Search Documents

By L. L. Oriard

In order to predict the influence of blasting on slopes, one must first understand the action of explosives, the manner in which rock is broken or displaced, and how seismic waves are transmitted, and the nature of these seismic waves. In this paper, the author describes the action of high explosives on rock masses, beginning at the source of the explosion, extending through the zone of rupture to a distance where only elastic waves of low energy persist. The paper describes the relationships between explosives charge quantities and distances, including the character and intensity of the seismic waves in various types of terrain. In looking at the analysis of slopes subjected to seismic waves, it has been common practice to assume a simplified model in which the anticipated acceleration is applied horizontally to the slope as an equivalent static force, or a model in which there is a rigid base subjected to mechanical shaking. Such models do not accurately portray blasting activity taking place within or near the slope in question. In dealing with blasting effects, it is important to under- stand seismic wave types, wave lengths, attenuation and transmission paths, as well as vibration intensity. In most cases, those slopes that are the least stable under static loading will also be the least stable under dynamic loading, although there may be rare exceptions. Thus, the more that is known about a slope statically, the better will be the assessment of it dynamically.

Jan 1, 1983

By Walter E. Hopper

The Caddo oil-field, shown in Fig. 1, is located in Caddo parish, northwestern Louisiana. The known producing territory of oil is covered by townships 19 N, 20 N, 21 N, 22 N, and ranges 15 and 16 W., shown in Fig. 2. The center of the field may be taken as Oil City, 24 miles north of Shreveport, on the Kansas City Southern railway. Shreveport is the second largest city in the State, and is the connecting point of five railroad-lines. Drilling at the present time, however, is going on all over northern Louisiana, especially in Caddo and the neighboring parishes. During the winter of 1908-09 I spent 'four months in the Caddo field, under the direction of the Louisiana Geological Survey and the U. S. Geological Survey. II. History and Development. Natural gas escaping at the surface is found at numerous places in northwestern Louisiana. At Shreveport, the plant of the Shreveport Ice & Refrigerating Co. has been lighted by natural gas for 20 years. The well was drilled for water, but was abandoned on account of the gas. A test well, put down in 1905 near the western limits of Shreveport, was driven to 1,650 ft., and encountered indications of gas and oil at various depths, but did not succeed in finding enough to be profitable. Attention was first attracted to the Caddo field in 1895 by indications in water-wells from 40 to 60 ft. deep, in which the pressure of natural gas was noticeable. This indication of gas in a shallow well led to the drilling of the first well in the Caddo field, the old Savage Brothers & Morricell, or the Caddo Lake Oil and Pipe Line No. 1. The rig for this well was erected in May, 1904, and drilling began in June, 1904. The well was bailed Mar. 23, 1905, with a small amount of oil. It was deepened July, 1905, and converted into a "gasser" Jan. 3, 1906. It was abandoned January, 1907. In consequence of the finding of oil in the Savage well, drilling-operations were pushed with energy; and in April, 1905,

Jan 1, 1912

By H. G. Schneider

The Smackover oil and gas field lies in Ouachita and Union Counties, Ark., in the south-central part of the state, in T.15 and 16S., R.15, 16, and 17W. It is 10 miles north of El Dorado, the principal business and railroad center in the south-central part of the state, and extends from the town of Smackover in all directions. Productive territory having an aggregate area of nearly 55 sq. mi. has been developed. It extends 6 miles from north to south and 12 miles from east to west. The field may be divided into two parts: the east district, which includes the area east of the town of Smackover, and the west district, which includes the area west of the town of Smackover. In relation to the neighboring productive fields of Arkansas, the Smackover field is 9 miles north of the El Dorado oil and gas field, 8 miles slightly west of north of the East El Dorado oil and gas field, and 16 miles east of the Stephens oil field. Smackover was discovered in May, 1922, when the Oil Operators Tnist drilled well No. 1 on the J. T. Murphy farm, in the southeast quarter of sec. 8, T.16S., R.15W. This well is located almost on the top of the Norphlet dome and was drilled to the Nacatoch sand. It had an initial open flow volume of 30,000,000 cu. ft. of dry gas per day, and a rock pressure of 950 lb. per sq. in. In July, 1922, the V. K. F. Co. completed the first oil well in sec. 29, T.l5S., R.l5W., on the north side of the Norphlet dome, and 3 miles north of the first gas well. This well started the active development of the north and northwest sides of the dome.] The field was extended westwards, when oil was discovered in the Nacatoch sand, during October, 1922, in sec. 4, T.l6S., R.l6W., 51/2 miles west of the original gas well. This opened up the so-called "light oil district," which is located on a structural terrace, for which the name

Jan 1, 1924

By D. C. Lindley, D. H. Gaucher

The displacement of oil by water in a waterflood project is accomplished by the action of transient viscous, gravitational and capillary forces which drive fluid through interconnecting pore spaces toward production wells. The relative importance of each of these forces to the effectiveness of the displacement and the production history depends on properties of the reservoir itself and the manner in which it is operated. There has been considerable discussion'-3 concerning the importance of these factors and the extent to which they control the performance of individual waterflood projects. No data have been presented, however, to demonstrate the effect on waterflood behavior of variations in rock permeability, water-injection rates and mobility ratios in three-dimensional reservoir systems in which viscous, gravitational and capillary forces are allowed to assume the proper relative influence on fluid flow. Much information relevant to water flooding has been gained from the study of field case histories. But, the complexity of the systems involved, the difficulty of defining geometry and obtaining sufficient data, and the fact that the same reservoir is never flooded twice with the same initial conditions, all obscure the role of process variables such as rate. Further, mathematical calculations of waterflood behavior are restricted at this time by available mathematical techniques to highly simplified situations. Scaled models, however, do offer an approach at the present time to evaluation of the effects of the pertinent variables. Several investigators have predicted prototype reservoir behavior from observations of model waterflood performance under a variety of conditions. Two-dimensional aspects of waterflood pattern efficiency have been investigated by Muskat, Aronofsky, Dyes, et al, raig, et al,' and Rapoport, et al. he effects of gravity segregation, viscous fingering and permeability stratification have also been studied in two-dimensional models. Craig, et al," studied the importance of gravitational forces on frontal displacement in three-dimensional models with wells on a five-spot pattern. This work in- vestigates the tendency for water to segregate in homogeneous reservoirs because of gravity and to under-run the oil for a range of water-inject ion rates. The effects of permeability stratifications were investigated by these authors using miscible fluids to simulate water-channeling through permeable strata in systems of negligible capillary force. In this investigation, a three-dimensional model of a five-spot pattern flood was designed to represent typical prototype conditions, and the sand and liquid properties were selected so that capillary, gravitational and viscous pressure gradients were scaled. It was not, however, possible to achieve exact similitude regarding viscous fingering when the more viscous oil was used. The effects of rock stratification on waterflood behavior were studied by changing both the permeability ratio and the position of the more permeable sand stratum in a two-layered, horizontal model. For each type of stratification, constant-rate floods were performed and the rates were varied, in separate experiments, over a tenfold range. To observe the effect of mobility ratio on flood performance, two series of constant-injection-rate floods were performed on the most highly stratified reservoir at a water-oil viscosity ratio of one.

By J. L. Tokich, A. R. Troiano

Since 1921, when Hull1 discovered that cobalt can exist in the face-centered cubic and hexagonal close-packed modifications, the transitions that occur in cobalt have been extensively studied. It is generally agreed that on heating the hexagonal lattice changes to the cubic structure at ternperatures ranging from 400° to 500°C although considerable doubt exists as to the exact temperature. Data concerning the temperature of the transformation on cooling are much less concordant and their interpretation has not been satisfactory. The study is further complicated by the fact that many investigators have reported the existence of a high temperature allo-tropic change in the range 850 to 1020°C, at which the cubic lattice reverts to the hexagonal modification. The transition on cooling, which has been reported as Occurring at various temperatures from approximately 400 to 100°C, is of particular interest. Troiano and Greninger2 have recently suggested and considered the possibility Of allotropic transformations occurring in pure metals by a shear-type, diffusionless (martensite) transformation. The case of cobalt was specifically discussed and certain observations of previous investigators evaluated in terms Of this type of Of Table 1 briefly outlines the methods and results Of previous investigators Of the transformation temperatures of cobalt. Materials and Methods The major portion of this investigatioll was performed with cobalt sheet containing a total of 0.2 pet impurities with carbon present to the extent of o,I pct. After melting in an induction furnace under an atmosphere of hydrogen, the carbon con. tent analyzed 0.03 pct. Some observations were repeated with hydrogen reduced cobalt compresses analyzing 99.9 pet pure. No significant variations in results were observed employing the as-received sheet, the remelted stock, or the cobalt compresses. Filings for X ray diffraction analysis were sealed in evacuated glass ampoules. Pyrex glass tubing was used for temperatures below (600°C and for higher temperatures clear fused quartz was satisfactory. After appropriate heat treatment at various ternperatures, the specimen ampoules were furnace cooled, air cooled or quenched by crushing under distilled water. This allowed a range of cooling velocities from less than one degree C per set to greater than 1,0oo°C per sec. X ray diffraction patterns were taken with a Debye camera and filtered characteristic cobalt K-alpha radiation. The of of the existing phases was roughly approximated by visual examina-

Jan 1, 1949

By James Hance

INTRODUCTION SEVERAL years ago the writer was connected with the Mint and Assay Service of the Federal Government as Assistant Assayer at the-Salt Lake Assay Office. At that time cyanide bars formed approximately half of the bullion purchased by that office. Disagreement in valuation between the producer and the office was not infrequent and to a lesser extent between the Assay Office and the Mint, this latter issue being soon obviated, however, by adopting uniform methods of sampling the bars. A nice problem seemed to offer itself for research and the writer began a series of experiments which were soon terminated, however, by his going into other work, and which he regrets have not since been completed. The results attained may suggest lines of approach to this problem and are, therefore, offered in this article. Frederick P. Dewey, Assayer of the Mint Service, U. S. Treasury, has had abundant opportunity to study this phase of metallurgy, and has published several articles relative thereto.1 In the last article cited Dewey quotes analyses of cyanide bullion similar in content to that with which the writer worked, and which show some of the variations met with. In the discussion of these papers,2 comparison has been made in terms of copper bullion, but to the writer this seems of questionable value. Copper bullion may resemble silver bullion, but its similarity to, gold bullion with little or no silver content is another thing. The freezing-point diagram of Roozeboom, reproduced on page 881 of the discussion cited, is for the gold-silver series as stated. The original problem under discussion, however, is not this alloy but gold with base metals other than copper. As for the statement that the corners are the worst places or

Jan 2, 1916

By L. C. Raymond

Valuations in the mineral industry differ from those of other enterprises because mines and oil wells have a definite life so cannot be considered a perpetuity. This requires that in any mineral-property evaluation the recovery of invested capital is necessary during the life of the property. Capital write-offs for nonextractive industries are assumed to be continuously plowed back to sustain the operation and produce yields on the capital invested. The extractive or mineral industry, however, generally attempts to return to the investor both interest and principal during the life of a property. Normally this is done currently and the dividend includes both items. Where the mineral property possesses large reserves and the life factor approximates a perpetuity, the return on investment is generally comparable to that of industrial stocks. The valuation of a mineral property, at best, is based on educated estimates and judgment factors. This is particularly true as it relates to estimating selling prices over a long term or assessing the quality of management. Also, it is possible to make various assumptions as to rapidity of working out the deposit, varying time for start-up of operations, varying earning rates, so as to obtain different results with the same basic facts. Thus it is not surprising that two engineers, irrespective of their abilities, may not agree exactly even when given the same facts, but their results should be close enough to be used in establishing a fair value for trading purposes. The valuation is no better than the source of basic data and the soundness of judgment factors. Fundamentally the basic principles of mineral valuation are similar for base metals, sulfur, oil, or any other mineral. Each mineral, however, requires an engineer to have a knowledge of such factors as its occurrence, distribution, mining and processing methods, and marketing problems in order to gather and analyze all the facts and data that have a bearing on the earning potential of the property. Present Value of a Mineral Property In essence the present value of a mineral property is a sum of money in today's dollars that future income from the property are worth. It differs from the total anticipated earnings by the amount of the interest that the unrecouped investment could be expected to earn during the period of recoupment. Thus, if one could accurately estimate what a mineral property will earn during its life, after deducting all operating, administrative, capital, interest, and tax charges, the determination of present value would be a relatively simple mathematical calculation. Normally, where the expected life of the mineral property extends beyond 20 or 25 years, the discounted value of earnings beyond this period is relatively small. The petroleum industry generally discounts the annual cash flow of an operation rather than earnings since, for tax-saving purposes, earnings are kept

Jan 1, 1976

By AIME AIME

THE Tuesday afternoon session", H. A. Bedworth chairman and T. S. Fuller, vice-chairman, was opened with D. J. McAdam, Jr.'s paper entitled "The Influence of Cyclic Stress on Corrosion." This paper dealt with the influence of cyclic stress on corrosion of alloy steels, corrosion-resisting steels, monel metal and aluminum alloys. The paper was discussed by T. S. Fuller, who pointed out that steels under stress corroded more than unstressed steels when subjected to steam.

Jan 1, 1930

By B. F. Fackenthall

The Durham Iron Works of Messrs. Cooper & Hewitt, near Riegelsville, Pa., occupy a site which has been almost continuously the scene of iron-manufacturing industry since 1727. Doubtless if Anthony Morris and his thirteen associates, who in that year erected a blast-furnace on the Durham Creek, a short distance above where the Durham Iron Works now stands, could have had a vision of the improved and enlarged apparatus of their successors, they would have been not less astonished by the huge stack, the hot-blast ovens, and the blowing-engines of the modern blast-furnace, than by the railroad which now follows the bank of the river on which their clumsy " Durham boats " once floated pig-iron to Philadelphia. In one particular, posterity must confess their snperiority. We are told that in November, 1728, they shipped three tons of Durham iron to England. The proprietors of the Durham Iron Works are not now shipping iron to England. The present Durham furnace was built (in place of two smaller ones) in 1874 and 1875, and made its first blast in 1876. A description of it, with other works of the same proprietors, at Trenton, N. J., by A. L. Holley and Lenox Smith, was published in London Engineering for January 31st, and February 21st, 1879. Since that time, a number of improvements, dictated by experience, have been made in the details of the furnace and fittings; and the recent roilclusion of a long and successful blast presents a convenient opportunity for a description of the works and a statement of the results of practice. The accompanying drawings will show the general arrangement of the works. The furnace, Plate I., Figs. 1 and 2, is 75 feet high by 19 feet bosh. The hearth is 11 feet 4 inches in diameter, with seven tuyeres 5 feet 6 inches above hearth-line. The tuyeres project 9 inches into the furnace, making the interior tuyere-circle 9 feet 10 inches in diameter. The front is a modification of Luermaun's

Jan 1, 1886

By H. J. Ramey, I. S. Bousaid

Experimental results on the oxidation reaction kinetics in the forward combustion oil recovery process are presented. A total of 48 runs were made wherein a stationary thin layer of coked, unconsoli-dated sand was burned isothermally in a combustion cell. Individual runs were made at various temperature levels to permit determination of the effect of temperature upon the reaction. An expression was obtained for the burning rate of carbon as a function of carbon concentration, combustion temperature and oxygen partial pressure. The carbon burning rate for two types of crude oil indicated a first order reaction with respect to both carbon concentration and oxygen partial pressure. The effect of combustion temperature on the reaction rate constant matched the Arrhenius equation. The activation energy was similar for the two crude oils examined. The activation energy decreased for a porous media containing clay. The rate of oxidation of crude oil at reservoir temperature was found to be significant. Other significant findings included information on hydrogen-carbon content of fuel residues, fuel reactivity and the products of combustion. INTRODUCTION The production of crude oil by underground combustion has been studied in the laboratory by many investigators.1-5 Results of laboratory and field experiments have been reported in the literature describing the forward combustion process. But as yet, no qualitative or quantitative study of the kinetics of fuel combustion involved in this process has been reported. The fuel concentration and the rate at which fuel is burned at the front are important factors governing the air requirement in a forward combustion operation. Although the fuel is essentially unrecoverable crude, the air required to burn the fuel is an important economic factor in this process. Because fuel is burned, the heat transport associated with forward combustion is a key and unique feature of this new oil recovery method. Many investiga-tors5-9 have presented information on the heat transmission and fluid mechanics involved in forward combustion. Berry and Parrish10 demonstrated the utility of considering reaction kinetics in reverse burning. From differential thermal analysis, Tadema11 presented a qualitative discussion of the nature of reactions between oil and oxygen in combustion oil recovery. Although little quantitative work has been done on the reaction kinetics involved in forward combustion oil recovery, an extensive literature does exist on combustion of carbons and oils, and carbonaceous residues from cracking catalyst pellets. Dart, et al., 12 studied the combustion rate for oxidation of carbonaceous residues on clay catalyst pellets, and found the reaction to be second-order with respect to carbon concentration, and first-order with respect to oxygen partial pressure for carbon concentrations less than 2 weight percent of the catalyst weight. The reaction appeared to be first-order with respect to carbon concentration for concentrations greater than 2 percent. Metcalfe13 noted that other workers had found that aging of the fuel during the combustion process was responsible for changing coke properties, and it accounted for the apparent second-order carbon concentration effect found by Dart, et al. It appears that burning of residues from cracking pellets is first-order with respect to both carbon concentration and oxygen partial pressure. Dart, et al., also observed that hydrogen in the hydrocarbon residue appeared to react faster than the carbon. Lewis, et al.,14 studied oxidation of charcoal, coke and graphite in a fluidized bed. Gas velocities were high enough to partially lift and circulate the carbon particles. Their results indicated first-order reaction dependency with respect to both carbon concentration and oxygen partial pressure. One

Jan 1, 1969

By AIME AIME

IN many countries the lack of liquid petroleum supplies has centered interest upon the hydrogenation of coal and coal tars for the preparation of motor fuel. In the United States, hydrogenation has been of greater interest for grading up low-value petroleum fractions to the more valuable volatile fuels and for the preparation of a variety of premium products, including aviation gasolines, solvents, Diesel fuels, and lubricating oils. Chemically, the basic reason for this process is that, as shown in Table 1, the ratio of hydrogen to carbon (H/C ratio) in available raw materials is quite different from that characterizing the products sought.

Jan 1, 1936

By T. L. Joseph

The extent to which hot metal from the blast furnace affects open-hearth practice and the quality of steel produced has been discussed widely. Open-hearth operators have attributed difficulties experienced in making satisfactory steel to characteristics of the pig iron not disclosed by ordinary analysis. The commonest criticism of the iron has been that it is "physically cold" or "dirty." Often when the blast furnaces are working irregularly the quality of the iron is questioned. A cold hearth, slipping and hanging, the use in the past of unsintered flue dust, and the use of ores difficult to smelt have been associated with the production of iron of poor quality. The difficulty of the situation is that we have no proven yardstick for quality aside from ordinary analysis. Uniformity in analysis is recognized as being important, but the difficulty of changing the open-hearth practice when the iron analysis varies widely may not always be fully appreciated. Although the problem of correlating the characteristics of steel with those of pig iron is admittedly obscure, the effort of producers of quality steel to investigate all factors that may have a bearing on the final product is justified. This report contains data on the oxides in several hundred casts of basic iron produced in a furnace during the course of normal operation on Lake ores. Incidental to the study of the oxides in the iron, it was desirable to follow closely the temperature of the iron. The effect of temperature of the iron upon the silicon and sulphur present is discussed. A general relation between the basicity of the slag and the sulphur in the metal was developed. The amount and composition of oxides in the hot metal and in the steel bath during various intervals between melt-down and tap are discussed. Heats of rimmed steel, killed steel, and semikilled steel were investigated. The hot metal on individual heats was either all taken from a mixer or consisted partly of direct metal and partly of metal from the mixer. Samples of the iron for oxide determinations were

Jan 1, 1937

By Arthur Forsyth

A SEARCH through the available literature shows that the cobalt-nickel-silicon system has not been systematically studied. This seems rather odd because all three elements are fairly abundant and have better than average corrosion resistance; however, they have high melting points, which makes experimental work difficult. Cobalt and nickel form a continuous series of solid solutions and each metal dissolves about 7.5 per cent silicon. Many ternary alloys have been studied and the results have been published in a great many different ways, but to present such data in a short but clear and understandable manner is still a problem. The following pages describe the results of the study of 76 alloys from which the partial ternary diagram (Fig. 1) of the cobalt-nickel-silicon system has been drawn. The alloys were chosen according to the plan in Fig. la by taking definite ratios of cobalt and nickel, such as 70 Ni, 30 Co or 40 Ni, 60 Co, and adding silicon in various percentages. Each section was studied in detail by means of thermal analysis and microscopic examination, but only two of these detailed sections were thought necessary in the point perspective drawing to give a comprehensive picture of the liquidus, solidus and solid transformations that take place over the temperature ranges studied. Complete thermal analyses and microscopic data are given in Table 1.

Jan 1, 1940

By Paul A. Filteau

Asbestos ranks among the leading minerals produced in Canada. It is also mined in Russia, Rhodesia, South Africa, Cyprus, Italy, the U.S.A., Japan, China and several other countries. The most abundant variety, chrysotile, and also the most valuable form of asbestos produced, makes up 90% of the world's supply. In Canada, chrysotile is found in the provinces of British Columbia, Ontario, Newfoundland as well as in Quebec, the latter accounting for almost 90% of all the fibre produced in this country. A number of developments emerging this year could make 1968 a record production and export year for Canada's asbestos mining industry. Asbestos fibre consumption in increasing in the U.S., Canada, up 10% to date this year, Japan and in Latin America. Demand in Western Europe is again on the upswing, following a cut-back last year. As a result, shipments from Canadian mines for the first eight months of this year reached some 916,968 tons versus 873,402 in 1967, an increase of 43,566 tons or 5%. Indications are that Canadian asbestos production will for the first time ever top 1.5 million tons in 1968.

Jan 1, 1969

By D. B. Hobbs, L. W. Kempf, R. S. Archer

SILICON is one of the most important elements in the metallurgy of aluminum. It is always present in small amounts in the ordinary grades of "pure" aluminum, and hence in all alloys made therefrom. Within the last few years binary alloys containing up to 13 per cent. of silicon have come into extensive use for castings. Silicon is also added, beyond the amount present as an impurity, in alloys containing one or more other elements such as copper, manganese, magnesium and nickel. The binary aluminum-silicon alloys are not yet heat treated to any extent in commercial practice, although, as will be shown, their properties are affected to a very considerable degree by heat treatment. There are other aluminum alloys that develop higher strength, but the special characteristics of the silicon alloys may well lead to the application of heat-treating processes on a commercial scale. The role of silicon in the heat treatment of aluminum alloys is more important than would be indicated by consideration of the binary alloys alone, because many of the alloys that are heat treated in regular commercial practice contain some silicon in addition to that derived from the aluminum ingot as an impurity. Among these may be mentioned the heat-treated 195 alloy castings, and the wrought alloys 25S, Special 17S and 51S of the Aluminum Co. of America, and the German wrought alloy, Lautal. It is the purpose of this paper to present the results of experimental work and the conclusions derived therefrom regarding the heat treatment of the binary aluminum-silicon alloys. The products heat treated included forgings, chill castings and both "normal" and "modified" sand castings. REVIEW OF LITERATURE The literature on the heat treatment of aluminum-silicon alloys is not very extensive. The following review gives the principal references of which the authors are aware, in which appreciable information may be found.

Jan 1, 1928

By O. F. Kammerer, W. E. Miller, D. H. Gurinsky, J. Sadofsky, J. R. Weeks

Zirconium and titanium inhibit solution mass transfer of steels by liquid bismuth, mercury, and lead. It is shown that in bismuth and mercury, these adsorb on the surface of the steels and subsequently react with nitrogen and possibly carbon from the steels to form inert, adherent surface layers of ZrN, TiN, or TiN + Tic. Data are presented which describe the condition under which thase deposits form. These inhibitors decrease the solution rate of iron into bismuth, and require a higher supersaturation for precipitation of iron from bismuth. USE of the low-melting heavy metals (bismuth, lead, mercury, and their alloys) as coolants has been limited because solution mass transfer of steels occurs in these liquids; i. e., iron dissolves in the hot sections of the heat transfer circuit and deposits in the colder sections. The rate of solution of iron and the temperature coefficient of solubility are sufficiently great to cause complete or partial stoppage by the deposition in the coldest section of a closed circuit in finite time, even though the actual solubilities are extremely low. In the development of the mercury vapor turbine by the General Electric Co., Nerad and his associates1 discovered that the addition of as little as 1 ppm Ti or Zr to magnesium-deoxidized mercury reduced the mass transfer of ferrous alloys by mercury to a negligible amount. Reid2 reported that titanium was detected chemically on the surface of steels contacted with this mercury alloy in amounts varying from 2.0 to 2.6 mg per sq in., the greatest amount being found in the hottest portion of the circuit. Reid stated that the titanium forms the intermetallic compound Fe2Ti by reaction with iron on the surface of the steels. This compound was presumed to be highly insoluble in mercury. More recently, El-gert and Egan3 have reported a greater than 100-fold reduction in the rate of mass transfer of a 5 pet Cr steel by liquid bismuth upon the addition of titanium (in excess of 50 ppm) and magnesium (350 ppm) in the liquid metal, during experiments performed in thermal convection loops* over the temperature differential 700° to 615° C. Also, Shep-ard and his associates' have reported that the addition of titanium to liquid bismuth and Pb-Bi eutec-tic produced a marked decrease in the rates of solution of both iron and chromium from type 410 steel capsules under static conditions. This inhibiting effect increased with repeated reuse of the capsules. Tests performed in this laboratory under carefully controlled conditions have shown that the addition of zirconium and magnesium, or titanium and magnesium, to liquid bismuth or lead greatly reduces the rate of mass transfer of chromium alloy steels and carbon steels in thermal convection loops with a maximum temperature of 550°C.5-9 The present paper will review the data obtained to date at this laboratory on the behavior of iron and steels in contact with liquid bismuth alloys containing titanium or zirconium, and will attempt to explain the role of the above additives in reducing solution mass transfer. Reaction between the Zirconium or Titanium Dissolved In Liquid Bismuth and an Iron or Steel Surface Reaction between Zirconium Dissolved in Bismuth and the Surface of Pure Iron-—A small pure iron crucible (analyzed by the supplier to contain 0.8 ppm N was contacted with bismuth containing approximately 0.1 pet Mg and varying amounts of a radioactive zirconium tracer. The crucible was then inverted at the temperature of contact. The thin residual layer of adherent bismuth was dissolved in cold, concentrated nitric acid. The crucible surface and the solidified bismuth were then analyzed for radioactive zirconium. An analysis of the activity loss on the crucible surface and the weight loss of the crucible during the nitric acid treatment showed that the acid treatment removed the zirconium that had originally been dissolved in the adherent bismuth, but not any zirconium that may have reacted with the crucible surface. The crucible was then pickled in warm aqua regia to remove all surface activity, hydrogen-fired at 600°C, and recontacted with a new liquid alloy. The results of the experiments contacted 1 hr at 450°C show, Fig. 1, a Langmuir-type adsorption with an adsorption free energy of approximately 17 keal per g atom Zr.5 This deposit was estimated to contain 1 atom of zirconium for each 7 to 8 iron atoms on the crucible surface, assuming a surface roughness factor of the pickled crucibles to be five. Increasing the temperature to 520°C caused consi-

Jan 1, 1959

By Edna A. Dancy, Gerhard J. Derge

The specific conductance of FeOx,-CaO melts in contact with iron was found to decrease from 200 ohm-1 cm-1 for FeO, to 40 ohm-1 cm-1 for a melt containing 26.3 pct CaO at 1400°C. The temperature coefficient was positive at all compositions, but became smaller at high CaO contents. Current efficiencies for electrolysis increased from 2.5 pct in FeOx to 17.3 pct at the high CaO composition, indicating a change from predominantly electronic conduction to conduction with a substantial ionic contribution. It was shown that Ca++ ions as well as Fe++ ions carry the ionic current. A subsidiary investigation on the apparent effect of atmospheres of argon, helium, and nitrogen on the electrical conductivity showed that this could be correlated with surface temperature losses, which varied with the thermal conductivities of the gases and resulted in precipitation of metal by the reaction 3 Fe++ = 2 Fe+++ + Fe. The work described in this paper is offered as a contribution to the general fund of knowledge concerning metallurgical slags. Measurement of electrical conductivity and electrolysis are comparatively trouble -free methods for investigating molten materials, but, although these methods had been used for complex slags, it was not until the work of Bockris et al.1 that the approach of examining simple binary slag systems was employed, and CaO-SiO2, MnO-SiO2, and Al2O3-Si9 were studied. Two groups have performed work of particular relevance to the present investigation. Inouye, Tomlinson, and chipman2 studied the conductivity of wustite as a function of temperature and of the addition of 5 mol pct of a number of oxides, including CaO. They concluded that molten FeOx in equilibrium with iron is a semiconductor. Simnad, Derge, and ceorge3 demonstrated the ionic nature of liquid iron silicate slags and also concluded that, although the conductivity of FeOx in equilibrium with iron is predominantly electronic in nature, there is a small ionic contribution. The work reported here on FeOx,-CaO slags consists of three main parts, namely, the determination of the specific conductance over a wide composition range, an investigation into the nature of the conductivity through current-efficiency measurements over the same composition range, and an attempt to identify the current-carrying ions, as well as a subsidiary investigation on the apparent effect of the nature of the inert atmosphere on the conductivity. EXPERIMENTAL Materials. The slags, varying in composition from FeOx to 27 pct CaO, were prepared by heating reagent- grade Fe2O3 in an ingot iron crucible with a suitable amount of CaCO3 and, in some cases, powdered iron, in air. This prefused material was then used for the runs. At the end of each run the cell was removed from the furnace and quenched by immersing the bottom half in water. After crushing, the slags were analyzed for calcium and total iron by the usual wet methods. The oxygen content was obtained by difference. Specific Conductance: Apparatus and Method. Fig. shows the experimental setup, with the conductivity cell and leads of ingot iron. The standard four-probe method for measuring high conductivities was used. In this, the potential drop across the unknown resistance is compared with the potential drop across a known resistance connected in series, i .e., same current through both resistances. Thus there are both current and potential leads to the center electrode and to the crucible, which acts as th other electrode. Both ac and dc circuits were available for the measurements; they have been described in earlier work performed in this laboratory.4,5 The geometry of the cell was such that the center electrode was equidistant from the bottom and sides of the crucible. This ensured that the current path was the same irrespective of the magnitude of the conductivity of the material in the cell. Cell constant were measured with KC1 or NaCl solutions, which have considerably lower conductivities (0.0013 to 0.25 ohm-' cm) than the slags, and this precaution in design made sure that the determined cell constants applied to the cells with contents of any conductivity. The cell-constant determinations were made with the ac measuring circuit to prevent polarization. The four-probe method eliminates lead resistance but not the resistance of those parts of the center

Jan 1, 1967

Jan 1, 1901

By Dilip K. Das, Douglas T. Pitman

ONE of the major uses of barium in metallic form is as a getter material in vacuum tubes. Because of the high chemical reactivity of the metal, Ba-Al alloys are extensively used. Numerous methods for the preparation of Ba-Al alloys have been published, a few of which1-4 are cited here. Most of these methods were found to be quite elaborate, involving the reduction of BaO, and not too well adapted for the close control of the final composition of small amounts of alloys prepared for laboratory use. A simple laboratory method for the preparation of Ba-A1 alloys in small batches starting from pure metals was devised, so that it was possible to control the desired compositions to within 1 pct. The pertinent features of the alloy system Ba-Al5 are 1) an intermediate compound BaAl, with the melting point of 1050°C, and 2) a eutectic between aluminum and BaAl4 at 98 pct Al. The accompanying sketch shows the experimental arrangement for the preparation of the alloys. Weighed amounts of aluminum and barium were placed in an alumina and a stainless steel crucible, respectively. According to the supplier's specification, the purity of the metals used in the alloys is as follows: a) aluminum rods—99.9 pct Al, and b) barium rods—99.5 pct Ba. The stainless steel crucible, tapered at the bottom and having a 1/16 in. diam hole, rested on top of the alumina crucible. The assembly was placed inside a graphite sleeve which rested on a refractory platform. The platform moved the assembly up and down through the field of a radio frequency coil. A glass bell jar was placed between the crucible assembly and the radio frequency coil to maintain a steady flow of helium around the melt. A small window was cut out on the wall of the alumina crucible to observe the progress of the re- action and to record the temperature with an optical pyrometer. The platform was first raised high enough to move the barium out of the radio frequency coil field in order to allow only the aluminum to melt. The assembly was then lowered so that the barium began to melt and flow out through the small orifice into the molten aluminum. In order to keep the violence of the exothermic reaction under control, the rate of flow of barium was carefully regulated by raising or lowering the crucible assembly. All the samples prepared by this technique were examined by a Norelco X-ray diffractometer using CuKa radiation, The diffraction specimens were prepared by placing the finely powdered samples in flat specimen holders. The Ba-Al alloys prepared with a high barium content were found to consist mainly of BaAl4. The structure of BaAl4 has previously been reported by Alberti and Andress.8 They found that BaAl4 was body-centered-tetragonal with an a0 = b0 = 4.530Å and c0 = 11.14Å. An alloy whose composition was found by chemical analysis to be almost 100 pct BaA1, was used to determine the relative intensities. The d-spacings were obtained from the same alloy to which a small amount of tungsten had been added as a calibrating material. Accurate values for a, and c, were calculated according to the method proposed by Taylor and Floyd.' The calculated values are: a, = b, = 4.566Å and c0 = 11.250Å. The measured d-values for BaAl4 are shown in Table I along with relative peak intensities above background and hkl indices. Acknowledgment The authors are grateful to L. J. Cronin, the head of the Techniques Dept., for suggesting the problem and for his constant interest. References 1Froges and Camargue: German Patent No. 809107, 1951. French Patent No. 935324, 1949. 2E. Bonnier: Annales de physique, 1953, vol. 8, pp. 259-312. 3M. Orman and E. Zemhela: Prac Institute of Metals; 1952, vol. 4, pp. 437-445. 4E. Fujita and H. Yokomizo: Reports Gov. Chemical Industrial Research Institute, Tokyo, 1952, vol. 47, pp. 291-297. 5E. Alberti: Ztsch. fur Metallkunde, 1934, vol. 26, p. 6. 6E Alberti and K. R. Andress: Ztsch. fur Metallkunde, 1935, vol. 27, p. 126. 7 A. Tnslor and R. W. Floyd: Acta Crystallographica, 1950, vol. 3, p. 285.

Jan 1, 1958

By C. S. Barrett, A. Smigelskas

There have been no publications of the deformation and recrystallization orientations of the metal beryllium, yet pronounced textures would certainly be anticipated since it is close-packed hexagonal in structure. Having an axial ratio approximately that of magnesium, beryllium probably deforms by nearly the same slip and twinning mechanisms that operate in magnesium, and the textures are likely to be similar or but slightly different from the magnesium textures. In the tests reported below this is found to be the case; the textures are found to differ from those of magnesium only in the details of the scatter from the average orientation. This report covers not only samples rolled at room temperature, but some rolled at elevated temperatures. Since magnesium has been suspected by some investigators of altering its crystallo-graphic deformation mechanism at elevated temperatures, it was considered possible that beryllium might do so and alter its textures accordingly. No pronounced alterations were found, however. Unfortunately, the theory of deformation textures is not in a state of development that permits one to deduce the deformation mechanism from a knowledge of the textures, which means that the similarity of textures at different rolling temperatures, reported here, cannot be taken as definite evidence that the deformation mechanism is actually the same at all temperatures. The general similarity of the deformation textures of magnesium and beryllium also extend to the recrystallization textures of the two metals, judging by the pole figures for recrystallized sheet presented in this report. Samples were prepared in the form of composite sheets made up of small pieces stacked in a pile. Each piece was trimmed with scissors so that an edge was parallel to the rolling direction, dipped in paraffin, and assembled into the pack by aligning it under the cross hair of a microscope. As the desired orientation was obtained on each piece it was secured in place by touching with a hot wire to melt the paraffin. A stack of ten or fifteen pieces was built up in this way, then trimmed to the shape of a T; the portion to be X rayed was then etched to the shape of a wire about 0.045 in. diam with 6N HCl. This method of shaping the sample is a modification of that used by Bakarian on magnesium.' The absorption of the rays in the sample was so slight that it caused no difficulty in interpreting the films. Exposures were made with a 0.030 in. diam pinhole, using molybdenum radiation (40 kv, 25 ma, Type A film at 5 cm, 2 to 3 hr exposures). With the recrystallized specimens it was found necessary to oscillate the specimen so as to reduce the spottiness of the lines. A range of oscillation of 5" was SUB- cient to produce reasonably satisfactory patterns, though the quality was somewhat inferior to that of the deformation texture patterns, and only two degrees of intensity were read from the arcs on the films. Typical photo-grams for each of the deformation textures and the recrystallization texture are assembled in Fig 1. The pole figures were plotted in the usual way with the intensity of the various portions of the diffraction rings estimated by eye. Seven to nine films were made of each sample and each was carefully read in plotting the pole figures. Typical series included exposures with the beam normal to the rolling direction and at 11, 26, 41, 56 and 71" to the cross direction, plus two exposures with the beam normal to the cross direction, and at 11 and 79" respectively to the rolling direction. The rolling was in each case considered sufficient to develop the final texture: the reduction by cold rolling was 84 pct (from 0.0045 to 0.0007 in. thickness), following prior hot rolling in longitudinal and transverse directions and recrystallization; the reduction by hot rolling at 800°C was 90 pct (0.010 to 0.001 in.), following similar prior treatment; the reduction by rolling at 350°C was 88 pct (from 0.005 to 0.0006 in.) after similar prior treatment. The recrystallization texture was determined on a sample rolled at 350" to a reduction of 88 pct (0.0165 to 0.002 in.) after similar prior treatment, then mounted between steel strips to keep it flat and annealed at 700" in an atmosphere of argon. Discussion of Results The results of the X ray determinations are assembled in the pole figures of Fig 2, 3, 4 and 5 for rolling at

Jan 1, 1950