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By N. H. van Lingen

A laboratory stud], has been made to determine what factors affect the penetration rate of roller bits, diamond bits and drag bits in rock drilling with clay /water muds. The rather simple relations that exist when pressures in and around the borehole are equal become more conzplicated when under down-hole conditions the penetration rate is hampered by the existence of a pressure differential between the mud at the hole bottom and the pore liquid at cutting depth. Expressions that have been derived for both the penetration rate and the magnitude of the pressure differential in permeable rock together fully account for operating, rock, mud and bit variables. In impermeable rock a similar pressure differential is caused by the bit action itself. In all cases, the pressure difierential and the reduction in penetration rate increase with the effectiveness of the plastering at the bottom of the hole by mud particles. Where bits are employed whose action is largely that of crushing, however, the plastering may become even more effective owing to the addition of rock particles rubbed into the pores of the rock. With roller bits, a plastically hehaving layer may be formed, which causes a further reduction in penetration. In the case of bits whose action is chiefly scraping, moreover, penetration may be arrested by the bit's becoming balled-up. The various adverse effects are reduced by thorough scavenging of the hole bottom. This paper shows how with jet bits the efficiency of such scavenging may he improved by suitable choice of the position of the nozzles. INTRODUCTION The reduction in a bit's penetration rate with increasing depth of hole has been the subject of many investigations. Various investigators ',' have independently reached the conclusion that this reduction occurs not so much because the rock-breaking process becomes more difficult as it does because the lifting of the rock fragments is impaired by a fluid pressure differential holding the fragments down. When such a pressure differential can be avoided, as in air drilling and to a smaller extent in water drilling, penetration rates remain high. Although the range of applicability of these techniques is being extended, most oil wells still have to be drilled with mud. In this paper we present the results of laboratory experiments carried out to determine what factors govern the hold down effect encountered in mud drilling. In the course of this investigation, the well known importance of bottom scavenging came more and more into prominence. Not only may it reduce the magnitude of the hold-down forces, but also it appeared to be a means of preventing the accumulation of a plastic mass of cuttings and mud on the hole bottom and bit which may cause penetration to cease almost completely. So that the effects of fluid pressures may be more readily understood, the factors that govern penetration rate in the absence of these pressures will first be discussed. The effect of down-hole pressures will then be assessed for the case of permeable rock where fluid pressures are well defined, and it will be demonstrated how rock strengthening due to confining can be accounted for. Subsequently, fluid pressures in less-permeable rock will be examined; we will show that in impermeable rock it is the bit action that governs fluid-pressure distribution and hold-down. In the case of poor scavenging and/or high bit load. cutting cake manifests itself. The effect, like various others. appears to depend on the type of bit used. From the very beginning, therefore, we shall base our discussion on the three main types of bits used in rotary oil-well drilling— roller bits, diamond bits and drag bits. Since space is limited, it will be impossible to make more than a passing reference to many aspects of the problem. Moreover. certain relations that are not of primary irnportance to our argument will unavoidably have to be stated in a somewhat dogmatic fashion, and the experimental data on which these are based necessarily must be omitted. EQUIPMENT The drilling experiments were performed on three machines, of which one has been designed for the realistic simulation of down-hole pressure conditions. HIGH-PRESSURES MACHINE In this machine (diagramed in Fig. 1) the mud, pore and confining pressures can all be adjusted independently. The foil-covered rock sample contained in the inner pressure vessel is confined by oil that is pressurized by means of a hand pump. The pore space of the watersaturated sample is connected to an arrangement which keeps the pressure in the pore space constant regardless of the rate of filtrate flow through the sample.

By D. M. Waldorf

Steam permeability measurements have been made in the laboratory on several samples of natural reservoir materials. The steam temperatures and pressures were selected to simulate conditions which might exist in a reservoir during the injection of steam. For each sample tested, the experimental permeability to superheated steam was comparable to that measured with air and no evidence of plugging was detected. Some samples were exposed to water at various temperatures and plugging was found to occur in materials which contained significant quantities of monmorillonite clay. Temperature had little effect on the degree of plug-ning between 75 and 325 F. The measured pemeabilities tended to increase slightly with temperature, but the changes were small compared with the initial loss of per~neability on wetting. Sequential pemzeability measurements were made on two samples using air, water, steam, water and air, in that order. Both samples were water-sensitive and plugged extensively after the initial injection of water. Upon exposure to superheated steatm the samples dehydrated and their permenbilities to superheated steam were comparable to those initially measured with air. The remaining measuretnetzts with water and air confirmed that the water plugging was reversible and that the samples were not seriorrsly damaged during the tests. INTRODUCTION The swelling of water-sensitive clays during water floods has long been recognized as a potential source of reservoir damage. The recent extensive application of steam injection and stimulation has compounded this problem since both hot water and steam (as well as fresh water at reservoir temperatures) are, at sume time, in contact with the producing zone adjacent to the bore of a steam injection well. The purpose of this paper is to present data which compare the sensitivity of some natural sedimentary rock samples to water at various temperatures, and to super-heated steam. Some properties of montmorillonite clay are briefly reviewed, and comparisons are drawn between empirical data and the predicted behavior of the montmorillonite known to be present in the samples. PROPERTIES OF MONTMORILLONIT E CLAY Water initially adsorbs on dry N a -montmorillonite clay in discrete layers in the interlaminar space between clal platelets. The platelet spacing, which is 9.6 A (angstroms) for a dehydrated clay, has been observed to expand in discrete steps to 12.4, 15.5, 18.4 and 21.4 A spacings, indicating the formation of four discrete layers of regularly oriented water molecules.' The first two layers are easily formed by hydrating a dry sample to equilibrium in an atmosphere with carefully controlled humidity. The formation of the higher layers is more difficult. The usual X-ray diffraction patterns of the more highly hydrated samples indicate a gradual increase in the average spacing betwcen 15.5 and 19.2 A, followed by a discontinuous expansion to 31 A when the weight ratio of water to dry clay is between 0.5 and 1.2.' Platelet expansion above 31 A proceeds monotonically as the moisture is increased and no regular arrangement of the platelets ib observed. Water-sensitivity in sedimentary rocks is usually associated with Na-montmorillonite clay when it is in the noncrystal-line state. Mering3 found that the average lattice spacing of sodium montmorillonite hydrated at 68 F and 70 per cent relative humidity was 15.5 A, and that the spacing, at 92 per cent humidity was 16.5 A. The water adsorbed at the higher humidity has the same free energy as liquid water at 65.6 F. Kolaian and Low' used a tensiometer to measure the thermodynamic properties of water in diffuse suspensions of montmorillonite clays relative to pure water. They observed that water in suspensions as dilute as 6 per cent clay became partially oriented when left undisturbed. The bonding associated with this orientation was not extensive because the free energy difference between the water in suspension and pure water was only a few millicalories per mole. They also found that the measured free energy difference decreased rapidly with temperature and became negligible above 100 F. This evidence indicates that montmorillonites contained in sedimentary rocks would dehydrate to a crystalline structure when exposed to superheated steam, and that the rock permeability measured with steam would be equivalent to that measured with air. The effect of elevated temperatures on the swelline of montmorillonite clays in aqueous suspensions has not been investigated. The Gouy-Chapman diffuse-ion-layer theory has been used to predict the swelling pressure of clay suspensions in dilute salt solutions at room temperature with reasonable success. theory also correctly predicts the direction of the thermal response of Na-mont-morillonite swelling pressures in dilute salt suspensions, 9 Over the temperature range of 33 to 68 F, an increase in

Jan 1, 1966

By J. B. Conway

Stress-vuptuve data for several of- the refractory metals are frequently found to yield a linear relationship between the Larson-Miller parameter and the logarithm of the applied stress. In such cases linear stress-rupture isotherms result with slopes bearing a definite relationship to the temperature. It also follows that the stress to produce rupture in a certain period of time will be linear in temperature. Data for several refractory metals have been reviewed and excellent linearity is shown in this type of isochronal plot. In addition, the af ore - mentioned lineavity leads to a linear relation between the log of the stress to produce rupture in a certain time and the homologous temperature. This has been illustrated for the Group VI-A metals, tungsten and molybdenum. EXTENSIVE use has been made of the Larson-Miller' parameter in the interpolation and extrapolation of stress-rupture and creep data. In those cases where this particular parametric approach is applicable a convenient and fairly straightforward procedure is made available for the correlation of experimental stress-rupture data. It is quite common to employ this parameter in the form of a master rupture plot in which the parameter, T(C + log tr), is expressed as a function of log stress. In many cases this functional relationship in log stress is linear within acceptable accuracy and hence the following relation results: where P is the parameter, C is the Larson-Miller constant, T is the absolute temperature, t~ is the rupture time, a is the stress, and a and b are constants. Examples of such a relationship are contained in the work of Green, Smith, and 01son2 dealing with high-temperature rupture behavior of molybdenum and in the work of Green' dealing with the high-temperature behavior of tungsten. In addition, pugh4 has shown a similar linearity for some fairly low-temperature data for molybdenum. It can be shown that when the relationship in Eq. [I] is exhibited certain generalizations can be made concerning the form of the stress-rupture isotherms. For example, rearranging yields: For a given material (constant C) at a given temperature the first term on the right-hand side of Eq. [2] is a constant and hence this equation defines a straight line when log stress is plotted as a function of log-rupture time. This is recognized as the standard form usually employed in this type of data presentation. Such linearity then suggests the linear form of the Larson-Miller parameter. Or, in other words, the linear parametric relationship in Eq. [2] results only when the stress-rupture data are linear on a log-log plot of stress vs rupture time. Another interesting observation can be made in regard to Eq. [2]. It can be noted that the slope of the stress-rupture isotherms is given by - T/b and hence a direct calculation of the constant b is available. It also follows that since the value of b is the same for all temperatures the slopes of the various isotherms on the log-log stress-rupture plot cannot be the same. Indeed, the existence of the relationship in Eq. [2] precludes a system of parallel lines on this common stress-rupture plot. As a matter of fact it further specifies that in addition to being nonparallel the slope of these isotherms must decrease (i.e., become more negative) with increasing temperature. Such a condition is indeed found to exist in the case of the stress-rupture data reported for molybdenum.' As a corollary to the above, it may be stated that stress-rupture data which do not lead to a linear log-log stress-rupture plot or whose isotherms do not exhibit a decrease in slope as the temperature increases will not yield the linear relationship of Eq. [I]. Applying Eq. [2] to two different temperatures and solving for C yields: Eq. [3] affords a simple and rapid method for calculating the Larson-Miller constant from the log-log stress-rupture plot. The slope of a given linear isotherm is measured and the value of "b" calculated based on Eq. [2] as: slope = - -Tb Then at an abscissa value of 1.0 hr (making log tr in Eq. [3] equal to zero) read the stress corresponding to rupture for two different temperatures. Substitution in [3] yields: A value of the Larson-Miller constant can thus be calculated from a few simple mathematical procedures employing data read directly from the log-log plot of the stress-rupture data. Of course, it is not to be overlooked that the above reasoning has been based on the linear relationship of Eq. [I] being applicable. However, if as mentioned above the log-log plot is

Jan 1, 1967

By J. L. Gillson

Historically, rock deposits and sand deposits of titanium minerals came into production about the same time, although there may be some argument as to what is meant by production. Beach deposits of heavy minerals in India (Figs. 1-4) and Brazil (Figs. 5) were worked for monazite about the turn of century, but as there was then no market for titanium minerals, these were thrown away. The rock rutile deposits at Roseland, Va., Fig. 6, were worked to supply rutile for titanium chemicals and for coloring ceramics long before there was a titanium pigment business. The pigment industry started about the middle twenties, both in Europe and the U. S., and almost simultaneously the rock deposits at Ponte Vedra Beach near Jacksonville, Fla., were worked for titanium content. Since those days, production from both types of deposits has continued to grow at a rapid rate; many deposits of both types have been found, and reserves have grown to very large figures. In total tonnage of reserves, there is no doubt that the rock deposits are far ahead of the sand deposits; nevertheless there is a very large tonnage of commercial sands available. It is the quality of titanium mineral in the sand and the relatively lower costs of operating sand deposits that have kept them abreast, at least in annual tonnage produced, with the rock deposits. The principal titanium mineral used is ilmenite, but as soon as that mineral began to be sought as a titanium ore, it was obvious that there are ilmenites and ilmenites. Textbook ilmenite should have the composition FeOTiO2 and should analyze 52.6 pct TiO2 and 36.8 pct iron as Fe. The Indian ilmenite, for almost a generation the standard ore for manufacturing pigment in the U. S., was found to analyze about 60 pct TiO, and only 24 pct. Fe, and most of the iron is in the ferric condition. The whole process of pigment manufacture in the U. S. was built up on the use of a raw material of that grade, and the American chemical engineers who operate the pigment plants shuddered at the thought of using a rock ilmenite with 45 pct or so of TiO, and nearly 40 pct Fe. Intensive search was made around the world to find other deposits of rich black sand, like the Indian beaches, but although a few were found, there was some objectionable feature about each. A deposit in Senegal, south of Dakar (Fig. 7), was worked for a while, but an organic coating on the grains made attack by acid difficult. Modern practice would have included a scrubbing operation, in a caustic soda bath, to eliminate the organic coating. Brazilian deposits were numerous, but individually small, and shipping from them difficult. Deposits on the east coast of Ceylon had many attractive features, but the ilmenite analyzed only 54 pct TiO2 and could have been used only with a penalty. Sand deposits with 2 pct ilmenite, like those now worked in Florida, would not have been considered commercial ore, even if they had been known at that time. Most rock ilmenites are associated or mixed with hematite or magnetite, which accounts for the lower titanium and higher iron values than in the sand ilmenites. The Norwegians, English, and Germans, with cheap Norwegian rock ore at hand, learned to install in their pigment plants adequate capacity on the black side, as it is calltd, and counterbalanced the extra cost of plant, and larger amount of acid used, by the lower cost of ore. When World War II arrived, two of the largest pigment manufacturers in the U. S. had to learn how to use the Adirondack ilmenite, but one of them very gladly went back to sand ores when the Florida deposits came into large-scale production after the war. The other continues to use Adirondack ilmenite and finds it commercially attractive to do so. Rutile is not a raw material for titanium pigment manufacture by the sulfate process, since it is insoluble in sulfuric acid. In addition to its small consumption in chemicals and ceramics it began to be used in quantity in welding rod coatings. With the outbreak of World War 11, and the tremendous need for welding rods in shipbuilding and other structural steel construction, rutile suddenly became in heavy demand. The sand deposits on the eastern shore of Australia (Fig. 8A) which had been worked in a small way since 1934 were brought into production, and some stream placers in Brazil were worked and rutile concentrates shipped to American

Jan 1, 1960

By Charles H. Grant

Some of the limiting factors relative to explosive crushing of rock and ways to overcome a few of these problems are presented. Relationships between borehole diameters, bench heights, and spacings, along with a review of the influence geometry has on energy as these are changed, are discussed. Efficiency in use of explosives and the decay of energy as it moves through rock and is absorbed and dissipated, is described, along with fragmentation as a function of spacings and energy zoning, etc. Communications are one of the major problems encountered. In an effort to provide a better understanding of the use of explosives, it is necessary to take a little different view of what explosives are, how to look at them as tools to fragment rock, and some of the problems encountered in doing so. First, take the explosive: although there are many factors involved, consider these as being reduced to only two — shock-strain imparted to the rock by the high early development of energy, and the gas effect which is a combination of heat, moles of gas formed, rate of formation of these gases which develop pressures, etc. First, consider shock energy by itself and assume there is no gas effect in the reaction. Fig. 1 illustrates a block or cube of rock, in the center of which is detonated an explosive charge which is 100% shock energy. Tensile slabbing would be seen on the surface and probably the cube of rock would generally hang together even though microcracks were formed. If the situation is reversed and an explosive whch has no shock energy and only gas effect (Fig. 2) is considered, the cube of rock would act as a pressure vessel and contain the pressure from the gas effect until it exceeded the rock-vessel strength; then the rock would break in a few large pieces. If these two kinds of energy are put together and the area of shock-strain around the explosive (Fig. 3) is considered, the two energies will be seen working together to furnish broken rock. The gas effect applies pressure to the microcracks formed from the shock energy to weaken the rock-pressure vessel and propagate these cracks to break the rock apart. It not only will be broken more finely, but will break apart at a lower pressure than the gaseffect case, since the shock energy has first weakened the rock vessel. Although tensile spalling from the shock-strain imparts momentum to the rock, the main source of displacement comes from the gas effect. The term "rock" is being used to mean any material to be blasted. These energies are absorbed by the rock in different ways. First, classify rock into two main categories: "elastic" and "plastic-acting." Elastic rock should be thought of as rock which can transmit a shock wave and is high in compressive strength, such as granite or quartzite. Since this elastic rock transmits a shock wave well, it makes good use of the shock energy from the explosive-forming cracks, etc., for the gas effect to work on. Plastic-acting rocks are rock masses which are relatively low in compressive strength and absorb shock energy at a much faster rate, thereby making poor use of the shock energy by not developing as extensive a cracked zone for the gas effect to work on. Rocks of this type are generally softer materials such as some limestones, sandstones, and porphyries. For the most part, the shockenergy part of the explosive reaction is wasted in plastic-acting rock, leaving most of the work to the gas effect. Since the ratio of gas effect to shock energy is different in different explosives, it is easy to understand why some explosives perform well in elastic rock and poorly in plastic-acting rock, and vice versa. Some of the most difficult blasting situations arise when mixtures of plastic-acting and elastic rock are encountered (Fig. 4). Fig. 4 shows an example of granite boulders cemented together with something like a decomposed quartz monzonite which is plastic-acting. The elastic granite boulders will transmit the shock-strain within itself, but when this shock tries to move through the monzonite to the next boulder, its intensity is absorbed by the monzonite and little shock-strain is placed on the adjoining boulder. In addition to this loss by absorbtion, shock reflection at the surface of the boulder will effect tensile spalling. The net effect is poor breakage of the boulders which do not have drillholes in them as they simply will be popped out with the muck. The same is true (Fig. 5) when layers and joints make

Jan 1, 1970

By J. C. Martin

A theoretical analysis of steam stimulation is presented for single sands. The analysis includes the effect of steam production and most of the effects of heat conduction. The results show the effects of a number of important variables on the performance of an idealized well under steam stimulation. Calculated responses are presented which indicate the effects of steam production, amount of steam injected, water production, formation thickness and formation damage. Results indicate that steam production can cause large reductions in the heat contained in the formation. This effect can be eliminated by drawdown control. Water production reduces the amount of oil produced during stimulation. The optimum amount of steam to inject depends on economic factors as well as the well response. In many cases, the increased temperature resulting from stimulation reduces oil viscosity near the well sufficiently to overcome the effects of formation damage even if the damage is not removed during steam injection. Calculated responses for thin sands are more favorable than anticipated. INTRODUCTION Little has been published on the theory of steam stimulation'-' despite the interest it has created and the wide variation in well responses. The results of the present analysis provide an insight into steam stimulation, and the methods employed provide a foundation for future work. Analyses presented in Refs. 1 and 2 are very limited and apply to gravity drainage conditions. Ref. 3 contains an analysis similar to the one presented here. The idealized models used and the assumptions made in Ref. 3 are different from those used in this paper. The analysis assumes that after steam injection has heated a small portion of the volume within the radius of drainage of a single uniform sand, a shut-in soaking period is allowed before returning the well to production. The effects of gravity, capillarity, transient pressure and water-sensitive sands are neglected. The injection and soaking times are assumed short compared to the stimulated production time. The initial temperature is assumed uniform; thus, the results apply primarily to first-cycle stimulation. The effects of gas production other than steam are neglected, and the water-oil ratio during production is assumed constant. Steam stimulation involves the simultaneous variation of the temperature, pressure and saturations. General mathematical equations for these variations are complicated and can be very difficult to solve. Simplified equations based on idealized models are used to reduce the mathematics sufficiently to allow approximate solutions to be obtained. DISCUSSION INJECTION An idealized model for which heat conduction is neglected is used to represent the behavior of a well during steam injection. The mathematics for this model is presented in Appendix A which also contains an approximate solution for the behavior of the no-conduction model. SOAKING During soaking, the well is shut in. Only the temperature, pressure and saturation distributions at the end of soaking are needed in the analysis. During soaking the heat is considered to be conducted in a uniform medium from an initially uniformly-heated circular cylinder confined to the producing interval. At the end of soaking the saturations and pressures are assumed to correspond to the cold zone. Analysis of the heat flow during soaking is included in the next section. The radius of the heated cylinder is calculated from the following heat balance (for constant quality steam injection). At the end of the soaking period it is assumed that little or no free gas is present near the well, and that the soaking period has been sufficiently long that the steam zone has had time to expand and the steam has condensed. The condition where there is no soaking is considered in the next section. PRODUCTION In this section, an approximate method is presented for solving the equations of heat and fluid flow associated with the production of oil and water during steam stimulation. Where initial pressure drawdowns are sufficient to cause steam to flow into the wellbore, steam production is assumed to occur within a short initial adjustment period (Appendix B). The production practices followed soon after the well is returned to production can have a large influence on the amount of oil produced during the stimulation cycle. Under most conditions, there is a period of time in which some or all of the water in the heated zone is converted into steam and produced. This flashing of hot water is caused by the pressure in the heated zone dropping below

By E. P. Burtchaell

A method is presented for evaluating the effect of gravity drive upon the reservoir performance of a high relief pool. Conventional forms of reservoir analysis do not consider the alterations in the basic material balance data caused by gravity segregation of reservoir fluids. A procedure is outlined for structurally weighting physical and chemical data for use in the material balance equation. It is demonstrated how actual pool performance data can be utilized to evaluate the future reservoir performance of a gravity drive pool. INTRODUCTION Conventional reservoir engineering. procedure is inadequate for the analysis of an oil pool which has considerable structural relief, steep dips, and good permeability development. In, pools of this type, gravity drainage has an important part in the movement of oil to the wells and the effects of gravity on the overall pool performance should be included in any analysis of reservoir behavior. Many engineers have the opinion that the force of gravity in the movement of oil is not important until the later life of a pool.' Probably the basis for this belief is that gravitational effects may not be readily discernible until a pool is nearing depletion. This would be especially true for pools not having a high degree of structural relief and permeability development. Actually the effects of gravitational forces are at a maximum when the pool pressure is high, for during this period the hydrostatic head of the oil column is at a maximum and the viscosity of the oil is at a minimum. Oil recoveries from pools having favorable gravity drive characteristics may equal or even exceed recoveries which might be expected from water displacement. Field evidence indicates that in some reservoirs gravity drive has resulted in recoveries greater than that which could have been expected from gas expansion or water drive.'.3 Unfortunately, the possible effects of gravity drive on pool performance have been underestimated and other reasons have been sought to explain the high recoveries obtained. There are unquestionably many reservoirs to which the principles of gravity drainage can be effectively applied. It is the purpose of this paper to illustrate one method whereby gravity drive is included in the reservoir analysis of an oil pool. A hypothetical pool, typical of many California reservoirs, is used as an example. As used in this paper, "gravity drive" is defined as the overall effect of gravitational influences on the recovery of petroleum from the reservoir; "gravitational segregation" as the gravity separation of oil and gas within the reservoir; and "gravity drainage" as the downward movement of oil as caused by the force of gravity. SAND VOLUME DATA Fig. 1 presents a structural contour map of the pool under study. Maximum closure is 1950 feet with dips on the south flank approaching 45". The original gas-oil interface was set at -5200 feet. Average thickness of the producing sand was 200 feet. For use in subsequent calculations ill this paper, the pool was subdivided into 100-foot vertical increments and the sand-volume content of each increment was obtained. If the gross sand thickness is small, under 100 feet, the sand-volume content can be obtained by superimposing an isopachous map upon a structural contour map and planimetering the average thickness of each 100-foot increment. For sand thicknesses over 100 feet, one approacli would be to construct a sufficient number of cross-sections of the pool from which the weighted sand-volume of each 100-foot increment could be obtained. Variations in the sand body with depth, as determined by core data, can also be included in the above process. Table I presents a summary of sand-volume calculations, core data, and the original distribution of reservoir hydrocarbons in the pool. Fig. 2 illustrates the structural distribution of the sand-volume content. A total of 171,398 acre-feet is contained within the productive limits of the pool. Assuming an average porosity of 25% and an interstitial water content of 20%, the original hydrocarbon content was computed to be 227,075,000 barrels. DEPTH-PRESSURE DATA The determination of the initial vertical pressure arrangement in the pool is necessary for PVT and material balance calculations. Whenever sufficient data are available, a plot of pressure versus subsea depth of measurement should be made. From this plot a representative fluid pressure gradient can be established. Lacking sufficient initial pressure data, an initial pressure gradient may he estimated or calculated from avail-

Jan 1, 1949

By E. P. Burtchaell

A method is presented for evaluating the effect of gravity drive upon the reservoir performance of a high relief pool. Conventional forms of reservoir analysis do not consider the alterations in the basic material balance data caused by gravity segregation of reservoir fluids. A procedure is outlined for structurally weighting physical and chemical data for use in the material balance equation. It is demonstrated how actual pool performance data can be utilized to evaluate the future reservoir performance of a gravity drive pool. INTRODUCTION Conventional reservoir engineering. procedure is inadequate for the analysis of an oil pool which has considerable structural relief, steep dips, and good permeability development. In, pools of this type, gravity drainage has an important part in the movement of oil to the wells and the effects of gravity on the overall pool performance should be included in any analysis of reservoir behavior. Many engineers have the opinion that the force of gravity in the movement of oil is not important until the later life of a pool.' Probably the basis for this belief is that gravitational effects may not be readily discernible until a pool is nearing depletion. This would be especially true for pools not having a high degree of structural relief and permeability development. Actually the effects of gravitational forces are at a maximum when the pool pressure is high, for during this period the hydrostatic head of the oil column is at a maximum and the viscosity of the oil is at a minimum. Oil recoveries from pools having favorable gravity drive characteristics may equal or even exceed recoveries which might be expected from water displacement. Field evidence indicates that in some reservoirs gravity drive has resulted in recoveries greater than that which could have been expected from gas expansion or water drive.'.3 Unfortunately, the possible effects of gravity drive on pool performance have been underestimated and other reasons have been sought to explain the high recoveries obtained. There are unquestionably many reservoirs to which the principles of gravity drainage can be effectively applied. It is the purpose of this paper to illustrate one method whereby gravity drive is included in the reservoir analysis of an oil pool. A hypothetical pool, typical of many California reservoirs, is used as an example. As used in this paper, "gravity drive" is defined as the overall effect of gravitational influences on the recovery of petroleum from the reservoir; "gravitational segregation" as the gravity separation of oil and gas within the reservoir; and "gravity drainage" as the downward movement of oil as caused by the force of gravity. SAND VOLUME DATA Fig. 1 presents a structural contour map of the pool under study. Maximum closure is 1950 feet with dips on the south flank approaching 45". The original gas-oil interface was set at -5200 feet. Average thickness of the producing sand was 200 feet. For use in subsequent calculations ill this paper, the pool was subdivided into 100-foot vertical increments and the sand-volume content of each increment was obtained. If the gross sand thickness is small, under 100 feet, the sand-volume content can be obtained by superimposing an isopachous map upon a structural contour map and planimetering the average thickness of each 100-foot increment. For sand thicknesses over 100 feet, one approacli would be to construct a sufficient number of cross-sections of the pool from which the weighted sand-volume of each 100-foot increment could be obtained. Variations in the sand body with depth, as determined by core data, can also be included in the above process. Table I presents a summary of sand-volume calculations, core data, and the original distribution of reservoir hydrocarbons in the pool. Fig. 2 illustrates the structural distribution of the sand-volume content. A total of 171,398 acre-feet is contained within the productive limits of the pool. Assuming an average porosity of 25% and an interstitial water content of 20%, the original hydrocarbon content was computed to be 227,075,000 barrels. DEPTH-PRESSURE DATA The determination of the initial vertical pressure arrangement in the pool is necessary for PVT and material balance calculations. Whenever sufficient data are available, a plot of pressure versus subsea depth of measurement should be made. From this plot a representative fluid pressure gradient can be established. Lacking sufficient initial pressure data, an initial pressure gradient may he estimated or calculated from avail-

Jan 1, 1949

By G. F. Bolling

STUDIES of grain boundary migration in zone-refined metals have all shown that the rate of migration is greatly reduced by small added solute concentrations. However, it is apparent that a difference exists between boundary migration during normal grain growth and single boundaries migrating in a bicrystal to consume a substructure. To effect the same reduction in velocity in the two cases, much more solute is required for grain growth than for the single boundary experiments. One case is available for direct comparison; both Bolling and winegardl and Aust and utter' added silver and gold to zone-refined lead to study grain growth and single boundary migration, respectively. For comparable reductions in migration rates, about 500 times more solute was required to retard grain growth than to retard the single boundaries. A reason for this difference is suggested here. The rate of grain boundary migration is dependent on solute concentration and must therefore also depend on the solute distribution; i.e., regions of higher solute concentration encountered by a moving boundary must produce greater retardation and thus could determine any observed rate. A dislocation substructure can be the source of a nonuniform solute distribution since it can attract an excess concentration of certain solutes. In fact, it is probable that the solutes which impede grain boundary migration most would segregate most severely to a substructure for the same reasons. Thus a dislocation substructure present in a crystal being consumed could locally magnify the concentration of solute confronting an advancing grain boundary. In the single boundary experiments a low-angle substructure, within single crystals obtained by growth from the melt, was used to provide the driving force to move a grain boundary; in grain growth, no substructure of this magnitude was present. The increased solute concentration at subboundaries should be given approximately by C, = G e c,/kT, where t, is a binding energy and CO the bulk concentration. To account for the difference between the two experiments in the Pb-Ag and Pb-Au cases, C, must be the concentration impeding the single boundary migration, and a value of t, = 0.25 ev is necessary. This is reasonable, even though calculation on a purely elastic basis gives t, = 0.12 ev. because electronic effects must enter for silver and gold in lead. The compound AuPbz forms3 and the metastable compound AgrPb has been reported to nucleate at dislocations prior to the formation of the stable, silver-rich phase.4 Other observations support the hypothesis that a magnified solute concentration impedes the single boundary migration. For example, some crystals were grown by Aust and Rutter at concentrations of ~ 0.1 wt pct Sn and 2 x X at. pct Ag or Au which exhibited a cellular substructure, and in these crystals no boundary migration was observed. It is therefore evident that the higher concentrations at cell boundaries drastically inhibited migration. Inclusions would not have been responsible for this inhibition since according to recent work on cellular segregation,5 no second phase should have occurred in the segregated regions at the cell boundaries for the conditions of growth used, at least in the Pb-Sn system. In the purest lead, only the "special" boundaries observed by Aust and Rutter gave rise to the same activation energy as that obtained in grain growth. It is reasonable to suppose that the structure of special boundaries does not favor segregation at low concentrations and thus solute, or an inhomogeneity in its distribution, would have no effect. Random boundaries, on the other hand, are affected by solute and the substructure would enhance residual concentrations in the zone-refined lead, leading to a higher activation energy. It is clear, even without a detailed theory, that the apparent activation energies and exact solute dependence in the two experiments must be different as long as the non-uniform solute distribution produced by the substructure is important. Recrystallization experiments should also be susceptible to the same kind of local segregation at subboundaries or disloca tion cell walls; a suggestion similar to this has been made by Leslie et al.' Following the arguments presented here, the effects of a given solute concentration would be like those observed by Aust and Rutter if segregation occurred, and like those of grain growth otherwise. This work was partially supported by the Air Force Office of Scientific Research; Contract AF-49(638)-1029.

Jan 1, 1962

By Raymond D. Sloan

During 1944, substantial gains were recorded in practically every phase of the petroleum industry in Oklahoma. With the spotlight of activity focused on other states during the more recent years, the production momentum that was achieved in Oklahoma through the discovery and development of such outstanding pools as Oklahoma City, Fitts. and major pools in the Seminole area during the late 1920's and early 1930's was practically spent by the end of 1943. However, with much of the industry's exploratory efforts greatly reduced in Illinois, Indiana and Kentucky, the strong demand for Mid-Continent crude and the optimism created by some discoveries in the state toward the end of 1943, Oklahoma has again become the recipient of much activity and interest, with its 1944 drilling activity, production and refinery runs to stills registering substantial gains over the preceding year. Development and Exploration Since the discovery of the West Edmond pool in April of 1943, with the substquent drilling and development boom, the scene of exploratory activity has shifted from the central. south and east portions of the state to the general trend of the . Granite Ridge, where leasillg and wild-catting were greatly activated within a wide radius of this high subsurface feature. Leasing activity, however, jumped the confines of the Granite Ridge trend and extended into all of the northwestern counties in the state. Seismograph activity at once began following and keeping pace with this shift in the leasing and exploration locale, by the concentration of a large number of seismograph crews in the area. At one time during the year,35 crews were concentrated in Oklahoma, the majority being west of the Granite Ridge and extending into the northwestern counties. To illustrate the increase in geophysical work done in the state during the year, records indicate that 377 crew months were worked in 1944, which is a 21 per cent increase over the 311.5 crew months activated in 1943. With the discovery in 1943 of several encouraging prospects and the finding of West Edmond as an incentive, drilling operations increased some 54.3 per cent, for a total of 1986 completions during the year. This is compared with a figure of 1287 for wells drilled in 1943, an increase of 699 wells. The industry, with a total of 1064 oil producers, enjoyed a success percentage of 53.6 per cent. Gas wells completed were 223, while 699 dry holes were drilled. In 1943, completions included 587 oil wells, 127 gas wells, and 573 dry holes. The number of oil producers completed during the Year was almost double the numher of wells in 1943. Of the total drilling wells completed in the state, 350, or 17.6 per cent, were wildcat operations—an increase of 5.1 per cent over the 194.3 total of 333. The wildcat success percentage was 13.4 per cent, 47 successful wells being completed for an average initial potential of 160 bbl. In the state, 23 gas wells were completed with an average initial production of

Jan 1, 1945

By Charles H. Jacoby, Stanley J. LeFond

Salt, or halite, has a long and most varied history. While we know the Chinese were producing salt as early as 3000 B.C., the first written reference to salt appears in the book of Job recorded about 2250 B.C., which reads: "Can nothing which is unsavory be eaten without salt?" We do not know when man first used or realized that he needed salt. Perhaps one of our early Eolithic ancestors noted a piece of salt shining along the shore of a salt lake or a bay. He may have been attracted by its shining luster and tasted it. He found that it had a tart, zesty, distinctive flavor and perhaps chewing a large piece, became ill. However, by experimentation he soon learned that taken in the proper proportions salt was a very pleasant additive to his food. He may have noticed, too, that it increased his feeling of well-being. Thus, when the curtain of recorded history rises, we find man using salt for his health's sake, seasoning his food with it, feeding it to his animals, and using it in many superstitious and religious ceremonies. These uses, however, are a far cry from the uses for salt today. The first attempts of white man to make salt in continental United States were reported in the year 1614, while the first commercial production was in 1753 from the Kanawha licks. Practically all this salt was for human consumption, preserving food, and curing hides. Prior to the coming of the white man, Indians are known to have made salt from salt springs such as those that existed at Avery Island, LA, Charleston, WV, Saltville, VA, and Onondaga, NY. In 1862 the first rock salt was mined in the US from the Avery Island salt dome. Almost immediately thereafter, rock salt was mined at Saltville, VA and then at Retsof, NY in 1885. Of the more than 39 million tons produced annually in the United States, about 58% or 23 million tons are consumed by the chemical industry in the production of chlorine, caustic soda, hydrochloric acid, sodium metal, and some 30 other basic chemicals. These basic chemicals, in turn, are used in the preparation of approximately 14,000 chemicals which range from soap and detergents, to such chlorinated hydrocarbons as DDT, BHC, carbon tetrachloride, etc. Utilization of cavities created in salt beds and domes has grown rapidly since 1947 until now the waste salt is creating an ecological problem. The uses for both dry- and solution-mined cavities range from the storage of liquid hydrocarbons to containerized storage of toxic wastes, from compressed air for the peak shaving of power to storage of nuclear wastes. Geology Mineralogy Properties: Because of its simple structure, halite, the mineralogical name for salt, was the first structure to be analyzed by X-rays. It has the following properties: Formula: NaCl (Na-39.34%. Cl2-60.66% ) Crystallography: isometric, hexoctahedral, 4/m 32/m Space group: Fm3m A0: 5.627 kX Cell contents: Na4CI4 Habit: usually cubic, rarely octahedral, massive, granular to compact Physical properties: Refractive index: 1.554 Twinning: observed on {111} Cleavage: {001} perfect Fracture: conchoidal, brittle

Jan 1, 1983

By D. C. Shelton

This paper discusses the metallurgical testing procedures and their applications at the laboratories and mills of Pima Mining Co. The author shows, using discussions and case histories, that routine sampling and evaluation of daily and monthly data can be as valuable as thorough laboratory investigations and mill test work. A great deal of valuable information can be made available this way. This paper discusses laboratory and mill metal-lurgical testing procedures and their applications at Pima Mining Co., located about 25 miles southwest of Tuscon, Ariz. The Company, incorporated in 1951 (the year the orebody was found) in California to operate the Pima mine, is jointly owned by Cyprus Mines Corp., Utah Contruction and Mining Co., and Union Oil Co. Milling started in December 1956. The main Pima orebody is a contact metamorphic vein of copper-bearing hornfels with an average dip of 45° to the south with an east-west strike. The hanging and footwalls are quartzitic pyroclastics (arkosite) containing some sulfides. Barren igneous intrusions are also present. Conglomerates and alluvial wash cover the deposit to a depth averaging about 200 ft. The principal copper mineral is chal-copyrite. Native copper, chalcocite, and minor amounts of chrysocolla and other copper minerals are also present, together with sphalerite and some molybdenite. Generally, it has been noted that the ratio of chalcocite to chalcopyrite is higher in the lower grade ores, while as the grade increases, there are only minor amounts of chalcocite. Open pit mining is employed at Pima, using both trucks and an inclined skiphoist system. A detailed description of Pima Mining Co. operations was presented by Spaulding et all. More recently another orebody to the north and east of the present pit has been discovered and will be placed in operation within a few years. This ore is of a porphyritic rather than a lode nature since values are disseminated in both igneous and metamor- phosed sedimentary rocks. The new orebody is expected to be harder and cleaner than the present deposit. The views expressed in this article are those of the author and do not necessarily reflect those of Pima Mining Co. nor of the profession in general. PlMA MILL The following outline of milling practice is presented to furnish a background for later chapters of this report wherein specific problems will be detailed and analyzed. Run of mine ore is crushed in three stages, using conventional equipment to 85% minus 1/2-in. for feed to two 10 x l6-ft rod mills operating in open circuit. Each rod mill discharge is split between two 10% x 13-ft ball mills in closed circuit with three 20-in. cyclones. In addition, a 7 x 12-ft ball mill with one 20-in. cyclone receives part of the discharge from one of the rod mills. This equipment was manufactured by Allis Chalmers and Equipment Engineers. The cyclone overflows are combined, sampled and, after joining the regrind cyclone overflow, are distributed into 12 10-cell Fagergren 66-in. flotation machines. The primary rougher concentrate produced

Jan 1, 1965

By D. O. Wyble, L. O. Bacon

THERE has been considerable speculation among mining geologists and mining men in general as to the relative merits of gravity methods in iron-ore exploration. Most of the investigations which have been carried out in recent years have been done by mining companies, and few if any of the results have been published. Three gravity surveys have been made in the Iron River-Crystal Falls area,' " one by the U. S. Bureau of Mines, with inconclusive results, and the other two by Radar Exploration Co. for the Cleveland-Cliffs and the M. A. Hanna companies, with results not known to the writers. Both the last-mentioned surveys were detailed investigations, the stations being spaced as close as 10 ft along traverses,' and were made to determine the feasibility of locating iron ore by gravitational methods. Because of the presence of a large body of ore already extensively drilled, Dr. Harold L. James of the U. S. Geological Survey, Iron River, Mich., suggested that a further test of gravitational methods of exploration be made in the Round Lake area of Iron County, see Figs. 1 and 2. This survey indicated a considerable regional gradient and led to a study of the surrounding gravity field and its relation to the major structural features of the syncline within which the iron formation lies. The southwestern part of Iron County presents a series of hills and hollows elongated in a roughly north-south direction. The bedrock topography is of pre-glacial origin. Relief is moderate; a maximum elevation difference of approximately 350 ft was observed during the survey. Major drainage is dendritic with the larger streams: the Brule to the south, the Paint to the north, and the Iron in the central part. Hills are thickly grown with hard- woods, and lowland areas, not under cultivation, are usually covered by second-growth softwoods. The area covered in this paper includes the southern half of Iron County, Mich., with a deep synclinal basin occupying the central part of the area, and the southeast corner of Gogebic County, immediately to the west of Iron County. The upper Huronian iron formation, slates, and graywackes which form the synclinal basin rest upon a greenstone basement. The basin has not been completely outlined by exposures, drill records or other means, as outcrops are scarce and the thick mantle of glacial drift makes geological investigations extremely difficult. Glacial drift varies in depth up to 300 ft or more. The drift is usually thickest under the hills and is thinnest in the depressions and along drainage courses where most of the bedrock exposures occur. The area over which gravity investigations were made is almost, entirely covered by glacial material. Bedrock of the basin consists of a complexly folded series of iron formation, slates, and graywackes. One of the series of slates has a high magnetic susceptibility due to the fine-grained magnetite it contains. This formation can be detected readily. by magnetic methods and provides a marker horizon which can be easily followed. The magnetic slates are stratigraphically above the iron formation, and much of the geological interpretation of the area is based upon the magnetic anomalies they produce.

Jan 1, 1953

By L. O. Bacon, D. O. Wyble

THERE has been considerable speculation among mining geologists and mining men in general as to the relative merits of gravity methods in iron-ore exploration. Most of the investigations which have been carried out in recent years have been done by mining companies, and few if any of the results have been published. Three gravity surveys have been made in the Iron River-Crystal Falls area,' " one by the U. S. Bureau of Mines, with inconclusive results, and the other two by Radar Exploration Co. for the Cleveland-Cliffs and the M. A. Hanna companies, with results not known to the writers. Both the last-mentioned surveys were detailed investigations, the stations being spaced as close as 10 ft along traverses,' and were made to determine the feasibility of locating iron ore by gravitational methods. Because of the presence of a large body of ore already extensively drilled, Dr. Harold L. James of the U. S. Geological Survey, Iron River, Mich., suggested that a further test of gravitational methods of exploration be made in the Round Lake area of Iron County, see Figs. 1 and 2. This survey indicated a considerable regional gradient and led to a study of the surrounding gravity field and its relation to the major structural features of the syncline within which the iron formation lies. The southwestern part of Iron County presents a series of hills and hollows elongated in a roughly north-south direction. The bedrock topography is of pre-glacial origin. Relief is moderate; a maximum elevation difference of approximately 350 ft was observed during the survey. Major drainage is dendritic with the larger streams: the Brule to the south, the Paint to the north, and the Iron in the central part. Hills are thickly grown with hard- woods, and lowland areas, not under cultivation, are usually covered by second-growth softwoods. The area covered in this paper includes the southern half of Iron County, Mich., with a deep synclinal basin occupying the central part of the area, and the southeast corner of Gogebic County, immediately to the west of Iron County. The upper Huronian iron formation, slates, and graywackes which form the synclinal basin rest upon a greenstone basement. The basin has not been completely outlined by exposures, drill records or other means, as outcrops are scarce and the thick mantle of glacial drift makes geological investigations extremely difficult. Glacial drift varies in depth up to 300 ft or more. The drift is usually thickest under the hills and is thinnest in the depressions and along drainage courses where most of the bedrock exposures occur. The area over which gravity investigations were made is almost, entirely covered by glacial material. Bedrock of the basin consists of a complexly folded series of iron formation, slates, and graywackes. One of the series of slates has a high magnetic susceptibility due to the fine-grained magnetite it contains. This formation can be detected readily. by magnetic methods and provides a marker horizon which can be easily followed. The magnetic slates are stratigraphically above the iron formation, and much of the geological interpretation of the area is based upon the magnetic anomalies they produce.

Jan 1, 1953

By Howard I. Epstein, John R. Buzek

Thickeners are simply large tanks, usually circular in shape, which are designed to allow settling of solids and to operate with continuous overflow of clear water and underflow of thick pulp. The dimensions of the thickener are usually such that dewatering of very fine pulps may be accomplished while still overflowing clear water. Some thickeners such as the Center, Hardinge and Hydrotator types combine thickening with filtering2 while others such as the Dorr type are pure thickeners. l .2 , 3 A schematic diagram of the traction type Dorr thickener is shown in [Fig 1]. This type is appropriate for tanks over 15 m (50 ft) in diameter. This tank employs a rotating raking mechanism which moves the settled material toward the central discharge. For this and other thickeners, it is common to have a shallow conical tank bottom in order to conform to the geometry of the raking mechanism, and it is often desirable to elevate the tank for ease of access to the product. When the tank does not rest on the ground, the forces resisted by the cone are large, and thick plates must be employed. The fabrication of these tanks requires temporary supports in order to erect the cone. A flat-bottomed tank could also be used because the settled material would soon form a hardened conical surface. However, because of the presence of large bending forces, even larger plate thicknesses are required than for the conical bottom. Significant cost savings often can be realized by the use of a scalloped-bottomed tank such as the one partially shown in [Fig. 2]. The particular scalloped bottom discussed in this paper employs radial beams forming the outline of the cone-shaped bottom. These beams are supported directly by columns. Cone segments are hung between adjacent beams. The exact geometry of these segments depends upon the cone angle and radius, the number of radial beams, and their inclination. The geometry is chosen to satisfy certain clearance restraints and to utilize the material as efficiently as possible. The resulting thickness of these segments is significantly less than that of the equivalent plate for the tank with a conical bottom. This result, along with the simpler fabrication procedures required, accounts for the cost savings associated with this design. The raking mechanism employed may be the same as for the conventional conical bottom since the settled material soon forms a conical surface. Determination of the internal force mechanism for the scalloped bottom leads to designs that utilized material efficiently and thus maximize the cost savings. The complicated geometry of these bottoms along with the difficulty in analyzing the structure are factors which may have limited the use of scalloped-bottomed tanks to date. When such tanks have been built, the uncertainties associated with the internal forces have led to designs that are somewhat inefficient. In this paper, equations relating the geometric parameters are presented along with simplified closed-form solutions for the internal forces in the cone segments, from which the loads applied to the beams and the loads carried to the cylindrical tank shell can be deduced. An example is presented to show the magnitude of the savings which may be realized with this configuration.

Jan 1, 1979

By D. B. Jugle, J. B. Darby

The equilibrium solubility limits of the transition elements Ti, V, Cr, Fe, and Co in liquid tin were determined in the temperature range from 827" to 1211°K. Since the equilibrium concentration of Ti, V, or Cr in liquid tin is moderately dilute in the temperature range investigated, the solubility data were employed to estimate the partial molar enthalpy and the partial molar excess entropy of solution for the three solutes in liquid tin. The reference state s for titanium or vanadium were selected relative to the solute in an intermetallic compound. The thermodynamic quantities for chromium were calculated relative to pure chromium. RECENT experiments1 have shown that the rate of solution of several transition elements in liquid aluminum can be qualitatively predicted from a knowledge of the temperature dependence of the solvent-rich liquidus. In order to extend the analysis to binary tin systems,' it was necessary to know the equilibrium solubility of several of the first-long-period transition elements in liquid tin. Since solubility data for the tin-rich portion of binary systems are meager, the present investigation was undertaken to determine the equilibrium solubility limit of Ti, V, Cr, Fe, and Co in liquid tin in the temperature range from 850" to 1200°K. EXPERIMENTAL PROCEDURE A useful technique3 to determine the equilibrium solubility of a solute in a liquid-metal solvent consists essentially of placing a pure solute in contact with a pure solvent and allowing sufficient time for equilibrium to be attained at the temperature of interest. Subsequently, the solvent is removed and the equilibrium solute concentration in the solvent is determined by an appropriate analytical procedure. The technique can be applied very successfully to relatively simple systems such as the copper-germanium system.3 However, in many binary systems of transition elements with tin, several intermediate phases are known to exist and precipitation of the phases from solution, in solubility experiments, can lead to an erroneously large solubility. The difficulty was avoided in the present work by equilibration of the most solvent-rich intermediate phase with the pure solvent over a range of temperatures. The compounds employed in this investigation, and the temperature range over which each compound is in equilibrium with liquid tin are listed in Table I. No stable intermediate phases are reported in the chromium-tin system4 and, therefore, pure chromium was utilized as the solute. The stoichiometric compounds were prepared by arc-melting on a water-cooled copper hearth in a helium-argon atmosphere. The elemental tin employed in.this investigation was 99.998 pct pure, and typical lot analyses of the transition elements were reported elsewhere.' A sample of an appropriate solute, in the form of a button and in sufficient quantity to exceed the equilibrium solubility, and the pure tin solvent were placed in a high-purity recrystallized-alumina crucible. The crucible and contents were placed in a horizontal furnace under a high vacuum (10-6 torr) and held at temperature for periods varying between 24 and 72 hr. A water-cooled quench tank, partially filled with diffusion-pump oil, was attached close to one end of the

Jan 1, 1970

By W. Crafts, J. L. Lamont

Secondary hardening in tempering has long been recognized as a typical characteristic of steels containing large amounts of carbide-forming alloys. These steels, when quenched and tempered, tend to soften somewhat after tempering at low temperatures, and to reharden at intermediate tempering temperatures before finally softening to low hardness. This behavior in tempering has been studied by many investigators, chiefly with respect to thc secondary hardening of high-speed steels. The initial softening has usually been ascribed to decomposition of martensite and growth of iron carbide particles. The secondary hardening has been explained by formation of fresh martensite from residual austenite, formation of very fine alloy carbide particles and by precipitation hardening of metallic compounds in the ferritic matrix. However, factors derived for the calculation of tempered hardness in low-alloy steels1 indicated only a tendency toward retarded softening rather than a discontinuous rehardening. A study was, therefore, made to determine whether fresh martensite from residual austenite and precipitation hardening are essential to rehardening and the degree to which tempered martensite could be rehardened by precipitation of alloy carbides. The mechanism of carbide rehardening was also investigated to determine the nature of the process. The causes of secondary hardening in high-speed steel have received serious consideration for about thirty years. Among the earlier workers Bain and Jeffries2 in 1923 recognized residual austenite as a significant factor, but in addition, emphasized the effect of the formation of alloy carbide particles of "critical" size. They conceived that freshly quenched martensite forms low-alloy iron carbide at low tempering temperatures; with further tempering the iron carbide is then modified by alloying elements that can diffuse most readily at intermediate temperatures (850°F); and that the iron carbides grow in size by coalescence so that the steel tends to lose hardness. At higher tempering temperatures carbide stability rather than alloy availability becomes the controlling influence and in high-speed steel "iron-tungsten carbide is the most stable one and forms to the elimination of the earlier formed carbides. . . . The iron-tungsten carbide particles reach approximately the size for critical dispersion after a short reheat at II00 F." This concept, the formation of alloy carbide nuclei, redissolving of the iron carbide, and diffusion of carbon to the alloy carbide, was restated for vanadium steel in 1932 by Houdremont, Bennek, and Schrader. Subsequent studies have confirmed that iron carbide changes to alloy carbide at 1000 to IIOOOF, but the mechanism of the process has received little consideration.

Jan 1, 1949

By J. M. Hodge, H. M. Reichhold, R. D. Manning

The work reported in this paper represents the first of a series of investigations of the factors governing notch toughness in ferritic materials. This paper is concerned with two of these factors, namely, the effect of ferrite grain size, and the effect of an alloy content of 3.64 pct nickel. Every effort has been made to hold other variables constant in order to isolate the effects of these two. The compositions chosen for study were 0.02 pct carbon in order to eliminate the variable of carbide distribution, one steel being a plain carbon steel and the other alloyed with 3.64 pct nickel. Both steels were fully killed with silicon, without an aluminum addition, so that the variable of deoxidation practice was held constant. Finally, all samples were water quenched from 1200°F and tempered 24 hr at 300°F in order to hold the quench aging variable constant and to decrease the tendency for grain boundary carbide precipitation. The ferrite grain size was varied by heat treatment over the range of A.S.T.M. grain size numbers of about 2 to 6 in each steel so that the effect could be evaluated individually and the notch toughness of each steel could be compared at comparable ferrite grain sizes. Materials and Experimental Procedure MATERIALS The materials for this investigation were obtained from Battelle Memorial Institute as 250 Ib induction melts which were forged into 134 in. square bars and then rolled into 0.6 in. square bars. Both steels were deoxidized with silicon, the aluminum content being held to a minimum. Check analyses of these materials are shown in Table 1. HEAT TREATMENT FOR GRAIN SIZE The grain size was varied by varying both the cooling rate and the austeni- tizing temperatures. The heat treatments used and the corresponding grain size values are tabulated in Table 2. A semicontinuous network of grain boundary carbide was observed in the microstructure of both the plain carbon and nickel steels in the as rolled condition and an additional heat treatment was necessary to eliminate this variable. Therefore, all samples were water quenched from 1200°F and tempered 24 hr at 300°F as a final treatment before testing. This heat treatment served to eliminate to a great extent the grain boundary carbide network and to hold the quench aging effect constant. IMPACT TESTING Standard keyhole Charpy impact tests were machmed after heat treatment. A bath of acetone and dry ice was used for refrigeration of the samples down to temperatures of —94°F (—70°C) and a bath of either methyl-cyclohexane or isopentane, cooled by

Jan 1, 1950

By Pradeep K. Rohatgi, Clyde M. Adams

Dendritic aggregate of ice formed on freezing of aqueous soluitions has been studied. Chlorides of sodium, potassiutn, lithiunz , and hydroget1 were used as solutes. The spacing between ice platelets or den-drites was experimenlally found proportzonal to the square root of freezing time when the freezing rate was constant from beginrting to end of solidification; the constant freezing rates were obtained during freezing of small droplets of aqueous soliitions surrounded by relatively large heat sinks. The transverse growth velocity of the ice platelets is proportional to the square root of the freezing rate. During unidirectional freezing from a constant temperuture chill, the solution at each location is subjected to a spectrum of freezirtg rates. The freezing rate is ini- FREEZING of solutions has been a subject of investigation in many disciplines. Aqueous solutions offer the advantage of transparenty; their study is of special significance due to the increasing interest in freezing processes for desalination. In addition dendritic solidification of aqueous solutions is in many ways analogous to freezing of metallic solutions. Aqueous solutions of most ionic salts freeze with tially low, passes through a maximum, and then decreases until solidificatimz is complete. The den-drite spacing increases linearly with the distance from the chill surface; it is inversely profiortional to the square root of the maximum freezing rate. The dendrite spacings in the two systems (the constanl freezing rate and the varying freezing rate) are equal, when the maximum freezing rate of the varying freezing rate system equals the average freezing vale of the constant freezing rate system. Mass transport in interdendritic liquid duriug solidificatiotz is analyzed; the experimental observations indicate that maximum concentration difference (AC) and supercooling (AT) in the interdendritic liquid are indepexdent of freezing rate. the separation of practically pure ice crystals from the liquid phase; with very few exceptions there is no solid solubility of ionic salts in ice. As an ice crystal grows there is rejection of solute from the moving interface into the liquid. Since the rejected solute moves primarily by diffusion, concentration gradients are established in the liquid. The highest solute concentrations are found in liquid immediately adjacent to liquid-solid interfaces and lowest concentrations farthest from the interface. Two-phase equilibrium obtains only at the solid-liquid interface; at other locations the liquid becomes supercooled because temperature gradients are negligible compared to concentration gradients. This is an immediate consequence of the fact that thermal diffusivities are considerably higher than mass diffusivities.

Jan 1, 1968

By D. E. Peacock, B. Harris

The mechanical behavior of a niobium (columbium)TUNG alloy containing 20 wt pet Ta. 15 wt pet W, and 5 wt pct Mo has been studied in the temperature range 77° to 423°K. All specitrzens tested, apart from those into which oxygen was introduced deliberately, were fully recrystallized at 1500°C, had an average grain diameter of approximately 0.03 mm, and a combined carbon, ox-vgen. nitrogen, and hydrogen content of not not more than 250 ppm The meckatnical behavior of this alloy was found to be similar in seine respects to that of unalloyed bcc transilion metals. Both yield and flow stresses were sensililae to changes in deformation rate and both increased rapidly as the temperature was lowered below 150°C. A detailed examination revealed, however, that most of the temperature dependencc of the yield stress could be accounted for by the temperature dependence of the elaslic, modulus, whish is not true of the unualloyed metals. In lension at moderate strain rates, the trunsition fvom ducfile to hvittle behavior occurred just belour room teunperature bur incveasing the oxygen content from 190 to 200 pptn raised the transition temperature to about 4000K. TUNGSTEN and molybdenum have been found to be very effective high-temperature solid-solution strengtheners of niobium, but the amounts of these elements that can be added are limited if the alloy is to retain useful room-temperature ductility. It has been shown, however, that partial replacement of niobium with tantalum lowers the ductile-to-brittle transition temperature of such alloys and allows larger additions of molybdenum and tungsten to be made. Some of the high-temperature properties of niobium alloys containing these elements have been reported by Bartlett et al.,' and the work presented here describes the low-temperature behavior of one of these, a solid-solution alloy containing, by weight, 20 pct Ta, 15 pct W, and 5 pct Mo. The elastic modulus, the temperature and strain-rate dependence of the yield and ultimate tensile stresses, and strain-hardening effects are discussed and compared with those of unalloyed niobium. EXPERIMENTAL MATERIAL AND PROCEDURE The material used in this investigation was produced from a 6-in.-diameter, double arc-melted ingot. This was can-extruded at about 1150°C to a 3-in.-diameter billet, and after annealing for 1 hr at 1345°C the billet was heated to 1315OC and part rolled and part forged to 0.5-in.-thick plate. The resulting material exhibited a cold-worked structure

Jan 1, 1965