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By J. S. Marsh

JOSEPH PRIESTLEY prepared oxygen on Aug. 1, 1774, and noted with great surprise "that a candle burned in this air with a remarkable brilliant flame." On Aug. 2, 1774, some ironmaker possibly began to wonder if this substance could be used to increase his rate of production; at any rate, there is no disputing the fact that the notion of using oxygen for steelmaking in concentrations greater than that available in great abundance-as air-has been in existence for years. Action was delayed by the lack of enough oxygen at a cost within reach of the steelmaker. Within the last several years enough has been available to permit large-scale tests of its use for both combustion, with which this paper is concerned, and for decarburization. The literature is now enormous and easily available; it is sufficient here to cite three items of historic- importance in that all are about 25 years old and in that all are remarkably consistent as far as they go, with what is known today.1,2,3 SIGNIFICANCE OF HIGH-TEMPERATURE HEAT The principal 'function of the open-hearth furnace is to supply sufficient, high-temperature heat to melt the charge and then to increase its temperature to a range suitable for tapping, ordinarily in the neighborhood of 2900°F. That heat is required to make steel everybody; however, there seems to be some confusion now and then about the significance of high-temperature heat. Transfer of energy-and heat is energy is always from a point of higher potential to a point of lower potential and, other things being equal, the greater the potential difference, the greater is the rate of transfer of energy. In the open hearth the flame, of course, is the high-potential source. Perhaps the most satisfactory approach is through the notion of theoretical flame temperature; which is the ratio of heat input to the heat content of the combustion products,* the former is composed mainly of heat of combustion of the fuel plus sensible heat of the fuel plus sensible heat of the combustion air. Thus, flame temperature can be increased by increasing the value of the numerator, by decreasing the value of the denominator, or both. The first method is as old as the open-hearth process and, of course, makes use of preheated air; its possibilities have been by no means exhausted. The second method can be put into effect only by changing the composition of the combustion air, since the combustion of a given quantity of fuel produces a definite quantity of product, and since the denominator includes the non-reactive fraction of the air, principally nitrogen. In other words, the denominator consists of the volume of exit gas multiplied by its heat capacity and that volume consists of carbon l is understood by dioxide and water vapor as reaction

Jan 1, 1948

By R. N. Orava, L. A. Rice

One of the difficulties encountered in the preparation of titanium specimens for transmission electron microscopy is the formation of a surface hydride phase during the thinning operation at ambient temperatures. This necessarily destroys contrast, obscures features of interest, and often leads to misleading results. By cooling the polishing solution to temperatures below 0°C this problem has been overcome in the past.' However, since the cooling procedure is somewhat inconvenient, a technique was developed at this laboratory for thinning titanium at room temperature. The material examined was A-70 grade commercial-purity titanium purchased from the Crucible Steel Co. of America. The mechanical and thermal treatments, described elsewhere,* yielded a recrystallized grain size of 4 to 5 p. A slice, 0.5 mm thick and 1.5 mm wide, was cut from a bulk specimen2 using a diamond cut-off wheel. The sample was then coated with paraffin wax. Two concentric holes, about 0.03 in. in diam, one at each broad face, were scribed through the wax to the surface of the metal. Subsequent polishing for several minutes resulted in a preferentially thinned or "dimpled" region. Thereafter, the wax was removed and the entire specimen polished to the point of breakthrough at the base of the dimple. Polishing was effected chemically in a solution comprised of 30 pct HF and 70 pct HN03 by volume, kept at room temperature (20" to 25OC). The specimens were mounted in a stereo holder and examined at 100 kv in a Philips l00 B Electron Microscope. A micrograph from a foil prepared in this way is shown in Fig. 1. Several points are noteworthy. This electron micrograph shows neither evidence for the formation of a hydride phase due to specimen preparation nor, moreover, any obvious surface contamination in electron-transparent areas of a freshly prepared foil. Localized variations in foil thickness observed in some specimens seem to be a characteristic of this chemical polish but do not seriously detract from foil quality. With care, the lifetime of a good specimen exceeded 2 hr in the beam. On the other hand, the exposure of a sample to air at atmospheric pressure, when still warm from the beam, clearly resulted in the deterioration of a formerly clean area just previously in the field of view. An example in Fig. 2 of a contaminated region reveals features, and "spots", not unlike those observed in much purer material by Yamane and Ueda. Consequently, one can conclude that: 1) titanium can be thinned satisfactorily in a solution at room temperature for transmission electron microscopy; 2) large-scale precipitates, >50A in diam, are absent in commercial-purity, recrystallized, furnace-cooled, A-70 titanium containing about 3800 wt ppm interstitials and the same amount of iron; 3) care must be taken not to attribute surface contaminants to precipitates. The authors are grateful to the Franklin Institute for financial support and permission to publish.

Jan 1, 1967

By H. T. Bowman

FOR more than 80 years the Bessemer process has depended upon the ability, skill, and judgment of the blower, although as early as the 1860's it was recognized that the process would benefit by some type of instrumental control.1 However, instruments with sufficient recording speeds did not exist, so the end-point determination was always dependent upon the blower's eye. This placed an obstacle in the way of precise experimental work, because of the absence of the necessary records and reference points as reported by Work.2 The use of the photocell provided the instantaneous record of the blow that made this experimental work possible and provided more scientific control for the process as discussed by Graham3' A brief description of the progress of the blow will illustrate the recording function of the instrument. The silicon in the iron is being oxidized during the first minutes of the blow, as pointed out by Henning4 in a table showing the order of metalloid elimination. The product of this oxidation is a solid that remains in the converter, so there is virtually no flame during this part of the blow. This low flame luminosity is illustrated by the flame recording shown in Fig. I, where the silicon blow is plainly marked. The dull flame of the silicon blow gradually gives way to the brilliant carbon flame as the increasing quantities of carbon monoxide formed inside the converter burn to dioxide upon contact with the atmosphere above the vessel. When the carbon reaches some low value under 0.20 per cent, there is insufficient monoxide formed to maintain the dioxide flame, so its intensity drops. Throughout the flame drop carbon continues to burn, until at some value around 0.05 per cent an arrest occurs in the recorded drop. This point has been designated as the end point. The period of time from this end point until the vessel is turned upon its side and blowing has stopped has been called the afterblow. This afterblow is used as a measure of the degree of metal oxidation, and uniformity demands that it be controlled within narrow limits. Iron and blowing conditions are likely to change several times during a turn, necessitating corresponding changes in end-point control. It is the purpose of this paper to discuss these changes, the factors that make them necessary, and their bearing upon the quality of steel. CARBON-FEO RELATIONSHIP In the Bessemer process oxidation relationships are precise. Fig. 2 shows a graph of the carbon-FeO relationship. The familiar "bomb-test" method, described by McCutcheon and Rautio,5 was used for obtaining these and all other dissolved FeO values herein reported, all tests being taken from the converter before deoxidation unless otherwise noted. All tests of 0.10 per cent carbon and above were obtained from metal blown for duplexing. McGinley and Woodworth6 reported iron oxide values for blown metal, but their tests were obtained by a different method than were those

Jan 1, 1942

By J. G. Mravec

The SO-called gas-tube method as developed by Hare, Peterson and Soler for determining the type and content of gases in molten steel is particularly adapted for determining the hydrogen content in molten steel. The development of this method has been quite completely discussed in a paper published by these co-workers in 1937.' The purpose of this paper, therefore, is to familiarize with this method those who arc not well acquainted with it. The principle of the gas-tube method is as fol1ows: One end of an evacuated gas tube is sealed with a very thin copper disk. when this end of the tube is immersed in a test spoonful of molten steel, the copper disk melts almost immediately, allowing a portion of the steel to be drawn up into the evacuated space. Any dissolved gases, and those produced by reactions between the components of the steel during freezing, are liberated into the unfilled portion of the sampling tube. A blob of steel that forms on the immersed end of the tube after the sample is drawn up seals up the end, making it airtight again. The evolved gases are subsequently drawn out of the gas tube through a suitable valve and analyzed by means of an Orsat apparatus. The volume of the sampling tube is sufficiently large so that a pressure considerably below atmospheric is produced after the gas evolution. The low pressure is necessary to effect a nearly complete removal of gases from the steel. Construction oF Sampling Tube The sampling gas-tube apparatus is illustrated in Fig. I. Seamless S.A.E. tubing used for section A is first cut into 7-ft. lengths. Through cxperiencc it was found necessary to use two sizes of tubing for this part, "is-in. and 3/4-in., respectively. The smaller tubing is generally used on the hotter or lower carbon steels. If the inside wall of the tube A is coated with grease or oil, it should be burned out before being machined as follows: One end is machined on the inside diameter to a depth of 34 in., so as to form a seat for a 7/8-in copper disk, which is stamped out from 0.005 to 0.007-in. thick copper sheet. The other end is machined on the outside diameter to a diameter of 1 5/16 in., to take a small reservoir or trap member I?. About 4 in. below the same end, a 1/2-in. hole is drilled to receive the 1/2-in. copper tubing leading to the large reservoir C. The inside of tube A is then thoroughly cleaned with a round wire brush, such as is generally used to clean out shotgun barrels. It is very important that the surface be absolutely free of rust or any nonmetallic coating. Next, the thin copper disk is soldered in place with low-melting silver solder.

Jan 1, 1945

By Maurice Rey, H. Beavers

THROUGH circumstances connected with the war, the senior author lost his records, therefore it has been impossible to include numerical data in this paper. The arsenical quicksilver ore investigated had been roasted, with poor metallurgical results. The vapor-tension temperature curves of mercury and arsenious trioxide are similar, and the arsenical compound hampers the coalescence of mercury drops in the condenser and is the cause of large stack losses. The ore was a gray limestone carrying small amounts of carbon and mineralized with cinnabar and two arsenic minerals, realgar (As2S2) and arsenopyrite (FeAsS). The proportion of realgar often exceeded that of cinnabar; the proportion of arsenopyrite was smaller. The grade of the ore varied between 0.8 and 4 per cent Hg. The problem was to make a high-grade mercury concentrate, as free from arsenic as possible. The water used throughout the testing was hard, having a pH of about 8. FLOTATION OF REALGAR Realgar showed a very strong tendency to float. It formed a film at the surface of the pulp and floated in abundance with only pine oil. Therefore an attempt was made to float the realgar before the cinnabar, but this was not very successful; the percentage of mercury in the realgar concentrate could never be brought below 2 or 3 per cent. Cinnabar slimed easily and floated with pine oil, so that some of it always accompanied the realgar. There was also the question of the cinnabar-arsenopyrite separation. On further investigation it was found that realgar can be floated not only with pine oil but even better with a combination of hydrocarbons and pine oil. Washing the ore with ether revealed that it contained hydrocarbons, which helped to float the realgar. In this connection it belongs to the same class as carbon, sulphur and talc. It can be floated also with a xanthate, when activated by a heavy-metal salt. The conditions favoring the two types of flotation are opposed, as activation by a copper salt facilitates xanthate flotation (in fact, is even necessary to it), whereas it hinders pine oil and petroleum flotation. One type of flotation can be termed nonpolar and the other polar, a distinction that has been stressed in a previous paper.1 DEPRESSION OF REALGAR AND FLOTATION OF CINNABAR 'Many chemicals were tested in an attempt to float the cinnabar and depress the realgar. Finally starch rendered soluble with caustic soda was tried, also several grades of commercial soluble starch, and dextrin was found to be the best and the most convenient reagent. Several of these starch preparations have a strong flocculating effect on the pulp, which is a distinct disadvantage. Dextrin, with its low flocculating power, is excellent. It is noteworthy that starch preparations are also depressants for carbon and talc, so that the fact apparently has a general

Jan 1, 1941

By Ronald J. Roman

Research pertaining to flow of solutions in leach dumps has generally been neglected. This technical note proposes a method for evaluating the flow patterns and incorporating the results into dump-leaching models. Three dump-leaching models1-3 have been proposed to scale up laboratory test data to expected field results. These models are based on the same physical picture in a dump and differ only in the importance of diffusion or surface chemical reaction rate. Selection of this rate-controlling phenomemon is based on type of ore (sulfide or oxide), physical dimensions of the particles being leached, and the leach heap itself. All three models are applicable to specific types of operations. The models are similar in the use of a size distribution analysis for the dump material and the assumption that the leach solution flows around each particle. Transport of the leaching agent to the interior of the particle takes place by diffusion [(Fig. 1)]. However, normal dumps are of a higher bulk density than the material in a laboratory column used to generate the scale up data. How does this difference in bulk density affect the scale up equations? Increasing the bulk density can be expected to give more particle-to-particle contact; therefore, individual particles will be blinded by each other. As blinding increases with bulk density increase, the particles will behave like larger particles with a coarser apparent size distribution. The extreme will occur when the bulk density reaches that of the undisturbed rock, the entire dump behaving as a single particle with the dimensions of the heap itself. Harris4 alluded to this phenomenon in his paper. An alternative method of describing the same phenomemon is to consider the flow paths of the solution. At high bulk densities leach solution no longer surrounds each particle, but flow paths are separated by several particles and channeling is said to take place. Instead of the particle radius being the maximum distance through which the leaching agent must diffuse, the maximum distance is half the separation distance of the solution flow path. Particle size distribution must then be replaced in the models by the concept of channel separation distribution. Like size distribution, channel separation distribution specifies the cumulative percentage of the rock in the dump situated less than a specified distance from a solution channel. Thus, [ ] Distribution of the solution channels is a function of how the dump was built (among other things), and therefore it cannot be determined in the laboratory. Accordingly, it becomes necessary to determine a range for d and a in existing operations or measuring these parameters before leaching starts. Howard5 gives a clue to one possible technique of measuring solution channel distributions. When his paper was published little was known about the phenomemon of leaching; the importance of this type of data was not recognized. [Fig. 2] is a Y-Y log for one hole drilled

Jan 1, 1978

By A. E. Perkins

fractured ingot will show a complete diagonal structure. If the temperature is lowered, the equi-axed zone is larger and the pine tree growth is less. A small ingot, though, is prone to this columnar structure, even though the casting temperature is kept down. The speed of cooling after solidification is slower in the hollow ingot than in the solid, therefore the granulation, which takes place after the crystals have formed from the liquid metal, is apt to produce larger grains than in the solid ingot. This is not a detriment. The original crystal size is of much more importance. The size of the grains due to this granulation constantly varies in response to mechanical work and subsequent heat treatment. Surface weakness, as shown by seaming and checking on the exterior when working or by cracking in hardening, is in some measure the result of the surface stresses of the ingot when cast. The temperature of the ingot mold or speed of freezing of the exterior of the ingot is of great importance and much seamy and cracked steel is caused by a too quickly cooled skin. Ingots that are turned or milled all over will not seam very much in working, in fact they are practically free from seams, whereas an ingot rolled without a preliminary machining operation is full of seams and cracks, some long and some short. It has been said that these short seams and cracks in the surface of the bar are the result of elongated depressions in the surface of the ingot and that if an ingot is cast very smooth it should give fewer surface defects. This is partly true, but an ingot cast very hot and having a very smooth skin will crack and seam very badly in the mill, as will the surface of an ingot poured very cold, which is very crinkly, because of the low temperature of the metal. The cause of the cracks and seams in one is not the cause of the cracks and seams in the other. The tube method of hollow drill steel manufacture is superior to the older method because of: (1) Greater freedom from external and internal straining; (2) the inherent small crystal size; (3) absence of harmful segregation, resulting in weakness of wall of hole. (4) less liability for steel to crack in inside of hole during forging or hardening; (5) toughening effect, arising from mild steel wall of hole limiting the intense hardening on quenching. Breakage and Heat Treatment or Rock-drill Steel By A. E. Perkins, Pittsburgh, Pa. Actual figures showing the superiority of one section or another are difficult to obtain. In a given size of steel, however, the cruciform sec -tion shows the most breakage; it is inherently a weak section. It contains less steel per foot than any other standard section of the same size and when rolled the wings tend to cool off setting up cooling stresses.

Jan 1, 1922

By William H. Spice

The fault zone of south central Texas showed renewed activity during I940 along a trend roughly paralleling the old established Balcones fault-line group of producing fields. This was a result of the new discoveries in the Wilcox (Eocene) formation in southeastern Texas and Louisiana. As of the end of the year, one new field producing from the Wilcox formation had been discovered on the Washburn ranch in La Salle County, along the southwestern limits of the district, and several projected tests into that formation were under way. In the western part of the district, par-titularly in the part of the Rio Grande embayment that is in Dimmit, Webb and Zavala Counties, there has been renewed leasing activity with the shallower sands in the Navarro-Taylor formations (Upper Cretaceous) as the objective in several projected tests for the early part of 1941. Three new fields have been discovered along the old fault-line trend, but these have been comparatively small, producing either from Dale lime, Austin chalk or Buda lime. No new fields were discovered during the Year in the Edwards (Lower Cretaceous) lime horizon. Approximately 260 wells were drilled in the district during 1940, which resulted in four new oil fields. Twenty-seven new wells were completed in the Proven Edwards lime fields of Darst Creek, Luling and Salt Flat and seven were added to production in the Pearsall field. Approximately 160 wells in 18 counties were completed as failures during the year. The district produced 7,659,634 bbl. during 1940, which was a 9 per cent decrease under production for 1939. In all, 3559 wells were producing at the end of I940, compared with 3562 wells producing at the end of the previous year; 104 new producing wells were completed and 163 wells were abandoned in the producing fields of the district. During 1940 considerable exploratory work was carried on along the Wilcox trend within the district, particularly by major companies employing various types of geophysical methods, and leasing activity increased considerably. At the end of the year, the total number of acres of nonproducing leases held by major companies in the district increased about 10 per cent. It is anticipated that this activity will continue into the first part of 1941 and will be supplemented by several exploratory test wells. New Fields B,, Creek, Caldwett County.— . R. Ogden NO. 2 Talley, discovery well of the Bee Creek field, in the northeastern part of Caldwell County, was completed on March 16, I940, in Dale lime from 2091 to 2238 ft., pumping 85 bbl. per day, 39° A.P.1. gravity. The discovery of this field can be credited to a combination of subsurface geology and magnetometer work, which indicated the presence of a serpentine intrusion. At the end of the year, ,3 producing oil wells had been completed and the field has produced a total of 47,050 barrels.

Jan 1, 1941

By John R. Spencer

A capillary tube variable volume cell is described, which has operated satisfactorily over a range of 100°F and 3,500 psi to 550°F and 1,500 psi. The cell contents are entirely visible over the length of the capillary with the exception of a space at the top amounting to three per cent of the total volume. Observations on the critical behavior of simple systems have been greatly facilitated by the apparatus, it being possible to establish the critical conditions for a particular mixture in the course of a day's run. INTRODUCTION Many types of apparatus have been designed for obtaining data on the phase relationships of hydrocarbon systems. Such apparatus can in general be subdivided into two classifications; (l), indirect measurement of phase volume, and (2), direct visual observation of phase volume, each of which has outstanding advantages and disadvantages. Indirect measurement of phase volume requires the use of rather elaborate apparatus including internal probes in which are located the device for determining the locus of the interface between phases. Such equipment is by its very nature costly, and is complex from the standpoint of operating technique. Probing techniques can be used, however, over wide ranges of temperature and pressure with a high degree of reproducibility. Apparatus for visual observation of phase behavior obviously has the advantage of enabling the experimenter to see exactly what takes place, but because the material to be tested is contained in a cell constructed of both metal and glass, is limited severely as to the temperature range of operation. Furthermore. the maximum pressure usually is limited by the choice of material used for sealing the glass to the metal, and by the strength of the glass itself. In the interest of increased efficiency of observation, as much of the cell as possible should be visible to the eye. Glass capillary tubes have been used successfully but have always given difficulty at the metal-to-glass seal. An apparatus has been devised to overcome the problems of sealing and resistance to temperature effects that have heretofore been the limiting factor with glass apparatus in the observation of phase volumes at elevated temperature and pressure. APPARATUS The objective which dictated the general arrangement of the apparatus (Figs. 1 and 2) was simplicity of operation. The air bath, A, was constructed of an iron framework to which was attached approximately one inch of glass wool bats which were covered on the outside with "Masonite." A roughly octagonal center piece was installed to provide forced circulation of the air by the fan, B, past the heaters, D, cell, F, and thermoregulator, C, respectively. The entire top of the box is removable to facilitate charging of the cell and to permit easy maintenance. Two windows are provided before and behind the cell to allow the operator to observe the contents against the background fluorescent light, E. The heaters,

Jan 1, 1951

By Louis A. Panek

The purpose of this paper is to present a method of designing safe and economical arch structures that are to be constructed of concrete or directly of original earth materials. The experimental data used to illustrate the design method are taken from Bucky and Fen tress,1,2 and the application of the ideas presented by them is extended by obtaining an additional set of curves from which arch structures may be designed. This design method is based upon the following principles of similitude: A scalar model made of the same material as that of the full sized structure will behave similarly to its prototype if the density of the model is increased in the same proportion as its linear scale is decreased. Let R represent the scale or model ratio, namely, the ratio of a prototype linear dimension to the corresponding model linear dimension. The effect of increased density may be obtained by rotating the model in a centrifuge at a speed such that the centrifugal held exerts on the model an accelerative force R times the accelerative force of gravity. Under these conditions; (I) model unit stresses are equal to corresponding prototype unit stresses, (2) the ratio of the prototype deformation at a given point to the model deformation at a similar point is equal to the scale ratio, R, and (3) the model and the prototype will behave similarly within and beyond the elastic limits of strain. According to the above relations, such models can be used to solve the following problems: I. The dimensions of the most economical safe arch structure for a given load. 2. The miaximum safe roof span underground for given geologic conditions. The procedure is described briefly as follows. Tests are made by rotating in a centrifuge a number of models that repiesent a variety of prototype loads and dimensions. From the experimental data, curves are plotted to show the relations between these loads and dimensions. The curves are used to solve directly the problems stated above. Structural design is based upon the working (safe) stress of the material of construction, which is established by applying a factor of safety to the experimentally determined ultimate strength of the material. In conformity with this principle, each model is gradually loaded until failure occurs. A safety factor is then applied to the results. If a safety factor of 4 is used, a given model at failure represents a safe prototype, the linear dimensions of which are equal to one-fourth the model ratio at failure times the corresponding model dimensions. The safe model ratio is computed from the following formula: Safe R =(1/4)4p2n2r/g=p2n2r/g [I] in which: n = centrifuge revolutions per second at model failure; r = radius of rotation of the model in feet; g = 32.2 ft/sec2.

Jan 1, 1949

By John R. Spencer

A capillary tube variable volume cell is described, which has operated satisfactorily over a range of 100°F and 3,500 psi to 550°F and 1,500 psi. The cell contents are entirely visible over the length of the capillary with the exception of a space at the top amounting to three per cent of the total volume. Observations on the critical behavior of simple systems have been greatly facilitated by the apparatus, it being possible to establish the critical conditions for a particular mixture in the course of a day's run. INTRODUCTION Many types of apparatus have been designed for obtaining data on the phase relationships of hydrocarbon systems. Such apparatus can in general be subdivided into two classifications; (l), indirect measurement of phase volume, and (2), direct visual observation of phase volume, each of which has outstanding advantages and disadvantages. Indirect measurement of phase volume requires the use of rather elaborate apparatus including internal probes in which are located the device for determining the locus of the interface between phases. Such equipment is by its very nature costly, and is complex from the standpoint of operating technique. Probing techniques can be used, however, over wide ranges of temperature and pressure with a high degree of reproducibility. Apparatus for visual observation of phase behavior obviously has the advantage of enabling the experimenter to see exactly what takes place, but because the material to be tested is contained in a cell constructed of both metal and glass, is limited severely as to the temperature range of operation. Furthermore. the maximum pressure usually is limited by the choice of material used for sealing the glass to the metal, and by the strength of the glass itself. In the interest of increased efficiency of observation, as much of the cell as possible should be visible to the eye. Glass capillary tubes have been used successfully but have always given difficulty at the metal-to-glass seal. An apparatus has been devised to overcome the problems of sealing and resistance to temperature effects that have heretofore been the limiting factor with glass apparatus in the observation of phase volumes at elevated temperature and pressure. APPARATUS The objective which dictated the general arrangement of the apparatus (Figs. 1 and 2) was simplicity of operation. The air bath, A, was constructed of an iron framework to which was attached approximately one inch of glass wool bats which were covered on the outside with "Masonite." A roughly octagonal center piece was installed to provide forced circulation of the air by the fan, B, past the heaters, D, cell, F, and thermoregulator, C, respectively. The entire top of the box is removable to facilitate charging of the cell and to permit easy maintenance. Two windows are provided before and behind the cell to allow the operator to observe the contents against the background fluorescent light, E. The heaters,

Jan 1, 1951

By W. R. Aufricht, E. H. Koepf

The theory, measurement, and application of capillary forces in reservoir rock have been treated ex-tensively in the various petroleum publications.1,2,3,4 These forces are of prime importance in oil production, and data on capillary properties are among the most important tools used in the study of reservoir mechanics. The principal application of measured capillary pressure data by the production and reservoir engineer is in the determination of the initial distribution and mobility of fluids in the reservoir. The distribution refers to the magnitude of the oil and interstitial water saturations under capillary equilibrium conditions and to their variation throughout the reservoir as a result of changes in rock properties and nearness to free water. The magnitude of the water (or oil) saturation, as well as the porosity, is required in volumetric calculations of oil in place. In low permeability reservoirs, where long transition zones are common, the magnitude of the oil content, even below the depth interval where commercial rates of flow of oil can be obtained, must be evaluated since this oil contains energy available to the production of the remainder of the reservoir. The mobility of the water phase is of particular importance in water-flood calculations since mobile water may condemn what would otherwise be a successful water flood. In reservoirs with predominantly small pores, high immobile water contents are possible. Conversely, reservoirs with predominantly large pores may contain mobile water even though the interstitial water contents are relatively low. This presentation reviews the distribution and mobility of interstitial water contents as determined from capillary pressure data and shows typical data for various types of carbonate reservoirs. A discussion of the variations found in different types of carbonate reservoirs is given. DISCUSSION Interpretation of Laboratory Data Fig. 1 is a typical laboratory capillary Pressure curve where water saturation as Per cent of Pore space is plotted vs capillary Pressure (psig) for an air-water system. This par- ticular curve was obtained by measurement on a sample of San Andres dolomite with intergranular-type porosity. The sample studied had a permeability of 10.0 md and a porosity of 18.8 per cent. The capillary pressure-saturation relationship illustrated is an inherent property of the rock (a function of the size and distribution of the pores) and represents the ability of this water-wet rock to retain water against the pressure differential exerted by a non-wetting fluid (oil or gas) to remove it. In the laboratory a known pressure differential is exerted from a pressure source; in the reservoir the pressure differential is controlled by the density difference between the hvdrocarbons and the water. The laboratory capillary pressure values may be converted into terms of equivalent height of water column using known values of reservoir oil and water density and measured or average values of interfacial tension

Jan 1, 1958

By William H. Spice

The fault zone of south central Texas showed renewed activity during I940 along a trend roughly paralleling the old established Balcones fault-line group of producing fields. This was a result of the new discoveries in the Wilcox (Eocene) formation in southeastern Texas and Louisiana. As of the end of the year, one new field producing from the Wilcox formation had been discovered on the Washburn ranch in La Salle County, along the southwestern limits of the district, and several projected tests into that formation were under way. In the western part of the district, par-titularly in the part of the Rio Grande embayment that is in Dimmit, Webb and Zavala Counties, there has been renewed leasing activity with the shallower sands in the Navarro-Taylor formations (Upper Cretaceous) as the objective in several projected tests for the early part of 1941. Three new fields have been discovered along the old fault-line trend, but these have been comparatively small, producing either from Dale lime, Austin chalk or Buda lime. No new fields were discovered during the Year in the Edwards (Lower Cretaceous) lime horizon. Approximately 260 wells were drilled in the district during 1940, which resulted in four new oil fields. Twenty-seven new wells were completed in the Proven Edwards lime fields of Darst Creek, Luling and Salt Flat and seven were added to production in the Pearsall field. Approximately 160 wells in 18 counties were completed as failures during the year. The district produced 7,659,634 bbl. during 1940, which was a 9 per cent decrease under production for 1939. In all, 3559 wells were producing at the end of I940, compared with 3562 wells producing at the end of the previous year; 104 new producing wells were completed and 163 wells were abandoned in the producing fields of the district. During 1940 considerable exploratory work was carried on along the Wilcox trend within the district, particularly by major companies employing various types of geophysical methods, and leasing activity increased considerably. At the end of the year, the total number of acres of nonproducing leases held by major companies in the district increased about 10 per cent. It is anticipated that this activity will continue into the first part of 1941 and will be supplemented by several exploratory test wells. New Fields B,, Creek, Caldwett County.— . R. Ogden NO. 2 Talley, discovery well of the Bee Creek field, in the northeastern part of Caldwell County, was completed on March 16, I940, in Dale lime from 2091 to 2238 ft., pumping 85 bbl. per day, 39° A.P.1. gravity. The discovery of this field can be credited to a combination of subsurface geology and magnetometer work, which indicated the presence of a serpentine intrusion. At the end of the year, ,3 producing oil wells had been completed and the field has produced a total of 47,050 barrels.

Jan 1, 1941

By B. L. Averbach, E. E. Underwood

The vapor pressure of zinc in equilibrium with solid ß AgZn alloys has been measured by the dew-point method. The thermodynamic activities of silver, and the molar heats of formation have been calculated. Similar measurements have been made for the ternary alloys formed by adding gold to AgZn. An apparent particle size effect has been observed for AgZn filings. The vapor pressure of zinc over filings is 15 to 20 pct higher than over the solid alloys. STATISTICAL methods have been used to inter pret the thermodynamic activities of the components of a solid solution in terms of average equilibrium atomic configurations. In some cases, the atomic arrangements can be measured by X-ray methods, and the results are usually expressed in terms of short range order parameters. Only in the cases of Cu³Au and AgAu have there been sufficient X-ray and thermodynamic data to verify the assumed correlation between the X-ray and the thermodynamic measurements. In Cu³Au the agreement is good; negative deviations from Raoult's law are observed and the number of Cu-Au nearest neighbor pairs predicted on the basis of the thermodynamic treatments agrees quite well with the number of such pairs observed by the X-ray methods. The ß brass alloys present a different set of conditions. The ordering is so rapid in these alloys that the disordered state cannot be retained on quenching. In contrast, the disordered state in CuAu is easily retained on quenching. On heating, the ordered ß brass loses its long range order continuously as the critical temperature is approached; in Cuau the order decreases slightly on heating and then drops discontinuously to zero at the critical temperature. These differences indicate that the short range order configurations in ß brass systems may be of a different character than in Cudu systems. However, X-ray measurements of local order cannot be made in the Cu-Zn alloys because of the similarity in scattering factors. The alloy AgZn is isomorphous with CuZn, however, and recent experiments have indicated that there is a good possibility of observing short range order in this system. Another complication arises in the case of ß AgZn. The disordered body-centered cubic structure exists above 280°C. On quenching from above this temperature an ordered structure of the cesium-chloride type is formed. On slow cooling, however, a complex hexagonal structure, the 3 phase, is produced; and if an ordered quenched alloy is reheated the phase begins to form above 80°C. It is thus difficult to study local order by X-ray methods in single crystals of AgZn since the C phase formed on heating does not necessarily return to a single crystal of the original orientation. This problem has been met, however, by adding a few percent of gold to the AgZn. The gold suppresses the formation of the c

Jan 1, 1952

By Kenneth C. Vincent, A. M. Gaudin

TEN years ago Taggart, Taylor and Ince1 described a workable, convenient apparatus for the measurement of contact angles between cleaved, ground or polished particles and captive bubbles. Wark and Cox2 and Wark and Sutherland3 have done an immense amount of experimental work with this apparatus. Their work has had as principal object the determination of "contact curves." Contact curves are cartesian charts in which pH (or some other variable) is plotted against quantity of modifying agent. The rectangular area is broken into two or more curvilinear areas separated by the contact curve. The curve indicates that a sharp demarcation exists between conditions that bring about sticking of particles to bubbles and conditions that do not produce sticking. The type curve appears in the TRANSACTIONS as Fig. 1, page 248, volume 112. Wark and Cox offer data to show that the contact angle has a value determined by and characteristic of the agent used. Wark and Cox also make the statement that they believe this value is independent of concentration (ref. 2a, p. 209). They say: It is suspected that, given sufficient time and provided that there are no disturbing factors, the full ethyl xanthate angle (corresponding to a complete xanthate film) would be obtained in every case where contact occurs. Such a conclusion, if correct, would tend to substantiate the hypothesis of flotation collection by metathesis championed by Taggart and his associates4-8 and would argue against the adsorption hypothesis now adopted by Wark7 and by one of us.8 However, the data of Wark and Cox do not bear out the conclusion that there is a sharp passage from conditions of contact to conditions of noncontact. Rather, they indicate the existence of a transition zone of reagent concentration across which the contact angle varies with changes in reagent concentration from zero to a value near the maximum. This may be seen, for example, from Fig. 195 in the new text by one of us (ref. 8, p. 380), which presents the data of Wark and Cox in graphical form. The object of this study has been to explore the nature of the transition from conditions of contact to conditions of noncontact. The data of Wark and Cox to which reference has been made as showing that a gradual transition exists are marred by the fact that the region of critical-agent concentration is at an extremely small concentration. This condition suggests that diffusion may have played such a preponderant role that equilibrium was not reached within the time alloted. In the Wark and Cox data, the critical concentration was at about one part of xanthate per million parts of water. To form a monolayer of xanthate on the mineral surface would therefore require depletion of xanthate in the liquid to a depth of the order of

Jan 1, 1940

By James Terry Duce

In order to facilitate interpretation of the data in this chapter, we print the following excerpts from circulars to authors, compiled by Mr. Frank A. Herald when he was Vice-chairman for Production of the Petroleum Division, and revised in 1939. Generally in Table 1 the unit for prescntation of data is a field. For our purposes a field is defined as the whole of a surface area wherein productive locations are continuous. Such unit commonly includes and surrounds nonproductive areas. Such unit commonly includes a great variety of geologic conditions—several units of continuous productive reservoirs of distinctly different structure and of distinctly different stratigraphy. Therefore it is hoped that our authors will subdivide "field" so as to enable students to make analyses that may have scientific and /or commercial value. As to each spacc in the tabulation, it is citller (1) not applicable, (2) the proper entry is not determinable, (3) the proper entry is determinable, but not determinable from data available to the author, (4) the proper entry is determinable by the author. In spaces not applicable, the author will please draw horizontal lines; in spaces where the proper entries are not determinable, the author will please insert x; in spaces where the proper entries are detcrminable but not detcrminable from data available to the author, the author will please insert y; in spaces where the proper entries are determinable by the author he will, of course, make such entries. Generally, y implies a hope that in some future year a definite figure will be available. Inability to determine precisely the correct entry for a particular space should not lead the author to insert merely y. Contributions of great value may be made by the author in many cases where entries arc not subject to precise determination. In such rases the author should use his good judgment and make the best entry possible under the circumstances. For many spaces, the correct entries represent the opinion of the author (for example, "Area Proved") and in such cases the entries need not be hedged to such extent as in cases where the quantities are definite yet can be ascertained only approximately by the author. In cases under definite headings but where figures are only approximate, the author may use x. For example, if the total production of a field is known to be between 1,800,000 and 1,850,000, the author may report 1,8xx,xxx; or if the production is between 1,850,000 and 1,900,000, the author may report 1,9xx,xxx. Where a numeral is immediately to the left of x or y, such numeral represents the nearest known number in that position. As to quantity of gas produced from many fields the question will arise as to whether the figures should include merely the gas marketed or should include also estimates of gas used in operations and gas wasted. Although rough approximations

Jan 1, 1939

By S. F. Ravitz

IN his excellent book on the Principles of Flotation, Wark' makes the following significant statement concerning the theory of flotation: Two questions of first-rate importance must be considered . . . First, it must be decided whether the sulfide minerals require a collector in order that they may float, or whether as has been claimed, they possess an inherent floatability and need no collector. Second, it must be decided whether the xanthate type of collector can react with or be adsorbed by the unchanged sulfide minerals themselves, or whether, as many claim, reaction with the collector is dependent upon initial oxidation of the mineral surface. In the theory of flotation there are no two questions of greater importance than these. Ravitz and Porter' presented evidence that galena can be floated without a collector, and even without any reagent, provided oxidation products are thoroughly removed from its surface. They found also that thoroughly cleaned galena floated faster when xanthate was used than when a frother alone or no reagent was used, and that, without a collector, the recovery decreased gradually upon exposure of the mineral to air. Their work, however, has met with considerable criticism. I(127).3-6 This paper is presented to answer the objections that have been raised, and to present additional data that confirm their results. EXPERIMENTAL PROCEDURE The apparatus used to provide oxygen-free conditions for flotation has been described in detail by Ravitz and Porter. An atmosphere of purified nitrogen was maintained within the apparatus; all water and solutions used were freed of dissolved air, and could be transferred where desired by the use of nitrogen pressure; nitrogen was used as the gaseous medium for flotation. The flotation cell was essentially a glass cylinder 15 cm. long and 4.6 cm. in diameter. Near the bottom was sealed a fritted glass filter, which broke up the gas into small bubbles, and 6 cm. above this filter was a side arm through which the froth overflowed. The pulp was agitated by a glass impeller, which entered the cell through a mercury seal. For each test 17 grams of galena and 75 ml. of water were placed in the cell, after which the speed of the impeller and the rate of gas flow were adjusted. Water was added gradually during the test to keep the froth level at the proper height. The mineral was prepared and cleaned in the following manner. Exceptionally pure galena was crushed by hand on a clean bucking board, screened to - 150+ 200 mesh, and deslimed on a zoo-mesh sieve with a fine spray of water. It was then boiled on a hot plate for a number of hours with several changes of the desired cleaning solution, after which both the solution and the mineral were placed in the "mineral flask" of the apparatus. The cleaning solution was drained off, and the mineral was boiled with oxygen-free water

Jan 1, 1940

By James Terry Duce

In order to facilitate interpretation of the data in this chapter, we print the following excerpts from circulars to authors, compiled by Mr. Frank A. Herald when he was Vice-chairman for Production of the Petroleum Division: Generally in Table 1 the unit for presentation of data is a field. For our purposes a field is defined as the whole of a surface area wherein productive locations are continuous. Such unit commonly includes and surrounds nonproductive areas. Such unit commonly includes a great variety of geologic conditions-several units of continuous productive reservoirs of distinctly different structure and of distinctly different stratigraphy. Therefore it is hoped that our authors will subdivide "field" so as to enable students to make analyses that may have scientific and/or commercial value. As to each space in the tabulation, it is either (I) not applicable, (2) the proper entry is not determinable, (3) the proper entry is determinable, but not determinable from data available to the author, (4) the proper entry is determinable by the author. In spaces not applicable, the author will please draw horizontal lines; in spaces where the proper entries are not determinable, the author will please insert x; in spaces where the proper entries are determinable but not determinable from data available to the author, the author will please insert y; in spaces where the proper entries are determinable by the author he will, of course, make such entries. Generally, y implies a hope that in some future year a definite figure will be available. Inability to determine precisely the correct entry for a particular space should not lead the author to insert merely y. Contributions of great value may be made by the author in many cases where entries are not subject to precise determination. In such cases the author should use his good judgment and make the best entry possible under the circumstances. For many spaces, the correct entries represent the opinion of the author (for example, "Area Proved") and in such cases the entries need not be hedged to such extent as in cases where the quantities are definite yet can be ascertained only approximately by the author. In cases under definite headings but where figures are only approximate, the author may use x. For example, if the total production of a field is known to be between 1,800,000 and 1,850,000, the author may report 1,8xx,xxx; or if the production is between 1,850,000 and 1,900,000, the author may report 1,9xx,xxx. Where a numeral is immediately to the left of x or y, such numeral represents the nearest known number in that position. As to quantity of gas produced from many fields the question will arise as to whether the figures should include merely the gas marketed or should include also estimates of gas used in operations and gas wasted. Although rough approximations

Jan 1, 1938

By Frank A. Herald

Generally in Table 1 the unit for presentation of data is a field. For our purposes a field is defined as the whole of a surface area wherein productive locations are continuous. Such unit commonly includes and surrounds nonproductive areas. Such unit commonly includes a great variety of geologic conditions-—several units of continuous productive reservoirs of distinctly different structure and of distinctly different stratigraphy. Therefore it is hoped that our authors will subdivide "field" so as to enable students to make analyses that may have scientific and /or commercial value. As to each space in the tabulation, it is either (I) not applicable, (2) the proper entry is not determinable, (3) the proper entry is determinable, but not determinable from data available to the author, (4) the proper entry is determinable by the author. In spaces not applicable, the author will please draw horizontal lines; in spaces where the proper entries are not determinable, the author will please insert x; in spaces where the proper entries are determinable but not determinable from data available to the author, the author will please insert y; in spaces where the proper entries are determinable by the author he will, of course, make such entries. Generally, y implies a hope that in some future year a definite figure will be available. Inability to determine precisely the correct entry for a particular space should not lead the author to insert merely y. Contributions of great value may be made by the author in many cases where entries are not subject to precise determination. In such cases the author should use his good judgment and make the best entry possible under the circumstances. For many spaces, the correct entries represent the opinion of the author (for example, "Area Proved") and in such cases the entries need not be hedged to such extent as in cases where the quantities are definite yet can be ascertained only approximately by the author. In cases under definite headings but where figures are only approximate, the author may use 2. For example, if the total production of a field is known to be between 1,800,000 and 1,850,000, the author may report 1,8xx,xxx; or if the production is between 1,850,000 and 1,900,000, the author may report 1,9xx,xxx. Where a numeral is immediately to the left of x or y, such numeral represents the nearest known number in that position. As to quantity of gas produced from many fields the question will arise as to whether the figures should include merely the gas marketed or should include also estimates of gas used in operations and gas wasted. Although rough approximations may be involved, our figures should represent as nearly as possible the total quantity of gas removed from the reservoir. Wile we have not provided a column for showing the thickness of the productive zone, generally the difference between average depth to bottoms of productive wells

Jan 1, 1935

By Theron Wasson

No major oil-field discoveries were made County; the second in Marion township, in Michigan during the year 1940. Produc- Osceola County. Both are producing from tion for the year was maintained by the Stray sand at about 1350 ft. These discoveries made in 1938 and, as a result, is fields are on structures founci by core test-below the total for 1939. Several extensions ing through the glacial drift. The Six Lakes to old fields have been made, which have field, Montcalm County, discovered in helped to maintain production in the face 1934, is Michigan's largest gas-producing of rather rapid decline in the fields of the field. it has 195 wells producing from the southwestern part of the state. Important Michigan Stray sandstone and the Upper extensions were made in Overisel, Porter, Marshall sandstone. This field was devel-Sherman, and Adams fields. Important oil oped on a 40-acre spacing plan, and gas fields of the state are shown on the -map, Fig. I. WiI~dcat Drilling Michigan's production of 19,700,000 bbl. A test in sec. 29, Winterfield township, during 1940 was 3,800,000 bbl. less than Clare County, which is producing oil from the total for 1939, but about one million the Monroe of Devonian age at a depth of greater than 1938. This brings the total 3760 ft., and a well in sec. 31, Lincoln accumulated production for the state to a township, Osceola County, producing from little over 145,000,000 bbl. the Monroe at 3625 it., should be classed as wildcats that are sure to lead to further Active Oil Fields development in I94L The leading producer for the year was the At the end of the year the Gulf Refining Temple field, Clare County, where 29 new Company's deep test on the Kawkawlin wells were drilled. The Walker field, Kent structure in Monitor township, Bay County, was second, but drilled 183 new County, was preparing to drill deeper after wells in order to gain that position. In the having had a gas blowout from a depth of extension of the Overisel field in Allegan 7775 ft. This test is the most important one County, 115 new producers were drilled. drilling at the end of the year in Michigan, The Adams field, Arenac County, was for should it develop commercial produc- revived by several wells with initial production from deeper beds it will lead to deeper tions of over 1000 bbl. per day from the drilling on many well-known structures Dundee of Devonian age. that have been producing from shallower sands. Active Gas Fields Two important gas fields were discovered Exploration by Taggart Brothers during the year. The A small amount of reflection seismograph first was in Riverside township, Missaukee work was done in Clare, Osceola, and Glad-Win Counties during the year. Exploration Manuscript received at the office of the Institute March 28 1941 by shallow drilling for structural informa- tion on beds below the glacial drift con- 347

Jan 1, 1941