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By J. Chipman, J. C. Fulton

BECAUSE of the great importance of the ternary system Fe-C-Si in ferrous metallurgy a considerable amount of attention has been devoted to the phase relations, particularly those occurring in the solid state.' The information on graphite solubility

Jan 1, 1955

By P. Greenfield, P. A. Beck

RECENT work by J. Darby, Jr. in this laboratory has shown that the reported vanadium-rich limit of the s phase in the Co-V system at 1200°C is in error. The appearance of a second phase in s actually is restricted to alloys containing over 68 atomic pct V. The error in the original value is due apparently to a reaction that takes place along the numerous cracks in the s specimens between the alloy and the impurities present in the He + 8 pct H atmosphere in the annealing furnace. Such a reaction and the consequent appearance of a second phase can be suppressed if the alloys are sealed under vacuum in Vycor tubing. The new value of 68 atomic pct V for the vana-dium-rich limit of the s phase in the Co-V system effects slightly the s compositions calculated from average values of N, and N,. for various s phases. The standard deviation between experimental mean compositions and those calculated from the assumption that s is characterized by a constant number of 3d + 4s electrons per atom (N,), is slightly reduced from 9.1 to 8.8 pct. The maximum divergence for the V-Mn s phase is reduced from 15.5 to 14 atomic pct. The standard deviation calculated from constant electron vacancy numbers given by N.. = 4.66 (Mo + Cr + V) + 3.2 (Mn) + 2.2(Fe) + 1.71(Co) + 1.6(Ni) is now greatly reduced, as the maximum divergence for this correlation previously occurred in the V-Co system. This maximum divergence is reduced from 7.6 to 2.3 pct, and the standard deviation for all s- phases is reduced from 4.1 to only 2.9 pct. The correlation for electron vacancy numbers given by N. 5.66 (V when with Ni or Co) + 4.88 (V when with Mn or Fe) + 4.66 (Cr + Mn) + 3.3 (Mn) + 2.66 (Fe) + 1.71 (Co) + 0.61 (Ni) is made slightly worse, and the standard deviation increases from 2.8 to 3.9 pct. These changes, however, do not affect the conclusions of the paper.' The deviation between calculated and experimental s compositions is much less for either one of the electron vacancy correlations than for the correlation with the number of 3d + 4s electrons.

Jan 1, 1955

By Donald W. Scott, Adam Wesner

This paper describes the study of 23 nonmagnetic iron-formation samples from the Mesabi Range and shows the significance of their chemical, mineral, and physical properties in terms of their concentration. Data presented here resulted from a research project carried out from 1942 to 1952 by 10 major producers of iron ore, working in conjunction with Battelle Memorial Institute. THE inevitable depletion of Mesabi direct-shipping iron ores, hastened by recent wars, has increased the importance of developing methods to concentrate iron-formation materials. Many mining companies, independent research organizations, chemical companies, and equipment manufacturers are devoting attention to this important work. It is only natural that magnetic iron-formation materials have received major emphasis, since magnetic recovery methods apply and reserves of Mesabi magnetic taconites are large. However, the nonmagnetic* iron-formation materials are likewise believed to represent a large reserve and their study has not been neglected. tions over the years have shown that in addition to the unenriched taconite, which is dense and hard, and the direct-shipping ore, there are transition taconites grading into the friable wash, or intermediate ores. The transition taconites are less massive than the unaltered taconites and usually coarser-grained. This variation, coupled with the fact that there were no extensive drillings in the unaltered taconite, posed a most difficult problem of obtaining samples that would be representative of large tonnages of the fresh rock. The problem was increased by the tremendous extension of the nonmagnetic formation materials on the Mesabi and by the question of their accessibility to mining. A drilling program was evolved that would surmount these difficulties. Selection of samples was made by a committee representing producers in the area. The samples were procured from 1—taconite walls near bodies of stripping burden or wash ore and 2—from shafts in the process of being sunk through taconite for drainage or mining operations. Most of the samples were obtained from the cherty horizons because it became obvious early in the program that the slaty horizons represented an exceedingly difficult concentration problem, owing to the character of the gangue minerals and the fine grind required for liberation of the valuable minerals. More samples were procured from the lower cherty horizon than from the upper cherty because it was more accessible to mining. It is not known how well the samples selected represent the nonmagnetic iron-formation material. However, they were chosen by people Well acquainted with the geology of the Mesabi range and the mining problems involved. It is believed that they represent a fair cross-section of the types of materials that will be encountered. Table I gives data on the origin of the 23 samples and the horizon footages from which they were obtained. Samples 1 through 10, and 15 and 16

Jan 1, 1955

By Carville E. Sparks, Rollin Farmin

Edward Thomas (U.S. Bureau of Mines, Washington, D. C.)—This excellent article on an ingenious and successful installation of wooden rock bolts loses much of its effectiveness through an attempt by the authors to establish the general adaptability of this type of support. Possibly because they have only local experience as a guide, they imply erroneously in the first paragraph that the Bureau of Mines has been opposed to wooden bolting, although later in the article reference is made to a Bureau publication on the subject. In 1947 the Bureau of Mines decided to sponsor experiments in roof bolting in coal mines because the experience of the St. Joseph Lead Co. had indicated that this type of roof support appeared to be a roof-fall accident-prevention measure that might be adopted and also effect economies in operating cost. Justification for this belief has been borne out, particularly in coal mining. This program has been carried out under the following general program: 1—The Roof Control Section of the Bureau of Mines has advocated and initiated underground experiments under controlled conditions with many different ideas related to rock bolting since 1947. In no instance has cooperation in developing an idea been refused, no matter how ridiculous it may have seemed at first glance, if it has been requested by a mining company. 2—The Bureau of Mines has no police powers over the selection of roof-support devices and seeks none. 3—At the request of an operator, the Bureau of Mines will make comparative tests on various types of bolts underground and will submit resultant data for the operator's consideration. 4—Wherever possible, the Bureau publicizes successful installations, so that others may benefit from this experience; however, it is careful not to discriminate between manufacturers of bolts or bolt-installation equipment. Unsuccessful experiments probably should also be publicized, but from a practical standpoint it is usually not feasible. In other words, the role of the Roof Control Section of the Bureau is in line with the original purpose for which the Bureau was first organized: to serve industry through gathering, analyzing, and disseminating factual data. It would seem to be logical that the starting point for any experimentation on roof bolts in coal mines should be the time-proved practice of the

Jan 1, 1955

By L. W. Brandt

Studies of liquid-vapor equilibria of gas mixtures at the Bureau of Mines Amarillo Helium Plant Laboratory require that the equilibrium cell be maintained uniformly at any desired temperature from approximately room temperature to -320° F. The temperature-control system must also tolerate a substantial heat input, in the form of warm gas flowing into the cell, without loss of control. Temperatures between the sublimation temperature of carbon dioxide (-109° F.) and the boiling point of liquid nitrogen (320° F.) are usually obtained by methods utilizing a hydrocarbon liquid bath cooled by liquid nitrogen.4/5/6/7/ Owing to the fire hazard attending such baths, a safer method of temperature control was desirable.

Jan 1, 1955

By R. W. Holliday

To determine the copper and nickel content of reported ore occurrences in the Chippewa mine near Rockmont, Douglas County, Wis., the Bureau of Mines reopened and sampled the old shaft and workings during the summer and fall of 1953. Occurrences of native copper near Rockmont and others near Gordon, also in Douglas County, Wis., are in lava flows, which extend from the Keweenaw Peninsula of Upper Michigan southwest across Wisconsin and into Minnesota. Sporadic attempts have been made to find additional economic copper deposits in these flows since profitable mines were developed in Upper Michigan nearly 100 years ago. The Rockmont and Gordon areas were explored extensively more than 50 years ago. More recently, from August 1944 to duly 1945, an occurrence near Gordon was investigated by the Bureau.2/

Jan 1, 1955

By W. H. Oppelt

To provide a relatively structurally stable form of dried lump lignite, two North Dakota lignites from Mercer County were dried by the Fleissner process in an atmosphere of saturated steam at 200, 300, and 370 p.s.i.a. pressure, corresponding to steam temperatures of 382°, 417°, and 437° F., respectively. Two series of experiments were made at each test pressure with the individual lignites. In one series, the autoclave was preheated to the processing temperature before charging the lignite; in the other the lignite was charged into the autoclave at room temperature. In each case, heat losses were determined by blank tests of steam consumption over a similar operating cycle with the empty autoclave. The degree of moisture removal and net steam consumption were calculated from material balances. The amount of water removed as a liquid from the two North Dakota lignites during the heating and steaming periods was compared with results calculated from previously published data on drying Austrian lignite and Australian brown coal. These lignites, covering a wide geographical area, had original moisture contents ranging from 35 to 49 percent. The Austrian lignite and Australian brown coal are considered to be of Miocene Age, and the Dakota lignites belong to the Paleocene.

Jan 1, 1955

By J. Chipman, J. C. Fulton

Reduction of silicon from blast-furnace-type slags by carbon-saturated iron is a very slow reaction even under conditions of rapid stirring. Equilibrium under atmospheric pressure of carbon monoxide was approached from both sides, and the silica-silicon relation was established at temperatures of 1425º to 1700°C for slags containing up to 20 pct Al2O3. Silicon carbide is formed by reaction of graphite with high silica slags and the conditions for its formation were determined. Activities of SiO2 and of CaO in their binary solutions at 1600°C were determined. The effects on the activity of SiO2 were established for additions of 10 to 20 pct AI2O3 and of 10 pct MgO. STUDIES of chemical reactions between blast-*>-5 furnace slags and metal have been focussed on the transfer of sulphur from metal to slag. The important role which silica reduction plays in this process' has led to a study of the transfer of silicon from slag to metal and the equilibrium represented by the equation SiO2 (in slag) + 2C (graphite) = Si + 2CO (g). [I.] The authors2 have published an account of the experimental method employed in attacking this problem and of three series of experimental results at 1600°C. This paper contains data on some additional compositions and extends the observations to cover the temperature range 1425° to 1700°C. The data are used to determine the activity of silica in the slags. As in the earlier experiments, the atmosphere was carbon monoxide which flowed through the furnace at 150 ml per min. In certain heats designated in the tables and figures, the gas was bubbled through the melt using a graphite tube. The latter increased in porosity during a run and in some cases bubbling ceased as indicated by cessation of surging. Some results were discarded for this reason. Experimental Results The new data are shown in Tables I through V and both old and new data are plotted in Figs. 1

Jan 1, 1955

Jan 1, 1955

By J. J. Forbes

'"THE Federal Coal Mine Safety Act (public Law T. 552. 82nd Congress) was approved oil July 16, 1952. It incorporates, as Title I, the Coal Mine Inspectio1.1 and Investigation Act of May 7. 1941 (Public Law 49, 77th Congress), which gave Federal inspectors only the right to enter. coal mines for inspection and investigation purposes but no power to require compliance with their recommendations. Title 11 contains the enforcement provisions of the act; its purpose is to prevent major disasters in coal mines from explosions, fires. inundations. and man-trip 01. man-hoist accidents. At this point a brief account of events that preceded the enactment of the Federal Coal Mine Safety Act seems appropriate. The hazardous nature of coal mining was recognized by the Federal Govermment as long ago as 1865, when a bill to create a Federal Mining Bureau was introduced in Congress. Little was done, however, until a series of appalling coalmine disasters during the first decade of this century provoked a demand for Federal action. As a result an act of Congress established a Bureau of Mines in the Department of the Interior on July 1, 1910. The act made it clear that one of the foremost activities of the Bureau should be to improve health and safety in the mineral industries. One of the first projects selected by the small folce of engineers and technicians then employed was to determine the causes of coal-mine explosions and the means to prevent them. By investigations aftel mine disasters the fundamental causes and means of prevention were soon discovered, and the coal mining industry was informed accordingly. However, despite this knowledge and the enactment of State laws and the Federal Coal Mine Inspection and Investigation Act of 1941, mine disasters continued to occur with disheartening frequency and staggering loss of life. The devastating explosion at the Orient No. 2 mine on December 21, 1951, resulted in the death of 119 men. The Orient disaster rekindled the memory of the Centralia. Ill., disaster of March 25. 1947, which caused the death of 111 coal miners. These two tragedies ultimately brought about enactment of the Federal Coal Mine Safety Act. The act is a compromise measure. Senator Matthew M. Neely of West Virginia and Congressman Melvin Priec of Illinois introduced almost identical versions in the 82nd Congress, but they were considered too drastic. The final version was introduced by Congressman Samuel K. McConnel, Jr., of Pennsylvania, after considerable discussion and amendment in committee hearings. It was passed by the Congress and became effective when signed by the President on July 16, 1952. The act is somewhat limited in scope because it applies only to approximately 2000 coal mines in the United States and Alaska that employ regularly 15 or more individuals underground. It exempts approximately 5300 mines employing regularly fewer than 15 individuals underground and all strip mines, of which there are about 800. Moreover, it covers only conditions and practices that may lead to major disasters from explosion, fire, inundation, or man-trip or man-hoist accidents. According to Bureau records, such accidents have resulted in less than 10 pct of all the fatalities in coal mines. It is important to mention that the law is not designed to prevent the day-to-day type of accidents that have caused the remaining 90 pct or more of the fatalities, because it was the specific intention of the Congress to reserve the hazards which caused them to the jurisdiction of the coal-producing states. Many who opposed any Federal legislation that would give the Federal inspectors authority to require compliance with mine safety regulations claimed that such legislation would usurp or infringe upon States' rights. To assure that the principle of States' rights would be preserved, the act provides for joint Federal-State inspections when a state desires to cooperate in such activities. The Director of the Bureau of Mines is required by the act to cooperate with the official mine-inspection or safety agencies of the coal-producing states. The act provides further that any state desiring to cooperate in making joint inspections may submit a State plan for carrying out the purposes of this part of the act. Certain requirements are listed: these must be met by a state before the plan can be accepted. The Director of the Bureau of Mines, however, is required to approve any State plan which complies with the specified provisions. The Director may withdraw his approval and declare such a plan inoperative if he finds that the State agency is not complying with the spirit and intent of any provision of the State plan. When this paper was prepared, agreements for joint Federal-State inspections had been entered into with Wyoming and Washington. A few other states have indicated their desire to submit a State plan and negotiations toward that end are now under way. Reluctance to enter into such agreements may be due to the mine operators' knowledge that in the states that adopt a cooperative plan they are prohibited from applying to the Director of the Bureau of Mines for annulment or revision of an order issued by a Federal inspector and must appeal directly to the Federal Coal Mine Safety Board of Review for such action. Experience has proved that review by the Director as provided in the act is a less expensive and time-consuming procedure to all concerned than applying to the Board. Reluctance also may stem from the fact that joint Federal-State inspections somewhat restrict the movements of the State mine inspectors and tend to reduce the number of inspections of mines. Where a State plan is not adopted, the Federal coal mine inspector is responsible under the law to take one of two courses of action if he finds certain hazardous conditions during his inspections. The first action involves imminent danger. If a Federal inspector finds danger that a mine explosion, mine fire, mine inundation, or man-trip or man-hoist accident will occur in a mine immediately or before the imminence of such danger can be elim-

Jan 1, 1955

By A. U. Seybolt

The solubility of oxygen in a iron has been determined in the range between 700° and 900°C. The solubility is a function of temperature and varies from about 0.008 pct oxygen at 700°C to atureandabout 0.03 pct at 900°C. The heat of solution is approximately +15,500 cal per mol. AS pointed out in a recent paper by Kitchener et al.,1 there has been a lack of agreement among many investigators even as to the order of magnitude of the solid solubility of oxygen in the various forms of iron. This lack of agreement is attributable in large part to the difficulties in the determination of a small oxygen solubility; but because the problem has remained so long unsettled, it also indicates a lack of interest which is rather surprising when the demonstrated importance of small amounts of soluble nonmetallic impurities in iron is considered. The work of Kitchener et al. apparently leaves the solubility of oxygen in iron in a satisfactory state, but no attempt was made to investigate the solubility in a iron. The solubility of oxygen in a iron is actually of greater interest, since it is in this form that iron and mild steels are employed ordinarily. That the effect of oxygen in iron is of more than theoretical interest has been well established by Fast,' and more recently by Rees and Hopkins," who demonstrated that oxygen in the range between 0.0008 and 0.27 wt pct has a pronounced effect upon the mechanical properties. Previous Work and Methods Used To report in detail the literature relating to the solubility of oxygen in a iron would require an inordinate amount of space. For those interested in reviewing this work, a bibliography4-13 of the more significant papers is appended. In general, two methods of studying this problem have been used. One is the gas-metal equilibrium method where the H2O-H2-Fe or the CO2-CO-Fe equilibria have been used. The other is the more direct approach of the oxidation of thin strips of pure iron by packing in mill scale or by air or gaseous oxygen at some desired temperature. In this method oxygen is allowed to oxidize the surface and then to diffuse inward until saturation is obtained. In the gas-metal equilibrium method the oxygen dissolved in solid iron at a given temperature is proportional to the ratio of the water vapor-hydrogen pressures or the CO2-CO pressures over the sample for small ratio values. If the ratio becomes higher than a critical value, then an oxide phase makes its appearance (the solution becomes supersaturated). In principle, it is possible to use a series of H2O/H2 or CO2/CO ratios and to find by analysis the corresponding amounts of oxygen in solid solution at constant temperature. At the point where a very small increase in the gas ratio (increase in oxidizing powder) produces a large increase in oxygen content, the solid solubility limit is reached. Alternately, if the critical ratio is known, it is possible to use the procedure of Kitchener et al.1 and to use a ratio which is near but below the critical one. The solubility corresponding to this lower ratio will not be the saturation solubility at the temperature employed, but the saturation solubility can be calculated by multiplying the measured solubility by the critical ratio over the ratio used. However, in the case where oxygen gas is the oxidizing medium, the saturation solubility is not a function of pressure, providing the pressure exceeds the dissociation pressure of FeO in equilibrium with iron. This is 1.2x10-16 mm at 800 °C, according to Dushman." As pointed out by Darken17 in discussing the FeO phase diagram, most of the possible errors tend to yield high values of oxygen solubility. For example, one circumstance which evidently caused the reporting of many high values was the use of finely divided or powdered iron in the gas equilibrium method. Because of the large surface area of such a sample, and the likelihood of some surface contamination if only by exposure to air, the results tended to be high. The direct oxidation method which was used in this work has the advantage in that it is simple and direct, but it suffers from one disadvantage: equilibrium can only be approached from the low oxygen side. The important factors to be kept under control are the following: 1—use of high purity iron to avoid internal oxidation (oxidation of readily

Jan 1, 1955

By J. S. Ll. Leach, J. B. Cohen, M. B. Bever

IN the work reported here, the heats of formation of a copper-rich Cu-Sn (a) solid solution and of the Cu.Sn (0 phase were measured by tin solution calorimetry. An approximate determination of the heat effect attending the precipitation of 6 from a supersaturated a solid solution was also made.

Jan 1, 1955

By P. Greenfield, P. A. Beck

The phase is a hard and extremely brittle material with a tetragonal crystal structure, containing 30 atoms per unit cell' It occurs in many binary and ternary alloys of the transition elements. The existence of twelve a phases has been reported in binary alloys of metals from the group vanadium, chromium, molybdenum, and tungsten with metals from the group manganese, iron, cobalt, and nickel. It is a characteristic fact that the composition of the o- phases in the various binary systems is not the same. Rather, there is a gradual shift in composition, for instance in the series of chromium a phases, approximately as follows: CrMn,, FeCr, Cr3Co,. In recent years several ideas have been put forward to account for this variability of composition. SullyZ proposed that a was a type of electron compound, characterized by 1.7 electrons per atom in excess of the number required to fill the Pauling atomic orbitals. These excess electrons were supposed to just fill the first Brillouin zone of the u structure. However, later work indicated that the phase is ferromagnetic at low temperatures, so that a- is unlikely to be a full zone compound.~ Another proposal,* which is also based on the structure of the transition elements advanced by Pauling, and in fact leads to essentially the same a compositions as Sully's theory, suggests that the u phase is characterized by a constant number of electron vacancies per atom. The electron vacancy numbers N,. used were originally the same as those in the Pauling theory, but were later modified empirically vn order to bring about better agreement with data for the p phase in certain ternary systems. For alloys, N,, was calculated on the assumption of simple additivity from the electron vacancy numbers of the components, as follows: N,. = 4.66 (Mo + Cr + V) + 3.2 (Mn) + 2.2 (Fe) + 1.71 (Co) + 1.6 (Ni). On this basis a reasonably constant value of N, = 3.4 was obtained for all of the binary u phases and a fairly constant value of N,, = 3.1 for the various p phases. More recently, Bloom and Granta pointed out that a similar correlation with the total number of 3d and 4s electrons per atom is also fairly well fulfilled and concluded that no reference need be made to the Pauling theory. This proposal does not lead to the same binary a compositions as the one described above, so that the relative merits of the two proposals may be determined on the basis of direct comparison with experimental composition data. The purpose of the present paper is to provide such a comparison. Since the experimental data for the composition ranges of several of the known u phases were rather incomplete, it was decided to carry out new experimental determinations for many of the binary systems. Experimental Procedure The alloys were prepared by induction melting in recrystallized alumina crucibles, either in vacuum or in helium atmospheres. Some aluminum was picked up from the crucibles in the alloys of high vanadium content, but this was minimized by keeping the alloys in the molten state for as short a time as possible. The maximum aluminum impurity was 0.13 wt pct by chemical analysis, in an alloy containing over 50 wt pct V. In general, the as-melted compositions agreed accurately with those obtained by chemical analysis. In the case of manganese, however, losses inevitably occurred; consequently all manganese alloys were analyzed. Specimens of all alloys were annealed at temperatures ranging from 1000" to 1300°C in an atmosphere of purified 92 pct helium and 8 pct hydrogen mixture. All manganese alloys were sealed in quartz tubes under vacuum before annealing. The specimens were held at temperature for between four and eight days before being quenched into cold water. Alloys were prepared for microscopic examination by mechanical polishing, usually followed by electrolytic etching. X-ray diffraction specimens were prepared by crushing the homogenized alloys, and by reanneal-ing the obtained powders in evacuated quartz tubes for a few hours at the temperature of the lump anneal. X-ray diffraction patterns were made with unfiltered chromium radiation, using an asymmetrical focusing camera of high dispersion. Using microscopic and X-ray techniques jointly, the accuracy

Jan 1, 1955

By A. U. Seybolt

The solubility limit of oxygen in columbium has been determined in the range between 775' and 1100°C by means of lattice parameter measurements and microscopic examination. The solubility is a function of temperature and varies, in the range given above, from 0.25 to 1.0 pct O, respectively. BECAUSE of the marked deleterious effect of oxygen upon the mechanical properties of some of the transition metals, it is desirable to know something about the solubility of oxygen in these metals. The brittleness caused by oxygen in solution is particularly marked in the case of the group VA elements, vanadium, columbium, and tantalum. The solubility of oxygen in vanadium has already been reported in an earlier paper,' and Wasilewski2 has given a value (0.9 wt pct) for the solid solubility of oxygen in tantalum at 1050°C. Brauer3 in 1941 investigated the Cb-0 system up to Cb2O5, but made no real effort to investigate the extent of oxygen solubility in the metal. He made the observation, however, that this solubility must be less than 4.76 atom pct (0.86 wt pct) oxygen. This estimate was made from X-ray diffraction results on the alloys CbO, CbO, and CbO; all alloys consisted of the terminal (Cb) solid solution plus CbO, but the last alloy containing 4.76 atom pct 0 showed only three very weak CbO lines. It is surprising that Brauer, by examining only three alloys, arrived at an estimate of the solubility which agrees very well with the results to be reported herein. Experimental Procedure A columbium strip obtained from Fansteel Metallurgical Products was cut into strips, 0.020x1/2x2 in. Two holes, about 3/16 in. in diameter, were made near the ends of the strips in order to hold them against a flat steel block for mounting in a General Electric X-ray spectrometer for lattice parameter measurements. The same holes were used to hang the specimens inside a fused silica vacuum furnace tube which was part of a Sieverts' gas absorption apparatus. The apparatus and method of adding oxygen gas has been previously described.1 According to the supplier, the columbium obtained had the analysis given in Table I. After degreasing the samples, approximately 0.001 in. was etched from each side of the samples in order to remove possible surface impurities from the last rolling operation. For this purpose the following cold acid pickle was found satisfactory: 8 parts HNO3, 2 parts H2O2 and 1 part HF. Various Cb-O compositions were obtained up to 0.75 wt pct O by the gas absorption and diffusion technique. After the sample had absorbed all the oxygen gas added at 1000°C, an additional 24 hr was allowed for homogenization. This treatment appeared to be adequate, as shown by the linearity of the lattice parameter-composition plot. More concentrated alloys were prepared by arc melting mixtures of Cb and Cb2O5 since it was very time-consuming to make Cb-0 alloys in the neighborhood of 1 pct O, or over, by the diffusion method. When the flat strip specimens were used, they were ready for the X-ray spectrometer after cooling from the Sieverts' apparatus. The cooling rate obtained by merely allowing the hot fused silica furnace tube to radiate to the atmosphere (when the furnace was lowered) was sufficiently fast to keep the dissolved oxygen in solution. Arc-melted alloys were reduced to —200 mesh powder in a diamond mortar, wrapped in tantalum foil, sealed off in evacuated fused silica tubes, and then heat treated as indicated in Table 11. The fused silica tubes were quickly immersed in cold water without breaking the tubes after the heat treatments. The tantalum foil prevented reaction between the fused silica and the sample; there was no reaction between the powdered samples and the foil at 1000°C, but some trouble was experienced at 1100°C. At this temperature level a reaction between the sample and the foil was sometimes observed, which resulted in erroneous parameter values. Experimental Results Hardness Tests: Since most of the X-ray samples were in the form of flat strip, it was convenient to obtain Vickers hardness numbers as a function of oxygen content. Compared to the V-O case,' oxygen hardens columbium much more slowly, presumably because of the larger octahedral volume in colum-bium (about 12.0 compared to 9.3Å3 in vanadium), hence, requiring less lattice strain for solution. The plot of VHN vs wt pct O is shown in Fig. 1.

Jan 1, 1955

By R. E. Maringer, A. Schwope

IT has been recognized that oxygen in minute quantities is extremely detrimental to the room-temperature ductility of molybdenum. Early fracto-graphic studies' of the cast metal indicated that oxides are formed preferentially at the grain boundaries. Additional verification of this preferential segregation has been obtained from internal friction studies on poly crystalline molybdenum (average grain diameter varied from 0.039 to 0.065 mm) and from observations of the effect of oxygen on specimens of extremely large grain size. Specimens A, B, and C, of 0.040 in. diameter commercial molybdenum wire (Lot FW 13-40) were heat treated in the vacuum furnace described by Few and Manning according to the specifications given in Table I. Internal friction studies of these specimens were carried out using a low frequency (approximately 1 cycle per second) torsional pendulum completely enclosed in a vacuum tank. As the pressure of oxygen in the heat treating atmosphere changed, the portion of the internal friction vs temperature curves ascribed to grain boundary relaxation changed correspondingly, Fig. 1. The decrease in the damping capacity at high temperatures as the pressure of oxygen in the heat treating atmos-

Jan 1, 1955

By L. F. Willmott

The production operation of a Kerpely gas producer at Louisiana, Mo., is described. This unit, originally designed for airblown operation was modified to permit using oxygen in the blast in place of air. The first runs J for test purposes, were made in June 1950. After this, seven production runs were made and these are the subject of this report. Total gasification time was 245 days. In each run, Nut or Pea coke or mixtures of both at a rate varying from 1,700 to 2,300 pounds per hour was converted with oxygen and saturated steam to produce synthesis gas - primarily carbon monoxide and hydrogen -approximating a predetermined rate of 80,000 to 95,000 cu. ft. per hour and a predetermined hydrogen-carbon monoxide ratio, The requirements per 1,000 std. cu. ft. of (CO + H2) were 21.6 to 30 pounds of coke, 213 to 267 std. cu. ft. of oxygen, and 3L4 to 47.B pounds of steam.

Jan 1, 1955

By A. U. Seybolt, R. L. Fullman

THE Hume-Rothery rule relating the relative sizes of the solvent and solute atoms in a substitutional solid solution for moderate to extensive solubility is, of course, well known and much used in the design of alloys. No such rule has been obtained for interstitial solid solutions, although a qualitatively similar relationship would be expected. Among the most common interstitial elements, oxygen, carbon, and nitrogen which can dissolve in important amounts in the transition metals, only in the case of oxygen is there enough solubility data available for an examination of the possibilities of a simple relationship between the extent of solubility and the properties of the metal solvents. Three properties were examined: 1—size of the octahedral space V into which oxygen atoms fit, 2— the elastic modulus E, and 3—the free energy ?F of formation of a low oxide, such as is known to be, or would be expected to be, in equilibrium with the terminal solid solution. The size factor or octahedral volume is so closely associated with the well known Hume-Rothery con- cept of size factor that additional development of this subject is hardly necessary. The octahedral volume used was not corrected to an elevated temperature, as this correction would have made no significant difference. The second factor, Young's modulus E, must be considered, since it is a measure of the strain energy required to force neighboring atoms apart so that an oxygen atom may enter the octahedral volume. The temperature dependence of the elastic modulus of many metals has been reported by Köster,1 but for a rather limited temperature range. Since the

Jan 1, 1955

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 J. D. Marchant

In the spring of 1953 a series of heats were made using a 3-phase, size ST, Pittsburgh Lectromelt arc furnace to develop a method suitable for melting, refining, and granulating cobalt powder produced by the Calera Mining Co., at Garfield, Utah. According to specifications stipulated by General Service Administration, the granules had to pass a 2-inch screen and be retained on a 6-mesh screen, be low in phosphorus and sulfur, and contain a minimum of 98.7 percent cobalt plus nickel. Various combinations of water temperature, water jets, and rate of pouring were tried early in the campaign to produce desirable granules. It soon became evident that a properly refined and deoxidized molten bath was the major requirement for a satisfactory product. The physical characteristics of the granules were improved also if, just before pouring, the surface of the molten metal bath was pre-pared by a method involving the use of silica flux. The Bureau processed 107,750 pounds of cobalt powder. A total of 104,810 pounds of cobalt granules meeting General Service Administration specifications was returned to the producer. The refining slag, which was also returned to the company, contained 1,781 pounds of metal.

Jan 1, 1955

Ore from the Hill 50 Gold Mine, consists essentially of pyrrhotite, with minor amounts of pyrite, chalcopyrite, galena and gold, replacing "jaspilite." The gold is associated with the sulphides as shotty particles. About 8 per cent. of the particles are less than '0.010'mm.The Hill 50 Gold Mine, at Boogardie in the Murchison goldfield, about 300 miles north-west of Kalgoorlie, was first operated in 1898. From 1898 to 1917 it yielded 20,000 short tons of ore for a recovery of 6,225' fine oz. gold, equivalent to a recovery grade of 6.22 dwt. gold per ton.The present company since the beginning of its operations in September 1936 to June 30, 1954, produced 811,081 short tons of ore for a recovery of 242,554 fine oz. of gold, equivalent to a recovery grade of 5.98 dwt. gold per ton.The grade of ore (recovery grade) has shown a remarkable variation with depth. From the 120 ft. Ievel to the 300 ft. level, it averaged about 7.5 dwt. Au per ton. Below the 300 ft. level it declined, and from 300 ft. to 400 ft. averaged 4.9 dwt. per ton, falling further with increasing depth to about 4.5 dwt. per ton at the '600 ft. level.On the 820 ft. level the grade improved sharply to about 14 dwt: per ton, and this grade has persisted down to and on the 1060 ft. level.The orebody has been described by Finucane (1953) as a series of lenses of finely banded jaspilite conformably enclosed by greenstones. The jaspilite is tightly folded and faulted and intruded by dykes of felspar porpnyry.Mineralization is practically restricted to the jaspilite.

Jan 1, 1955