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By M. M. Mebta, G. W. Dean, W. H. Somerton

With the advent of underground heating operations, interest has developed in the alteration of rock properties by high-temperature treatment. In the present work a number of sandstones were heated to temperatures in the range of 400°C to 800°C under both atmospheric and simulated reservoir pressures. Pertneabilities increased by at least 50 per cent and sonic velocities and breaking strerlgths decreased by an equivalent amount. Differential thermal expansion and other reactions of constituent min-era1 grains are the causes of these alterations. INTRODUCTION In the underground combustion of petroleum reservoirs, temperatures of the order of 600C are reported to have been reached in the combustion zone.' At this temperature rocks are subject to extensive thermal alteration. Temperatures of this magnitude and higher may also occur in subsurface formations when subjected to bottom-hole heating, thermal drilling operations, and underground nuclear explosions. Temperatures of this magnitude might also be generated by conventional rock drilling methods at points of bit-tooth contact. In earlier work, the permanent deformation of rocks resulting from heating was reported. Major structural damage of rocks occurs due to differential thermal expansion of mineral constituents. A number of mineral alterations including crystal inversions, loss of water of crystallization and dissociation, may also contribute to changes in physical structure and properties of rock. In the present work, samples of three typical sandstones were heated to several temperatures up to a maximum of 800C and then allowed to cool to room temperature. Heating was done under both atmospheric pressure and simulated reservoir pressure conditions. Physical properties of the samples were measured before and after heating and comparisons made. Measured properties included permeability, sonic velocity, breaking strength and fracture index. Changes in physical properties were compared to changes in mineralogical characteristics as determined by thin-section. X-ray diffraction and chemical tests. EQUIPMENT AND PROCEDURE Two outcrop sandstones (Bandera and Berea) and one sub-surface sandstone (St. Peter) were selected for the tests. These samples have a wide ranee in composition and physical properties as shown in Table 1. The first series of tests was made on 2-in. diameter by 5-in. long test specimens. Test specimens used in all later work were 3/4-in. diameter by 1 1/8-in. long, this being the specimen size required for heating at simulated reservoir pressures. After careful washing, the cores were oven dried at 100 ± 5C for a minimum of 24 hours before the tests were run. Test specimens were heated in an electric furnace at a constant rate of temperature increase of 3C per minute. When maximum temperature of the run was reached, the sample was allowed to soak for one hour. The furnace was then cooled to room temperature at the same rate of 3C per minute. The entire heating operation was designed for reproducibility without subjecting the test specimens to excessive thermal shock. For samples heated under simulated reservoir pressures, a pressure cell designed by Dean was used (Fig. 1).3 The core sample was inserted into a thin-walled (0.006 to 0.01-in.) copper cup which was then mounted in a high-pressure cell. Provisions were made for the application of internal pore pressure as well as confining pressure. Tests showed that the thin-walled copper cup closed tightly around the core and satisfactorily transmitted confining pressure to the core. The core was heated by placing the entire cell into the electric furnace. The heating program was the same as that used in the atmospheric pressure runs: tempera-ture rise of 3C per minute to maximum temperature of the test, soaking at maximum temperature for one hour, and cooling at a rate of approximately 3C per minute. The cell was designed to withstand 5,000 psi at 1,000C. However, since it was considered likely that repeated heating and cooling would in time weaken the steel, 2,000 psi at 850C was set as a working limit. In the present series of tests, the pore pressure was held constant at 750 psi and the confining pressure at 1.500 psi. The pressure source was a high-pressure nitrogen tank. The two pressures were controlled manually but are accurate well within ± 50 psi.

Jan 1, 1966

By Brian F. Dyson

The surface tensions at 1550°C of some Fe-S alloys (in the range 0.008 to 0.052 wt pct S), Fe-Sn alloys (0.31 to 48.4 wt pct Sn), Fe-P alloys (0.038 to 2.38 wt pct P), Fe-Cu alloys (2.15 to 22.8 wt pct Cu), and Fe-1 pct C-S alloys (0.005 to 0.076 wt pct S) along with the surface tension of the base iron have been measured by the sessile-drop method. A mean value of 1754 dynes per cm was found for the surface tension of the base iron. Sulfur was found to be highly surface-active, the surface-tension results being in quantitative agreement with existing data. Tin and copper were found to be less surface-active than sulfur while phosphoms was completely nonsurface-active. The surface tensions of Fe-1 pct C-S alloys were found to be lower than those of the Fe-S alloys containing the same sulfur content. This was shown to be a mmzifestation of the increase in the thermodynamic activity of suZfur by carbon. It is only in recent years that attempts have been made to measure the surface tension of liquid iron of known high purity.1-3 Earlier measurements4-7 were made on liquid iron containing variable amounts of what are now known to be surface -active solutes. The exact value of the surface tension of liquid iron is still, however, open to some doubt. Halden and Kingery' reported a value of 1720k 34 dynes per cm at 1570°C, Kozakevitch and Urbain8 gave 1790k 25 dynes per cm at 1550°C, while Van-Tszin-Tan et al. obtained a value of 1865k 37 dynes per cm at 1550°C. The first systematic investigation into the effect of controlled solute additions on the surface tension of iron was made by Halden and Kingery.' They showed that sulfur and oxygen were highly surface-active, whereas nitrogen was only slightly active, and carbon inactive. A subsequent investigation by Kingery indicated that two other group-6B elements, selenium and tellurium, were also surface-active. This highly surface-active nature of sulfur and oxygen has recently been substantiated by Kozakevitch and Urbainla and Van-Tszin-Tan et al. l1 Kozakevitch and Urbainl2 have also conducted an experimental survey of the effects of a number of metals on the surface tension of liquid iron. Their surface-active nature was, in all cases, less than that of the group 6B elements. The present investigation was undertaken to study in more detail the surface tensions of dilute Fe-S alloys and to measure the surface tensions of binary alloys of iron containing phosphorus, copper, and tin. The effect of sulfur additions on the surface tension of Fe-1 pct C alloys was also determined. EXPERIMENTAL PROCEDURE The sessile-drop method was employed in the present investigation. An apparatus was built similar in principle to that described by Humenik and Kingery.lS It consisted of a horizontal silica tube, which could be evacuated to pressures less than 10-5 torr, with its central portion surrounded by a water jacket within which was a high-frequency coil. This generated heat in a tantalum susceptor placed inside the silica tube, which in turn radiated heat to the specimen mounted on a recrystallized alumina plaque. Temperatures were measured by an optical pyrometer and photographs of the molten drop were taken on a fixed-focus plate camera giving a magnification of X2. Surface-tension values were determined from the resultant drop using the method described by Baes and Kellogg.l4 The high vapor pressure of molten iron made it necessary to conduct all the experiments under a 1/4 atm of argon (greater than 99.995 pct purity). The analysis of the base iron used in the investigation is given in Table I. Each sample was approximately 3 g in weight and had a hemispherical base to ensure a uniform advancing contact angle on melting. The iron alloys were prepared individually in the sessile-drop apparatus by drilling a hole in the top of each sample and adding the required amount of solute, the drops being analyzed after the experiment. This method of preparation had the advantage of ensuring a consistent minimal contamination by oxygen due to refractory attack and also allowed surface tension to be measured at the same time. Every precaution was taken to ensure that the specimen was not contaminated by grease when it was introduced into the apparatus, the samples being cleaned in acid, dried in alcohol, and rinsed in petroleum ether. All handling was done with tweezers. Once the specimen had been placed inside the susceptor, the furnace was evacuated and the Sample leveled. The furnace was then degassed at approximately 1000"C before the argon was introduced. In every case the surface tension was determined at 1550" C.

Jan 1, 1963

ALABAMA America.-Foreman, J. T. Ashland.-Sturdevant, J, C. Altalla; Henderson, R. M. Bessemer.-Ball, E. M. Maschmeyer, W. L. McKenzie, W. C., Jr. Birmingham.-Abbott, C, E. Aldrich, T. H. Aldrich, T. H., Jr. Aufderhaar, H. C. Berg, H. A. Blair, C. S. Bush, M. W. Clark. G. H.

Jan 1, 1929

By Donald W. Petrasek

The effects of selected alloying elements on the elevated-temperature tensile properties of copper alloy -tungsten fiber reinforced composites were invcstigated. A cornparison of the elevated-temperature tensile properties of copper alloy - tungsten fiber reinforced composites, representing soluble systems. was made with copper - tungsten fiber reinforced composites, representing a mutually insoluble system. A linear relation between tensile strength and volume percent fiber content existed at elevated temperatures for all the systenzs investigated. The copper alloy composites were weaker in tension at high volume percent fiber contents than copper composites in which alloying with the fiber did not occur. The tensile strength of the alloyed tungsten fiber decreased with increasing penetration of the alloying element into Ihe tungsten fiber. THE technique of combining strong fibers with relatively weak matrix materials so that the fibers are load-carrying members has been utilized for many years in the reinforcement of plastics with glass fibers. This type of strengthening is currently being extended to include the reinforcement of metals with metallic fibers. Investigations of the room-temperature tensile properties of metal-fiber-reinforced metallic composites have been numerous,'-" but the study of tensile properties at elevated temperatures has been limited. In previous work done at the Lewis Research Center' composites consisting of mutually insoluble constituents were investigated. Composites were made of copper reinforced with uniaxially oriented tungsten fibers. The stress-strain behavior and tensile properties of the composites were related to the tensile properties of the base materials. The tensile strength of the composite was directly proportional to the volume percent of tungsten fiber present, and the full strength of the fiber was realized. Few metal fiber - metal matrix systems exist that are mutually insoluble, and those that do exist are not generally practical. An extension of this work was an

Jan 1, 1967

By J. E. Pavlick, W. W. Mullins, H. W. Paxton

The growth of nitrogen-austenite during nitriding of large-gvained ferrite between 650" and 800°C has been studied as a functimz oJ time and nitrogen potential of the atmosphere for a variety of alloying elements dissolved in the ferrite. Whereas no preferential grain boundary penetration by aistenite takes place in zone-refined iron, the addition of aboit I zot pct oj' V, Ti, Cr. Si, or A1 produces significant protrusion of austenite down former 0-0 boundaries. This group of elernents also produces ragged y-0 interfaces in the a grains which advance more slozuly than those in zone-refined iron. 1 zut pct of Ni, Co, Mn, or Mo dissolved in ferrite leads to essentially smooth 7-a interfaces, which advance at rates very sinzilar to those in zone-refined iron. The reasons for this effect are not clear. Two possible limiting hypotheses, not necessarily exclusive, are discussed. One involves p.referentia1 grain bozindary diffusion of nitrogen. the other the production of a zone of ferrite, stpersatcirated with respect to nitrogen, from which austenite precipitates helerogeneozisly on the a-a gyain boundaries. In many phase transformations which occur by nu-cleation and diffusion-controlled growth, information on the parameters which control the rates of nuclea-tion and of growth is frequently not quantititative. The present work describes a continuation of efforts to obtain quantitative data on growth rates in systems where thermodynamic and kinetic factors are known independently, and thus where comparison with models of the growth process is possible. The work has been conducted on iron-base systems for two reasons. Firstly, there are several interesting transformations in this system, many of which are of practical importance. Secondly, the information on phase diagrams, activities, and diffusion coefficients is more complete in this system than in any other. These data are still inadequate to check all the effects of alloying elements, but at worst it is possible to make estimates and thus examine order-of-magni-tude agreement with proposed models. It will be necessary to do this in the present work. The problem studied was the growth of nitrogen-austenite in from the surface of large-grained columnar crystals of alloyed ferrite exposed to an NHs/Hz atmosphere. Earlier work by Grozier et al.' had suggested that growth of austenite may occur preferentially along grain boundaries of alloyed ferrite, whereas zone-refined (ZR) iron shows no such effect, Fig. 1. Growth of nitrogen-austenite into single crystals of zone-refined ferrite is planar provided sufficient nu-cleation sites for austenite are present, and is controlled by volume diffusion of nitrogen through the

Jan 1, 1967

By F. W. Bloecher, A. M. Gaudin

Using an adsorption-column technique the partition of dodecylamine between quartz and water has been determined at concentrations ranging from 0.5 to 4000 mg per liter. The adsorption varies as the square root of the concentration. Attachment of dodecylamine to quartz is reversible. The amount adsorbed in a flotation operation giving almost complete recovery is under 5 pct of the amount required for a monolayer.

Jan 4, 1950

By L. M. Barker

The New Cornelia Branch of the Phelps Dodge Corporation is at Ajo, Pima County, Ariz. It is at the southern terminus of the Tucson, Cornelia and Gila Bend Railroad, which connects with the Southern Pacific Railroad at Gila Bend, Ariz., approximately 43 miles to the north. History Early history of the Ajo district has been related by A. W. Allen1 and by T. A. Rickard.2 Briefly, steps looking to the large-scale development of the ore body were instituted as early as 1912. This work culminated in the equipment of the property for open-pit mining by steam shovels. Ores initially mined carried economic amounts of copper carbonates as the principal copper-bearing mineral. Treatment methods developed for the extraction of the copper content involved leaching and a 5000-ton leaching plant was constructed and placed in operation in early 1917. Description of methods and equipment employed in this plant has been given by A. A. Tobelmann and James A. Potter.3 As exhaustion of the carbonate ore body neared, and mining operations exposed an adequate tonnage of sulphide ores, a 5000-ton concentrator was constructed for their treatment. That plant has been described by H. Kenyon Burch.4 Construction was completed and the plant was placed in operation in early 1924. Changes made in the original plant to improve practices and increase production will be the subject of subsequent paragraphs of this paper. Geology Description of the geology of the Ajo district has been published by Ira B. Joralemon5 and by James Gilluly.6 The ore occurs chiefly in the porphyritic facies of Cornelia quartz monzonite, though appreciable

Jan 1, 1939

By L. M. Barker

The New Cornelia Branch of the Phelps Dodge Corporation is at Ajo, Pima County, Ariz. It is at the southern terminus of the Tucson, Cornelia and Gila Bend Railroad, which connects with the Southern Pacific Railroad at Gila Bend, Ariz., approximately 43 miles to the north. History Early history of the Ajo district has been related by A. W. Allen1 and by T. A. Rickard.2 Briefly, steps looking to the large-scale development of the ore body were instituted as early as 1912. This work culminated in the equipment of the property for open-pit mining by steam shovels. Ores initially mined carried economic amounts of copper carbonates as the principal copper-bearing mineral. Treatment methods developed for the extraction of the copper content involved leaching and a 5000-ton leaching plant was constructed and placed in operation in early 1917. Description of methods and equipment employed in this plant has been given by A. A. Tobelmann and James A. Potter.3 As exhaustion of the carbonate ore body neared, and mining operations exposed an adequate tonnage of sulphide ores, a 5000-ton concentrator was constructed for their treatment. That plant has been described by H. Kenyon Burch.4 Construction was completed and the plant was placed in operation in early 1924. Changes made in the original plant to improve practices and increase production will be the subject of subsequent paragraphs of this paper. Geology Description of the geology of the Ajo district has been published by Ira B. Joralemon5 and by James Gilluly.6 The ore occurs chiefly in the porphyritic facies of Cornelia quartz monzonite, though appreciable

Jan 1, 1939

Conquista, the uranium mining and milling complex owned jointly by Continental Oil Co. and Pioneer Nuclear, Inc., has begun operations in Falls City, Texas. The mill has been designed to produce 1.5 million lb of U3O, from 600,000 tpy of ore mined. Currently, the plant processes a maximum 2000 tpd of ore. Mine Planning Texas ore deposits are small and scattered in comparison to other uranium mining districts. Those to be mined at Conquista range from a few acres to more than 100 acres in size. Ore thickness ranges from a few inches to over 15 ft, and depth from less than 20 ft to more than 170 ft below ground surface. Distance from the mill ranges up to 35 mi.

Jan 8, 1972

By William C. Sleppy

The nmgnetic susceptibility of heat-treatable aluminuin alloys is sensitive to chanyes such as solution or dissolution of solute and the precipitation of mew phases. By measuring the change in the magnetic susceptibility of aluminum alloys caused by various heat treatments, an empirical relation was found from which atomic arrangements in dilute binary alloys of copper, zinc, and magnesiutn in aluminum have been delineated. The relation predicts the ultimate formation of C1LA12 when copper is precipitated from solid solution in aluminum. Euidexce joy silovt- range order is found for copper in solid solution in aluminum in the sense that copper atoms avoid being nearest neighbors to an extent greater than would result from a purely random arrangertzeizt. Hume-Rothery has predicted such short-range order joy solid solution of copper in aluminum The Al-Zn system agrees with evidence obtained from X-ray scattering at small angles and predicts a tendency for zinc atoms to cluster in solid solution in aluminum. In the Al-mg system, the empirical relation indicates an approach to randor distribution of magnesium in solid solution in aluminum with a tendency for magnesium segvegation which increases with incveasing temperature. ThE magnetic properties of metals are complicated by the fact that contributions are made to them both by electrons of a "metallic" type which belong to the crystal as a whole, and by electrons in states localized on particular atoms. An expression1'2 for the bulk magnetic susceptibility of aluminum may be written as the sum of three contributions: where XA1 is the bulk susceptibility of aluminum per gram of material (in the cgs system, the units are those of reciprocal density); Xa1+3 is the diamagnetic contribution of the electrons localized in ion cores; Xa1 is. the paramagnetic spin contribution of conduction electrons often called Pauli paramag-netism: Xa1 is the diamagnetic contribution of the conduction electrons often called Landau diamag-netism. Ion core diamagnetism arises from the precession of the electron orbits which occurs when a magnetic field is applied to a system of electrons moving about a nucleus. Its contribution to the magnetic suscepti- bility is small, temperature-independent, and unaffected by alloying. The conduction electron diamagnetism is also temperature-independent and arises from the translatory motion of the electrons. For perfectly free electrons this contribution should be exactly one-third of the Pauli spin paramagnetism, but this relation is seldom even approximately true. Blythe2 determined the conduction electron diamagnetism in pure aluminum and found it to be extremely small. Any change in the conduction electron diamagnetism caused by alloying is neglected in this work. The Pauli paramagnetic contribution3 to the magnetic susceptibility of aluminum depends upon the number of electrons that occupy excited states and whose spins can be turned parallel to an applied magnetic field. The number of electrons free to turn in the field is proportional to the temperature and each spin contribution to the susceptibility is inversely proportional to the temperature. A slight temperature dependence of Pauli paramagnetism occurs when the number of electrons occupying excited states cannot increase sufficiently to balance the inverse dependence on temperature of each spin contribution. The decrease of the magnetic susceptibility of aluminum with increasing temperature is attributed to a temperature dependence of the Pauli paramagnetism. Estimates of the Pauli paramagnetism of aluminum have been made by several workers.2,4,5 All of the values are in reasonably good agreement with each other. In this work Xal at 17°C is taken as 0.761 X 10-8 cu cm per g. An expression similar to [I] can be written for the magnetic susceptibility of an aluminum base alloy containing a fractional weight percent x of solute:' Xa = (1 -x)XAl+3 +xXsoluteion * XaPauli +Xadia) [2] where X, is the magnetic susceptibility per gram of alloy, Xal'3and Xsolute ion are the ion core diamag-netic contributions, and xpauli and xdia are the Pauli and diamagnetic contributions of conduction electrons in the alloy. If the components of a mixture are not alloyed but simply mixed together in their pure states without producing a new phase, then the magnetic susceptibility of the mixture is given by the Wiedemann additivity law: Xm =x1X1 +x2x2 + ..xnxp [3] where X, is the susceptibility per gram of mixture and xnXp are the weight fractions and susceptibilities, respectively,-. for the pure components. The additivity law is not applicable to alloys because the outer electronic structures of the components are changed by alloying.' Both the Pauli paramagnetism and Landau diamagnetism are affected; hence the magnetic susceptibilitv of an alloy is usually different from that calculated using the additivity law. In this work the difference, X, -X,, is taken as a measure of the change caused by alloying.

Jan 1, 1968

By O. C. Baptist

The Umiat oil field is in Naval Petroleum Reserve No. 4 between the Brooks Range and Arctic Ocean in far-northern Alaska. The Umiat anticline has been tested by 11 wells, six of which produced oil ; however, [lie productive capacity and recoverable reserves of the field are subject to considerable speculation because of unusual reservoir conditions and because several wells appear to have been .seriously damaged during drilling and completion. Oil is produced at depths of 275 to 1,100 ft; the depth to the bottom of the permanently frozen zone varies from about 800 to 1,100 ft, .so that most of the oil reserves are in the permafrost Reservoir pressures are estimated to range from 50 to 350 psi, increasing with depth, and the small amount of gas dissolved in the oil is the major source of energy for production. Laboratory tests were made on cores under simulated permafrost conditions to estimate oil recoverable by solution-gas expansion from low saturation pressures. The cores were also tested for clay content and susceptibility to productivity impaiment by swelling clays and increased water. content if exposed to fresh water. The results indicate that oil can be produced fronz reservoir rocks in the permafrost and that substantial amounts of oil can be produced from depletion-drive reservoirs by a pre.s.r~lrr drop of as little as 100 psi below the saturation pressure. Freezing of formation water reduces oil productivity much more than that due to increased oil viscosity: Failure of we1ls drilled with rtuter-base mud to produce is attributed to freezing of water in the urea immediately surrounding the wellbore. Swelling clays apparently contributed very little to the plugging of the wells. INTRODUCTION Naval Petroleum Reserve No. 4 lies between the Brooks Range and the Arctic Ocean in northern Alaska. The Umiat oil field is located in the southeastern part of the Reserve and is about 180 miles southeast of Point Barrow (the only permanent settlement in the Reserve and the primary supply point for drilling of the wells at Umiat). Eleven wells were drilled for the U. S. Department of the Navy, Office of Naval Petroleum and Oil Shale Reserves, between 1944 and 1953 to test the oil and gas possibilities of the Umiat anticline. Six of these wells produced oil in varying quantities and the best one pumped about 400 B/D.' Estimates of recoverable oil range from 30 to 100 million bbl. The main oil-producing zones are two marine sandstone beds in the Grandstand formation of Cretaceous age: these are referred to as the upper and lower sands. Good oil shows were found throughout the sand settions in the first three wells drilled on the structure, but the highest rate of oil production obtained on any 01 the many tests was about 24 BOPD. These first wells were drilled with conventional rotary methods using water-base mud; later wells were drilled either with cablc tools using brine or rotary tools using oil or oil-base mud. These experiments were successful as is shown by comparing the oil production from Well No. 2 with that from No. 5. These two wells are only 200 ft apart and are located at about the same elevation on the structure. Well No. 2. drilled with a rotary rig using water-base mud, was abandoned as a dry hole after all formation tests were negative. Well No. 5. drilled with cable tools and reamed with a rotary using oil, pumped 400 BOPD which was the maximum capacity of the pump and less than the capacity of the well. These field results indicated that the producing sands were extremely "water sensitive" and it was assumed that the cause of this sensitivity was the presence of swelling clays in the sands. Because of the very unusual reservoir conditions and the difficulties encountered in completing oil wells in the permafrost. the Navy asked the U. S. Bureau of Mines to make laboratory studies under simulated permafrost conditions to assist them in estimating the production potential of the field and the recoverable reserves. These tests were designed to determine the cause of the plugging of wells in the permafrost and to test oil recovery from frozen sand by solution-gas expansion with the oil gas-saturated at very low pressures. EXPERIMENTAL METHODS AND PROCEDURES Samples Analyzed Core samples were analyzed that represent the lower sand in Umiat Well No. 7, the upper sand in No. 3. and both the upper and lower sands in No. 9. These sands should be productive in all of the wells because of their location on the structure. Core samples from

By J. E. Berry

AII evaluation is made of the acoustic velocity log for measurement of formation porosity. Plots of field-observer1 velocities vs core-measured porosities of sandstones and limestotnes with inter intergranular porosity show that the velocity log gives a useful measure of porotity, in agreement with published data. A new method of plotting electrical and velocity log data makes it easier to recognize hydrocarbon-water coritnct~ from log darn and to make serni-quantitative estinlates of hydrocarbon saturation. Two examples of this interpretation technique are given. This paper also discusses the various factors that affect acoustic velocity and shows how corrections can be made for some of these factors. INTRODUCTION Although the continuous velocity log was developed primarily as an aid to seismic interpretation, it is finding widespread use for measurement of porosity. The purpose of this paper is to evaluate this use of the log. Results are presented for the velocity-porosity relationship in many sandstones and one limestone. Practical applications of porosity values derived from the velocity log to improve interpretation of electrical surveys are presented. Various parameters which affect velocity in porous media are considered. Porosity, composition, cementa-tion, pressure difference (overburden pressure minus fluid pressure), fluid saturation, and wellability are discussed. Some of the ideas are opinions based on general considerations of well logging problems while others are supported by published data and our own observations. Major conclusions from these studies arc given in the body of the paper and detailed discussions of some of the various factors affecting porosity are given in the Appendix. POROSITY Sandstones The primary factor affecting the velocity of sound in porous media is porosity. Wyllie, et al,1 have reported a time average equation for the relationship between velocity and porosity.* This has found considerable acceptance in the industry. Other relationships between velocity and porosity have been proposed, none of which are entirely satisfactory. It is doubtful that any one relationship will completely describe all situations. We have tried an empirical relationship based on correlating log velocities with core-measured porosities. Measured porosities were averaged over a depth interval equal to the spacing used in recording the velocity logs. The depth range for the information used was from 2,000 to 12,000 ft. Velocity measurements were normalized for the effects of depth and overburden pressure. A detailed discussion of the basis for this normalization is given in the Appendix. The change is usually insignificant and when working with individual formations it can be neglected. All velocity measurements were normalized to a depth of 10,000 ft. The velocity-porosity data for sandstones in Fig. 1 came from 20 wells scattered throughout the Mid-Continent and Gulf Coast areas. The scatter of the data points is attributed to three causes: 1. There is no theoretical basis for expecting an exact velocity vs porosity relationship and it is not possible to correct precisely for the effects of such factors as impurities, grain shape, manner of cementation, etc. Some of these factors are discussed in the Appendix. 2. Porosities measured by core analysis are not necessarily representative of what the velocity log "sees". 3. Inaccuracies appear in the velocity log reading. This is particularly true of velocities from one-receiver logging tools.*" A linear-time curve (time-average equation) is plotted in Fig. 1 along with the best straight line through the points. Velocities used for the linear-time curves were 19,500 ft/sec for the matrix velocity (zero porosity) and 5,500 ft/sec for fluid velocity. For clean sandstones with velocities greater than 10,000 ft/sec, there is little difference between the velocity-porosity and the time-porosity curves. Both curves are well within the scatter of data points. The data points in Fig. 1 were restricted primarily to clean sandstones, using the SP and/or gamma-ray logs as clues to the lithology. Where a lithologic de-

By T. G. Nilan

Steels containing 0.4 and 0.8 pet C have been transformed isothermally at pressures up to 34 kbuv. Decomposilion mechanisms are so intimately related to phase equilibvia that, as the equilibria shift under high pressure, the microstruclures of the decomposition producls change, maintaining at pressure the same correspondence between a given phase equilibrium and a given microstructure as a1 1 atm. A bainitic unicvo-structure occurs in these steels at high pressure that IS observed only at 1 aim abole 1.4 pct C. This strrrcl111,e 1s ruliorzalized in terms of the effect of pressure on the transformation to lower bainite. The pressuve depetlderlce of the kinetics of pearlile formation is descrihed by an absolute rule theory amalysis. The activation volume for the transformation is 7 cu cm per mlole, which is indicative of a phase-interface transformation-rate cotntrol mechanism. This fortmulation, when expressed in terms of known solule effects on the energelics of tvansformation, gives promise of explaining the effects of alloying elemenls on hnrden-abilily, particularly that of 'coball. KINETIC processes in solids are functions of the primary thermodynamic variables of state: composition, temperature, and pressure. Until the development of high-pressure techniques' that permitted the generation of sustained high pressure at high temperatures, metallurgical studies of such reactions were largely limited to isobaric conditions at atmospheric pressure. The data so obtained, and theoretical deductions based on these data, were necessarily incomplete For the particular case of austenite decomposition, a knowledge of the phenomenology of the reaction in terms of all the state variables should lead to a clarification of the process. This deeper understanding should facilitate a decision between conflicting theories that have been proposed to rationalize these phe- nomena. An analysis, derived from an understanding of the transformation mechanisms, may aid in the optimization of alloy steel development. The first studies of the effect of pressure on transformations in steel were made by Kulin et al. in 1952.' In a study of the influence of applied stress on mar-tensite formation in a 30 pct Ni steel, they found that the martensite start (M,) was depressed 8°C per kbar* by hydrostatic pressure. Jellinghaus and Friedewold3 were apparently the first to investigate the effect of pressure on isothermal transformations above the Ms. They found that the bainite transformation rate in a 1.2 pct C, 3.8 pct Mn steel was reduced by a factor of 3 by a hydrostatic pressure of 4 kbar. In both of these investigations,2,3 the M, of the steels studied was below room temperature. Austenitizing and quenching were done at atmospheric pressure, followed by the decomposition of the metastable austenite under pressure. The maximum temperature at pressure in the bainite study3 was 350°C. Until the advent of the present high-pressure devices, it was not possible to conduct isobaric high-pressure heat treatments from austenitizing through isothermal decomposition and quenching. The exploitation of high pressure as a variable in metallurgical studies was greatly advanced by the apparatus and techniques developed by Hall4 and co-workers. Utilizing these techniques, Radcliffe et a1.5 and Hilliard6 etermined the pressure dependence of phase equilibria in the Fe-C system. Hilliard and cahn7 examined the pearlite transformation rate in an AISI 1080 steel and also in a high-purity 0.92 C Fe-C alloy at 1 atm and at 34 kbar and found a 700-fold reduction in rate at pressure in the 1080 steel but only a fivefold reduction in the high-purity alloy. In agreement with the shift of phase equilibria under pressure, the microstructures were hypereutectoid at 34 kbar pressure, whereas they are eutectoid at 1 atm. Determination of the effect of pressure on carbon diffu-

Jan 1, 1968

By W. O. Hotchkiss

Rock exposures are usually a very small part of the surface area in any mining district and the prospector and geologist must base their deductions as to the area, extent, and structure of various formations upon exposures that seldom form 5 per cent. of the area studied. Most often, outcrops form less than 1 per cent. of an area, so that exploration for mineralized contacts or mineral-bearing formations necessitates drilling, test pitting or tunneling, shaft sinking, and other underground work. In these days of high costs any method that will give definite facts regarding rock? obscured by soil or other material should be used to the greatest possible extent. In the early days of the Lake Superior iron districts, mines were located in the few places where ore was present in outcrops. Later, larger orebodies have been found, in depressions, obscured by soil and other foreign material. Mineralized rocks are oftentimes more weathered, softer, and more easily eroded than unmineralized rocks. It is quite natural, therefore, to expect that such orebodies (particularly where large enough to influence erosion in former physiographic conditions) should lie in depressions and be obscured by later debris. It is not difficult to believe that the history of the development of Lake Superior iron mining may be duplicated in other mining districts, that even larger orebodies than those first mined may be found in areas where the rock exposures, which led to original discoveries, are few or lacking. The chief properties of rocks that can manifest themselves through an obscuring cover are magnetism, electrical effects, radio-activity, gravity, and sound transmission. All of these have been used, to a small extent, to tell us a few things about what lies below the surface that we could not otherwise determine, but none has been used so long and so widely as

Jan 1, 1923

By W. O. Hotchkiss

Rock exposures are usually a very small part of the surface area in any mining district and the prospector and geologist must base their deductions as to the area, extent, and structure of various formations upon exposures that seldom form 5 per cent. of the area studied. Most often, outcrops form less than 1 per cent. of an area, so that exploration for mineralized contacts or mineral-bearing formations necessitates drilling, test pitting or tunneling, shaft sinking, and other underground work. In these days of high costs any method that will give definite facts regarding rock? obscured by soil or other material should be used to the greatest possible extent. In the early days of the Lake Superior iron districts, mines were located in the few places where ore was present in outcrops. Later, larger orebodies have been found, in depressions, obscured by soil and other foreign material. Mineralized rocks are oftentimes more weathered, softer, and more easily eroded than unmineralized rocks. It is quite natural, therefore, to expect that such orebodies (particularly where large enough to influence erosion in former physiographic conditions) should lie in depressions and be obscured by later debris. It is not difficult to believe that the history of the development of Lake Superior iron mining may be duplicated in other mining districts, that even larger orebodies than those first mined may be found in areas where the rock exposures, which led to original discoveries, are few or lacking. The chief properties of rocks that can manifest themselves through an obscuring cover are magnetism, electrical effects, radio-activity, gravity, and sound transmission. All of these have been used, to a small extent, to tell us a few things about what lies below the surface that we could not otherwise determine, but none has been used so long and so widely as

Jan 1, 1923

By Leonard P. Skolnick

PROPERTIES of materials containing a hard con-stituent dispersed in a metallic matrix are dependent on the distribution of the hard phase.'-' The grain growth of titanium carbide in liquid nickel was studied in order to understand microstructural development in this and similar systems. Smith" has examined the influence of surface energy on the distribution of phases in alloys. The grain growth of tungsten carbide in cobalt has been the subject of many conflicting theories. Those prior to 1950 have been summarized by Goetzel.' Recently, Gurland and Norton3 and Gurland8 have indicated that growth occurs primarily by diffusion through the liquid phase in order to lower the inter-facial energy between the carbide and the liquid metal. In the development of the Ti-C-Ni ternary phase diagram, Stover and Wulff9 have shown that both eutectiferous dendritic titanium carbide, and primary titanium carbide which had developed crystals of cubic symmetry, were rounded by heating below the solidus, and that if primary carbide was already present the typical eutectic decomposition products were not formed. Experimental Procedure The infiltration technique was used to study the grain growth of titanium carbide in nickel. In contrast to sintering, infiltration more readily assures uniform dispersion of the two phases, and the problems associated with mixing by milling; i.e., mill contamination, breakdown of original carbide size in the operation, development of interfering surface films, etc., are avoided. In addition, the complicating effect of densification by shrinkage is eliminated. The titanium carbides used were commercial grades. Their chemical analyses, size distributions and shapes are summarized in Table I. Size analysis was conducted by microscopic count on a minimum

Jan 1, 1958

By M. N., Short

TIE Pioneer mining district, better known as the Superior district, from its principal town, is located in Pinal County in south-central Arizona about 80 miles east of Phoenix and 22 miles west of Miami. The region embraces a confused series of mountain ranges of moderate FIG. I.----SUPERIOR, LOOKING NORTH FROM SOUTH BANK OF QUEEN CREEK. MAGMA MINE IS INDICATED BY WASTE DUMP IN GULCH TO RIGHT OF CENTER. height but precipitous slopes, between which lie irregular valleys filled with alluvial detritus. The average elevation is about 2800 ft. in the valleys and the summits of the ranges reach 2000 ft. above this. Superior is situated on the north bank of Queen Creek where it emerges from one of those ranges into a more or less basin-shaped valley. The drainage of Queen Creek is to the southwest and the flood waters spread out and lose themselves in the desert northeast of Florence, the county seat of Pinal County.

Jan 2, 1926

By R. P. Corbett

Since the beginning of operations at the Kelley mine in 1952, Anaconda has emplaced more than 150,000 cu yd of concrete underground. Concreting practices have changed over the years but the net result is still the same- lower costs along the line and more versatility.

Jan 7, 1961

By C. D. Hall, F. E. Dollarhide

Fluid Ioss agent.s for crude oil and for water have been studied in dynamic tests. A treatment using a spearhead with a fluid loss agent followed by plain fluid appears feas ible in crude oil, but not in water. An equation for spearhead depletion shows that spurt loss relative to fracture width must be low, if the portion of spearhead fluid in the treatment is to be small. The presence of colloidal matter in crude oils aids the fluid Ioss agent. Unlike in kerosene, where flow limited the agent deposition, in crude oils the filter cake continually formed and leak-off declined. The volume-time relation varied somewhat for different crudes, but was best described by a square root of time function. Spurt loss was inversely proportional to agent concentration. After the fluid loss agent initiated the filter cake, the crude oil colloids built on it effectively. A 2-minute or a 5-minute spearhead with double the normal agent concentration gave the same fluid Ioss curve as the same concentration did for a 30-minute test. The agents tested in water gave fluid Ioss plots on which, for the first few minutes, volume was proportional to the square root of time, but later became proportional to time. For fracture area calculation the customary square root of time function is a satisfactory approximation. Leak-off rates and spurt losses were higher in water systems than in oils. The spurt Ioss tended to be inversely proportional to concentration. In spearhead tests, the filter cakes were not eroded by water flow. However, the rather high spurt loss values make spearhead treatments impractical for water-based fluids. Introduction The effects of dynamic testing conditions on the performance of fluid loss agents in kerosene have been studied previously.' We have extended the work to include crude-oil- and water-based fracturing fluids. An understanding has been gained of the mechanisms of formation and functioning of the filter cakes of fluid loss agents. The practical aspects of evaluating performance of agents in relation to fracture area calculations also are considered. The feasibility of using the fluid loss agent in a spearhead stage of the treatment is examined further for both types of fluids. Experimental Procedure The dynamic fluid loss tests were performed in an apparatus similar to the high-pressure apparatus described in a previous publication.' A fracturing fluid was circulated over a rock surface located in a closed pressurized loop. The fluid flowed axially over the cylindrical surface of a core 2 in. in diameter X 3.5 in. long, mounted (with the flat ends sealed off) in a pipe, with 0.117 in. annular clearance. The filtrate was collected in a central hole in the core and led through valves to graduated cylinders. Provision was made for changing quickly the circulating fluid during the test (spearhead runs) without interrupting the filtration pressure. The only modifications were to add heating tapes and water jackets for the tests with crude oils, all conducted at ISOF, and to change all parts exposed to the test fluid to stainless steel for the tests with water-based fluids. The latter tests were made at room temperature, 80F. Three crude oils were tested. A mixed crude, obtained from a local refinery, contained a considerable amount of light ends. For safety reasons, it was stripped to 250F vapor temperature before use in the fluid loss tests. The other two oils were used as obtained from lease tanks. One was a greenish-brown, 37" API paraffinic crude, and the other was a black, 32" API asphaltic crude. The fluid loss agent for oil, here designated for brevity as Agent A, was Adomite@ Mark II*, a granular solid commercial agent, the same as previously tested in kerosene.' Three different compositions of fluid loss agents were tested in Tulsa tap water. Agent B was adomit& Aqua*, a solid commercial fluid loss agent, comprising clays and hydrophilic gums principally derived from starch. Agent C was a mixture of three parts of Agent B with two parts of silica flour. Agent D was Dowel1 J137, a mixture of guar gum and silica flour. The test cores were cut from contiguous blocks of Berea or Bandera sandstones. For the oil tests, the cores were oven dried, evacuated, saturated with kerosene, and the kerosene permeability was measured. The cores used with the water-based fluids were pretreated by saturating with 3 percent calcium &loride solution to minimize pemeability damage by the fresh water due to clay migration. The

Jan 1, 1969

By David D. Rabb

Under the auspices of the Atomic Energy Commission, the Lawrence Radiation Laboratory of the University of California analyzed an experiment to provide information as to whether the chimney of broken rock produced by a deeply buried nuclear explosive could be "drawn" by conventional techniques. Since many low-grade disseminated ore-bodies occur in a granite media, the experiment took place in a granodiorite-quartz monzonite intrusive porphyry in the Nevada Test Site as a follow-up to the Department of Defense's Hardhat detonation in February 1962. For emplacement of the nuclear device, a 12 ¼ - in. pilot hole was reamed to a diameter of 44 in. and a depth of 950 ft in one pass using a Hughes multiple-cluster rotary bit. It was then cased to 36 in. ID. The center of the explosive device was located 938.85 ft below the collar. The yield of the device was predicted to be 5 kilotons, or an equivalent of 5000 tons of TNT; the yield was later confirmed by chemical means to be 5.4 kilotons.

Jan 3, 1964