Search Documents

By A. Spilners, M. Simnad

The rates of formation of the different oxides on molybdenum in pure oxygen at 1 atm pressure have been determined in the temperature range 500° to 770°C. The rate of vaporization of MOO, is linear with time, and the energy of activation for its vaporization is 53,000 cal per mol below 650°C and 89,600 cal per mol at temperatures above 650°C. The ratio Mo03(vapor.lzing)/MoOS3(suriace) increases in a complicated manner with time and temperature. There is a maximum in the total rate of oxidation at 6W°C. At temperatures below 600°C, an activation energy of 48,900 cal per mol for the formation of total MOO, on molybdenum has been evaluated. The suboxide Moo2 does not increase beyond a very small critical thickness. At temperatures above 725°C, catastrophic oxidation of an autocatalytic nature was encountered. Pronounced pitting of the metal was found to occur in the temperature range 550° to 650°C. Marker movement experiments indicate that the oxides on molybdenum grow almost entirely by diffusion of oxygen anions. USEFUL life of molybdenum in air at elevated temperatures is limited by the unprotective nature of its oxide which begins to volatilize at moderate temperatures. Although the oxide/metal volume ratio is greater than one, the protective nature of the oxide film is very limited. Gulbransen and Hickman' have shown, by means of electron diffraction studies, that the oxides formed during the oxidation of molybdenum are MOO, and MOO,. The dioxide is the one present next to the metal surface and the trioxide is formed by the oxidation of the dioxide. Molybdenum dioxide is a brownish-black oxide which can be reduced by hydrogen at about 500°C. Molybdenum trioxide has a colorless transparent rhombic crystal structure when sublimed, but on the metal surface it has a yellowish-white fibrous structure. It is reported to be volatile at temperatures above 500" and melts at 795°C. It is soluble in ammonia, which does not affect the dioxide or the metal. In his extensive and classic investigations of the oxidation of metals, Gulbransen2 has studied the formation of thin oxide films on molybdenum in the temperature range 250" to 523°C. These experiments were carried out in a vacuum microbalance, and the effect of pressure (in the range 10-6 yo 76 mm Hg), surface preparation, concentration of inert gas in the lattice, cycling procedures in temperature, and vacuum effect were studied. The oxidation was found to follow the parabolic law from 250" to 450°C and deviations started to occur at 450 °C. The rates of evaporation of a thick oxide film were also studied at temperatures of 474" to 523°C. In vacua of the order of 10- km Hg and at elevated temperatures, an oxidation process was observed, since the oxide that formed at these low pressures consisted of MOO, which has a protective action to further reaction in vacua at temperatures up to 1000°C. Electron diffraction studies showed that, as the film thickened in the low temperature range, MOO8 became predominant on the surface. Above 400°C MOO, was no longer observed, MOO, being the only oxide detected. The failure to detect MOO, on the surface of the film formed at the higher temperatures does not militate against the formation of this oxide, since according to free energy data MOO3, is stable up to much higher temperatures. At the low pressures employed, this oxide would volatilize off as soon as it was formed. Its vapor pressure is relatively high and is given by the equations" log p(mm iig) = -16,140 T-1 -5.53 log T + 30.69 (25°C—melting point) log p(mm He) = -14,560 T-1 -7.04 log T+1 + 34.07 (melting-boiling point). Lustman4 has reported some results on the scaling of molybdenum in air which indicate a discontinuity at the melting point of MOO, (795°C). Above the melting point of MOO,, oxidation is accompanied by loss of weight, since the oxide formed flows off the surface as soon as it is formed.5,6 Qathenau and Meijering7 point out that the eutectic MOO2-MOO3 melts at 778C, and they ascribe the catastrophic oxidation of alloys of high molybdenum content to the formation of low melting point eutectics of MOO3 with the oxides of the melts present. Fontana and Leslie -explain the same phenomenon in terms of the volatility of MOO,, which leads to the formation of a porous scale. Recent unpublished work by Speiser9 n the oxidation of molybdenum in air at temperatures between 480" and 960°C shows that the rate of weight change of molybdenum is controlled by the relationship between the rates of formation and evaporation of MOO,. They have measured the rates of evaporation of Moo3 in air at different temperatures and estimated an activation energy of 46,900 cal. This compares with the value of 50,800 cal per mol obtained by Gulbransen for the rate of sublimation of MOO, into a vacuum.

Jan 1, 1956

By R. Maddi, I. R. Kramer

The delay time for the initiation of slip was studied in single crystals of a brass, aluminum, and ß brass. A delay time for slip was found in ß brass when the specimens were tested below room temperature; however, one was not found for a brass or aluminum. A general theory for the existence of the brittle transition temperature is proposed. A LTHOUGH a considerable amount of effort has A been devoted to the study of the deformation and fracture of single crystals, the vast majority of the work was concerned with static tests or with tests carried out at relatively slow strain rates. The necessity for the study of a possible incubation time for slip becomes apparent when the various theories which have been postulated for the elucidation of the mechanism of slip are considered. The existence of an incubation period would strongly indicate that slip occurs by a process of nucleation and growth; whereas the absence of an incubation would present rather convincing evidence that slip occurs by a cataclysmic process. In addition to shedding light on the process of plastic deformation, an understanding of the early stages of plastic deformation may be helpful in finding an explanation for the brittle behavior of the body-centered metals under certain conditions. It is well known that these metals, such as iron, molybdenum, tungsten, ß brass, etc., will become brittle as the test temperature is lowered or the strain rate is increased. In spite of the fact that this subject has received considerable attention since the turn of the century, no adequate theory exists today which explains the phenomenon. In the ductile temperature range the metal breaks with a "fibrous" fracture after considerable slip has taken place. In the brittle temperature range the metal fails essentially by cleavage on the {loo) planes: however, some plastic flow is always present even in the most brittle fractures. It is possible, as will be explained later, to ascribe this brittle behavior to the length of the incubation time for slip. Clark and Wood,' using polycrystalline metals, showed that a delay time existed for the yield point in mild steels and that the delay time depended upon the applied stress. These authors stated that the delay time was observed only with those materials for which the stress-strain curve showed a definite yield point. In their work only the mild steel specimens exhibited a delay time at the yield point, while the other materials studied-type 302 stainless steel, SAE 4130 normalized steel, SAE 4130 quenched and tempered steel, 24s-T aluminum—did not show a delay time. These authors' in an extension of their work, found that as the temperature was lowered the delay time was increased. It is, then, the purpose of this investigation to measure or to set an upper limit on the delay time for plastic flow in single crystals of a brass, aluminum, and ß brass. The delay time will also be studied as a function of temperature. The incubation time may be measured by determining the length of time the specimen will support a stress without slip occurring when the stress is greater than the static critical resolved shear stress. In order to accomplish these measurements use was made of a pendulum which was so designed that a single crystal specimen could be placed at various positions along its length. When a pendulum is struck by another pendulum of the same length, an elastic wave is transmitted down the bar with the velocity of sound in the material and is reflected from the far end of the bar. The reflected wave then travels back and unloads the stress until it reaches the impacted end of the bar and the two pendulums separate. The length of time that the specimen is subjected to the stress is equal to the time it takes for the stress wave to travel twice the distance from the specimen to the end of the bar. The stress applied to the specimen is governed by the velocity of impact of the two pendulums. The stress at which the specimen first suffers plastic: deformation was determined in these experiments by examining the specimen under the microscope for the first appearance of slip lines and by measuring the residual strain after each impact. In these experiments the critical resolved shear stress was approached from the low stress side and no attempt was made to determine it exactly. To determine it exactly, it would have been necessary to find that stress at which slip would have just started. However, since the stresses were increased in rather small increments the critical stress is believed to be approached rather closely, as will be seen from the experimental results. The critical stress will be taken as the highest stress obtained before the onset of plastic deformation. The stresses

Jan 1, 1953

By Franklin Bache

There seems to be in the public mind, and even in the minds of some coal-operators not experienced in mines subject to dust-explosions, a feeling that there has been somet-hing mysterious at the bottom of a number of recent American colliery-exploaions. It has been declared in cases of accidents in mines regarded as particularly well equipped, in which every preventive precaution was said to have been taken, that the explosions were incomprehensible, and resulted from causes beyond the present knowledge of the practical coal-operator. But it is safe to say that no explosion has taken place which could not be explained by reasons well understood by most operators. The U. S. Geological Survey Testing Laboratory, recently inaugurated at Pittsburg for the reported purpose of investigating scientifically the matter of explosions in mines, will discover no new explanation of explosions. It can, however, co-ordinate the previous investigations of similar boards in England and on the Continent; and it may do a vast amount of good by promulgating widely, and in a form comprehensible to the most unlettered miner, certain facts and obvious deductions that cannot but have an effect in reducing the number and extent of the mine-disasters which, in the last few years, have been so terrible in frequency and magnitude.

Jan 1, 1910

By M. D. Hassialis

THE object of a technical paper is to communicate new technical knowledge, the paper being the vehicle of communication and the existence of new knowledge its reason for being. It follows that the development of information worthy of communication, the criterion being novelty, is prerequisite to exercising the privilege of communication. The act of communication is achieved when the reader perceives the nature of the new knowledge, i.e., when he understands it. A paper achieving this objective is an acceptable technical paper. Development of new knowledge has as one of its purposes the increase of the existing state of knowledge and the enjoyment of the benefits derived therefrom. Technical knowledge is a collection of facts so ordered as to make apparent, relations existing between the facts. When the interrelations have been exposed the facts have been interpreted or explained Three broad, overlapping categories of technical papers may be recognized: papers consisting of (a) a report of facts, (b) an explanation of facts, or (c) a combination of a report and an interpretation. Ideally a technical paper should belong to one of the last two categories but current practice is to accept papers belonging to any of the three categories. Based on a small sample drawn from the scientific and engineering literature, the relative frequency of the three types is a: b: c:: 20:1:14. If the sample be limited to engineering literature, the ratios become a:c::2:1; type (b) being nonexistent. This large departure from the ideal is a consequent of the

Jan 1, 1948

By F. N. Speller

ASIDE from the Tuesday symposium on gases in metals, the Iron and Steel Division swung into action for the first time on the third day of the meeting with a discussion of iron and steel alloys. Dr. E. S. Davenport opened the discussion on Wednesday morning by presenting the paper written by himself in association with E. C. Bain and W. S. N. wiring on the equilibrium diagram of iron-manganese-carbon alloys. A written discussion by Mr. Scott showed qualitative agree- ment, but some quantitative disagreement. Messrs. Marsh and Sisco discussed the paper at length, pointing out non- agreement of certain conclusions with the phase rule. Dr. Krivobok, although differing with the authors on some points, stated that in his opinion the information collected would be valuable in the practical use of these alloys.

Jan 1, 1932

By J. Burns Read, S. Tour

It is the purpose of this paper to summarize, as far as possible, the metallurgical information and experience gained by the Ordnancc Department, during the war, in the manufacture of artillery cartridge cases, to describe the tests to which artillery cartridge cases were put, and to summarize the knowledge and experience gained in this testing. The authors wish to acknowledge the aid given by manufacturers, army officers, and civilian employees of the Department in obtaining data. Artillery cartridge cases are cold drawn from circular disks punched from strips of rolled brass. The rnanufacture involves from 25 to 30 main operations, which are done almost entirely on a punch press. Descriptions of the operations have appeared in various periodical:: and, therefore, will not he given here. After each cupping, or drawing, operation, except the last, the cases are annealed at from 540" to 650" C. (1000" to 1200°F.), to remove all the hardening stresses set up in the metal and to allow complete recrystallization. After each annealing, the cases are pickled in niter cake or sulfuric-acid solution and then washed in water to remove all traces of acid. In some instances, the cases arc then immersed in a cyanide-salt solution, and afterwards rinsed in water, to remove the thin layer of copper that forms on the surface of the cases during the acid pickle. The last cold-drawing operation is followcd by the heading operation which, by flattening the head of the case on the outside, causes the metal to flow on the inside to approximately the proper finished dimensions. The mouth, or open end, is then annealed at 430" to 450" ('. 1800" to 900" F.) by immersion in a salt bath or by gas flames. After being washed, the eases are tapered, when they arc ready for machining, inspection, and testing. Cartridge-case Disks Good disks of proper composition and physical properties are essential to the production of good cartridge cases. The Ordnance Department

Jan 1, 1923

By J. Burns Read, S. Tour

It is the purpose of this paper to summarize, as far as possible, the metallurgical information and experience gained by the Ordnancc Department, during the war, in the manufacture of artillery cartridge cases, to describe the tests to which artillery cartridge cases were put, and to summarize the knowledge and experience gained in this testing. The authors wish to acknowledge the aid given by manufacturers, army officers, and civilian employees of the Department in obtaining data. Artillery cartridge cases are cold drawn from circular disks punched from strips of rolled brass. The rnanufacture involves from 25 to 30 main operations, which are done almost entirely on a punch press. Descriptions of the operations have appeared in various periodical:: and, therefore, will not he given here. After each cupping, or drawing, operation, except the last, the cases are annealed at from 540" to 650" C. (1000" to 1200°F.), to remove all the hardening stresses set up in the metal and to allow complete recrystallization. After each annealing, the cases are pickled in niter cake or sulfuric-acid solution and then washed in water to remove all traces of acid. In some instances, the cases arc then immersed in a cyanide-salt solution, and afterwards rinsed in water, to remove the thin layer of copper that forms on the surface of the cases during the acid pickle. The last cold-drawing operation is followcd by the heading operation which, by flattening the head of the case on the outside, causes the metal to flow on the inside to approximately the proper finished dimensions. The mouth, or open end, is then annealed at 430" to 450" ('. 1800" to 900" F.) by immersion in a salt bath or by gas flames. After being washed, the eases are tapered, when they arc ready for machining, inspection, and testing. Cartridge-case Disks Good disks of proper composition and physical properties are essential to the production of good cartridge cases. The Ordnance Department

Jan 1, 1923

By Dorsey Hager

THE possibilities of finding new oil pools in Oklahoma and Kansas are far from promising. In 1916, the only new pools of importance were the Franchot pool near Bixby, the Garber, and the Billings pools in Oklahoma, and the Virgil and Utopia fields in Greenwood County, Kansas. In the first 8 months of 1917, a small pool of unknown extent was opened south of the Stone Bluff pool in Oklahoma, and a pool near Casey, Paunee County, Oklahoma. In Eastern Kansas, interest has been. caused by the sinking of new wells near the old Iola pool, but nothing of magnitude has yet been found. The outlook for new pools is far from encouraging, especially as geological surveys have covered all of Oklahoma and Kansas. There are a few areas where geological surveys throw little or no light on the subject, as exposures are poor, but the chances of finding new pools in such areas are slight indeed, if one can judge from the past history of such areas. So far the geologists have based their opinions largely upon the presence or the absence of geologic structure, such as anticlines, domes, and terraces, but some pools will most certainly be found where no surface structure exists, but where local changes in the sand body favor oil accumulations. However, the possibilities of new pools off structure are small, as fully 90 per cent. of the oil pools are on definite structure. In the past, it is estimated that one test in 150 "wild cats" or new tests has brought in a new field. The writer feels safe in asserting that the proportion will decrease still further, so that but one out of 500 new tests may bring in a pay well in a new area. From now on the principal field of work in Oklahoma and in Kansas will consist in developing the present pools. The years 1915, 1916 and 1917 saw the high peak of Oklahoma and Kansas oil production. The Eldorado and the Augusta oil fields present the largest possibilities for continued production in Kansas. These two pools have been scarcely more than one-third developed, and have greater potentialities than any of the present Oklahoma pools. In Oklahoma, pools of magnitude should

Jan 10, 1917

By R. D. Sprague, C. B. Richardson

The year 1938 was the most active and successful in the history of the oil industry in southern Louisiana. Drilling showed a 16 per cent increase over that of 1937, with a total of 538 wells drilled, which yielded 315 oil wells, 19 distillate wells, 4 gas wells and 200 dry holes. Nineteen new fields were discovered during the year, all but three of which were completed by plugging back to sands previously drilled through. Electrical logging played a large part in these new discoveries as well as in the discovery of new sands during routine development of fields. Fourteen of the new discoveries produced oil, and five produced only gas and distillate. Southern Louisiana continues to lead the world in depth of drilling, which is in part due to the great thickness of comparatively young deltaic sediments near the coast and the existence of numerous sands. The present development is rather evenly distributed over a coastal strip 100 miles wide. New Fields North Tepetate, Acadia Parish.—Atlantic Refining Company's No. 1 Klumpp was completed for a new field through perforations from 7960 to 7970 ft. The initial production was 65 bbl. of 54" gravity distillate and 4 million cubic feet of gas daily through a 1/4-in. choke with tubing pressure of 2850 Ib. and casing pressure of 2930 lb. The well is in see. 12, 7 S., 2 W., just north of Tepetate field. It was drilled to a depth of 8705 ft. and plugged back for its final completion. Atlantic's NO. 2 was completed in a new sand at 8300 ft., also for distillate. South Crowley, Acadia Parish.—Humble Oil and Refining Company's No. 1 Boyd Finch was completed in July 1938, as an oil well through perforations from 7318 to 7325 ft. after plugging from a total depth of 10,222 ft. After making several hundred barrels of oil, the well went to

Jan 1, 1939

By C. B. Richardson, R. D. Sprague

The year 1938 was the most active and successful in the history of the oil industry in southern Louisiana. Drilling showed a 16 per cent increase over that of 1937, with a total of 538 wells drilled, which yielded 315 oil wells, 19 distillate wells, 4 gas wells and 200 dry holes. Nineteen new fields were discovered during the year, all but three of which were completed by plugging back to sands previously drilled through. Electrical logging played a large part in these new discoveries as well as in the discovery of new sands during routine development of fields. Fourteen of the new discoveries produced oil, and five produced only gas and distillate. Southern Louisiana continues to lead the world in depth of drilling, which is in part due to the great thickness of comparatively young deltaic sediments near the coast and the existence of numerous sands. The present development is rather evenly distributed over a coastal strip 100 miles wide. New Fields North Tepetate, Acadia Parish.—Atlantic Refining Company's No. 1 Klumpp was completed for a new field through perforations from 7960 to 7970 ft. The initial production was 65 bbl. of 54" gravity distillate and 4 million cubic feet of gas daily through a 1/4-in. choke with tubing pressure of 2850 Ib. and casing pressure of 2930 lb. The well is in see. 12, 7 S., 2 W., just north of Tepetate field. It was drilled to a depth of 8705 ft. and plugged back for its final completion. Atlantic's NO. 2 was completed in a new sand at 8300 ft., also for distillate. South Crowley, Acadia Parish.—Humble Oil and Refining Company's No. 1 Boyd Finch was completed in July 1938, as an oil well through perforations from 7318 to 7325 ft. after plugging from a total depth of 10,222 ft. After making several hundred barrels of oil, the well went to

Jan 1, 1939

By F. B. JEWETT

TWENTY FIVE years of doing, finding, and encouraging others to do scientific research in' industry, and of organizing the machinery for the` smooth 'and effective conduct of such research, have left me with a feeling that so far as this branch of human activity is concerned the problems in 'essence are- not, materially 'different from those met elsewhere. Years ago, in a less mature period of life, I may have thought that the effective industrial research man was a being somewhat different from his fellow workers in adjacent 'fields, but I have long since 'changed my views. The rank and' file of the modern industrial research organization are relatively easy to find, though some¬times difficult to get in sufficient numbers. Mistakes in choosing them are not particularly serious to the or¬ganization, however unfortunate they may be for the misplaced individual who persists too long in the wrong environment. The reason for this is obvious from the fact that, taken by and large, the work of the rank and file is at best necessarily a work of detail done under guidance of the more experienced. In this respect the situation of the rank and file in an industrial research organization is not different from that class in any other group activity, whether concerned with industry, the university, or the church. This does not mean, however, that we are not all anxious to have the best possible material obtainable in the rank and file, or that we are indifferent to the utmost of encouragement and stimulation to its individual members.

Jan 1, 1929

By J. T. McGrath, G. B. Craig

Tensile tests on aluminum single crystals, grown from the melt, revealed that the yield stress of these crystals was raised as the amount of striation substructure was increased. The number of striation-type boundaries was varied by changing the rate of growth of the crystals. The results are interpreted in terns of a blockage of dislocation movement by striation boundaries. IMPERFECTIONS are known to have a large effect on the mechanical properties of metals. Teghtsoonian and Chalmers 1 studied a block or striation-type substructure in tin and found that the formation of the striations depended upon rate of crystal growth and orientation. They found that the angular misorienta-tion between neighboring striations varied between 15 min and 5 deg. Atwater and chalmers2 investigated striations in tin and lead, and found that purity was another factor which influenced their formation. There was a limiting purity above which the striations were straight and regular. There is little information in the literature concerning how substructures in melt-grown crystals affect strength. washburn3 introduced small-angle boundaries into zinc by a shear process and found a subsequent increase in yield stress which he attributed to the presence of these boundaries. Lauriente and pond4 found the critical resolved shear stress in aluminium crystals grown from the melt, to increase with etch pit density. The etch pits were used as an indication of growth imperfections. In Hibbard's5 work on lineage structure in copper crystals grown from the melt, he tested one crystal containing interlineage boundaries, and found a 50 pct increase in the critical resolved shear stress. Fleischer and Chalmers6, in a recent paper, mention briefly that, in the production of aluminium crystals from the melt when the growth rate was raised from 1.2 to 18 cm per hr, the yield stress increased 50 pct. They felt that the increase in yield stress with rate of growth might be attributed to a higher concentration of impurities in the gage length and also might be affected by the increased number of small-angle boundaries (striations). The present investigation was undertaken to determine the effect of the striation substructure on the strength of aluminum single crystals. EXPERIMENTAL PROCEDURE Aluminum single crystals of 99.9992 purity were grown from the melt using a technique described by Chalmers.7 The growth rate was varied from 0.6 to 20 mm per min, thus producing crystals with varying numbers of striation boundaries. To avoid prior deformation, the crystals were chemically cut to the desired length with a saturated solution of cupric chloride. They were then annealed at 580°C for 24 hr and allowed to cool slowly in the furnace. Finally, the specimens were electropolished using an electrolyte of 5 parts ethyl alcohol and 1 part perchloric acid. Each specimen was approximately 5 in. in length and 0.125 sq in. in cross section. The average orientations of the 5 series of crystals studied are shown on the stereographic projection of Fig. 1. The crystals were strained approximately 2 pct in a soft tensile machine. The strain sensitivity was 3.6 x 10-4 cm over a 5-cm gage length.

Jan 1, 1960

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members) The following is a partial list of members and guests who called at Institute headquarters during the period Mar. 10, 1917, to Apr. 10, 1917. George S. Blair, Pittsburgh, Pa. E. P. Mathewson, Toronto, Canada. H. M. Boylston, Cambridge, Mass. T. Poole Maynard, Atlanta, Ga. F. J. Brule, Toronto, Canada. . W. J. Mead, Madison, Wis. M. B. Cohen, Miami, Ariz.. D. G. Miller, Denver, Colo. W. M. Corse, Buffalo, N. Y. P. N. Moore, St. Louis, Mo. F. G. Cottrell, Washington, D. C. R. H. Morris, Ansted, W. Va. E. C. Cross, Cleveland, 0. W. J. Morrison, Toronto, Canada. Nelson Dickerman, San Francisco, Cal. M. F. Ortin, Petrograd, Russia. F. N. Flynn, Chuquicamata, Chile. G. W. Paymal, New York, N. Y. F. L. Garrison, Philadelphia, Pa. Edward H. Perry, Boston, Mass. J. S. Grasty, Charlottesville, Va. 0. G. Petersen, Somerset, Ky. H. D. Hibbard, Plainfield, N. J. H. C. Price, Bartlesville, Okla. H. L. Hollis, Chicago, 111. C. A. Richardson, Toronto, Canada. F. H. Jackson, Marysvale, Utah. Hallet R. Robbins, Vancouver, B. C., Can. W. Strickler Jones, Silver City, N. M. A. H. Rogers, Boston, Mass. E. B. Kirby, St. Louis, Mo. H. G. Smith, Princepulca, Nic. J. M. Lovejoy, Electra, Tex. Edwin G. Steele, Van Horn, Tex. A. F. Lucas, Washington, D. C. 'S. A. Taylor, Pittsburgh, Pa. Edwin Ludlow, Lansford, Pa. A. P. Thompson, Salt Lake City, Utah, E. Francis McCrossin, Birmingham, Ala. Milton A. Allen is now engaged in the New York office of Messrs. Arthur L. Pearse & Co. Percy E. Barbour, managing editor of the Engineering & Mining Journal, has been appointed, by Governor Whitman, Deputy Superintendent of Police of the State of New York.

Jan 6, 1917

By Avnulf Muan, Egil Aukrust

The activity-composition curve for cobalt oxide in (Co,Fe)304 solid solutions with spinel-type stmcture has been determined experimentally by studying the equilibrium between the spinel phase and a coexisting cobaltowüstite phase, "(Co,Fe)O", at 1200°C. A large negative deviation from ideal behavior prevails in the spinel at low cobalt oxide concentrations and a positive deviation at high cobalt oxide concentrations. The activity-composition curve for iron oxide in the solid solution is determined from the above curve by integvation of the Gibbs-Duhem equation along the join Co3O4,-Fe3O4. The standard free energy of formation of cobalt ferrite, CoFe2O4, from the oxide components CoO and Fe2O3 is calculated to be -8.2 kcal. ThERMODYNAMIC properties of (CO,Mn)3O4 solid solutions with spinel-type structure have been presented recently.' The present paper deals with similar relations in another spinel solid-solution phase, that represented by the system Co3O4-Fe3O4. The principles involved in measurements and calculations of thermodynamic properties for the system Co3O4-Fe3O4 are analogous to those used and discussed in detail in the work on (CO,Mn)3O4. A (CO,Fe)3O4 solid solution coexists in equilibrium with a (Co.Fe)Ot solid solution over a considerable Here acOo1.33 and aao are the activities of cobalt oxide in the spinel and the oxide solid solutions, respectively, pO2, is the oxygen pressure of equilibration, and pb, is the oxygen pressure at which CoO and CosO4 coexist in equilibrium in the binary system Co-O at the same temperature. The activity-com position curve for cobalt oxide in the (Co,Fe)O solid solution in contact with metal has been determined in a previous investigation by the present authors.' The system shows a small positive deviation from linear behavior. Because of the large defect concentration in wiistite and in (Co,Fe)O solid solutions, one cannot assume that the activity-composition relations in the oxide phase coexisting with a spinel phase at relatively high oxygen pressures are the same as those prevailing in the oxide solid solution coexisting with metal. However, a Gibbs-Duhem integration over the ternary Co-Fe-0 solution can be used to determine activities of cobalt and iron, and hence of CoO and FeO, from a knowledge of the oxygen potentials. Several papers have dealt with the subject of application of the Gibbs-Duhem equation to multi-component systems. 3-6 In the present case, it was

Jan 1, 1964

Now producing 35,000 tpd of coal from a deposit whose estimated reserves total 1.1 billion t, the Navajo mine of Utah International Inc. near Farmington, N. M., is the largest open-pit coal operation in the US. The history of this mine began in 1953 when, foreseeing the growing need for electrical power in the southwest, Utah International obtained a prospecting permit from the Navajo tribe. The lease, now covering 31,000 acres of the 12-million acre New Mexico-Utah-Arizona Navajo Indian reservation, was entered in 1957; in the next 3 years, Utah International negotiated with the State of New Mexico for water rights on the San Juan River, and finalized an agreement with the Arizona Public Service Co. to provide coal for the proposed Four Corners power-generating plant near Farmington.

Jan 10, 1974

It has been established that molybdenum sesquisulphide, not molybdenite, is in equilibrium with molybdenum metal and sulphur vapor in the vicinity of 1100°C. The S2 pressure for this system has been obtained using the Knudsen orifice method and the standard free energy for the dissociation of S2. THIS work was undertaken to help in determining the thermodynamic properties of the molybdenum sulphide which is in equilibrium with metallic molybdenum and sulphur vapor in the temperature range 1025" to 1150°C. From the results of MontoroL and of Parravano and Malquori' molybdenite would be expected to be in equilibrium with molybdenum metal, while the results of Guichard indicate that a lower sulphide must be in equilibrium with the metal. Thus it was concluded that the problem warranted reconsideration, especially in view of the suspiciously low temperature independent term for the standard free-energy function for the reaction MoS² Mo + S,. The reaction was calculated and duly noted as being low by Richardson and Jeffes,' using the data of Parravano and Malquori.' Experimental Method The general method used in this investigation is that of the Knudsen orifice method for the determination of equilibrium pressure. The apparatus and technique are similar to those described for the determination of the vapor pressure of silver.% owever, a closed-end McDanel tube instead of fused silica was used to maintain the vacuum, a molybdenum effusion cell with a replaceable lid was employed instead of a silica cell, and a titanium getter maintained at run temperature was used to assure that no oxidation of the molybdenum or molybdenum sulphide was taking place. All runs were made at a residual pressure less than 10-5 mm Hg. The data are given in Table I. Runs 1 through 13 were obtained using molybdenite, analyzed 98.5 pct, from the Molybdenum Corp. of America. The remaining runs were done with a sample from the Climax Molybdenum Corp. which was their grade No. 3 and analyzed 59.87 pct Mo. The weight loss of the cell during heating up and cooling down was subtracted from the total weight loss of the cell during the run. Also, when the tem- perature was changed, the Knudsen cell was placed in the vacuum chamber and heated at temperature for several hours in order to allow the sulphide and the metal to adjust their compositions to the equilibrium values, to desorb or adsorb gases into or from the molybdenum cell itself, and to desorb any water from the molybdenum sulphide or molybdenum powder inside the cell. Water may have been adsorbed inside the cell because, after each run, the top of the cell was removed and the material in the cell was stirred to insure that a layer of molybdenum metal would not build up and obstruct the passage of sulphur vapor into the gas phase. It was established that the molybdenum cell alone decreased in weight an inappreciable amount when heated at the highest run temperature for long periods of time. There are two questions to be answered before the data in Table I can be used to calculate thermodynamic functions: 1—Which molybdenum sulphide is in equilibrium with molybdenum metal and sulphur vapor? 2—What sulphur species are present in the vapor phase? It can be assumed safely that no molybdenum is vaporized, since its vapor pressure is almost negligible at these temperatures. It will be shown subsequently that no sulphide of molybdenum is volatile. Question 1 was answered in the following way: The especially purified molybdenite, obtained from the suppliers mentioned previously, was charged

Jan 1, 1956

By Utley Wedge

(Cleveland :Meeting, October, 1012.) In general, the art of securing copper from sulphide ores or concentrates may be said to consist of : (1) separation, in the molten state, of copper sulphide with some iron sulphide, from the great bulk of gangue-material, followed by (2) elimination of sulphur and iron from the molten matte, by oxidation and fluxing, leaving metallic copper. The definition is made broad enough to cover the general practice, whether or not the ore or concentrate is given a preliminary roast for the removal of surplus sulphur. The above process, which I will designate as the smelting process, makes necessary the presence in the ore, or the addition thereto, of such silica, lime, and iron as may be necessary for the formation of a light and fusible slag, together with sufficient sulphur and iron for the formation of copper-matte, and also the addition to the matte of sufficient silica for the oxidation and fluxing-out of the iron. These items, together with the cost of fuel sufficient for melting the mass, constitute important items of cost in the copper-smelting process. Numerous cases where fluxing-materials are scarce or dear, or where fuel is expensive, have caused special attention to be given recently to the wet process of copper-extraction, which may be designated as consisting of forming soluble copper salts which are then washed or leached out of the ore or concentrates by dissolving in water or acid. Metallic copper may then be secured from the solution of copper salts by electrolysis; by cementation; or copper can be brought out of the solution as a * Presented also at the Joint Meeting of the Institute and Section IIIa, Metallurgy and Mining, of the Eighth International Congress or Applied Chemistry, New York, N. Y., September, 1912, and here published by mutual agreement.

Dec 1, 1912

By WILLARD HAYES

(Glen Summit Meeting, June, 1911.) THE determination of the question whether the Mayari and Moa mining-claims of the Spanish-American Iron Co. have been rightly denounced under the third section of the law of bases rests on the findings in the following questions of fact: 1. Is the mineral an iron-ore? 2. Is the iron-ore a bog iron-ore? 3. Is the iron-ore ocher? 4. If ocher is present, can it be mined separately and independently of the iron-ore ? 1. IS THE MINERAL AN IRON-ORE? Since the material is shown by a large number of analyses to contain from 41. to 50 per cent. of metallic iron and less than 0.02 per cent. of phosphorus, and since it has been and is being actually used on a commercial scale for the production of iron and steel, it must be classed as an iron-ore. 2. IS THE IRON-ORE A BOG IRON-ORE? Bog iron-ore has certain invariable characteristics of chemical composition, physical appearance, geological relations, and origin by which it can always be recognized with certainty. In chemical composition, it is the hydrated sesquioxide of iron, limonite, or a mixture of limonite and other closely-related iron hydrates. It never contains the anhydrous oxides-hematite or magnetite; is never magnetic, and never contains either nickel, chromium, or cobalt oxides. On the other hand, it is invariably high in phosphorus-content. In physical appearance and texture it is a yellow or reddish-brown amorphous spongy material, and always contains water-worn sand-grains, silt, clay, and plant-remains. In its geological relations it is wholly independent of the rock

Mar 1, 1911

By J. P. Murphy, T. E. Leontis

DURING the last few years, the trend in the aircraft and automotive industries has been toward higher and higher operating engine temperatures. This has created considerable interest in the effect of temperature on the properties of alloys. In the magnesium field, it has been recognized for many years that the addition of cerium imparts high strength and good resistance to creep at elevated temperatures. Beck,1 in his treatise on-magnesium, has summarized the work of German investigators. This includes the unpublished data of Menking, showing the increase in strength and hardness of extruded alloys containing 2 to 20 per cent Ce at temperatures from 200 to 300°C. (68° to 572°F.) and the results of Vosskühler, who demonstrated the improved resistance to creep of alloys containing 6 per cent Ce plus 2 per cent Mn and 0.5 per cent Ce plus 2 per cent Mn at 150°C. (302°F.). Wellinger and Keil2 have also reported the creep properties of a forged magnesium-cerium-manganese alloy at 200° and 250°C. (392° and 482°F.). Haughton and Prytherch have determined the tensile properties of various forged magnesium alloys containing cerium, cerium plus manganese, cerium plus calcium, cerium plus nickel, cerium plus nickel plus manganese, and cerium plus cobalt plus manganese at temperatures up to 290°C. (554°F.). Magnesium-cerium alloys have been used in some commercial applications. It is reported that an alloy containing 3 per cent Ce plus 0.5 per cent Mn plus 0.5 per cent Ca is being used on a forged impeller in Great Britain. Two forged parts made from an alloy with a nominal composition of 5 per cent Ce and 2 percent Mn have been found on the German .BMW-801D aircraft engine. These two forgings consist of a supercharger impeller and a rear cam-follower guide. In this country, several types of pistons have been made experimentally in both .the cast and the forged conditions from an alloy containing 6 per cent Ce plus 2 per, cent Mn and in the cast condition from an alloy of magnesium plus 10 per cent Ce. The cast pistons have been tested in various types of internal-combustion engines, with promising results. This paper presents the results of an extensive investigation on the properties of various cerium-containing magnesium alloys in both the cast and the forged conditions. Data are presented to show the beneficial effects of increasing amounts of cerium on the mechanical properties of magnesium at elevated temperatures. The effects of heat-treatment on the properties of these alloys and the attendant changes in the microstructure are discussed. The

Jan 1, 1946

By H. J. Wasson

DEVELOPMENTS in Venezuela during the past few months have been obscured by the hap-penings in Seminole and, more recently, those in southwest Texas. The question has been asked whether or not the opening of these vast new, prolific areas in the United States may not have depressed prices to a point so low as to give the developments in the Caribbean countries a serious setback. Nothing of the kind, however, has taken place, and on the contrary, there has been demonstrated the fact that Venezuela can profitably produce great quantities of oil under existing market conditions, and at the same time finance the foundation for further large expan-sion in the future. The three big factors which contribute to place Venezuela in a unique position and tend to insure the steady expansion of its oil industry are, in the order of their importance: I. Reasonable oil laws backed by a sound govern-ment, which comprehends the all-important fact that the country's prosperity depends on the prosperity of its industries, in a word, perceiving that the goose which lays the golden egg merits considerate treatment. II. The low cost of placing Venezuela oil on our At-lantic seaboard; not over $0.60 per barrel. III. The uniformly high average production per well and the large area of some of the individual pools. Under these conditions Venezuelan producers may be expected to continue steady and profitable ex-pansion even in the face of further market slumps. Their position is analogous to that of the low-cost copper producers, and unless artificial barriers, such as tariffs, come into play, Venezuela will steadily grow in importance. Within less than five years it should be second only to the United States among the oil-producing countries of the world.

Jan 10, 1927