in the light of an optimum tailing rather than a per-centage of extraction.

Jan 1, 1940

By Craig R. Barreft, Oleg D. Sherby

The steady-state creep characteristics of pure polycrystalline copper were studied in the temperature range 400" to 950°C and in the stress range 400 to 7000 psi. Tests were conducted in dry deoxidized hydrogen and all specimens exhibited high ductility before fracture. Two activation energies for creep were established as a function of temperature. Above about T/T, = 0.65, the activation energy for creep was 48,000 cal per mole whereas between 0.5 and 0.65 T, it was 28,000 cal per mole. The observed temperature dependence of the activation energy for creep follows the same trend as exhibited by the self-diffusion coefficient of copper in copper single crystals and silver in silver single crystals. It is therefore believed that the rate-cmtrolling mechanism in creep of copper in the stress and temperature range studied is diffusion-dependent and is probably associated with a dislocation-climb process. The low activation-energy region is attributed to enhanced volume difFusion from the presence of dislocations which act as short-circuit paths for diffusion. THERE is extensive experimental evidence1,2 that the activation energy for creep, Q,, for pure poly-crystalline metals tested at temperatures above one half the absolute melting temperature (0.5 Tm) is a constant and equal to the activation energy for volume self-diffusion, Qsd This equality is generally interpreted as meaning that creep in this temperature range is controlled by a dislocation-climb process. The existence of high-temperature creep activation energies not equal to the respective self-diffusion values has been suggested both theoretically3"5 and experimentally.6-8 Two examples of apparent nonequality between Q, and Qsd have been reported for the cases of silver7 and copper,' where activation energies for creep much lower than those for self-diffusion persist to rela- tively high temperatures (up to 0.6 T,). These observations suggest that dislocation climb may not be the only important process in the high-temperature deformation of these metals. That dislocation climb does indeed occur relatively slowly in these two metals due to their low stacking-fault energy has been suggested by many investigators.9-10 Although the creep behavior of copper has been studied extensively at low temperatures, the high-temperature activation energy for creep is not well-defined. The data of Feltham and Meakin8 indicated that Q, is temperature-dependent above one half the melting temperature, equaling a value of -30,000 cal per mole at temperatures up to 550°C and increasing to a value of -49,000 cal per mole at 700°C. No data has been reported above 700°C. The value of 49,000 cal per mole is very near the value of Qsd for copper reported by Kuper et al." as 47,100 cal per mole. In view of the lack of high-temperature creep data and the apparent temperature dependence of Q, for copper the present investigation was undertaken to determine the value of Q, over the temperature range of 400" to 950°C. It was hoped that such a study would clearly document the temperature dependence of Q, and yield significant information as to the nature of the rate-controlling creep mechanisms. MATERIALS AND PROCEDURES The material used in this investigation was high-purity OFHC copper. After rolling and recrystal-lization treatments spectrographic and chemical analyses showed only 0.0008 pct Ag, 0.0002 pctCa, 0.0002 pct H2, and 0.002 pct O2 as trace impurities indicating a purity of greater then 99.995 pct. Specimens were machined from cold-rolled sheet and the gage sections polished with 2/0 emery paper prior to annealing treatments. Annealing was done in both vacuum and dry deoxidized hydrogen atmospheres. No variation in creep strength was found as a result of the different annealing atmospheres. The final annealing temperature was either 700°, 800°, or 1000°C depending on the temperature range to be studied. These treatments resulted in average grain diameters of 0.03, 0.4, and 1.0 mm, respectively. The precise mechanical-thermal history of these

Jan 1, 1964

By W. W. Mullins, F. A. Nichols

Solutions are developed, assuming surface diffusion and both internal and external volume diffusion, for the relaxation of bodies slightly perturbed from spherical and cylindrical geometries. Combined with those previously published for the nearly planar case, these results provide a means of gaging the relative contributions of the two diffusional proc-cesses in any given case. It is shown that in all sintering experiments to date, and probably in any attainable in practice, surface diffusion has played the dominant role, although most previous authors have assumed otherwise. It is also shown that surface diffusion predominates in normal field-emission tip blunting and also for the coalescence of gas bubbles introduced into metals by a bombardment. The surface-diffusion solutions for a perturbed sphere are combined with previous results for volume diffusion to show that the inclusion of interface diffusion permits considerably larger spheres to develop in diffusion-controlled precipitate growth before the onset of instability. A mechanism is also proposed for the spheroidization of precipitate platelets as well as rods. In a previous paper1 the relaxation of a nearly plane surface to flatness by the combined action of the transport processes of viscous flow, evaporation-condensation (in a closed system), volume diffusion, and surface diffusion has been analyzed under the assumption that all surface properties are independent of orientation. In this treatment, criteria were developed for deciding which process predominates, and solutions valid in the latter stages of the sintering of small wires and particles to a plane were obtained. A numerical solution, valid throughout the entire particle-sintering process for the case of surface diffusion, was subsequently obtained by the present authors.' It was found that the analytic solution (which assumed small slopes everywhere) is accurate to within -10 pct when the maximum slope of the profile is less than 0.3; the wire-sintering problem has also been solved nu- merically for the case of surface diffusion and here again the results converge to the analytic small-slope solution at late stages of the process, the two solutions agreeing in this case to within 10 pct when the maximum slope of the profile is less than -0.6. The purpose of this paper is to extend the perturbation solutions to nearly spherical and nearly cylindrical geometries. We treat only the two principal diffusional processes, i.e., surface and volume, but for these geometries we discuss volume diffusion both inside and outside of the solid. Our results, when coupled with Mullins' solutions1 for nearly planar surfaces, provide criteria for gaging the relative contributions of surface and volume diffusion to the over-all transport process in three basic geometries. A very interesting feature in the cylindrical case is the occurrence of instability for longitudinal perturbations with wavelengths greater than the cylindrical circumference, a classical result. This instability of the cylindrical surface is applied to give a quantitative explanation for the often-observed "erratic" pore closure in the late stages of the sintering of wire compacts; also, the theory previously presented for the spheroidization of rod-shaped precipitates by surface (interface) diffusion' is expanded now to include volume diffusion inside and outside of the particle. The results for circumferential perturbations on a long cylinder allow quantitative estimates for gaging the relative importance of surface or volume diffusion in the early stages of the sintering of spheres or wires. The results here demonstrate clearly that surface diffusion has played a very important, if not dominant, role in all sintering experiments discussed in the literature, although the surface-diffusion contribution to the kinetics has usually been ignored. The results for the sphere (surface-diffusion case) are added to the results obtained previously by Mullins and sekerka3 concerning instabilities of a growing spherical precipitate particle (with interface diffusion disallowed) to obtain a general solution to this problem including interface diffusion. The inclusion of interface diffusion is found to increase significantly the range of stability of a growing spherical precipitate for typical metallurgical cases. The following assumptions are made: (i) the initial surface lies everywhere near and has a slope differing only slightly from that of the reference

Jan 1, 1965

By T. E. Scott, D. H. Sherman, C. V. Owen

Mechanical properties and optical metallographic characteristics of vanadium containing 53 ppm (wt) H were investigated from, 77° to 298°K. A sharp ductile to brittle transition induced by the presence of hydrogen was observed between 238° and 223°K and a mar-tensitically formed hydride appeared at 200°K. While there appears to be a subtle relationship between the hydride formation and the ductile-brittle transition, it was concluded that the hydride per se was not sufficietzt to cause the severe em brittletnent. On the basis of the metallographic experiments and the results of a Petch analysis it is suggested that the mechanism of the embrittlement involves a reduction of the true surface energy, or cohesion, of the uanadiunz. THAT hydrogen can severely embrittle vanadium is well-documented;'-5 however, the mechanism by which hydrogen induces the observed embrittlement has not been established. It is not known whether the embrittlement of vanadium is caused by the formation of vanadium hydride or by a more subtle role of hydrogen. Until very recently6>' the solid solubility of hydrogen in vanadium at temperatures in the,range of the embrittlement was not known to a useful accuracy. In general, a severe embrittlement of the type produced by the presence of hydrogen in vanadium can be caused by changes in either of two properties of a metal. Either the yield stress of the metal is raised to the extent that plastic deformation at the tip of a crack cannot occur or the cohesive properties of the metal are reduced, at least locally, to the point at which cleavage is the natural response to applied loads. Of course a combination of these is possible. It is not known which of these properties of vanadium is influenced most by the addition of hydrogen. The purpose of this investigation was to determine the role of hydrogen in the embrittlement of vanadium. Accordingly, the solubility of hydrogen in vanadium in the temperature range where embrittlement is most severe was determined, the appearance of vanadium hydride was examined in relation to the initial ductile to brittle transition temperature, and an attempt was made to evaluate the effect of hydrogen on the yield stress and cohesive properties of vanadium. MATERIAL AND PROCEDURES Sample Preparation. The vanadium used in this investigation was prepared by the iodide refining process described by Carlson and owen.' Three ingots, 3 in. diam by 6 in. long, were cold-swaged to 0.096 in. diam, cut into short lengths, and then arc-melted under purified argon into one ingot. This process was repeated to insure a uniform composition in the final ingot. Chemical analysis of the metal is given in Table I. On the basis of work of Loria et a/ .' the following sequence of treatments was performed in order to obtain a uniform equiaxed ultimate grain structure: a) cold swage q-in.-diam ingot to 0.230 in. diam; b) anneal 6 hr at 1000°C in vacuum; c) by cold swaging reduce 81 pct in area in three steps: 0.230 to 0.187 in. diam, 0.187 to 0.150 in. diam, 0.150 to 0.096 in. diam. This sequence provided the desired grain structure after subsequent annealing treatments. Because annealing in evacuated quartz capsules resulted in contamination by oxygen, all anneals in this investigation were performed in a 304 stainless-steel chamber under a dynamic vacuum of 10- I Torr with the vanadium wrapped in tantalum foil. Prior to all annealing treatments the wires were electropolished for 1 min at 16°C in an 80 pct methanol-20 pct sul-furic acid electrolyte at 12.5 v. Following the final reduction the 0.096-in.-diam wire was cut into 2-in. lengths. A 1-in. gage section was reduced to 0.090 in. diam by electropolishing as above. Five different grain sizes were obtained by annealing the 2-in. samples at different temperatures for 8 hr to insure uniform grain size and residual hydrogen removal. The annealing temperatures used and the resulting grain sizes are given in Table 11. The final step in sample preparation was to charge half of the specimens of each grain size with hydro-

Jan 1, 1969

By Carl F. Lutz, Robert F. Mehl

A layer of brass was formed on 0 brass using a vapor-solid reaction technique. The variation in composition with distance within the phase layer and across the a -ß interface was determined by an electron probe. The diffusivities were calculated as a function of concentration; the diffusion coefficient in brass was found to change by a factor of twenty-five over a compositional range of 8 at. pct. An explanation is proposed to account for the large change in the diffusivity, based on possible stresses in the diffusion zone; it is suggested that the concentration dependence of the thermodynamic factor might decrease the activation energy with increasing zinc content. ALTHOUGH the body of data on diffusion coefficients (D- values) in terminal solid solutions and in isomorphous systems is quite large, there is but little quantitative information for intermediate alloy phases. This paper recounts measurements of D-values for the ? phase in the Cu-Zn system. The experimental method employed consists in the forming of alloy layers and determining and analyzing the concentration-distance (c-x) curve. The experimental method employed could have been applied to several systems; the Cu-Zn system was chosen because the D-values in the a and ß phases are well known, and can thus be used for purposes of comparison. The rates of growth, of intermediate alloy layers are known for a number of systems. In nearly all cases the thickness varies parabolically with time, as to be expected if the rate of growth is controlled by the D-values. In a few cases, nonparabolic behavior has been noted.1 Nonparabolic growth may be the result of a) a variation of the composition at the phase interface with time, b) interface-controlled kinetics, c) short diffusion times coupled with long vacancy lifetimes (in vacancy diffusion),2 and d) crystal reorientation during diffusion in anisotropic systems.3 In the Al-Ni system4 and in the Al-u5 system parabolic growth kinetics are slowly approached after an initial transient period. In general those phases stable at a given temperature in a system A-B appear as separate phase layers when A and B are put in contact and given a diffusion he at-treatment. In most cases the compositions at the interface of adjacent phase layers are those read from the phase diagrams for the termini of the respective phases. This discontinuity in concentration is taken as independent of time, and the growth of one phase at the expense of another is assumed to be independent of interface kinetics, i.e., the rate of interface movement is controlled by volume diffusion in the phases concerned. wagner6 has given many solutions for multi-phase diffusion processes, assuming that the chemical diffusion coefficient, D, is independent of concentration, as have others. Jost7 has pointed out that the familiar Boltzmann-Matano solution is as valid for a (c-x) curve exhibiting concentration discontinuities at phase boundaries as for the usual single-phase case. Heumann and associates8,9 have applied this solution to the multi-phase case, but lacking concentration data within the several layers were forced to assume linear concentration gradients, thus calculating only average D-values. The purposes of the present study were: 1) to determine the dependence of D on concentration, 2) to calculate the intrinsic diffusion coefficients D?Cu and D?Zn, 3) to establish the time-law for the movement of the interface, 4) to determine the concentration limits at the ß-? interface, and, 5) to attempt to clarify the mechanism of diffusion. EXPERIMENTAL PROCEDURE The ? phase is exceedingly brittle; conventional solid couples and conventional sectioning methods were thus inapplicable. Vapor-solid couples were accordingly employed. Unfortunately the equilibrium vapor pressures of Zn for the ? phase are unknown; to escape this awkwardness, samples were enclosed in a capsule containing powder of an alloy of known composition, sufficiently large in quantity as to be effectively an infinite source, maintaining the concentration of Zn at the sample surface constant with time. The sources of Zn-vapor which can be employed in reaction with Cu, or a brass, or ß brass, to form a layer of ? brass satisfactorily wide in concentration range, are alloys of the phases ?, or ? + E or ? + d (depending on the temperature).

Jan 1, 1962

By S. R. Balajee, I. Iwasaki

The interaction between British gum 9084 and dode-cylammonium chloride (DAC) at quartz and hematite surfaces was established from coadsorption studies and streaming potential measurements. The cationic DAC interacts with the somewhat anionic British gum 9084, leading to the formation and adsorption of a binary complex of DAC-British Gum 9084 at the interface. The parallel ability to depress quartz along with hematite as a result of the interaction between DAC and British gum appears to be the main reason for the ineffective depressant action of starches and starch derivatives in the cationic flotation of iron ores. Amines are not particularly selective collectors for the flotation' of siliceous gangue from iron ores and, therefore, a suitable iron oxide depressant is needed for a satisfactory separation. Various starches and their derivatives have been extensively tested with oxidized iron ores,'-3 and it has been empirically established that British gums and dextrins are preferable. However, for the flotation upgrading of magnetite-taconite concentrates from 8 or 8.5% Si O2 to about 5% Si 02, British gums, which have been used so successfully on oxidized iron ores, have been found to have no effect and oftentimes are actually deleterious.4 In previous articles,5-7, starches were shown by adsorption measurements, flotation tests, and floccula-tion tests to interact with calcium ions in solution, and it was thought that a study on the interaction between starches and dodecylammonium ions would be able to shed some light on the anomalous flotation behavior described above. In fact, starches are known to interact markedly with paraffin-chain-type surface active agents and, thereby, to precipitate the starch or inhibit the iodine-starch reaction.8 From X-ray diffraction studies and viscosity measurements, the formation of a helical complex between mylose and a surface active agent has been postulated.9 The interaction with other types of hydrophilic colloids, such as synthetic polymers and proteins, has also been investigated and is usually explained in terms of van der Waals' force interaction and/or ion-ion interaction. In the present investigation, the interaction of British gum and dode cylammonium chloride on quartz and hematite was studied by adsorption and streaming potential measurements in an attempt to establish the mutual adsorption behavior of British gum and dode-cylammonium chloride on mineral surfaces and to clarify the anomalous depressant activity of British gum in the cationic flotation of iron ores. All the measurements were carried out at a natural pH of near 7 because dodecylammonium chloride gives maximum selectivity of flotation separation at this pH2 and to avoid any third parameter in the system. EXPERIMENTAL MATERIALS AND METHODS Minerals: The quartz and hematite samples used for the adsorption tests were prepared as described in a previous paper,"J except that the specific surfaces of the samples were increased to 5,860 and 16,000 Sq cm per gm, respectively. For the streaming potential measurements, the 48165-mesh fractions screened out of the original samples were etched with hydrochloric acid, washed repeatedly with water, and stored under water in Pyrex bottles. Reagents:DodecyIammonium chloride (DAC) was prepared1 1 by bubbling dry hydrogen chloride gas through a benzene solution of high-purity dodecylamine supplied by Armour and Co. British gum 9084, received from Corn Products Co., was solubilized by first dispersing it in water to produce a 0.05% solution and then homogenizing it in a blender for 5 min. Distilled water was used in the preparation of the samples and the solutions and for all test work. Adsorption Measurements: The procedure for the adsorption density determinations was also the same as that described in the previous paper.1° The residual concentrations of the British gum and the DAC in the supernatant solution were analyzed colorimetrically by the phenol-sulf uric-acid and amine-picrate methods, respectively. The validity of the mine-picrate method for the colorimetric analysis of DAC in the presence of British gum and the analysis of British gum in presence of DAC were checked by establishing calibration curves between optical density and concentration. Streaming Potential Measurements: The cell assembly for the streaming potential measurements was similar to that described by Fuerstenau.' The streaming potential

Jan 1, 1970