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By R. S. Dean. J. R. Long T. R. Graham, Roberson A. H., Armantrout C. E.

The general program of the Federal Bureau of Mines on the study of alloys made with electrolytic manganese has been extended to copper-manganese-aluminum alloys. The initial results of the work are presented in this report and concern a determination of the mutual solubilities of these three metals to form the alpha solid solution. The principal studies of this system, reported in the literature, have been focused on the Heusler alloys containing ro to 30 per cent Mn with 9 to 15 per cent Al. These investigations concern the ferromagnetic properties and the determination of the crystallization contours, with little emphasis on the phases present in the solid state outside of this area. Heuslerl recognized a breakdown of the beta solid solution of the magnetic alloy, which he says decomposes into the alpha, beta, and gamma phases of the copper-aluminum system, somewhat modified by the presence of manganese. Rosenhain and Lantsberry2 examined alloys ranging up to 10 per cent Mn and 10 per cent A1 but were unable to reach definite conclusions concerning the phase boundaries in that area. Krings and Ostmann3 made magnetic studies and examined the system by thermal analysis. They present contours of the liquidus surface but do not place any of the phase boundaries. Corson4 has drawn a hypothetical boundary for the alpha field with few, data to support such construction. The binary systems involved have rcceived considerable attention by numerous investigators, and their general features are well established. The copper-ahminum system (Fig. I) has been thoroughly examined by Stockdale,5 who places the limit of solubility of aluminum in copper at 7.4 per cent at the liquidus and 9.5 per cent at room temperature. Smith6 established the eutectoid temperature at 570°C. by a study of isothermal decomposition of the beta phase. The copper-manganese system (Fig' ') has been recently reviewed by Dean and CO-WorkersS.7 Using high-purity alloys,

Jan 1, 1947

By Armantrout C. E., R. S. Dean. J. R. Long T. R. Graham, Roberson A. H.

The general program of the Federal Bureau of Mines on the study of alloys made with electrolytic manganese has been extended to copper-manganese-aluminum alloys. The initial results of the work are presented in this report and concern a determination of the mutual solubilities of these three metals to form the alpha solid solution. The principal studies of this system, reported in the literature, have been focused on the Heusler alloys containing ro to 30 per cent Mn with 9 to 15 per cent Al. These investigations concern the ferromagnetic properties and the determination of the crystallization contours, with little emphasis on the phases present in the solid state outside of this area. Heuslerl recognized a breakdown of the beta solid solution of the magnetic alloy, which he says decomposes into the alpha, beta, and gamma phases of the copper-aluminum system, somewhat modified by the presence of manganese. Rosenhain and Lantsberry2 examined alloys ranging up to 10 per cent Mn and 10 per cent A1 but were unable to reach definite conclusions concerning the phase boundaries in that area. Krings and Ostmann3 made magnetic studies and examined the system by thermal analysis. They present contours of the liquidus surface but do not place any of the phase boundaries. Corson4 has drawn a hypothetical boundary for the alpha field with few, data to support such construction. The binary systems involved have rcceived considerable attention by numerous investigators, and their general features are well established. The copper-ahminum system (Fig. I) has been thoroughly examined by Stockdale,5 who places the limit of solubility of aluminum in copper at 7.4 per cent at the liquidus and 9.5 per cent at room temperature. Smith6 established the eutectoid temperature at 570°C. by a study of isothermal decomposition of the beta phase. The copper-manganese system (Fig' ') has been recently reviewed by Dean and CO-WorkersS.7 Using high-purity alloys,

Jan 1, 1947

THE problem of reaction rates in the open-hearth process is essentially that of trying to form a fairly clear picture of the "chemical mechanisms" in the bath. Quantitative data on reaction rates would perhaps not be of much practical importance even if they were available; however, what few approximate data there are can be used in combination with data given in Chapters 16 and 17 to sketch a picture of the "chemical mechanics" of the open-hearth process that is consistent with essentially all the present available evidence. The result may later be found incorrect in many details but even so it will illustrate certain useful methods for obtaining a clearer understanding of the process. Consistent with the treatment in Chapter 15, but in simpler terms, we may say that chemical reactions in general involve the following elements or steps: 1. The reacting molecules are mixed together in space in such fashion as to favor collisions among them. 2. Units of what is usually an intermediate molecular arrangement called an activated complex are formed at a certain rate, depending on temperature and concentrations. 3. These activated complex units decompose into the reaction products (this step usually assumed to be so rapid as never to limit the over-all process). 4. In any of these steps, heat energy may have to flow into, or away from, the reaction zone to permit the reaction to proceed. 5. The products of reaction will usually have to move out of the way to permit further reaction. The temperature factor enters mainly through step 2, and its effect is very marked. (What is called temperature is really the mean energy content of all the molecules of the substance involved; at any one temperature a certain proportion of the moleculea will have much higher energy content than the mean value.) Various reaction rates measured at around room tem-

Jan 1, 1951

By James B. Graham, Earle E. Smith

The value of all minerals produced in the United States for the years 1930 to 1932 averaged $3,460,000,000 annually, according to Bureau of Mines reports. Of this amount, approximately $1,280,000,000 represents nonmetallic substances, such as petroleum, gas, sulfur and salt produced as fluids. Thus, about.37 per cent of the country's mineral wealth is procured through wells drilled in the earth, which require casing to keep them open throughout their life. Deep well drilling has increased greatly in the last few years. Several strings of casing have been set deeper than 9000 ft.—one, a string of 7?-in. O.D. casing, 10,301 ft. long, run in a well drilled by the Gulf Production Co. in West Texas, holds the record up to this time. These are longer strings than were contemplated when the American Petroleum Institute Specifications were adopted 10 years ago, therefore it is necessary to consider whether the present joint standards are adequate for such strings, or for even longer strings that may be called for in the future. Petroleum engineers are asking: Is there a possibility that stronger joints can be designed without going to stronger and more costly steels than offered in present specifications? Without sacrificing too greatly the tensile properties of the joint, can its design be changed to allow more clearance in the open hole below the next larger string of casing, and thus avoid costly underreaming? What can manufacturers offer for drilling through heaving shale? Fundamentals of the Problem During the last few years considerable study has been given to casing joints and their limitations, and since attention must be given to this subject by those who will be required to drill deeper holes, it is timely to review the fundamentals of the problem. These will be recognized generally as the following: 1. No threaded joint can be stronger than the area of metal under the root of the first perfect thread, and this area must be large enough

Jan 1, 1935

By Leo Dana

As a part of an investigation conducted by the Cement Section of the Bureau of Standards, at the plant of the Security Cement & Lime Co., Security, Md., the High-temperature Measurements Section was called upon to measure temperatures in a dry-process, coal-burning kiln. Although the measurements were made only under the conditions existing in one plant, the methods employed and the conclusions drawn apply, in a general way, to those existing in most plants. As far as we have been able to learn, no sufficiently thorough methods of making accurate pyrometric measurements in the sintering zone and in the rear end of rotary cement kilns have been described. It is believed that in this investigation, data were obtained that can serve as a foundation for further study of the problems of pyrometry in cement kilns. IMPORTANCE OF TEMPERATURE MEASUREMENTS IN ROTARY CEMENT KILNS The manufacture of Portland cement is today fairly well standardized. The various steps in the manufacture have been developed to such an extent that the process is almost automatic. In spite of these strides the efficiency of utilization of heat in the kiln is very low and an undue proportion is wasted; for example, about 50 per cent; ordinarily goes up the stack. In order to prevent these losses, not only should means be provided to utilize the waste heat but instruments, such as pyrometers, should be installed to study and control the operation with the view of minimizing the losses. At the same time, such control will produce a more uniform product. The saving in-fuel that may be effected by the proper use of pyrometers would be much more than their cost. Where these pyrometers should be installed and what they can show are very briefly indicated in the following paragraphs and discussed in greater detail later.

Jan 9, 1919

By Anthony F. Lucas

Certain geological indications at Glady's station, four miles south of Beaumont, on the Sabine and East Texas railway (a branch of the Southern Pacific) induced me to undertake a thorough test of that locality by means of a well. I had been making reconnoissances for nearly two years in that part of Texas, before deciding upon this supreme effort. Three previous attempts had been made in the same place: one in 1894 by Messrs. Sharp & Co.; one in 1896 by Mr. J. Looney; and one in 1898 by Messrs. Savage Bros. They had all failed to pass though the immense thickness (500 ft.) of quicksand which underlies the surface soil, clay, etc. At first, I employed the system of boring which I had previously used in the Louisiana salt-deposits.* But I soon found that this method was inadequate, without modification, to deal with the quicksand. Accordingly, I adopted the use of large and heavy castings, and pipes of 12, 10, 8, 6 and 4 in. diameter, successively telescoped one into the other. Boring was begun by Messrs. Hamill Bros., of Corsicana, contractors, about the middle of October, 1900; and on January 10,1901, after many difficulties, a layer of rock containing marine shells was reached, at the depth of 1160 ft. For 150 ft. immediately above, the drill had passed through layers of sandstone and concretions of limestone. At this time there was about 600 ft. of 4-in. pipe, weighing at least 6 tons, in the well; and this, together with the next (6-in.) casing above, was filled with water. When the rock was penetrated the well " blew out," lifting the whole of the 4in. pipe. Mr. Hamill was on the top of the 60-ft. derrick when

Jan 1, 1902

By A. Q. Tool

THE necessity of accurate temperature measurements in the glass-making industries is today being much more widely appreciated than in the past. The introduction of the modern simplified and perfected pyrometric methods in connection with exact regulation of furnace temperatures has caused a marked improvement in the glass product with a quickened rate of production. An example of the processes in which much improvement has been and still can be made is that of annealing or heat-treating the glass. This is one of the most delicate processes in glass manufacture and one that requires a most careful furnace control. The heat treatment is undertaken to decrease the possibility of breakage and, in glass for fine optical instruments, to prevent serious warping of accurately ground and polished surfaces and to make the glass more uniform throughout to the passage of light waves. These objects are accomplished by removing all the harmful stresses that exist in a piece of glass when it has been cooled too quickly or unevenly. Such stresses exist, for example, after it has been pressed, cast, or otherwise worked. Thus the process of annealing consists of heating the glass evenly to the temperature at which it softens just enough to relieve these stresses in a reasonable time and then cooling slowly and uniformly until the glass hardens again. Accordingly, the things that must be investigated and determined in order to anneal glass without loss of time are, the annealing temperature, the time that the glass should be held at this temperature while the stresses relax, and the quickest cooling procedure that will give satisfactory results. After these characteristics of the glass are known the problem is one of pyrometry and temperature control entirely. In cases when it is known that a glass article will be required to withstand some definite type of heat or mechanical shock it is often possible, by a proper heat treatment, to produce such a distribution of the stresses in the glass that it will be enabled to resist these shocks more effectively.

Jan 9, 1919

By A. Sutulov

The segregation process, an alternative to benefi-ciation of oxidized and mixed sulfide-oxide copper ores, is studied here with particular emphasis placed on time, temperature, and coke and salt percentage factors. The results show that in a segregated charge, the copper assay of the coarsest fractions normally is of the same order as the copper assay of the tails obtained from grinding and flotation of the same charge. This observation suggests the possibility of limiting or even eliminating the grinding step from the flowsheet of a segregation plant. The segregation process, which offers an alternative to beneficiation of oxidized and mixed sulfide-oxide copper ores, was discovered in 1923 by Moulden and Taplin1,2 who were attempting to apply the Perkins process3'4 to a Chilean ore from the Sagasca mine. After a number of investigations and pilot plant tests,'-' the segregation process became a successful industrial operation.'r9 The process aroused considerable interest in Chile because of the existance of large reserves of oxidized copper minerals which could not be treated by conventional hydrometallurgical methods because of the high consumption and prohibitive cost of sulfuric acid. During the last two years, the Mineral Dressing Dept. of the Institute de Investigaciones Tecnology cas of University of concepci6n (Chile) has carried out a test program on 23 different ore samples representative of the national territory. These tests were carried out on a semi-continuous and batch scale with a rotary, automatically controlled and gas-fired furnace (supplied by Bartlett and Snow, Fig. 1). The results of these tests indicate that out of the 23 samples 20 can be successfully treated by this process with recoveries of copper ranging from 85 to 95%.10,11 The purpose of this paper is to treat some specific problems related to the segregation process. TIME AND TEMPERATURE FACTORS Time and temperature of calcination play an important role in the segregation process. When moderate salt and coke conditions were maintained (each of reagents was added in the quantity of 1 — % wt), systematic testing easily demonstrated the influence of these two factors on segregation and flotation recovery. The pertinent results are summarized in Fig. 2. To determine what specific changes the segregation process made on the ore, the samples, segregated at 700°C for different periods of time and under standard conditions, were granulometrically analysed and

Jan 1, 1963

By W. E. Keck

THERE is a considerable tonnage of iron ore in the Menominee Range Michigan that is unsalable only because it has too large a content of sulphur. Beneficiation of such ore is economically desirable, as a rela-tively large quantity of finished concentrate would be obtained (deleteri-ous sulphur mineral content being generally less than 5 per cent) and because large blocks of such ore have been developed incidentally during search for low-sulphur ore. Research on the flotation beneficiation of these high-sulphur ores consisted of: (1) a study of the flotative properties of the principal min-erals in a nearly puree state, (2) flotation of synthetic mixtures of these pure minerals and (3) application of this experimental information to samples of the ores. Gypsum in iron ores is extremely deleterious; but when sufficiently free from impurities it is a valuable commodity. In 1934, the United States produced 1,500,000 tons of calcined and uncalcined gypsum valued at $13,700,000'. Of this quantity and value, Michigan produced approxi-mately 19 per cent4. Thus this investigation may also prove to be of interest in connection with the gypsum industry if minerals separation, such as flotation, becomes necessary in the future processing of gypsum. Data on the flotative properties of gypsum would also be of interest to the science of flotation because such information has been extremely limited. The technical literature reveals one reference to the flotation of gypsum, in which was discussed the use of the mineral, with several others, to determine the relation between the floatability of minerals and the pH of the flotation solution2. This investigation necessarily was not comprehensive in regard to gypsum, but it did show that the mineral could be floated with oleic acid under varying pH conditions.

Jan 1, 1937

By D. J. Jr. McAdam

Fort the past five years, an investigation of the endurance properties of metals has been in progress at the U. S. Naval Engineering Experiment Station, Annapolis, Md. As a result of the investigations at this Station1-5 and other laboratories6-11 "endurance limits" of practically all kinds of carbon and alloy steels have been determined and have been correlated with other physical properties, especially with tensile strength. About a year and a half ago, the investigation at the Naval Experiment Station was shifted to non-ferrous metals. As a result, several papers discussing the endurance properties of numerous non-ferrous metals and alloys, especially the alloys of nickel and of copper12-16 have been published. In these papers, stress-cycle graphs illustrate. the endurance properties of each individual metal and alloy, and other graphs illustrate the effect of cold working, heat treatment, and chemical composition on endurance and other physical properties. Endurance tests of non-ferrous metals were made by the machines used in the endurance tests of ferrous metals. 1-4 The specimen for the rotating-cantilever tests, which has been described, 1,2,13 has a conical surface, with taper so adjusted that the stress is nearly uniform over a length of about 1 ½ in. Alternating torsion tests were made with the machine of the inertia types17 and usually by an accelerated-fatigue method.12 As the rotating-cantilever endurance limits of metals are about twice the alternating-torsion endurance limits, the former values are more generally useful in correlating the endurance properties of nonferrous metals. In several recent papers by the writer13-16 correlation of the endurance properties of a number of non-ferrous metals has been discussed.

Jan 10, 1925

By E. O. Kirkendall

The investigation reported herein was undertaken to obtain data to supplement those presented in an earlier paper,l particularly for longer times at a higher temperature. This information may further develop our knowledge of the mechanism of diffusion in substitutional solid solutions. Diffusion of solute atoms interstitially dissolved is not difficult to visualize: it can take place without much disturbance of the solvent atoms. The mechanism of diffusion of solute atoms substitutionally dissolved is not so easily understood. Many theories have been advanced. Rosen-hain,2,3 Frenkel,4 Smekal,5 Langmuir,3,6 Steigman, Shockley and Nix,' and Johnson8 all proposed theories to explain diffusion. Langmuir's proposed mechanism consisted of a simple cyclic interchange of atoms involving an interchange in lattice positions of four or more atoms. This mechanism, accepted by the author at the time of his previous publication,1 and apparently quite generally accepted, required a net exchange in positions of both solute and solvent atoms in equal numbers. In other words, the rate of diffusion of the solvent and solute atoms would be the same. That this cyclic interchange in lattice positions of solute and solvent atoms in equal numbers is the only true mechanism of diffusion is denied by the evidence presented in this paper. Experimental Procedure This modification of similar procedure1 will be outlined briefly. The method consisted of the following steps: I. A pure Muntz metal (60.6 per cent Cu, 0.1 per cent total impurities) that was almost all beta brass at 780°C. was chosen. 2. The brass was turned between centers in a lathe to a diameter of 0.5965 inches. 3. After the brass was cleaned, it was electroplated with pure copper to a diameter of about one inch. 4. The sample was heated slowly to 400°C. under reduced pressure and held at that temperature for 4 hr. to remove occluded gases. It was then cooled to room temperature. 5. The sample was heated to 780°C. ± 3°C. and held at that temperature for different lengths of time; then quenched. Samples were cut off each time after quenching. Metallographic samples 1/4 in. thick were removed at I hr., 6 hr., 24 hr., 96 hr. and 701 hr. After 96 and 701 hr. samples of about I in. were removed for X-ray analysis. 6. The metallographic samples were polished on the cross section and photomicrographs were taken. 7. The I-in. samples were polished and etched on both ends. With the aid of a microscope each was carefully mounted in a four-jaw chuck in a lathe, so that they could be accurately bored for an arbor. 8. Turnings were taken for each X-ray sample. After each set of turnings, the sample was heated in an oil bath for about 1/2 hr. at 300°C. It was then etched in 25

Jan 1, 1942

By E. O. Kirkendall

The investigation reported herein was undertaken to obtain data to supplement those presented in an earlier paper,l particularly for longer times at a higher temperature. This information may further develop our knowledge of the mechanism of diffusion in substitutional solid solutions. Diffusion of solute atoms interstitially dissolved is not difficult to visualize: it can take place without much disturbance of the solvent atoms. The mechanism of diffusion of solute atoms substitutionally dissolved is not so easily understood. Many theories have been advanced. Rosen-hain,2,3 Frenkel,4 Smekal,5 Langmuir,3,6 Steigman, Shockley and Nix,' and Johnson8 all proposed theories to explain diffusion. Langmuir's proposed mechanism consisted of a simple cyclic interchange of atoms involving an interchange in lattice positions of four or more atoms. This mechanism, accepted by the author at the time of his previous publication,1 and apparently quite generally accepted, required a net exchange in positions of both solute and solvent atoms in equal numbers. In other words, the rate of diffusion of the solvent and solute atoms would be the same. That this cyclic interchange in lattice positions of solute and solvent atoms in equal numbers is the only true mechanism of diffusion is denied by the evidence presented in this paper. Experimental Procedure This modification of similar procedure1 will be outlined briefly. The method consisted of the following steps: I. A pure Muntz metal (60.6 per cent Cu, 0.1 per cent total impurities) that was almost all beta brass at 780°C. was chosen. 2. The brass was turned between centers in a lathe to a diameter of 0.5965 inches. 3. After the brass was cleaned, it was electroplated with pure copper to a diameter of about one inch. 4. The sample was heated slowly to 400°C. under reduced pressure and held at that temperature for 4 hr. to remove occluded gases. It was then cooled to room temperature. 5. The sample was heated to 780°C. ± 3°C. and held at that temperature for different lengths of time; then quenched. Samples were cut off each time after quenching. Metallographic samples 1/4 in. thick were removed at I hr., 6 hr., 24 hr., 96 hr. and 701 hr. After 96 and 701 hr. samples of about I in. were removed for X-ray analysis. 6. The metallographic samples were polished on the cross section and photomicrographs were taken. 7. The I-in. samples were polished and etched on both ends. With the aid of a microscope each was carefully mounted in a four-jaw chuck in a lathe, so that they could be accurately bored for an arbor. 8. Turnings were taken for each X-ray sample. After each set of turnings, the sample was heated in an oil bath for about 1/2 hr. at 300°C. It was then etched in 25

Jan 1, 1942

By Charles A. Ashburner

[The statistics contained in this paper were collected for the United States Geological Survey and communicated to the Institute, by permission, prior to their publication in the report on the Mineral Statistics of the United States for 1887.1 The total coal-production of Alabama in 1887 was about 1,950,000 short tons, the spot-value of which, at the mines, was $2,535,000. The coal-regions of the State lie in the extreme southern part of the Appalachian coal-field, the northern part of which lies along the western New York-Pennsylvania State line; between these limits, New York on the north and Alabama on the south, portions of the

Jan 1, 1889

By R. M. Hudson

The removal of nitrogen from a nitrogenized low-carbon sheet steel that contained 0.011 wt pct N was determined during heat treatment in Hz-N, mixtures. TIze process followed a first-order rate law; that is, plots of the logarithm of nitrogen content in steel were linear with the time of treatment at a given temperature. The rate of removal increased with an increase in temperature from 900" to 1300°F. By 1400°F the rate in dry hydrogen had decreased to a value intermediate between the rates at 1200" and at 1300°F; in wet (2.47 vol pct water vapor) hydrogen the rate at 1400°F was less than the rate at 1300°F and nearly the same as the rate at 1200OF. The rate at a given temperature increased as the 3/2 power of hydrogen concentration in the atmosphere. While wet atmosplzeres were generally more effective than the corresponding dry atmosplzeres, the effect of water vapor was much less pronounced than the influence of hydrogen content. NITROGEN is the principal agent in the strain aging of ferrite, the effect of carbon being secondary.' To eliminate the return of the yield point after straining and aging, it is claimed2 that the amount of nitrogen in solution in steel must be reduced to 0.0002 wt pct. Strong nitride-forming elements (titanium, vanadium, zirconium, and aluminum) can act to eliminate strain aging by combining with nitrogen. It is extremely difficult to decrease the nitrogen content in commercial steels to the low level required by conventional coil annealing because of the poor contact between the strip surface and the reactive atmosphere. However, a variety of gas-metal reactions can be effected by use of the open-coil annealing method,3 in which the metal surface is fully exposed to the atmosphere. With this possibility in mind, the Applied Research Laboratory has studied the influence of time, temperature, and atmosphere composition on the removal of nitrogen from low-carbon sheet steel. MATERIALS AND EXPERIMENTAL WORK Samples from a commercial nitrogenized low-carbon steel (0.010 in. thick) in the cold-reduced condition were used. The chemical composition of this steel is given in Table I. The gas mixtures used are listed in Table 11. The moisture content in the "wet" annealing atmospheres was controlled at a +70°F dew point (2.47 vol pct water vapor) by passing the gas mixture through a glass tube packed with a solid mixture of 10 pct anhydrous oxalic acid and 90 pct oxalic acid dihydrate held at 127°F; this technique has been described previously.4 For "dry" atmospheres, the gas mixtures were passed through a cold trap immersed in liquid nitrogen. A hinged-top Hevi-Duty electric furnace was used with a Vycor-glass furnace tube. When the furnace was at the desired temperature, the gas mixture was passed through the furnace at a flow rate between 1.1 and 1.2 cfh; coupons (size 3 by 3/4 in.) of the steel were pulled into the center of the Vycor-glass

Jan 1, 1964

By Brian F. Dyson

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

Jan 1, 1963

By E. B. Hunt, T. M. Geffen, C. R. Stewart, V. J. Berry

Laboratory data .show that the gas-oil ratio performance of non-uniform porosity limestones produced by solution gas drive is sensitive to producing rate and to fluid properties. Nan-uniform porosity limestones are those for which laboratcry solution and external gas drive tests yield considerably different relative permeability ratio characterislics. The oil recovery performance by solution gas drive depends directly on the number of gas bubbles formed. Laboratory rates of pressure decline, which are 100 to 10,000 times greater than normal field rates. cause the formation of an unusually large number of gas bubbles. This results in abnormally high oil recovery efficiencies. Since it is impractical to reproduce the number of bubbles formed under field conditions, laboratory solution gas drive data on non-uniform porosity limestones are therefore not directly applicable to field operations. However, certain laboratory data can be used to make a conservative estimate of field performance. The concepts presented in this paper indicate the possibility that increased field oil recoveries may he obtained from non-uniform porosity limestones by rap- idly reducing reservoir pressure for a short interval of time. It has yet to be established that significant improvements in oil recovery from such reservoirs can he realized by varying the pressure decline rate within limits possible in the field. However, the possibility that recovery may be increased in this manner warrants further study. INTRODUCTION Limestone reservoir rocks can be divided into two general classes according to the nature of their pore space. One class has a comparatively uniform pore system composed mainly of voids between grains of the rock (intergranular type porosity). The other class, in addition to having intergranular porosity, has a secondary pore system composed of combinations of solution cavities, fractures, etc., and is considered to have non-uniform porosity. It has been shown in a previous publication' that the laboratory measured gas-oil flow behavior of uniform type porosity limestones is essentially the same for a test simulating a field solution gas drive as for one simulating an external gas drive. For non-uniform porosity type limestones a significant difference in gas-oil flow behavior was found. More efficient behavior was

Jan 1, 1955

By M. A. Westbrook, J. F. Redmond

A method is presented for obtaining porosities of consolidated formations from the drill returns. The method provides a means of determining the bulk volume of a large number of particles, such as drill cuttings, by employing a capillary diaphragm for removal of surplus surface liquid from saturated cuttings having pores of capillary size, which reduces tile amount of error present in former attempts to determine the porosity of drill cuttings. The method makes it possible to obtain a considerable amount of supplementary data on consolidated formations. Introduction Porosity is a direct measure Of the volume of the voids in a formation. It may be used for estimating the permeability of a formation provided that a correlation of these two properties has been obtained from the analysis of cores from the particular formation, and it forms a desirable aid in interpreting electric logs.1 These useful applications have emphasized the importance of developing a method for determining the porosity of the formations penetrated by a well by some means other than coring, for even in exploration wells it is neither economical nor practical to core all formations. Also, in wells where at the outset the coring program appears comprehensive, it is frequently found that, after certain layers are drilled. more complete information is required for evaluation. Porosity values, if obtainable, would be of great assistance in such cases. In soft formations it is usually possible to obtain porosities after drilling with cores taken by side-wall coring devices. In hard consolidated formations, that coring procedure is not alway practicable and other methods for determining porosities must be resorted to. A first choice is the examination of drill cuttings. if an analytical procedure is available that is both accurate and reasonably rapid. Such a procedure has been devised and is applicable to sand and limestone cuttings having pores of capillary size. Although imp,ovements can yet be made, it is believed that the new technique is sufficiently well developed to warrant description, Preparation of Sample The well samples containing the cuttings representative of the particular intervals are first washed through a No' 6 gauge screen. The cuttings remaining on the Screen are large enough to use lor the porosity measurements' From the sized sample, the cuttings to be examined are separated from the shale and Other extraneous particles. It is recommended that 10 to 15 c.c. of the selected cuttings be used for measurements, although only 4 to 5 c c. were used to make the comparative tests described later in this article. These cuttings are extracted and dried by the same methods used for preparing core samples for porosity and other measurements. The separation, which is at present being carried out by hand, is the most tedious

Jan 1, 1946

By M. A. Westbrook, J. F. Redmond

A method is presented for obtaining porosities of consolidated formations from the drill returns. The method provides a means of determining the bulk volume of a large number of particles, such as drill cuttings, by employing a capillary diaphragm for removal of surplus surface liquid from saturated cuttings having pores of capillary size, which reduces tile amount of error present in former attempts to determine the porosity of drill cuttings. The method makes it possible to obtain a considerable amount of supplementary data on consolidated formations. Introduction Porosity is a direct measure Of the volume of the voids in a formation. It may be used for estimating the permeability of a formation provided that a correlation of these two properties has been obtained from the analysis of cores from the particular formation, and it forms a desirable aid in interpreting electric logs.1 These useful applications have emphasized the importance of developing a method for determining the porosity of the formations penetrated by a well by some means other than coring, for even in exploration wells it is neither economical nor practical to core all formations. Also, in wells where at the outset the coring program appears comprehensive, it is frequently found that, after certain layers are drilled. more complete information is required for evaluation. Porosity values, if obtainable, would be of great assistance in such cases. In soft formations it is usually possible to obtain porosities after drilling with cores taken by side-wall coring devices. In hard consolidated formations, that coring procedure is not alway practicable and other methods for determining porosities must be resorted to. A first choice is the examination of drill cuttings. if an analytical procedure is available that is both accurate and reasonably rapid. Such a procedure has been devised and is applicable to sand and limestone cuttings having pores of capillary size. Although imp,ovements can yet be made, it is believed that the new technique is sufficiently well developed to warrant description, Preparation of Sample The well samples containing the cuttings representative of the particular intervals are first washed through a No' 6 gauge screen. The cuttings remaining on the Screen are large enough to use lor the porosity measurements' From the sized sample, the cuttings to be examined are separated from the shale and Other extraneous particles. It is recommended that 10 to 15 c.c. of the selected cuttings be used for measurements, although only 4 to 5 c c. were used to make the comparative tests described later in this article. These cuttings are extracted and dried by the same methods used for preparing core samples for porosity and other measurements. The separation, which is at present being carried out by hand, is the most tedious

Jan 1, 1946

By R. E. Carter, C. Wagner, F. D. Richardson

By means of inert markers of radio-platinum, it has been shown that cobalt metal oxidizes by out-ward diffusion of cobalt atoms through the oxide. Oxidation rates have been measured at various temperatures and oxygen pressures and have been found to agree with the rates calculated from the Wagner equation and the authors' values for the diffusion coefficient of cobalt in the oxide. The distribution of radio-cobalt in growing oxide loyers has been accurately measured and found to be different from that predicted from the Wagner oxidation theory. Attempts have been made to measure the change of lattice parameter of the oxide with composition. SEVERAL investigators have shown that cobalt metal oxidizes according to the parabolic law,1-3 but no detailed study has been made of the oxidation mechanism. Cobaltous oxide has a metal-deficient lattice, but the defect concentration which is dependent on the oxygen pressure is only approximately known.' From the similarities in the structures of "CoO" and "FeO" and the rate laws governing the oxidation of cobalt and iron, Gulbransen- as suggested that cobalt, like iron," oxidizes by diffusion of cobaltous ions through the oxide layer. To substantiate this hypothesis, he has attempted to measure the oxidation rate of cobalt as a function of the oxygen pressure but has been able to report only that the rate depends on a "small" power of the pressure. On the other hand, Preece," Valensi,' and Arkharov' all have suggested from indirect evidence that oxygen diffuses through the COO to the metal-oxide interface. The present authors, in a previous paper,' have shown that the rate of diffusion of cobalt in cobaltous oxide is dependent on the oxygen pressure. In that investigation, they also found that cobaltous oxide disks made by complete oxidation of cobalt metal were porous at their centers (Fig. 5L, ref. 4). Both these facts strongly suggest that oxidation of the metal proceeds via outward diffusion of cations. In order to establish the mechanism unequivocally, oxidation experiments were made with inert radioactive platinum markers, and the dependence of oxidation rate on oxygen pressure was measured. In addition, an attempt was made to determine the form of the cation vacancy gradient, which the marker experiment showed must exist across a growing oxide layer. This was done by depositing radioactive Co on the surface of a cobalt disk and then measuring the tracer distribution across the oxide layer produced by partial oxidation of the metal. Finally, an X-ray examination was made in an attempt to find the expected change of lattice parameter of COO with oxygen pressure. Experimental The apparatus and materials used were substantially the same as those previously described by the authors.4 Marker Studies: The use of inert markers to follow oxidation reactions was first attempted by Pfeil" in 1929, and radioactive markers have recently been used by Davies et al.' In the investigation reported here, the markers were applied as an (NH4)2PtCI6 slurry in several thin streaks across both faces of four disks of cobalt metal 1 mm thick and 14 mm in diameter. The disks were then oxidized almost to completion at 1200°C in pure oxygen. After oxidation, they were mounted and sectioned and auto-radiographs were taken to locate the markers. Oxidation Rate: The oxidation rate of cobalt was measured at 1148°C at oxygen pressures ranging from 0.0055 to 1.0 atm and at 1000°, 1148", and 1350°C under 1 atm of oxygen. The rate was deter-

Jan 1, 1956

By J. E. Willson, N. K. Bohidar

An evaluation of internal stress distribution based on photoelastic studies and destructive testing of simulation models shows that pillar failure is a function of the internal stress distribution, and that stability can be changed by altering the internal stress pattern. Induced stresses in three-dimensional epoxy disks subjected to uniaxial forces were evaluated by photoelastic studies. Stress profiles across different sections perpendicular to the loading direction revealed two maxima for each profile. Based on the stress distribution for the entire column, an attempt was made to explain pillar spalling and the hour glass pattern of failure in a mine pillar. For maximum stability and optimum design of mine pillars, it is necessary to consider the external forces, the nature and distribution of induced stresses and the characteristics of the pillar material as determined in the laboratory. This paper summarizes the research done by N. K. Bohidarl and Ben L. seegrniller2 as partial fulfilment of the requirement for Master of Science degree in Mining Engineering, University of Utah. It is an evaluation of a study to determine the stress distribution in short columns in order that regions of high stress concentration in mine pillars may be found and their effect on pillar failure be ascertained. The ratios of the dimensions of the columns studied are representative of those found in mines located in flat-bedded deposits. The weight of the overburden generally constitutes the major external force. This force is calculated by taking into account specific weight and thickness of the cover. Determination of the distribution of this force on pillars may often require a complex analytical study. There have been many investigations of the strength

Jan 1, 1968