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By R. R. Sayers

SILICOSIS is a term known to almost everyone today. Yet, in spite of a great deal of study, much is still to be learned regarding the disease. Government organizations are still continuing their investigations, begun near Joplin, Mo., 25 years ago. Work is also being done in several universities, as Harvard, Pennsylvania, Rochester, and Toronto, and at least two private organizations, the Air Hygiene Foundation of America, Inc., and the Saranac Laboratories for the Study of Tuberculosis, devote most of their time to this subject. Similar studies have been and are being made in many other countries.

Jan 1, 1939

By R. W. Nash, A. E. Schwaneke, V. R. Miller

The Bureau of Mines developed a detector for controlling sorting devices to separate the copper-bearing fragments from the barren portion of Michigan native copper and western prophyry copper ores. A successful sorter could be used to preconcentrate the ore and eliminate costly hoisting or hauling of waste. An induction balance unit was developed and used in sorting tests on crushed sized - 2.5 + 1. 3-cm (- 1 + 1/2- in.) ores from the Kingston (0.9% Cu) and Centennial (1.6% Cu) mines of Upper Michigan. Concentrates of 4.0% and 7.5% Cu, respectively, were obtained at recoveries of 85 and 80% of

Jan 8, 1978

By W. G. Sinclair

The wartime momentum of exploration continued throughout the year 1945 despite the end of hostilities in mid-August. The table below illustrates drilling activity in the various categories: Completed wells. . . . . . . . . . . . . . . . . . . . . . . . 401 Wildcats.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .104 Wildcat discoveries, oil.. . . . . . . . . . . . . . . . . . . 2 Wildcat discoveries, gas-condensate.. . . . . . . 4 Development wells.. . . . . . . . . . . . . . . . . . . . . .297

Jan 1, 1946

By Stanley Rajnak, John E. Dorn

The saddle-point activation energy for the nu-cleation of a pair of kinks is estimated as a function of the applied stress, the lattice constants, and the height and shape of the Peierls' hill by employing the line-energy model of a dislocation. The kinetics of disloration motion by the Peierls' mechanism are discussed and the microscopic dislocation velocities and macroscopic strain rates are formulated by the Arrkenius type of approach in terms of the activation energy for the formation of pairs of PEIERLS was the first to illustrate that a straight-dislocation line has its lowest energy when it lies in a potential valley parallel to lines of closest packing kinks. The log of the dislocation velocity is found to be approximately proportional to the log of the local applied stress. It is also shown that the low-temperature mechmical properties of several bcc metals might be explained in terms of the Peierls mechanism, good agreement being obtained between theory and experiment for the flow stress us ternperature, activation energy vs stress, and activation volume us stress curves for these metals. of atoms on the slip plane. When such a straight dislocation is moved rigidly from one valley toward the next, the atoms in the vicinity of the core of the dislocation change their positions and bond angles, causing the energy of the dislocation to increase. Midway between two adjacent valleys, the disloca-tion energy reaches a maximum value and any additional small displacement will cause the dislocation to fall down the hill into the next valley. The maximum shear stress necessary to promote such

Jan 1, 1964

By O. B. Bennett

WHEN diamond drilling was introduced in the Rhokana mines in 1939 it was used principally for pillar removal and for completion of the upper portions of shrinkage stopes which were being affected by increasing pressure. This method of drilling long blastholes proved so successful that it was extended gradually to cover stoping, pillar recovery, and hanging cave work. BY 1949 virtually all the ~roduction of Mindola and Nkana was being obtained by this method. At the present time 87,500 ft are drilled each month by the 80 diamond drills in daily operation. Responsibility for control and issue of diamond drilling equipment and crowns, as well as tabulation of all performance figures, was taken over by a sPecially formed Roto drill department, which also investigated the problems encountered with this new method. To assist this department a fully equipped test chamber, Fig. 1, was established underground where performances of various types of machines and equipment could be studied under conditions as nearly uniform as possible. Since the establishment of this department, which was eventually taken over and incorporated into the study department, considerable experimental work has been done on every aspect of the subject. The problems can be classified broadly under four headings: improvement of drilling equipment, crown design, machines, and stoping layouts. One of the major problems with drilling equipment has been to eliminate vibration. Owing to flexing of rods in the hole, severe friction is set up on the back end of the 'Ore barrel and On any high spots in the rods, inducing harmonic vibration in the string of rods and causing the crown to chatter against the face. This not only causes premature crown failure but also reduces penetration speeds and increases wear on the machines and rods used. In the early days, when only holes of EX size were drilled, vibration was largely overcome by periodic greasing of rods and core barrel during each run, but with the change-over to the larger BX hole it became obvious that application of grease by hand was inefficient and time-consuming, and attempts were made to perfect a self-lubricating core barrel. A series of these core barrels was made up and tested and a number of the latest type were used under normal operating conditions, but although footages up to 120 ft were drilled without refilling the overall performance was inconsistent, and the idea was shelved in view of the success of the stabilizer rods referred to later in this paper. At the same time tests were made with barrels 5 ft and later 6 ft long instead of the normal 2 ft. Although a slight improvement was noticed, greasing was still necessary. It was found that rod vibration increased as the core barrel became worn, and in an early test chamber experiment crowns drilled with a worn core barrel averaged 95 ft with a diamond loss of 4.76 carats, whereas the same type of crowns with a new barrel averaged 228 ft with a diamond loss of 3.13 carats. until then all BX drilling had been done with B-sized rods, but during a test on a string of BX-sized rods it was noticed that vibration was negligible. Because of the larger surface area of metal bearing on the sides of the hole, however, the friction and resistance of rods of this size rendered them impracticable on any but the most powerful of the machines, The use of stabilizers spaced evenly along the rods was the next logical step, and for this B couplings, see Fig. 2, were set with three tungsten carbide inserts 1 in. long placed around the periphery equidistantly and at an angle of 45" with a right hand lead. These were placed immediately behind the core barrel and then at 12-ft intervals, as it was found that vibration still occurred when the stabilizers were more than 15 ft apart. The effect of these stabilizers was immediately noticeable; holes were drilled with a minimum of vibration, penetration speeds were improved, and as it was no longer necessary to grease the rods there was a marked decrease in the overall drilling time for each hole. While tests were being made with the stabilizer comeb periodic were taking place with a set of tapered threaded rods, and because there was marked improvement in efficiency it was decided to incorporate the stabilizers and tapered threading in all new rods ordered for Rhokana. The feature of these rods is that only four full turns are required to tighten the coupling as against nine for the present type of B rods. Also, as they are self-centering it is virtually impossible to crossthread them. Each rod has a male 5" tapered Acme thread, Fig, 3, on one end and a female at the other, so that separate couplings are unnecessary, and every fifth rod has an

Jan 1, 1955

By L. C. Morganroth

Magnesites are of two general classes - massive and crystalline.

Jan 1, 1915

By Colin M. Sargent

THE electron diffraction pattern as seen in the electron microscope represents an approximately plane section of the reciprocal lattice. Identifying the zone axis of a diffraction pattern is often laborious for a crystal of low symmetry, especially if several crystal orientations are present. A program has been written in FORTRAN II (Version 2) for the IBM 1620 which will assist in plotting out reciprocal lattice sections. The calculation is performed by choosing a zone axis [uvw] and determining the d spacings and angle between the planes (Ow - v) and (wO - u). (This procedure is varied slightly for zone axes with Miller indices equal to zero.) Cartesian coordinates for the reciprocal lattice points are then calculated for these planes and for (ww— [u + v]). Any reciprocal lattice points within the parallelogram formed by the origin and these three points are then computed. The input and output are best described by use of an example (Monoclinic ZrO2) used in the author's work. Input consists of two cards: 1) The crystal parameters: a, b, c, a, 8, y, e.g., 5.1477, 5.2030, 5.3156, 90.000, 99.380, 90.000. 2) Three numbers, D, E, F, e.g., 5, 3, 3.0710-the first is the limit of the sum (u + v + w) considered; the second limits the absolute value of u, v, and w to (E- 1), e.g., 2, so that zones (221) would be the highest order considered in this example; the third, F, is the required constant, yL. Output is in the format shown in Table I. The reciprocal lattice sections may then be plotted on standard graph paper and compared with the unknown diffraction pattern. (Note that no attempt has been made to deal with systematically absent reflections.) A card deck for the program is available from Colin M. Sargent, ARZ, W-PAFB, Dayton, Ohio, 45433.

Jan 1, 1969

By T. B. Massalski, Horace Pops

Martensitic transformations were observed by optical metallography and electrical-resistivity measurements during cooling at cryogenic temperatures of the bcc pr-phase Au-Zn alloys. The com-position dependence of the MS, MF, AS , and AF temperatures have been determined. It is concluded that the martensitic platelets which grow mainly in the lengthwise direction and which are associated with a very small temperature hysteresis are "thermoelastic" martensite. In some cases the observed structure seems to have no definite crys-tallographic habit or consists of a mixture of- plates and broad transformed areas. THE majority of the bcc /3-phase alloys in systems of copper, silver, and gold with zinc and cadmium are unstable at low temperatures and undergo a transformation upon further cooling into another structure. A large number of such transformations are martensitic. The composition dependence of the Ms temperatures has been determined and reported for CU-~n,' Ag-Cd,' and AU-C~~ alloys. The 50 at. pct ordered Au-Zn p' alloy has been reported by Jan and pearson4 to transform martensitically at 58°K in connection with their study of the de Haas-van Alphen effect The p' phase in the Au-Zn system has the ordered CsC1-type structure. The phase field is shown in Fig. 1: it has the typical V shape which is characteristic of all copper-, silver-, and gold-based binary /3-phase alloys. There appears to be no a priori reason why the transformation should be limited to the equiatomic composition and the availability of a cryogenic stage for optical metallography5 has permitted studies down to the liquid-helium temperature of a series of alloys in this system. EXPERIMENTAL PROCEDURE Predetermined weights of 99.999 pct pure gold and zinc were melted and cast under a partial atmosphere of helium in sealed quartz capsules. Thorough mixing of the molten metals was achieved by vigorous shaking, followed by a rapid quench into a brine solution. All ingots were homogenized at 640°C for 4 days. The loss in weight was usually less than 0.04 wt pct and was assumed to be due to

Jan 1, 1965

By W. F. Flanagan, K. R. Evans

The strong temperature dependence of the flow stress of bcc metals has prompted considerable interest and controversy concerning the rate-controlling influence of the Peierls' mechanism upon deformation in metals.18"21 Dorn and Rajnak" recently offered a criterion for Peierls' deformation utilizing a line-energy model of a dislocation to estimate the saddle-point activation energy, for the nucleation of a pair of kinks as a function of applied stress and the height and shape of the peierls9- barrier. It was found that Un/2Uk, where 2Uk is the excess energy of a kink pair, was a unique function of where is the effective stress and 7p is the Peierls' stress as defined in Fig. 20. The relationship found by Dorn and Rajnak between is given by the solid line of Fig. 21. may be expressed in terms of the temperature of test, T, and the athermal temperature, T,, defined in Fig. 20. Considering the strain-rate, 9, of deformation for a thermally activated process to be given by where fo is nearly a constant, it is seen that and the theoretical relationship of Fig. 21 may be examined with readily obtainable experimental parameters. Dorn and Coworkers analyzed a large amount of experimental data in this manner for materials sus-

Jan 1, 1967

By B. M. Larsen, T. E. Brower

A perspective is presented of the steel plant sulphur distribution and elimination problem from coal to liquid steel ready for teeming, giving distributions of sulphur over a range of coke sulphur content, and some methods of sulphur control, in the blast furnace, external desulphuriza-tion between blast furnace and open hearth, distribution between fuel, slag, and metal, and methods and limitations of control of sulphur in the open hearth furnace. AS a part of the 1951 AIME symposium on sulphur in steelmaking, it was thought that a discussion of the distribution of sulphur throughout the whole series of operations, from coal and ore to finished steel ingots, might have some value in giving a perspective on the whole problem. The following discussion is an attempt to present such an overall picture. The order is that of the actual plant operations, beginning with a very brief consideration of the coking process. Sulphur in Coal and Coke Since by far the largest source of sulphur entering the steelmaking cycle is in the coal used to make coke for the blast furnace, it would seem reasonable to eliminate some of it, either from the coal, or the coke, or during the coking process. This has appeared impracticable up to the present, at least, for two main reasons: the low activity of the organic sulphur in either coal or coke, and because of price limitations involved in treating a low cost material such as coke. A variable portion, usually M or less, of the sulphur is present in coal in the form of pyrites or similar compounds, and a large part of this sulphur may be removed in the coal washery. Most of the sulphur, however, is normally present as "organic" sulphur, intimately associated with the coal structure. Its distribution prevents any separation by mechanical means. Its low activity makes improbable ' any rapid chemical removal, although hydrogen will remove sulphur from both coal and coke. Thus, prolonged recirculation of coke oven gas in the coking process would tend to leave a smaller percentage of the total sulphur in the coke residue. Table I shows a typical distribution of sulphur from coal into products in the coking process. As the sulphur in the coal increases, the sulphur in the coke tends to increase in about the same proportion. Sulphur in the Blast Furnace The best picture of the situation in the blast furnace is provided by a sulphur balance of raw materials entering, and of products leaving, the furnace. The difficulties in accurate weighing and sampling of the variable solid materials entering this process, and the number of hours required for the raw materials to descend through the furnace under variable operating conditions, make it difficult to obtain an accurate balance. However, balances made over periods of weeks or months tend to average out some of these uncertainties. Table I1 presents three typical sulphur balances similar to a number that the writers have calculated. In most of these the slag volume calculated from the sulphur balance is, in some instances more, and in other instances less, than the value corresponding to the best input and output balances of the other slag constituents (lime, silica, alumina, etc.). Probably the greatest source of error in these calculations is the sulphur content of the slag. Despite some possible inaccuracies the balances of Table II show rather definitely the following points: 1—That 87 to 95 pct of the total sulphur input is in the coke and 95 to 97 pct of the total sulphur output is in the slag. Also, that if any sulphur leaves the furnace with the gas it is relatively small, amounting to a possible 1 pct or less. 2—At the lower sulphur coke level of 0.86 pct the total amount of sulphur charged is 15 Ib of sulphur per ton iron increasing to 26 lb per ton at the higher sulphur, intimately associated with the coal struc-rare burdens containing sulphur-rich ores will the total sulphur burden fail to be nearly proportional to the content in the coke used. 3—The 7 to 9 pct of the total sulphur input from the limestone of furnaces B and C is due to the relatively high sulphur content of the stone, 0.226 and 0.265 pct, respectively. In the case of furnace A, the sulphur content of the limestone was only 0.06 pct which resulted in only 3 pct of the total sulphur input coming from this source. It is rather interesting to compare the sulphur balances of a typical ferromanganese furnace with

Jan 1, 1952

By Douglas Bunting

(Wilkes-Barre Meeting, June, 1911.) WITH the gradual exhaustion of the upper veins in the anthracite coal-fields, the problem of mining at greater depths acquires increasing importance and demands the consideration of a number of important factors, one of which is the greater earth-pressure and the consequent necessity of stronger support o for the roof. Under the pillar-and-chamber system, almost exclusively followed in the Northern anthracite-field, the highest economy in mining is generally secured by leaving, on first mining, pillars only sufficient to support safely the overlying strata. As to the necessary size of such pillars, the opinions of mining experts are widely divergent. In establishing the width of chambers and pillars, the thickness of vein and its depth below the surface have received little consideration. For. instance, it has been quite usual to work both overlying and underlying veins with the same width of chambers and pillars, when the lower vein was two and one-half times as thick, and twice as fits below the surface, as the upper. In view of the generally-accepted theory that the crushing-strength of coal-pillars of the same base-area becomes less with increased height, it is probable, in this instance at least, that the most economical mining has not been secured. This question of adequate pillar-support is economically less important down to about 800 ft. than at greater depths; and it is with reference to mining at these greater depths that the study of the subject here presented has been prompted. The necessity of leaving larger pillars, involving greater mining-costs per ton and also smaller yields per acre, is one of the troubles of deep working. To mine without leaving adequate pillar-supports will result, sooner or later, in a squeeze. Limited areas, it is true, have been mined at certain widths of

Sep 1, 1911

By S. E. Szasz, E. J. Moore, B. F. Whitney

An accurate value of formation water resistivity R, is essential in calculating formation porosity and fluid saturation from electrical well logs. In the cases where R, has not been measured directly, it must be obtained from other data, e.g., the SP curve. This paper deals with another approach: how to calculate R, from the chemical analysis of the formation water. INTRODUCTION It is known that the resistivity of aqueous solutions of pure salts depends on their concentration and on the temperature; the concentrations are given in MPL (mg of solute per liter of solution), or sometimes in ppm (mg of solute per kg of solution): MPL = ppm X specific gravity. Values for different pure salts are available in the literature, but not for solutions of mixtures which are of practical interest. The major component of the dissolved material in almost all formation waters being sodium chloride, it is customary to express the resistivity of formation waters in terms of equivalent sodium chloride concentration, i.e., the concentration of a solution of pure NaCl which has the same resistivity at a given temperature as that of the formation water under consideration. Thus, the problem of calculating R, from the chemical anaylsis can also be stated as how to convert the other constituents of the solute into equivalent NaCl concentration. Salts dissolved in water are at least partly dissociated into ions, and do not conserve their identity. If known amounts of several salts are dissolved in water, the solution does not necessarily contain the same salts in the original proportion, but perhaps some other combination of the ions, along with free ions in solution. This is why the chemical analysis of formation waters is often given in terms of ions, as if all dissolved salts were completely dissociated. Our problem then boils down to how to convert the concentrations of the various ions to equivalent concentrations of Na' and C1-. Dunlap and Hawthorne' have proposed to convert the concentration of all other ions to equivalent Na' and C1-concentrations by means of constant multipliers; e.g., 0.95 for Ca"; 2.0 for Mg"; 0.27 for HCO 3-; 0.5 for SO, -, etc. Their factors were based on measurements made at 68F on 26 formation water samples from the Texas Gulf Coast, ranging in concentration from 1,500 to 75,000 ppm. The Dunlap method is widely used in electric log interpretation, and is often extrapolated beyond its original concentration range. A comparison of R, values calculated by this method and values actually measured on formation water samples has shown large discrepancies, especially at higher concentrations. Therefore, two new methods were developed at Sinclair Oil Corp.'s Tulsa Research Center to calculate equivalent sodium chloride concentration from the chemical analysis of formation water samples. FUNDAMENTAL CONSIDERATIONS The resistivity of a solution, or its reciprocal the conductivity, at a given temperature is determined by the charge, concentration and mobility of the ions actually present. Monovalent ions such as Na' or C1- always carry the same charge. Compounds of polyvalent ions, however. may show incomplete dissociation, e.g., NaSO; + Na' instead of SO,-- + 2Na'. This happens especially in more concentrated solutions. Only very dilute solutions are completely dissociated, as assumed in the chemical analysis report. At higher concentration, the degree of dissociation depends not only on the nature and concentration of the particular salt under consideration but also on the nature and concentrations of the other solutes. Mobility of the ions depends on the viscosity of the solution. It also depends on the degree of hydration of the ions, which in turn is a function of the nature and the charge of the ions and also of the amount of free water available per ion, i.e., the total ionic concentration. The net effect is that the conductivity increases slower than proportional to the concentration, even if a solution contains only one salt such as NaC1, and is different for different salts (Fig. 1). Conductivity can even decline with a further increase in concentration, e.g., if additional salt is little dissociated but ties up some of the free water and/or causes an increase in viscosity. In solutions containing more than one salt, the contribution of one salt to the total conductivity depends not only on the fractional concentration of this same salt, but also on the concentration of all other solutes. A perfect method would give the conductivity or resistivity of a solution as a function of the concentrations of all solutes present. This is so complicated as to be impractical, and a simpler method must be found which is of acceptable accuracy. The Dunlap method, on the other hand. is too simple because it askmes that at any concentration the contrih-

Jan 1, 1967

Pumping coal to market may help Appalachian coal operators increase their share of the eastern seaboard fuel business. Transporting it by pipeline is already an accomplished fact, but until recently it had to be dewatered to be used in boiler furnaces. The campaign for these eastern markets was begun in earnest last November by the widely publicized announcement of successful plant-scale firing of a central station boiler with coal slurry pumped to the burners. This latest advance makes coal similar to oil and gas in convenience in handling and controlling at the consumption end of the pipeline. Slurry could be considered a new commodity for the fuel market. HUGE POTENTIAL MARKET The heaviest concentration of power plants in the U.S. is along the line Washington, Baltimore, Philadelphia, New York and Boston which makes this region the best hunting ground for selling pipelined coal brought from western Pennsylvania and northern West Virginia. Furthermore, if this region is assumed to consume 125 million tons of coal annually, on a comparable basis, the consumption of oil and gas would be about 180 million tons. Even if all of this fuel is not consumed in central stations, it is still a very big market for coal at the right price. Consolidation Coal Co. and Texas Eastern Transmission Co. are trying to line up customers in this area so that a pipeline can be built. This is not to say that there are not many other areas in the U.S. that could not be supplied advantageously by a mine-to-market pipeline.

Jan 1, 1962

By AIME

DURING the Revolutionary War an iron mining industry was born in the Adirondack region of New York State. New York State ores provided the iron from which were forged the links of the chain that, strung across the Hudson River, successfully kept British vessels from ascending. The industry flourished for a while and then became dormant. For the successful prosecution of World War II, the magnetite mines were revived and given considerable aid in the form of government financial support. The complete story appeared in a special issue Of MINING AND METALLURGY published in November 1943. Now, almost four years later, it is interesting to see that these "war babies" were not really such but are well-established enterprises with a bright future. A ten-day trip through the Adirondack region and to St. Lawrence County dispelled all thoughts that mining in northern New York State is a transitory industry. In addition to substan-

Jan 1, 1947

By AIME AIME

THOUGH the dust-control systems in the crushing plants and other buildings at Morenci do not differ materially from similar installations in other large copper reduction works, it is probable that in few other plants has as much attention been paid to the dust problem. Possibly the most striking feature of the Morenci installation is the manner in which the necessary equipment has been built into the various structures, and the absence of unsightly pipes, ducts, and fan houses. That this result has been attained is due, in no small part, to the basic conception that the control of the dust in a milling plant should be an essential part of the process itself and not something to be tacked on later after the plant is in operation. The control systems were designed and developed along with the general plant construction program and when the first car of ore was dumped into the crusher the dust-control equipment was ready.

Jan 1, 1942

By AIME AIME

JANUARY saw the completion of the 237-ft. Upper-Narrows hydraulic debris dam on the main Yuba River in northern California. This project which is the key unit in a series of four similar structures on the Bear, American, and Yuba Rivers, removes the last obstacle to the revival of California's vast hydraulic gold-mining industry. The Upper-Narrows dam is a single-arch type of structure, and embodies the latest developments in that type of construction. One of the principal innovations used is the series of air vents in the crown (that part over which the water spills) which serve to break the vacuum caused by the spilling water, thus reducing vibration to a minimum. Electric strain gages were also embedded in the concrete of the dam, and it is hoped that by careful study of these instruments true stresses can he determined.

Jan 1, 1941

The co-operation of the members of the Institute is earnestly sought by the Committee on Nominations, recently appointed by the Board of . Directors, in its work of formulating a ticket for officers and places falling vacant in the Board of Directors in February, 1916. The Committee must present the official ticket of nominations to the Board of Directors at its October meeting. Members are, therefore, urged to send promptly their nominations for officers and Directors in order that the Committee may have an opportunity to give them full consideration. The officers to be elected at the annual meeting in February, 1916, are: One officer, known as Director and President. Two officers, known as Director and Vice-President. Five officers, known as Director; The attention of members is called to Articles V and VII of the Constitution, and to By-Law XIII, which reads as follows: "The geographical districts to be considered by the Committee on Nominations shall he as follows, until otherwise ordered by the Board. District No. 1. New England, New York, and New Jersey, excepting New York City and district., which is provided for in the Constitution. (N. B.-New York City and district is designated District 0.) District No. 2. Pennsylvania. District No. 3. Ohio, Indiana, Illinois, Iowa, and Missouri. District No. 4. Minnesota, Wisconsin, and Michigan. District No. 5. Montana, North and South Dakota, Wyoming, Nebraska, Kansas, Washington, Oregon, Idaho, and Alaska. District No. 6. California and Nevada. District No. 7. Utah, Colorado, Arizona, and New Mexico. District No. 8. Louisiana and Texas. District No. 9. Other Southern States and District of Columbia. District No. 10. Mexico. District No. 11. Canada."

Jan 7, 1915

By A. Lubinski, C. R. Stewart, K. A. Blenkarn

Storage porosity has been considered one of the important pore geometry characteristics of heterogeneous-porosity limestones. Storage pores are only containers for fluids, in contrast to flow channel pores which both contain fluids and provide continuity for fluid flow. The concept of another geometry characteristic, "poro-striction", is presented as a second pertinent variable in describing limestone pore space. In simple terms, poro-striction is a measure of the flow resistance between storage and flow channel pores. Alternating-flow core-testing theory provides flow relationships which can be used to divide the pore space of heterogeneous-porosity media into flow channel and storage pores and to measure the "porostriction" of the latter. Experimental application of this theory to naturally occurring heterogeneous limestones shows that "porostriction" and the ratio of storage to flow channel pores can be estimated. Porostriction and porosity ratio are microscopic characteristics which should influence oil-recovery efficiencies during certain types of displacement processes. A knowledge of pore geometry should be valuable in designing or selecting the most effective oil-recovery process for heterogeneous limestones containing storage porosity. INTRODUCTION The primary and secondary recovery of oil from limestone (carbonate) reservoirs has been and will continue to be a major source of the world's supply of petroleum. Oil recovery from this type of formation is strongly influenced by the size, shape and arrangement of the pore spaces which hold the formation fluids. Therefore, it is expected that better knowledge of pore geometry would lead to design of more effective recovery processes. The concept of storage and flow channel pores has been presented as an important characteristic of limestone porosity.1 In this concept, storage pores are only containers for fluids, whereas flow channel pores are those pores which both contain and transmit the fluids. The work reported herein involves the concept of an additional pore characteristic called "porostriction". This characteristic can be visualized as the flow resistance between the storage and flow channel pores. This resistance is an important pore geometry characteristic because it determines how easily gas and oil can replenish fluids removed from the flow channel pores. Fatt and co-workers at the U. of California have studied the effect of storage porosity and a factor similar to porostriction on transient-flow response of models of porous media during a pressure build-up or drawdown test.55 These models consisted of porous sandstone cores with artificially simulated storage pores. It is the purpose of this paper to describe tests which permit the storage porosity and porostriction of actual reservoir core samples to be estimated. The tests used for this purpose involved not transient tests but, rather, an alternating-flow technique in which pressure and flow are varied according to a sine-wave relationship. This technique may offer advantages over transient methods. THE POROSTRICTION CONCEPT Before discussing alternating-flow (A.F.) tests in core samples, it is necessary to define the porostriction parameter. For this purpose attention is focused upon an elemental volume v representative of a porous medium having both flow channel pores and restricted-access storage pores. For such an elemental volume, it is considered that the storage porosity is combined to form a single pore and that the access into the storage porosity may be represented by a single capillary tube connecting the single pore to the flow channels of the elemental volume. Let the radius of the capillary tube be designated as Rc and its length as L,. When fluid flows into or out of the pore, the following equation (Poiseuille's law) relates flow rate q to pressure drop p, and the physical characteristics of the tube and the fluid of viscosity jx.

By Robert A. Rapp, Ronald L. Pastorek

Solid-state electrochemical measurements by three alternative experimental procedures were made with the cell FeO, Fe3O4 |Zro.85Cao.15O1.85 |Cu| Zr0.85CaO.15O1.85 | FeO, Fe304 to establish the solubility and diffusivity of oxygen in solid copper in the temperature range 800" to 1030°C. The solubility of oxygen in solid copper and the diflusivity of oxygen in solid copper Dgu = 1.7 X 10-2 exp(-16,000/RT) Cm2/sec were determined and confirmed in alternative experiments. The enthalpy of solution of oxygen in solid copper equals —10,000 cal per mole; the partial excess entropy of the oxygen atoms in the Cu-O dilute solution is approximately the same as that found for interstitial atoms in other metals. The diffusivity of oxygen in solid copper is consistent with that expected for an interstitial atom. RELIABLE values for the saturation solubility N(s) and diffusivity DO of oxygen in solid copper have not been unambiguously established in the literature. Following three early determinations by others,1"3 Rhines and Mathewson4 reported that the solubility of oxygen in solid copper increased from 0.007 at. pct 0 at 600°C to about 0.015 pct at 1050°C. Phillips and skinner,, using essentiially the same analytical procedure, reported that the solid solubility increases from 0.0018 at. pct 0 at 550°C to about 0.0075 pct at 1050OC. The only previous value for the diffusivity of oxygen in solid copper was reported by Ransley.6 Ransley deoxidized Cu-Cu2O alloys in an atmosphere of carbon monoxide gas to yield a solubility-diffusivity product. He used the solubility data of Rhines and Mathewson to calculate the diffusivity values. Another method for obtaining the solubility-diffusivity product (N(s) DO) is by measuring the widths of internal-oxidation zones in copper alloys as reported by Verfurth and Rapp.7 However, the calculated N(S)Do products depend upon the alloy content of the specimen, so that the internal oxidation of copper alloys does not follow ideal internal oxidation kinetics. As a result, unequivocal values for the N(s) DO product were not obtained by this procedure. A solid-state coulometric titration technique similar to that employed in this work was introduced by C. Wagner8 to study the dependence on silver activity of the Ag/S ratio in silver sulfide in the temperature range of 160" to 300°C. Similar experiments have been carried out by C. Wagner and co-workers9-11 to study the stoichiometry range of silver and copper tellurides, cuprous sulfide, and cuprous selenide. Numerous authors have carried out electrochemical measurements with a solid oxygen-ion-conducting electrolyte to determine the solubility and/or diffusivity of dissolved oxygen in several liquid metals.12-l6 Rickert and Steiner17,18 have used solid-state electrochemical measurements to determine the diffusivity of oxygen in solid silver from 760" to 900°C. Two different cell geometries were used. In the cell of linear geometry Fe, FeO | ZrO2 + (CaO) | Ag + [0 (dissolved)] [1] oxygen diffused from the interior of the silver electrode to the silver/electrolyte interface where the oxygen activity had been lowered from a fixed initial value to practically zero by the application of voltage to the cell. The diffusivity of oxygen in solid silver was determined from the solution of the diffusion equation and the time dependence of the cell current. However, this determination of the diffusion coefficient depended upon a knowledge of the solubility of oxygen in solid silver. A cylindrical geometry was used for the cell Pt, O2(Po2 = 0.21 atm) | ZrO2 + (CaO) | Ag + [0 (dissolved)] [II] which also allowed the diffusivity of oxygen in solid silver to be determined. These values were in agreement with other available data.l9 Recently, Raleigh20,21 used a method involving the measurement of diffusion-limited currents in a cell involving the AgBr solid electrolyte to determine the diffusion coefficient of silver in Ag-Au alloys at 400°C. Diffusivity values on the order of l0-14 sq cm per sec were measured in the alloy composition range 10 to 60 at. pct Ag in a single experiment. From numerous electrical conductivity and galvanic cell measurements,9'22"26 the solid solution Zr0.85 Ca0.15 O1.85 has been established as an electrolyte with predominant oxygen ion conduction over a wide range of intermediate and high oxygen activities. For interrelating the thermodynamics and the kinetics of the dissolution of oxygen in solid copper in this investigation, a galvanic cell was constructed with FeO-Fe3O4 as the reversible reference electrode, the Zr0.85Ca0.15 O1.85 electrolyte, and a pure copper specimen under-saturated in oxygen as the other electrode. THEORETICAL ANALYSIS Three variations of a high-temperature electrochemical technique were used in this study to provide two determinations each of the solubility and diffusivity

Jan 1, 1970

By J. A. Rowland, C. W. Funk

THIS investigation is a part of the United States Bureau of Mines work in conserving the Nation's resources. The isothermal sections presented were developed as a guide to a comprehensive investigation of the properties and fabricating characteristics of copper-base alloys containing manganese and tin. These alloys are being investigated as possible replacements for the commercial bronzes containing substantial quantities of tin. Development of the isothermal sections has, therefore, been limited to the area between 0 to 20 pct Mn and 0 to 25 pct Sn. Since Heusler1 reported the ferromagnetic properties of the Cu-Mn-Sn alloys in 1903, the system has been the subject of several investigations. These studies were largely concerned with correlation of magnetic properties and crystal structure.2-6 Vero,' however, established the solidus surface of the system, between 20 pct Mn and 40 pct Sn, by thermal and microscopic methods. The a, ß, and y solid solutions were also observed by Vero and reported to extend into the interior of the ternary system. For the present study, the annotated diagram of the Cu-Sn system prepared by Raynor' and the Cu-Mn diagram by Dean and coworkers9 were used as the binary borders of the ternary system. Procedure The metals used in this investigation were electrolytic manganese, washed cathode copper, and three-star tin. The manganese, produced at the Boulder City pilot plant of the Bureau of Mines, had a purity of 99.9 pct; the copper contained less than 0.004 pct Bi and 0.001 pct S; the tin contained 0.070 pct Pb, 0.070 pct Sb, 0.050 pct Fe, and 0.065 pct Si. Heats of 1 lb were melted in alundum crucibles with a 3-kw induction furnace. The heats were chill-cast in iron or copper molds to form 6-in. ingots 3/4 in. in diameter. Molds were washed with graphite or zirconia, depending on the manganese content, and preheated to 150°C. The maximum impurity content of any alloy was 0.03 pct Fe, 0.02 pct Si, and 0.02 pct Al; in most cases, they contained less than half this quantity of any of these impurities. Composition of the alloys and their treatment prior to homogenizing are shown in Fig. 1. Designations adjacent to each composition refer to the heat numbers. With a few exceptions, ingots containing 20 pct Sn or less were hot-swaged. These ingots were swaged, after a 24-hr preheat at 650°C, to obtain a total reduction of 70 pct in cross section. Intermittent reheating was necessary, and reductions were limited to either 0.025 or 0.050 in. in diameter per pass. Selection of a 200-hr homogenizing treatment was based on extensive experiments which indicated that virtual equilibrium was reached after 150 hr. Structures were retained by quenching in water. Grain sizes in the specimens homogenized at 350" and 450°C were generally small. These homogenizing treatments were preceded by a 50-hr anneal at 650°C to facilitate phase identification by increasing the grain size in these specimens. The specimens were furnace-cooled from this temperature to the homogenizing temperature, and the heat treatment was continued for the standard 200-hr period. The homogenized samples were bisected to provide an internal section for metallographic examination. Optimum definition of the microstructure was obtained by successive polishing and etching. Quarter-strength ASTM copper reagent No. 13 gave the most satisfactory results.10 Filings from interior sections of the samples were used for diffraction studies. These filings were annealed in evacuated glass tubes at homogenizing temperatures for periods exceeding 50 hr and quenched in water. During this treatment the manganese content was reduced by significant amounts, probably by vaporization. This change in composition was considered in applying the diffraction data, which were used only as a means of identifying phases where the data were consistent with the metallographic evidence. Phase Identification The a solid solution is readily distinguished by the copper-colored, twinned, polyhedral grains, as shown in Fig. 2, and a face-centered cubic X-ray pattern. Tukon indentations, using a 25-g load, indicate a Knoop hardness of 155 for a quenched from 650°C. Using white light developed by a Wratten 78 A filter, the ß grains in etched specimens have a dark brown tint in contrast to the lighter copper-colored grains of the a phase. Knoop hardness values of 284 were obtained for the ß structure in specimens quenched from 650°C. The ß structure was also distinguished from the a phase by its body-centered cubic lattice. The acicular structure appearing in Fig. 3 was evident in several alloys of higher tin content after quenching from either 750' or 650°C. Since a trans-

Jan 1, 1954