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By A. H. Geisler

INTRODUCTION THE correlation of property changes during precipitation with structure has progressed, sometimes rapidly but other times more slowly, since the fundamental discovery of Merica, Waltenberg and Scott.1 The predominent factor that hampered the progress has been limitations imposed by the various detection methods. Refinements in X ray diffraction techniques and in metallographic methods, which have been extended by the electron microscope, have contributed new information within the last few years. These permit an extension of the theory as proposed by Mehl and fetter in 1940.2 Now that a suffcient number of alloys has been investigated to establish a general mechanism of the precipitation process, a correlation of the facts into a generally applicable theory of age-hardening is both warranted and desirable. 'I he purpose of the paper is to provide an orderly correlation of the phenomenological facts of precipitation hardening. Speculation on mechanism of hardening will be confined to that consistent with existing theories of hardening. Age-hardening accompanies the formation of a new structure, the precipitate, as provided by an alloy system in which solid solubility decreases with decreasing temperature. Upon this premise alone all such systems would be expected to include age-hardenable alloys. Alas, this is not always the case. Few attempts have been made to explain the variable degree of age-hardening among different alloys or to explain the influence of small alloying additions upon the hardening. Dispersion hardening as originally postulated3 is not adequate.* Coherency hardening-the term that will be used to distinguish the properties of a two-phase mixture in the unique and unstable transition state at which the phases are strained into precise atomic registry (continuity or coherency) in planes

Jan 1, 1948

By J. S. Kennedy, A. A. Lerew, C. M. Judson, G. L. Simard

DITHIOPHOSPHATE collectors are commonly used in the flotation of sulphide minerals. Studies of the interaction of a typical dithiophosphate collector with galena surfaces have been previously reported from. these laboratories." These fundamental studies were carried out by employing phosphorus labeled radioactive dithiophosphate. Radioactivity determinations then could be used to measure readily and accurately the small concentrations of dithiophosphate that, are present under conditions of flotation processes. Measurements were made on ground mineral, determining the amount sorbed indirectly from the concentrations in solution; and studies were also made with single crystals, determining the amount sorbed directly by counting the crystal surface. The rates, isotherms and reversibility characteristics of dithiophosphate sorption, the competition between phosphate and dithiophosphate for the mineral surface, and the exchange of sorbed dithiophosphate with dissolved dithiophosphate were studied. These studies have now been extended by sorption measurements in flotations with a Fagergren, machine. For this work, the selective flotation of galena and sphalerite from quartz was chosen, using ammonium di-(sec-butyl) dithiophosphate as. the collector, sodium cyanide as depressant for sphalerite, and copper sulphate as an activator for sphalerite. While the selective flotation of galena and sphalerite using a single dithiophosphate collector is not typical of flotation practice (two different collectors are generally used), it was found that a reasonably good separation could be obtained by using zinc sulphate with the sodium cyanide in the galena flotation and by cleaning the sphalerite concentrate or by carrying out the sphalerite. flotation in an alkaline medium. Data of practical importance on the distribution of collector between the concentrates, tailings, and solutions were obtained, particularly with regard to the effect of copper sulphate and sodium cyanide. In addition to the. selective flotation of galena and sphalerite from quartz, single flotations of galena-quartz and sphalerite-quartz mixtures were carried out, along with blank flotations on quartz alone. The present paper describes the results of these experiments. As in previous papers, the term sorption is used to designate uptake of collector by the mineral, without implication as to the nature of the processes involved. Experimental Materials: The mineral system was a ground synthetic mixture of galena, sphalerite, and quartz. The galena was from Galena, Kans., and contained 75 pct lead (theoretical 85.6 pct Pb for PbS); the sphalerite, from Ottowa County, Okla., contained 63 pct zinc (theoretical 67.2 pet Zn for ZnS) ; and the quartz from Klondike, Mo., analyzed as 99.97 pet SiO2. Sulphur labeled radioactive di-(sec-butyl) dithiophosphate was prepared from S82 supplied by the Oak Ridge National Laboratory on allocation from the U. S. Atomic Energy Commission. The synthesis consisted of precipitating barium sulphate, reducing the barium sulphate to barium sulphide, acidifying to form hydrogen sulphide, and oxidizing the hydrogen sulphide with iodine to elemental sulphur.

Jan 1, 1952

By S. K. Nowak

The lithium solubility limit in solid aluminum was determined by the use of micro-graphic techniques. The solubility limit thus established was shown to be a true equilibrium by checking the reversibility of AlLi phase precipitation and dissolution around the equilibrium temperature. The experimental results fit a straight line by plotting log N(LI) against 1/T. The metallurgical reasons explaining the lack of agreement among previous investigations are discussed. THE solubility limit of lithium in solid aluminum was determined by Shamray and Saldau1 by micrography and by Grube et al.' and also Voss-Kiihler- by measurement of electrical resistivity. Since the addition of lithium induces extremely small changes in the aluminum lattice, X-ray techniques could not be employed for this purpose; in fact, the addition of lithium does not cause an expansion of the lattice as might be expected from a consideration of atomic radii, but causes a small contraction from 4.040 to 4.037A3, 4 when the solvent aluminum is saturated with this element. An analysis of the results from previous investiga-tions'" shows that with improvement of investigation techniques the solubility limit tends toward a lower lithium content. Again, some of the author's own experimental results on the action of atomic hydrogen on A1-Li alloys seemed to indicate that the solubility of lithium should be much lower, i.e., about 0.3 pet at 300°C: instead of 1.15 pet, the lowest published value.4 For the foregoing reasons it was decided to investigate this problem. The aluminum and the lithium used for this purpose were of the highest purity. The lithium solubility limit was determined by metallographic techniques, in particular by the use of a reagent especially developed for the purpose of revealing the AlLi phase. The solubility limit thus determined was shown to be a true equilibrium by checking the reversibility of AlLi phase dissolution and precipitation around the equilibrium temperature. All of the experimental work was carried out in 1951 at the Centre d'Etudes de Chimie Metallur-gique at Vitry, France, under the direction of Georges Chaudron.

Jan 1, 1957

By R. B. Basham, C. W. Macune

Very small anomalies in oil well temperatures are detected and measured by recording the difference in temperature existing between two thermally sensitive elements which are Spaced several feet apart on a small diameter carrier and lowered into the bore hole. The elements operate in a balanced electrical circuit, sending only a reference signal to the surface as long as normal gradient temperatures are encountered. When either element enters a temperature disturbance, the circuit is unbalanced and produces large recorder deflections for minute anomalies. The system is highly sensitive to small changes in thermal gradients caused by gas or fluid movements and to the boundaries between beds of different thermal conductivities. Typical logs show successful applications of the process to locating gas and water leaks in casing, gas entry. and gas-oil contact. INTRODUCTION Temperature measurements in oil wells have been made for many years in the search for additional sub-surface data. It has been generally agreed that many conditions in the bore hole cause temperature anomalies which, if located and measured, could yield useful information. But it has been recognized also that many of the irregularities, such as those produced by small water and gas leaks in casing, might be very small and therefore difficult to detect with certainty.' Although tem-perature measurements have been made which show anomalies of less than one degree deviation from normal gradient temperatures, the results are usually uncertain and unconvincing. The general practice, therefore. has been to apply temperature surveys only to well conditions known to produce appreciable disturbances, such as large gas movements and cement hydration. The recent demand for additional data has focused attention on the problem of making dependable temperature measurements in the many instances when anomalies are small but none the less significant. It was for the purpose of detecting these minute irregularities in bore hole temperature that the program described in the following text was undertaken. It is emphasized that this presentation is not offered as a complete study, for the process is still partially experimental. But it is believed that the results obtained thus far will be of interest to the industry and will indicate some of the system's potential usefulness. DIFFERENTIAL MEASUREMENT The chief value of differential measurement lies in the fact that a difference between two factors can be measured with a scale of values best suited to that difference, a scale that might be cumbersome or impractical if applied to the factors themselves. When it is known that all factors will be nearly equal in value, and therefore the differences consistently small, it is possible to select a scale which will permit very accurate measurement of the differences. This advantage is in contrast to the difficulty of measuring small increments of a single variable, where the increment must be measured by a large scale which is suitable for measuring the entire factor. Gradient temperatures are usually measured under this latter condition where temperature measuring apparatus must have a scale extending over the range of expected temperatures, say 50' to 25O°F, and it becomes almost impossible to detect small irregularities of less than one degree. The use of large strip chart recorders and divided multiple ranges tend to amplify the small anomaly and make it more pronounced. But the instability of instruments, both

Jan 1, 1952

By A. G. Weber, K. H. Coats, M. H. Terhune, R. L. Nielsen

Two computer-oriented techniques for simulating the three-dimensional flow behavior of two fluid phases in petroleum reservoirs were developed. Under the first technique the flow equations are solved to model three-dimensional flow in a reservoir. The second technique was developed for modeling flow in three-dimensional media that have sufficiently high permeability in the vertical direction so that vertical flow is not seriously restricted. Since this latter technique is a modified two-dimensional meal analysis, suitably structured three-dimensional reservoirs can be simulated at considerably lower computational expenses than is required using the three-dimensional analysis. A quantitative criterion is provided for determining when vertical communication is good enough to permit use of the modified two-dimensional areal analysis. The equations solved by both techniques treat both fluids as compressible, and, for gas-oil applications, provide for the evolution of dissolved gas. Accounted for are the effects of relative permeability, capillary pressure and gravity in addition to reservoir geomety and rock heterogeneity. Calculations are compared with laboratory waterflood data to indicate the validity of the analyses. Other results were calculated with both techniques which show the equivalence of the two solutions for reservoirs satisfying the vertical communication criterion. INTRODUCTION Obtaining the maximum profits from oil and gas reservoirs during all stages of depletion is the fundamental charge to the reservoir engineering profession. In recent years much quantitative assistance in evaluating field development programs has been provided by computerized techniques for predicting reservoir flow behavior. Because of the spatially distributed and dynamic nature of producing operations, automatic optimization procedures, such as those now in use for planning refining operations, are not now available for planning reservoir development. However, present mathematical simulation techniques do furnish powerful means for making case studies to help in planning primary recovery operations and in selecting and timing supplemental recovery operations. A number of methods have been reported which simulate the flow of one, two or three fluid phases within porous media of one or two effective spatial dimensions>-4 However, applying computer analyses to actual reservoirs have been limited mostly to two-dimensional areal or cross-sectional flow studies for two immiscible reservoir fluids. To obtain a three-dimensional picture of reservoir performance using such two-dimensional techniques, it has been necessary to interpret the calculations by combining somehow the results from essentially independent areal and cross-sectional studies. To the authors' knowledge, the only other three-dimensional computational procedure, in addition to those presented here, was developed by Peaceman and Rachford8 to simulate the behavior of a laboratory waterflood. Two computational techniques which may be used to simulate three-dimensional flow of two fluid phases are described in this paper. The first method, called the "three-dimensional analysis", employs a fully three-dimensional mathematical model that treats simultaneously both the areal and cross-sectional aspects of reservoir flow. The second method, called the vertical equilibrium (VE) analysis", is applicable

By M. C. Leverett, S. E. Buckley

The production of oil is accomplished as a result of its displacement from the reservoir by either gas or water, and the amount of oil recovery is limited by the extent to which the displacing gas or water accumulates. This paper describes the mechanism by which the displacement is effected and the advantages of water over gas as a displacing agent. In the light of the results of experimental observations of the flow of mixtures of oil and/or gas and/or water through sands, certain conclusions are drawn relative to the changing character of the displacement as depletion proceeds, and on the effects of the properties of the fluids and of producing conditions on the ultimate oil recovery. Introduction Crude oil has no inherent ability to expel itself from the pores of the reservoir rocks in which it is found; rather, it must be forcibly ejected or displaced by the accumulation of other fluids. Accordingly, a knowledge of the mechanism by which one fluid is displaced by another is essential to an understanding of the fundamental process by which oil is recovered. The displacing fluids normally available are gas and water, either or both of which may exist originally associated with the oil in a potentially usable form or may be supplied to the reservoir from external sources. Gas is present in most oil reservoirs. If the quantity is relatively small, it may exist originally completely dissolved in the oil, but if the quantity exceeds that which may be held in solution by the oil at the prevailing pressure, the excess will be found in the free state. Most reservoir sands appear to contain some water,l and in the majority of fields the oil is trapped in the structure and held over water. In certain conditions the entrapping water may advance into the oil zone and displace the oil therefrom. This paper describes in a qualitative manner some of the characteristics of the displacement of oil by either gas or water, with an attempt to elucidate somewhat the mechanism by which such displacement is effected. Role of Dissolved Gas When the pressure on an oil containing dissolved gas is reduced to the saturation or bubble-point pressure, gas escapes from solution and expands, imparting to the oil-gas mixture a high degree of expansibility and causing it to flow in the direction of reduced pressure. This expansibility has frequently been attributed to the oil; closer analysis, however, reveals that as gas escapes from solution the oil phase actually. contracts. Hence, it is the accumulation and expansion of the liberated gas that supplies the propelling force for the oil. It has been shown experimentally2-5 that within certain limits a sand containing oil, gas and water will permit the simultaneous flow of all three; the readiness with which they may flow depends upon the characteristics of the sand, of each of the fluids, and upon the relative amounts of the fluids in the sand. Thus, in the initial stages of production by the mechanism of dissolved gas drive, the liberated gas is present in the sand in low concentration and is unable to

Jan 1, 1942

By S. E. Buckley, M. C. Leverett

The production of oil is accomplished as a result of its displacement from the reservoir by either gas or water, and the amount of oil recovery is limited by the extent to which the displacing gas or water accumulates. This paper describes the mechanism by which the displacement is effected and the advantages of water over gas as a displacing agent. In the light of the results of experimental observations of the flow of mixtures of oil and/or gas and/or water through sands, certain conclusions are drawn relative to the changing character of the displacement as depletion proceeds, and on the effects of the properties of the fluids and of producing conditions on the ultimate oil recovery. Introduction Crude oil has no inherent ability to expel itself from the pores of the reservoir rocks in which it is found; rather, it must be forcibly ejected or displaced by the accumulation of other fluids. Accordingly, a knowledge of the mechanism by which one fluid is displaced by another is essential to an understanding of the fundamental process by which oil is recovered. The displacing fluids normally available are gas and water, either or both of which may exist originally associated with the oil in a potentially usable form or may be supplied to the reservoir from external sources. Gas is present in most oil reservoirs. If the quantity is relatively small, it may exist originally completely dissolved in the oil, but if the quantity exceeds that which may be held in solution by the oil at the prevailing pressure, the excess will be found in the free state. Most reservoir sands appear to contain some water,l and in the majority of fields the oil is trapped in the structure and held over water. In certain conditions the entrapping water may advance into the oil zone and displace the oil therefrom. This paper describes in a qualitative manner some of the characteristics of the displacement of oil by either gas or water, with an attempt to elucidate somewhat the mechanism by which such displacement is effected. Role of Dissolved Gas When the pressure on an oil containing dissolved gas is reduced to the saturation or bubble-point pressure, gas escapes from solution and expands, imparting to the oil-gas mixture a high degree of expansibility and causing it to flow in the direction of reduced pressure. This expansibility has frequently been attributed to the oil; closer analysis, however, reveals that as gas escapes from solution the oil phase actually. contracts. Hence, it is the accumulation and expansion of the liberated gas that supplies the propelling force for the oil. It has been shown experimentally2-5 that within certain limits a sand containing oil, gas and water will permit the simultaneous flow of all three; the readiness with which they may flow depends upon the characteristics of the sand, of each of the fluids, and upon the relative amounts of the fluids in the sand. Thus, in the initial stages of production by the mechanism of dissolved gas drive, the liberated gas is present in the sand in low concentration and is unable to

Jan 1, 1942

By S. Stutz

COAL, like most other minerals, only exceptionally occurs in a sufficiently pure state to he directly available for general manufacturing purposes. And even where this is the case, the small coal or slack is usually more impure than the lump coal, as the slate, clay, etc., from the roof and bottom of the vein become mixed with it in the handling it undergoes. These impurities often exceed ten or more percent in addition to the impurities of the coal itself. The most common impurities of the coal are slate, or shale, clay, and sulphur. The latter occurs in different forms, but most frequently as bisulphide of iron, or iron pyrites, and as sulphate of lime, or gypsum. In both cases the impurities add greatly to the amount of ash, and where they are present in considerable quantities the raw coal, and still more the coke made from it, is unfit for the, manufacture of iron. Coke will contain on an average at least ;fifty per cent, more ash and sulphur than the raw coal from which it is, made. To the manufacturer of iron every additional per cent. of ash which his coal or .coke contains is a source of additional expense, seemingly small, and yet very important in the aggregate. In the blast-furnace, for instance, the ash must be heated up to the melting-point, and, since it is composed largely of refractory substances, the consumption of carbon in melting it will be equal to at least one-half of its weight ; that is, a certain part of the coke is consumed for the melting and fluxing of the ash and is lost. Besides this, it is well enough known to the-iron-master that coke containing less ash makes the slag or cinder more liquid and less inclined to stick to- the walls of the furnace. Fuel containing much sulphur produces generally a white iron, poor in carbon, while from the same ore and flux, with a pure fuel, a good foundry iron might be obtained. The work of separating slate, sulphur, etc:, from the coal 'has as yet only been succesafully accomplished by the washing process. This process depends for its success on the differences in the specific

Jan 1, 1881

By J. N. Maycock, P. W. M. Jacobs

Previous measurements of the thermoelectric power of ionic crystals are reviewed briefly. It is concluded that, while extensive measurerements are available on systems in which the electrode M has a cation in cornon with the sall MX, there is as yet little modern work on systems in which the metal electrode M' does not haue a calion in common with the salt. We haue now measured the thermoelectric power of- single cryslals of KC1 and of KC1 + SrCl2 between plati.nu?n electrodes over a much wider range of temperature than before. individual ionic heats of transport, which, while probably not very accurate, are of a reasonable order of magnitude, are obtained from this data on the basis of an assumption that charge carriers do not cross the electrode/salt interface. RELATIVELY little work has been done on thermal diffusion in ionic crystals. Reinhold and coworkers1-I measured the thermoelectric power and Soret effect in silver and cuprous salts and their mixed crystals. One electrode was kept at constant temperature and electromotive force was measured as a function of the temperature gradient. This is not a satisfactory technique if the results are to be compared with theory; rather should the electromotive force be measured for small temperature differences as a function of the mean temperature of the two electrodes. They used electrodes having the same cation as the salt. Patrick and Lawsons measured the thermoelectric power of AgBr and of AgBr containing 0.25 mole pct CdBr2 using silver electrodes and temperature gradients of 10°C in the temperature range 100° to 400°C. The results were analyzed using the Teltow9 values of the ratio of the mobility of the two types of charge carrier (cation vacancies and interstitials) found from conductance measurements and the wagnerlo estimate of the heterogeneous contribution to the thermopower, Ohet They obtained values of qi = 0.017 ev and q$ = -0.385 ev for the heats of transport of interstitial Ag ions and cation vacancies, respectively. Their data has been reanalyzed by Haga using the corrections to the Wagner formula for ehet given by Howard andLidiard; Haga found ev. Christy et a1.14 have measured the thermopower of AgBr containing 0.01 to 1.0 mole pct CdBr,. They analyzed their results in terms of the theory of Howard and Lidiard and found that excellent agreement with the theory was obtained if q5 + : + hF was set equal to 0.70 ev at 175°C and equal to 0.58 ev at 250°C. Since Teltow's value for hF, the enthalpy of formation of a Frenkel defect pair, is 1.27 ev, this means that qt + q: increases in magnitude from -0.57 ev at 175°C to -0.69 ev at 250°C. This result is in poor agreement with Patrick and Lawson's value of -0.37 ev for pure AgBr (for which the corrections to the Wagner estimate for ehet are very small). christy1' has also reported thermopower measurements for pure silver halides and for the systems he finds that qr + qt for AgBr increases in magnitude from about -0.55 ev at 150°C to about -1.1 ev at 400°C. The temperature dependence of the sum of the heats of transport in AgCl is very similar in magnitude. The sum qi + q cannot be decomposed into the individual interstitial and vacancy heats of transport without a knowledge of the entropy contribution from the change in the lattice vibrational frequencies around the interstitial and vacancy. Despite this it seems an inescapable conclusion from Christy's analysis that and -6 = Q Ag are quite strongly temperature-de pendent and that -q: is much greater in magnitude than the corresponding activation energy for vacancy migration, +0.37 ev. It remains a mystery as to why the data for pure AgBr are fitted so well by the assumption of temperature-independent heats of transport if association of impurity ions and vacancies is neglected.l The values for q$ and q: so obtained are also much more in line with those expected from a simple kinetic interpretation of the heats of transport due to wirtz.17 Christy and Hsueh have also measured the thermopower of CuCl between copper electrodes; 0 for pure CuCl is comparable with that for the silver halides but, owing to the limited solubility of divalent cation impurities it was not found possible to deduce values for the heats of transport. In contrast to these extensive measurements on cells of the type M MX 1 M, there have been relatively few attempts to measure the thermoelectric power of cells of the form M' 1 MX I M'. (We specifically exclude from discussion cells of this type in which the metal electrodes M' are in contact with gas containing a controlled partial pressure of either M or X,, since in these cells the electrochemical reactions are analogous to those of the first type.) The thermoelectric power of Pb12, PbC12, TlC1, TlBr, TlI, NaNO3, and KNO 3 between platinum electrodes was measured by Thie1e.l3 In discussing these measurements Holtan20 asserts that the thermopotential initially fluctuated wildly and even changed sign before approaching a steady value. A high degree of irreproducibility is also evident in the work of Nikitinskaya and Murin21 who first studied the thermopower of NaCl and KC1 between platinum electrodes. Much better reproduci-bility was achieved in our earlier measurements on KC1;22 these were, however, confined to a relatively narrow temperature range and one of the objects of the work reported in this paper was to extend the temperature range of the measurements of the thermoelectric power 8 of KC1. The only other published

Jan 1, 1967

By C. Chiou, M. E. Fine

While Gunier-Preston zones are growing in Al-4.2 pct Cu at room temperature, Young's modulus, measured dynamically, increases about 0.4 pct. From the change in modulus with time the exponent of time in the rate equation for growth of the zones was deduced to be %. From a comparison of the rates of increase of modulus at 1, 28, and 42°C an activation energy of 12 to 14 Kcal per mole is computed. These findings support the idea that copper atoms are supplied along dislocation channels to growing zones. In alloys the elastic constants will be functions of the distributions of the atoms. If the degree of ordering or clustering is changed, one expects a corresponding change in the elastic constants. During age-hardening of aluminum-copper alloys at room temperature, the copper atoms cluster on 100-type planes in the aluminum lattice forming

Jan 1, 1959

By Lawrence Addicks

(San Francisco Meeting, September, 1915) THROUGH the courtesy of Dr. James Douglas I am permitted to give, a summary of some of the results obtained in leaching slimes tailings in a series of experiments conducted under my direction at Douglas, Ariz.. during the past year. While the test run for which the data are given deals with a particular case, much of the work is general in its application and may therefore be of interest. This work was done upon the ores of the Burro Mountain Copper Co. A description of the geology of the district will be-found in the paper by R. E. Somers published in the May, 1915, Bulletin of the Institute. The mineral is pyrite and chalcocite very finely disseminated throughout the gangue and a characteristic of all the ores is the large amount of alumina present. A representative analysis of the particular ore under consideration would be about as follows: Cu, per cent 2.35 S, percent 3.0 Ag, ounces per ton 0.05 CaO, per cent 0.5 Au None K202, per cent 4.0 Fe, per cent 1.5 SiO2, per cent 70.0 A120,, per cent 13.0 The leaching of the ore direct was early dismissed from consideration for the following reasons: 1. The ore would have to be quite finely crushed to liberate the mineral for leaching; concentrating after crushing would cost but a few cents a ton; and a higher total recovery would result from leaching tailings rather than ore. 2. Rough concentration would yield a suitable material for roasting to make sulphur dioxide or sulphuric acid in connection with the leaching scheme. 3. Such a program put the question of cost vs. recovery on a basis where flotation and discarding of tailings were directly comparable.

Jan 8, 1915

By W. Jolley

Decarburized iron and Fe-3.28 pct Ni alloys were impact and tension tested in the temperature range of ambient to 4°K. It was found that alloying with nickel improves the fracture properties of the ferrite matrix. The improvement in toughness of iron alloyed with nickel is attributed to the effect of the nickel addition on the temperature and strain rate dependence of the yield stress as well as on slip behavior. The Fe-Ni alloy exhibits wavy slip when strained at temperatures down to at least 50°K. This behavior contrasts with that of the unalloyed iron where a change It is a generally accepted fact that of the common alloying elements of steel only nickel and manganese improve both the room-temperature yield strength and the notch impact properties. It has been argued for a number of years that manganese refines the ferrite grain size, the pearlite spacing, and the grain boundary carbides in medium- and low-carbon steels and thereby increases resistance to brittle fracture.''' This hypothesis recently was confirmed for a 0.04 pct C iron containing manganese, but at the same time from wavy to planar slip occurs at about 120°K. The observed lower temperature and strain rate dependence of the lower yield stress in the Fe-Ni alloy as compared to the unalloyed iron may be attributed to this difference in slip behavior. In contrast to suggestions published previously, transmission electron microscopy showed that the uniform dislocation distributions and the lack of dislocation tangles which are produced by low-temperature straining of bcc materials cannot be attributed to the absence of cross slip at these temperatures. no increase in notch toughness was observed in a decarburized Fe-Mn alloy.3 It thus appears that manganese only increases the toughness of Fe-Mn-C alloys by refining grain boundary carbides and has no toughening effect in carbon-free iron. On the other hand, the mechanism whereby nickel improves toughness has not been established. Hodge et a1.4 have clearly shown that a 3.28 pct Ni addition lowers the impact transition temperature of 0.02 pct C steel approximately 35°C when the grain size is maintained constant. Recently, Wullaert and Tetelman6 stated that nickel refined the grain boundary carbides of an Fe-C alloy and consequently increased the toughness. They also observed the previously reporteda-'

Jan 1, 1969

By R. A. Cunningham, A. S. Murray

If a dense fluid such as mud or water is used for circulation, the formation drilled is influenced by a hydrostatic pressure. This pressure depends on hole depth arid drilling fluid density. Laboratory tests indicute that drilling rates in many forri~ations are decreased with increased pressure,—in some cases as much as 90 per cent. A comparison between laboratory and field tests indicates that drilling fluid head affects drilling rates in the field approximately the, same as in the laboratory. Drillirrg rates of many formations are increased by reducing drilling fluid head. INTRODUCTION For many years it has been noted that field and laboratory drilling rate tests did not agree even when the formations tested were the same. For instance, tests of some shales by the Hughes Tool Co. laboratory indicated drilling rates approximately 20 to 30 ft/hour, whereas in the ground this shale would drill only 3 to 5 ft/hour. A possible reason for this discrepancy is the effect of the high pressure which the drilling fluid exerts against the formation at the bottom of the hole. Consider a small element of rock (Fig. II that is to be removed by a rock bit. If the hole is filled with mud or water. the upper surface of the rock element is subjected to a pressure which depends on hole depth and fluid density. The mass of earth around this rock element presses against the circumferential surface and the lower surface. Because of the probability of shearing stresses between the rock element and the surrounding rock, this element is not under true hydrostatic stress. However, as a first approximation for test purposes the rock element was assumed to he under hydrostatic stress. The effect of hydrostatic pressure on some physical properties of rock has been studied.1,2,3 These tests show that the "differential" compres-sive stress:': necessary to cause rup- ture in rock cylinders is greater when tested under high hydrostatic pressure than when tested under atmospheric conditions. These tests were made with pressures greater than 20,000 psi which is in excess of those normally encountered in oil well drilling. Similar tests were made by the Bureau of Reclamation' using pressures equivalent to those encountered in oil well drilling. Again the "differential" compressive stress necessary to produce failure increased with increasing hydrostatic pressure. These tests indicated that drilling rates would probably decrease. Correlation between these tests and drilling tests was not practical. The purpose of this work is to study the effect of mud column pressure on drilling rate, assuming that the material drilled is in a state of hydrostatic strcss. This problem was initially investigated in the laboratory using variable bit loads and confining pressure;. Confirmation of laboratory results was obtained in the field from a series of carefully controlled drilling tests. Because of the necessity of testing many different types of formations. only results from representative formations will be presented here.

Jan 1, 1956

By Francis Collins, E. R. Brownscombe

A study has been made of the material balance-fluid flow method of estimating reserves and degree of water drive from pressure and production history data. By considering the effect of random pressure errors it is shown that in a particular example a standard deviation of three and one-half pounds in each of ten pressure survey? permits the determination of the reserves with a standard deviation of 8 per cent and the water drive with a standard deviation of 15 per cent, assuming that certain basic geologic data are correct. It is believed that this method of estimating reserves and water drive is useful and reliable in a number of cases. The method is particularly valuable when reservoir pressure data are accurate within a very few pounds, but may also be applied with less accurate pressure data if a relatively large reservoir pressure decline occurs early in the life of the field, as for example in an under-saturated oil field. INTRODUCTION A knowledge of the magnitude of reserves and degree of water drive present in any newly discovered petroleum reservoir is necessary to early application of proper production practices. A number of investigators have contributed to methods of relating reserves, degree of water drive, and production and pressure history. 1-8 Three types of problems of increasing complexity may be mentioned. If a reservoir is known to have no water drive. and if the ratio of the volume of the reservoir occupied by gas to the volume of the reservoir occupied by oil (which ratio permits fixing the overall compressibility of the reservoir) is known, then only one further extensive reservoir property remains to be determined, namely the magnitude of the reserves. A straightforward application of material balance considerations will permit this determination. The problem becomes very much more difficult if we wish to determine not only the magnitude of the reserves but also the magnitude of water drive, if any, which is present. In principle, a combination of material balance and fluid flow considerations will permit this evaluation. Finally, if neither the magnitude of reserves, the degree of water drive, nor the ratio of oil to gas present in the reservoir is known and it is desired to determine all three of these variables, the problem could in principle be solved by a fluid flow-material balance analysis which determines the overall compressibility of the reservoir at various points in its history. The change in compressibility with pressure would provide a means of determining the ratio of gas to liquid present, since the compressibilities of gas and liquid vary differently with pressure variation. However, in practice this problem is probably so difficult as to defy solution in terms of basic data precision apt to be available.' It is the purpose of this discussion to illustrate the second case, which involves the determination of two unknown variables, single phase reserves and degree of water drive, from pressure and production history and fluid property data, and to study the precision with which these unknowns can be determined in this manner in a particular case. Although an electric analyzer developed by Bruce as used in making the calculations to be described, numerical methods necessary in carrying out the process have been devised and have been applied for this purpose. Schilthuis,' for example, developed a comprehensive equation for the material balance in a reservoir. He combined this with a simplified water drive equation, assuming that the ratio of free gas to oil was fixed by geological data and that a period of constant pressure operation at constant rate of production was available to determine the constant for his water drive equation. On this basis he was able to compute the reserves and predict the future pressure history of the reservoir. Hurst developed a generalized equation permitting the calculation of the water drive by unsteady state expansion from a finite aquifer. He showed in a specific case how the water influx calculated by his equation, using basic geologic and reservoir data to fix the constants, matched the water influx required by material balance considerations. Old3 illustrated the simultaneous use of Schilthuis' material balance equation and Hurst's fluid flow equation for the determination of the magnitude of reserves and a water drive parameter from pressure and production history. He used this method to calculate the future pressure history of the reservoir under assumed operating conditions. As a basis for determining reserves, Old assumed a value for his water drive parameter and calculated a set of values for the reserves, using the initial reservoir pressure and each successive measured pressure. The sum of the absolute values of the deviations of the resulting reserve numbers from their mean value was taken as a criterion of the closeness of fit to the experimental data possible with the water drive parameter assumed. New values of the water drive parameter were then assumed and new sets of the reserves calculated until a set of reserves numbers having a minimum deviation from the average was established. The average value of- the re-

Jan 1, 1949

By E. R. Brownscombe, Francis Collins

A study has been made of the material balance-fluid flow method of estimating reserves and degree of water drive from pressure and production history data. By considering the effect of random pressure errors it is shown that in a particular example a standard deviation of three and one-half pounds in each of ten pressure survey? permits the determination of the reserves with a standard deviation of 8 per cent and the water drive with a standard deviation of 15 per cent, assuming that certain basic geologic data are correct. It is believed that this method of estimating reserves and water drive is useful and reliable in a number of cases. The method is particularly valuable when reservoir pressure data are accurate within a very few pounds, but may also be applied with less accurate pressure data if a relatively large reservoir pressure decline occurs early in the life of the field, as for example in an under-saturated oil field. INTRODUCTION A knowledge of the magnitude of reserves and degree of water drive present in any newly discovered petroleum reservoir is necessary to early application of proper production practices. A number of investigators have contributed to methods of relating reserves, degree of water drive, and production and pressure history. 1-8 Three types of problems of increasing complexity may be mentioned. If a reservoir is known to have no water drive. and if the ratio of the volume of the reservoir occupied by gas to the volume of the reservoir occupied by oil (which ratio permits fixing the overall compressibility of the reservoir) is known, then only one further extensive reservoir property remains to be determined, namely the magnitude of the reserves. A straightforward application of material balance considerations will permit this determination. The problem becomes very much more difficult if we wish to determine not only the magnitude of the reserves but also the magnitude of water drive, if any, which is present. In principle, a combination of material balance and fluid flow considerations will permit this evaluation. Finally, if neither the magnitude of reserves, the degree of water drive, nor the ratio of oil to gas present in the reservoir is known and it is desired to determine all three of these variables, the problem could in principle be solved by a fluid flow-material balance analysis which determines the overall compressibility of the reservoir at various points in its history. The change in compressibility with pressure would provide a means of determining the ratio of gas to liquid present, since the compressibilities of gas and liquid vary differently with pressure variation. However, in practice this problem is probably so difficult as to defy solution in terms of basic data precision apt to be available.' It is the purpose of this discussion to illustrate the second case, which involves the determination of two unknown variables, single phase reserves and degree of water drive, from pressure and production history and fluid property data, and to study the precision with which these unknowns can be determined in this manner in a particular case. Although an electric analyzer developed by Bruce as used in making the calculations to be described, numerical methods necessary in carrying out the process have been devised and have been applied for this purpose. Schilthuis,' for example, developed a comprehensive equation for the material balance in a reservoir. He combined this with a simplified water drive equation, assuming that the ratio of free gas to oil was fixed by geological data and that a period of constant pressure operation at constant rate of production was available to determine the constant for his water drive equation. On this basis he was able to compute the reserves and predict the future pressure history of the reservoir. Hurst developed a generalized equation permitting the calculation of the water drive by unsteady state expansion from a finite aquifer. He showed in a specific case how the water influx calculated by his equation, using basic geologic and reservoir data to fix the constants, matched the water influx required by material balance considerations. Old3 illustrated the simultaneous use of Schilthuis' material balance equation and Hurst's fluid flow equation for the determination of the magnitude of reserves and a water drive parameter from pressure and production history. He used this method to calculate the future pressure history of the reservoir under assumed operating conditions. As a basis for determining reserves, Old assumed a value for his water drive parameter and calculated a set of values for the reserves, using the initial reservoir pressure and each successive measured pressure. The sum of the absolute values of the deviations of the resulting reserve numbers from their mean value was taken as a criterion of the closeness of fit to the experimental data possible with the water drive parameter assumed. New values of the water drive parameter were then assumed and new sets of the reserves calculated until a set of reserves numbers having a minimum deviation from the average was established. The average value of- the re-

Jan 1, 1949

By W.C Ellis, Earle E. Schumacher

Nonferrous alloys upon which desirable properties can be conferred by heat treatment are becoming of increasing industrial importance. The alloys of copper with a constituent which has a solubility varying with temperature are materials of this character. Some of the constituents which are effective in producing a change in the mechanical properties of these alloys upon heat treatment are, according to Corson,' nickel and silicon, iron and silicon, cobalt and silicon, and chromium and silicon. In addition to these elements, Gregg2 states that the combination of beryllium and silicon is effective in producing age-hardening characteristics in copper. The effect of these elements, however, as dispersion-hardening constituents in the copper alpha solid solutions does not seem to have been studied in any considerable detail. This paper deals with the heat treatment and properties of three alpha brasses containing 3 per cent. of nickel plus silicon in the proportion necessary to form the compound nickel silicide, Ni2Si. Some information of a preliminary nature in regard to the hardening by heat treatment of phosphor bronze containing the same percentages of nickel and silicon is included. The method of hardening the alloys, which is effective in increasing the tensile strength and proportional limit, is similar to that used in the case of duralumin type aluminum alloys. It consists of a quench from a temperature at which the hardening constituent is in solid solution, followed by an aging at a lower temperature to precipitate the dissolved constituent in a dispersed condition. This results in an increased resistance of the alloy to deformation with an attendant improvement in the tensile properties.

Jan 1, 1929

By Earle E. Schumacher, W. C. Ellis

Nonferrous alloys upon which desirable properties can be conferred by heat treatment are becoming of increasing industrial importance. The alloys of copper with a constituent which has a solubility varying with temperature are materials of this character. Some of the constituents which are effective in producing a change in the mechanical properties of these alloys upon heat treatment are, according to Corson,' nickel and silicon, iron and silicon, cobalt and silicon, and chromium and silicon. In addition to these elements, Gregg2 states that the combination of beryllium and silicon is effective in producing age-hardening characteristics in copper. The effect of these elements, however, as dispersion-hardening constituents in the copper alpha solid solutions does not seem to have been studied in any considerable detail. This paper deals with the heat treatment and properties of three alpha brasses containing 3 per cent. of nickel plus silicon in the proportion necessary to form the compound nickel silicide, Ni2Si. Some information of a preliminary nature in regard to the hardening by heat treatment of phosphor bronze containing the same percentages of nickel and silicon is included. The method of hardening the alloys, which is effective in increasing the tensile strength and proportional limit, is similar to that used in the case of duralumin type aluminum alloys. It consists of a quench from a temperature at which the hardening constituent is in solid solution, followed by an aging at a lower temperature to precipitate the dissolved constituent in a dispersed condition. This results in an increased resistance of the alloy to deformation with an attendant improvement in the tensile properties.

Jan 1, 1929

By Donald J. Drinkwater, M. C. Fuerstenau

Many important contributions to the more fundamental aspects of mineral processing have been made this past year. Mular1 researched the flotation characteristics of pure zinc oxide and also samples that had been doped with Al+++ and Cu++. Correlation of the response of pure zinc oxide to oleate flotation with a calculated zpc (from solution equilibrium) suggests that adsorption of oleate ion is coulombic in nature. Doping the sample with Al+++ (which will make the ZnO more n-type) had a marked effect on the maximum value of pH at which 50% recovery was obtained at constant collector addition. That is, when 0.5 mole percent Al+++ was added, the pH for 50% recovery was reduced by about four units. Treatment with Cu++ was found to have little effect on the flotation response of zinc oxide, even for additions of one mole percent. Since the zero points of charge of the Al+++ doped powders were not measured, it was not possible to correlate flotation data of these samples directly with charge phenomena.

Jan 2, 1966

By E. S. Machlin, C. W. Chen

THIS investigation is concerned with the origin of the intercrystalline voids and cracks formed in metals and alloys subjected to stress at elevated temperature. There have been many suggestions in the recent literature relating to this problem. Greenwood' suggested that the voids may be produced by vacancy condensation. Zener has stated that shear-stress relaxation across grain boundaries could initiate high tensile stresses at the regions blocking grain boundary slip and thereby cause the formation of cracks. Chang and Grant3 have described the formation of cracks at grain boundary triple points and have experimentally verified Zener's mechanism for the grain boundary regions in the vicinity of a triple point. Subsequent to the completion of this investigation, Gifkins4 developed a model which made use of Stroh's5 mechanism of fracturing to produce sub-microscopic fractures that subsequently grow by grain boundary slip. Chen and Machlin,6 in answer to Gifkins, described a model deduced from the present investigation, in which grain boundary slip provides both the stress to fracture at grain boundary jogs and the deformation required to separate fractured jog surfaces. The possibility of gas condensation to form intercrystalline voids and cracks is eliminated as a basic mechanism because such voids and cracks are developed in vacuum melted material containing minute amounts, if any, of gaseous impurities. In a theoretical evaluation of this problem, Machlin7 concluded that void nucleation by vacancy condensation during creep-rupture is improbable but that vacancy condensation on supercritical sized voids to produce growth is probable. This investigation was begun to evaluate the suggested mechanisms for intercrystalline fracture. In particular, in order to correlate vacancy supersaturation ratios produced in creep with those determined by Bal-luffi and Seigle8 as critical for , the nucleation of voids, specimens were obtained from the same heat of brass as used by the latter authors, through the courtesy of Dr. Seigle. The experiments conducted in this investigation fall into the following categories: 1) Brass—observation of voids produced under a variety of conditions, including creep under compression, to evaluate the mechanisms of void nucleation and growth. 2) Bicrystal experiments to check the mechanism of void nucleation deduced in this investigation. 3) Morphology of intercrystalline voids produced in a variety of metals. Each set of experiments will be described and discussed separately. Experimental Techniques A special creep-rupture test rack was constructed which made it possible to apply the stress to the specimen in a controlled atmosphere of inert gas, reducing gas, or vacuum. All the creep-rupture tests on a-brass (30 pct Zn) were conducted in nitrogen under a pressure slightly above atmospheric. Either dead weight loading or constant elongation rate loading could be applied with the load measured by means of a strain gage dynamometer. In order to obtain a coarse-grained crystal structure stable at

Jan 1, 1958

By George S. Barnett

The Equis and El Roble projects are located in the Cordillera Occidental of Colombia. The Equis vein deposits have sulfide ore reserves of 95,955 mt (105,770 st) grading 8.51 g/mt (0.248 oz/st) gold and 12.4 g/mt (0.36 oz/st) silver with 0.94 % copper, 1.10 % lead and 11.06 % zinc. Ore reserves at El Roble are estimated as 1.1 Mmt (1.21 million st) grading 4.89 % copper and 3.39 g/mt (0.099 oz/st) gold. Geologically possible reserves at Equis may total 1.6 Mmt (1.76 million st). El Roble has the potential to contain several tens of millions of metric tons. Exploration included diamond drilling, trenching, channel sampling, rock and soil geochemistry, geophysics and tunneling. Erratic high grade samples affect the weighting of channel and drill core samples. Secondary reconcentration of gold is also a factor. Sample maps and graphs show the distribution of values to be highly variable. Geostatistical treatment of some of these data gave important guidelines for parameters such as sampling densities, drill hole spacing and confidence limits.

Jan 1, 1985