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By E. S. Machlin, W. R. Yankee

IN a previous study1 of the effect of heating com-mercial titanium in air on its subsequent friction coefficient against other metals, as well as itself, it was found that the friction coefficient markedly decreased from a value of about 0.7 to about 0.3. A tentative explanation was given that surfaces normally produced at room temperature are not contaminated sufficiently to prevent seizing or welding of the titanium to the softer mating metals. The latter tend to cleanse themselves during rubbing over the harder titanium. It was thought that the lack of a contaminant protective film on the titanium was due to the high solubility of titanium for oxygen and nitrogen and hence an inability to form a contaminant oxide or nitride. This explanation requires the ratio of the surface absorption rate to the diffusion rate to become much lower at room temperature than it is at high temperatures. In order to check the phenomenon further, commercial titanium specimens were nitrided or oxidized at 800°C for 20 hr in flows of prepurified N2 and 01, respectively, at about 1/2 in. H2O above atmospheric pressure. Friction runs were made in argon using a freshly cut copper hemisphere (cut in argon) on surfaces cut successively into the diffusion layers in the titanium (cut in argon) using the techniques described in a previous publication.' DPH values (100 gram load) were made as a function of depth into the diffusion layer using a Tukon tester. Also, micrographs were taken at separate cross sections to indicate the diffusion layers. The results obtained are presented in Figs. 1 and 2, which show the "static" friction coefficient vs hardness for the nitrided and oxidized specimens, respectively. A separate measurement of the friction coefficient of clean copper vs iodide titanium also was made. From results reported in the literature' giving the oxygen and nitrogen contents as functions of the hardness, cross plots were made showing the friction coefficients as functions of the amount of interstitial solute. These plots are given in Figs. 3 and 4. From micrographs of the diffusion layers and the phase diagrams, it was deduced that the data in Figs. l through 4 correspond to the single phase a region. The points observed on the compound regions have been excluded from the figures. It is apparent that nitrogen or oxygen in solution in the a titanium markedly affects the friction coefficient against a softer mating metal. Discussion of Results These results are extremely interesting from both a practical and theoretical viewpoint. The theoretical implications will be discussed first. According to Bowden, the friction coefficient should be given to a good approximation by the relation where a is the fraction of contact area that has welded, a is the shear strength of weaker component, and H is the hardness of softer component. Using this relation alone, it is difficult to understand the results because none of the terms should be affected by a variation in the oxygen or nitrogen content of the harder and stronger metal, titanium. Even if the ratio of S/H for titanium is used in Eq. 1, the ratio has been shown to be independent of oxy-gen or nitrogen content.' If a more rigorous equa-tion is used combining Eq. 1 and a result given pre-viously" for the case where welding is absent, then the relation obtained is µ = a S/H + (1-a) a W aß/H where a is constant and Waß is the work of adhesion between the two metals comprising the friction couple. This relation states that if a is less than 1/2 or so, variation in the work of adhesion Waß between copper and the titanium should affect the friction coefficient markedly. It is reasonable to expect that the work of adhesion will depend on the oxygen or nitrogen content of the titanium. Available data4 show that clean metals and oxides have much lower works of adhesion than the same metals against the

Jan 1, 1955

By W. O. Philbrook, H. W. Hosking, N. B. Melcher

A simple and inexpensive mercury-tracer method has been develohed to study rates and Patterns of gas flow in blast furnaces. A Pulse of mercury is injected into the hot blast, and its arrival at the sampling Point is recorded by an electronic circuit that measures resonant absorbtion of ultraviolet light by mercury vapor in the gas aspirated .through the detecting. cell. A rapidly developing interest in blast-furnace technology in recent years has created a strong demand for precise knowledge of the rates and patterns of gas movement through the stock column. Classical fluid-flow theory cannot supply the desired information because the complexity of the blast-furnace situation precludes the accurate determination of many of the parameters required for solution of the equations. In fact some of the terms employed in fluid-flow treatments become almost meaningless under blast-furnace conditions. The void fraction of the stock column, for example, varies widely from place to place and is affected by the segregation of charge materials, attrition of lumps during descent, and channeling. Gas density varies with changes in local pressure, temperature, and composition, while viscosity varies with temperature and composition. Even if mean values for these functions were acceptable, they would be either impossible or extremely difficult to determine with a high degree of accuracy since the value of the mean for all gas properties would depend upon the flow distribution itself. Attempts to study gas movement by the pitot-tube determination of kinetic pressures have met with little acceptance. Reproducibility of results is extremely difficult to achieve in a situation where alignment of the tube orifice with respect to the flow direction in tortuous channels cannot be guaranteed. Because of these difficulties it would appear that progress can be achieved only with a direct method of measuring gas velocities and determining the shape of flow paths through the stock. The establishment of such a method is described in this paper. SELECTION OF METHOD Direct measurement suggests the use of a tracer by means of which the progress of a "parcel" of gas can be followed through the furnace. Several requirements must be met before any selected material can be considered a suitable tracer. First of all, it must be a substance not normally present in blastfurnace gas or dust; otherwise its presence in a gas sample will have little significance. It should be volatile at temperatures normally existing within the furnace, to ensure that it will travel with the gas, as a gas. It should possess special properties enabling its presence in the gas to be detected readily, and it should not undergo exchange reactions with any material normally present within the furnace, including refractories and coke as well as all components of the metal and slag. Radioactive materials naturally are considered because their radioactivity renders them susceptible to detection. However, of the many radioactive materials available, almost all are eliminated from final consideration by their unsuitability in terms of other properties. Radioactive silicon, carbon, calcium, phosphorus, and many others have been considered and discarded, either because they are not volatile over the whole range of significant temperatures, or because they could be expected to undergo exchange reactions with burden or refractory materials. Others which might be suitable in terms of these properties are eliminated because of a low activity, short half life, or the necessity for fragile counting apparatus. Of the many elements available in radioactive form, perhaps radon is the only one suitable for blast-furnace gas-flow studies. This has been used in several investigations1-4 with considerable success. The use of radiotracers has certain inherent disadvantages. One is the cost. An appreciable sum must be allowed for materials each time a test is made. Also, special methods of handling must be employed, and very often the progress of an investigation must be governed by the availability of isotopes and the delivery arrangements that can be made for them. An advantage is immediately gained if the tracer material can be a substance which can

Jan 1, 1960

By Irving B. Cadoff, Stojan M. Zalar

AgInTe2, CuInTe2, and all Proportions of CuxAg1-xInTe, forMed homogeneous single phase alloys after direct solidification from the nielt. X-ray analysis indicated a zinc-blel~de strzccture typical of the chalcopyrite compounds, and the electrical resistivity and Sccbeck coefficient values were in the semiconducting range. AuInTe, and AuxA4g,-, InTe, formed by what appeared to be a peritectic reaction (the thermal analysis curves showing more than one arrest) and were conseyue~ztly polyphase. Substitution of copper into AgIrzTe, resulted in a continuous transition in the room tenzperature Seebeck coefficient from the negative AgIzTe, to the positive CuInTe,. A zero coefficient was obtained at about Cuo.55 Ago.45 InTe, . The temperatzire variation was similar to that observed for the stoichiometric compounds, that zs, tendency towards "p" concEuction at elevated temperatures. The thernzoelectric figure of merit for the compo~uzds, as determined by the Putley -Harmnn method were in the range 10- to 10-7 "K-l; the thermal conductivities in the order of 0.15 cal per sec-cm-oK. INCREASED interest in semiconducting intermetallic substances is expanding much of recent research from simple binary compounds into polyatomic systems and solid solutions. Ternary compounds A' represent a covalent extension of the binary semiconductors Within the a tin isoelec-tronic series, Ag-Cd-In-Sn-Sb-Te-I, divalent cadmium atoms in CdTe are being substituted for by monovalent silver and trivalent indium atoms to form the compound AgInTe, . By cross-substitution with elements of other isoelectronic series, a great number of ternary compounds A 'B"'c? is possible. In all of them, however, a necessary though not sufficient condition for the covalent, semiconducting bond—that there be four sharing orbital electrons per atom—must be fulfilled. In AgInTe,, each silver or indium atom is tetrahedrally surrounded by four tellurium atoms, while each tellurium atom is co-valently bound to two silver and two indium atoms. Synthetic chalcopyrites A'B"'c~ were first recognized as potential semiconduct&rs by Goodman and Douglas.' Austin, Goodman, and Pengelly discuss preparation difficulties and some electronic measurements on AgInS, , AgInSe, CuInSe, , AgInTe, , and CuInTe,. Chalcopyrites A B c2v are mentioned in papers attempting to classify and predict semiconducting behavior of intermetallic compounds; on the basis of saturated tetrahedral sp3 bonds,3 by specific selection criteria,' and by crystallographic considerations."

Jan 1, 1962

By F. R. Brotzen, D. L. Davidson

ALTHOUGH much effort has been devoted to the problem, the nature of plastic flow in bcc metals is still not fully understood. Some of the difficulties encountered stem from the scarcity of information on orientation effects and the uncertainty as to the glide system in these metals. In an attempt to provide some of this information, the present investigation was carried out, using zone-refined molybdenum single crystals deformed in tension and in direct shear. Considerable evidence exists to indicate that the primary slip system for molybdenum is (110) <111>.1,2 Figs. 1 and 2 indicate that this is, indeed, the case for direct shear at room temperature (see Ref. 3 for a description of the shear-testing equipment and procedure). Moreover, from Fig. 2, the shear stress on the (123) is lower than that on the (112). This would be the case if, as has been suggested,4,5 slip on these two planes is in reality com-

Jan 1, 1965

By B. C. Allen

The solubility of chromium in liquid silver and that of molybdenum and tungsten in liquid tin have been determined by equilibrating Ike Liquid in a crucible of the solule metal. Generally the weight of solute in solulion was delermined both chemically and from crucible weight losses. The resulting weight percent solubilily of chromium in silver as a function of absolule temperature T is given by log w = -6660/T + 4.02 in the range 960° to 1445°C, and that of molybdenlttrl in tin by log w = —5050/T + 1. 79 in the range 1200° to 2200°C. The values appear unaffected by minor changes in solute composition. Calculations aye made of the parlial molar heal and excess entropy of mixing. The estimated solubility of tungsten in tin is 0.001 pct at 2000°C. Evidence is presented that molybdenwm dissolves in tin without compound for mation and that tungsten and tin form W10Sn. RECENT developments in coatings, heat transfer, and brazing require a knowledge of equilibrium solubilities in a variety of systems at elevated temperatures. Of particular interest are solid-liquid interactions in metal systems involving dilute solutions. This investigation was undertaken since little is known about the phase relations or solubility of chromium in liquid silver or of molybdenum and tungsten in liquid tin.1,2 EXPERIMENTAL WORK As indicated in Table I, high-purity metals or those of known impurity levels were used. Crucibles were machined from chromium, molybdenum, and tungsten bar stock 1.3 cm diam and 2.2 cm long. Chromium rod was prepared by arc melting and extruding iodide process crystals.3 The five chromium impurity alloys were in the form of 0.6-cm-diam swaged rod. A Cr-0.06N* alloy was prepared by exposure to NH3 at 1150°C in a closed quartz capsule for 24 hr. Because significant nitrogen was lost during annealing in argon at 1600°C,4 the estimated level was 0.01 pct N. Chromium and Mo,W crucibles were outgassed at 1200" and 1600°C, respectively, at 3 X 10-5 mm. The solvent was placed In crucibles of the solute metal- 6 g Ag in chromium, 0.4 g Ag in the five chromium impurity alloys, and 4 g Sn in Mo,W crucibles. The silver and tin series were outgassed at 900" and 110O°C, respectively, and held at the desired solution temperature in a tantalum resistance furnace under 1.05 atm 99.995 pct Ar. An equilibration time of 0.5 to 1 hr was chosen since 0.3-, I-, and 4-hr anneals at 1235°C for Cr-Ag yielded similar results. Temperatures were measured optically to +10°C under essentially black body conditions which were checked against the melting point of silver. The Cr-Ag and Mo-Sn,W-Sn series were respectively equilibrated at 990° to 1400°C and 1200" to 2000°C. Vaporization losses were generally held to <1 pct by the argon. In the 1800" and 2000°C anneals for 0.5 hr, the crucibles were placed in tightly sealed tantalum cans which kept tin losses to <5 pct. After the anneals, the specimens were furnace-cooled. One anneal was made on small Mo-0.02 C, Mo-0.5Ti-0.lZr, and tungsten crucibles containing tin at 2200°C. The metals were sealed in an electron-beam-welded tantalum can of minimum volume. After the anneal, tin was still present in each crucible, none of which was severely attacked. After equilibration, the saturated solvent metal was selectively removed from the crucible by acid leaching. Weight losses sustained by the crucibles were determined from the initial weight minus the final blank-corrected weight after acid leaching. Chemical analyses were performed on some of the samples. Hot 1:l HNO3-H2O removed silver from chromium with the blank running <0.1 mg or <0.002 pct on measured solubility. Tin was removed from molybdenum and tungsten by hot concentrated HC1 with the respective blanks amounting to -0.004 and -0.0004 pct in the presence of tin. The insoluble residues were weighed and checked for composition. The leaching solutions contained traces of the solute metals which were analyzed by colorimetric methods, Diphenyl Carbazide for chromium, Thiocyanate for molybdenum, and Dithiol for tungsten. The total of the two percentages found from the residue and leaching solution minus the blank gave the desired solubility values. On the basis of annealing empty molybdenum and tungsten crucibles, weight losses due to MoO3 or WO3 volatilization were found to be generally 10.4 mg and affect measured solubilities by <0.01pct. RESULTS AND DISCUSSION Chromium-Silver . Since no intermediate compounds are reported to form in the Cr-An system,&apos; crucible weight losses and chemical analysis of the entire melt should provide reliable measures of the chromium in solution. Values obtained by the two methods are in agreement as shown by the results for unalloyed chromium in Table II and plotted in Fig. 1. Furthermore, the results are consistent with those previously determined by melting equilibrated silver out of the crucible and analyzing calorimetrically for chromium.&apos; On the basis of limited thermal analysis data, the solubility of chromium in silver has been quoted as 8 pct at the monotectic temperature of -1445°C.1 This investigation indicates an extrapolated solubility of 1.38 pct which is believed to be more reliable. At the eu-

Jan 1, 1968

By Mason J. Christner

Geology has become increasingly quantitative in the last 20 years. This trend has been accelerated by computer capability in the manipulation of data. The mining industry has been relatively slow to harness computer power, but the larger companies have moved in this direction in the past few years. Among the leaders in this progression is the White Pine Copper Co., and the following is a brief description of their computer system for processing, managing, and utilizing geologic data. Geology The White Pine mine is in the Upper Peninsula of Michigan, 6 miles south of Lake Superior and 80 miles west of the Houghton-Hancock area, center of the famous Copper country. The ore body of chalcocite, native copper, and minor native silver, is a tabular body in the basal 25 ft of the flat lying Nonsuch Shale and the top part of the underlying Copper Harbor Conglomerate. Twelve or more

Jan 1, 1972

By S. Floreen

Measurements have been mode of the effects of tempering and austenitizing heat treatments, the work-hardening characteristics, and the effects of test temperature and strain rate on the properties of a low-carbon Fe-18 pet Ni martensitic alloy. In many respects the alloy behaved quite similarly to cold-worked iron. One notable quality was the excellent ductility at temperatures as low as 20°K. Many of the qualities of the maraging steels could he related to the properties of the Fe-Ni matrix. THE 18 pet Ni maraging steels have demonstrated that unusual combinations of strength and toughness may be obtained by age hardening a low-carbon Fe-Ni martensite matrix.&apos; These properties must, to some extent, reflect the properties of this Fe-Ni matrix, and therefore an understanding of the properties of this matrix is a prerequisite to a complete understanding of the steels. There have been several recent studies of Fe-Ni-C martensites, but not much attention has been paid to alloys with very low carbon contents. At low carbon levels the crystal structure of these alloys is essentially bee.2 Electron transmission microscopic examination of a 20 pet Ni binary alloy showed martensite platelets separated by low angle boundaries.3 Plastic deformation of the low-carbon alloys has been shown to proceed by wavy glide.4 The hardness of these martensites is typically RC 28, and their yield strengths are 70 to 80 kg per sq mm.2, 5 Their ductility is excellent. Room-temperature tensile elongations of 18 pet and reductions of area of 70 pet have been observed in an Fe-18 pet Ni binary alloy.5 These observations have provided a qualitative understanding of the flow characteristics of these alloys. To date, however, no thorough study of their properties has been made. In particular, it is not known to what extent the deformation characteristics of low-carbon martensites are similar or dissimilar to those of pure iron or other bee metals. The present work was undertaken to provide more detailed information on the flow characteristics of a low-carbon Fe-18 pet Ni martensite. PROCEDURES, RESULTS, AND DISCUSSION Materials. A 40-lb heat of the Fe-18 pet Ni alloy used in this study was made by vacuum-induction melting. The charge materials were electrolytic iron and electrolytic nickel. A carbon boil was used to achieve deoxidation. After the boil the heat was refined by additions of 0.1 wt pet Ti and Al. These additions are commonly used in the maraging steels to keep the carbon and nitrogen contents in solid solution at a minimum. After casting, the heat was

Jan 1, 1964

By C. W. Davis, R. S. Dean

AMONG naturally occurring inorganic compounds, magnetite has many unusual and interesting properties, and it is the purpose of this paper to call attention to these properties and review possible uses of magnetite that might be based on them; in other words, to see what uses may be found for magnetite as a physical rather than as a chemical entity, as a mineral rather than as an iron ore. The Mineral Physics Studies initiated in the Metallurgical Division of the U. S. Bureau of Mines a few years ago gathered together much information on mineral properties, and they are therefore the principal source of material for this paper. Magnetic Properties Of Magnetite And Possible Uses As A Magnetic Material Magnetite is unique among minerals for its great magnetic susceptibility, approximately one-third that of soft iron, and some magnetites are permanent magnets, or lodestones. The literature contains many measurements of magnetic properties of individual magnetite crystals, but no systematic survey of the effect of mechanical preparation and heat-treatment was available until the recent investigations of the Bureau of which included not only susceptibility but coercive force and remanence as well. For the purpose of orientation, Table 1 gives the magnetic properties of several samples of magnetite and of a few other substances3. This table indicates that when ordinary magnetite is powdered it decreases in susceptibility and increases in coercive force and remanence, approaching the properties of lodestone. The properties of lodestone are in fact probably due to the development of very large internal surface on fine grain size4.

Jan 1, 1937

By W. W. Odell

ONCE it was believed that anthracite or coke were the only fuels generally available and suitable for the generation of water gas, particularly so when this gas was made in the generators of standard carburetted water-gas sets such as are commonly used in the manufacture of city gas. During the past 8 years, practice has changed considerably and it is -now common to find gas plants operating without anthracite or coke and using bituminous coal in the generator. This change in fuel has appreciably increased the marketability and sales of certain coal producers&apos; products; accordingly it is of interest to coal operators and others to know the reason for this change, the present trend in practice and the adaptability of various coals for generation of water gas. This paper briefly discusses these conditions and some of the factors relating thereto. BITUMINOUS COAL NOT IDEAL BUT CHEAPER THAN COKE In spite of many changes which have been made in both process and generating apparatus for using bituminous coal as generator fuel more efficiently, in general it is not an ideal fuel for this purpose. It is supplanting coke because it costs less; it is so much cheaper per ton delivered at the gas works that water gas made therefrom costs less per unit-volume than that made from coke, even though the quantity of generator fuel consumed per therm (100,000 B. t. u.) of gas made is greater with coal. This is the reason why so many city gas plants, as well as others, are using bituminous coal instead of coke.

Jan 1, 1927

By E. W. Edson, F. W. Hertal

In some fields the problem of mud fluid is simple and easy of solution. But in the Ventura Avenue field the acquisition and disposal of good drilling mud is not the least of the problems that confront the operator. In fact, mud fluid in the Ventura Avenue field is a very important factor in the drilling of the wells. It is quite probable that many of the factors affecting mud in this field will not be found in most of the fields with which the reader is familiar. However, in the fields where the mud fluid causes no apparent problem it is probable that some of the points brought out in this paper could be used to economic advantage. In fields where caving and squeezing formations and high gas pressures are present, as in the Ventura Avenue field, it is believed that application of methods outlined will be of great assistance in drilling wells. On account of the sandy nature of the formation and the lack of suitable shale bodies in the strata drilled through in the Ventura Avenue field, the wells make practically no mud during drilling. It is necessary therefore to supply drilling mud to the wells that will carry the drill cuttings to the surface, and also will " wall up" the drill hole and prevent the sandy formations from caving. Mixing and Handling Mud Fluid The clay used to make the mud fluid is obtained from a shale stratum in the upper Pico (Plioccne) formation found about a mile on either side of the field. Since high gas pressures and caving formations were first encountered in the Ventura Avenue field and mud fluid was needed to combat them, the mixing of this mud fluid has gone through a process of evolution. First, the clay was mined and hauled to the derrick, where it was shoveled into the well and left for the churning action of the bit to mix into a mud in the hole. The next move was the construction of a mixer to mix the clay to a mud fluid which was pumped into the well. These mixing

Jan 1, 1930

The work of the Committee on Industrial Preparedness* is well summed up in the following letter written by Thomas A. Edison, Chair-man of the Naval Consulting Board, after President Wilson and signed the army appropriation and army reorganization bills: "The Committee on Industrial Preparedness of the Naval Consulting Board, of which committee Howard E. Coffin is chairman, after a five months&apos; campaign in many ways unique in vigor and vision has played a very definite part in the measures for the national defense which have just become law. It is responsible for having laid the foundation for a true industrial preparedness in this nation. "Five months ago the committee, wholly non-partisan in make-up, acting with the civil, mechanical, mining and electrical engineers and the chemists of the country, members of five great scientific bodies, began its work in&apos; every nook and cranny of the land. The purpose was to prepare American industry efficiently to support the armed forces of America in the event of war. "The public, the business men and the legislators at Washington knew little regarding the demands on industry in connection with modern war. No department at Washington was charged with the duty of coordinating the needs of the army and navy with transportation, industry, and kindred functions. The purchasing, quartermaster&apos;s and ordnance departments of the army and navy were unable to buy military supplies except by competitive offering in the open market. No one had considered the need, and no legislative machinery was in existence, for preventing the presence of skilled workers on the fighting front when they would in time of war be needed in the factories, mills and mines of the country. Neither at Washington or elsewhere was there even a list of the industrial resources of the nation in such shape as could be used for practical purposes in case war should come. "The three things, then, that the committee headed by Mr. Coffin set out to do and that now have been brought about were as follows: First, to mobilize concretely the business men of America and their output against a day of need. This meant chiefly to discover in fullest detail just what equipment our manufacturers possessed that might be swung over to supply the army and navy swiftly and bountifully from the hour the colors were raised. In a few weeks this initial task, which has been a truly colossal one, will be at an end. A complete report of the equipment of practically every concern of substantial size in the country is now in the hands of the - committee. Directly in charge of the great inventory has been W. S. Gifford, Supervising Director of the Committee. The second step was to procure legislation making possible the placing by the war and navy departments of annual orders for munitions in small quantities to American manufacturers now not producing such things, so that quietly, efficiently and thoroughly they could learn in time of peace how to supply the government in time of war. The new laws make all this possible. It should be said here that this practice will bring about a geographical diffusion of munition plants all over our country, instead of affording us only a few such concerns for the most part near the exposed seaboards, as at present. It is obvious that this system will also throttle all talk of a munitions trust.

Jan 10, 1916

By Joseph E. Pouge

For the purposes of this analysis it is assumed that the petroleum industry has undergone a basic economic change whereby the degree of competition present in its operation is reduced by the collective control of production brought about by statme-directed proration. Formerly freely competitive in all its parts, the industry is now fully competitive only in its marketing, its manufacturing and transportation, its search for new oil supplies, its drilling operations (with some qualifications), and its capital movements. The practical problem before the industry in its new status is the maintenance of equilibrium, with planned control of crude-oil production (proration) substituted for competition and price as the regulatory mechanism at one point in the supply-demand system. It is further assumed that proration has become so firmly established in the legal and operating framework of the business that it may be looked upon as an institution. The purpose of this paper is to call attention to the effect of unregulated drilling upon the orderly functioning of proration. Economic Structure of Petroleum Industry The economic structure of the petroleum industry, under the current form of proration, may be visualized, in simplified form, as shown in Fig. 1. This diagram is designed to indicate the existing mechanism whereby supply and demand are equated. Demand is created largely by conditions external to the oil business, whereas supply is conditioned by a series of stages incidental to the discovery, development and production of a resource. The time elements involved in changes in demand and supply are of an entirely different order, the demand factor being much more flexible and "quicker" than the supply factors. It should be observed, also, that the position of price, formerly between "demand" and "supply," has been moved to a sidewise location where it still affects demand but influences current supply only through its bearing upon proration, drilling and search. Proration has been substituted for price as a throttle at the well head, but at this point only. The mechanism now works in this fashion: a declining price stimulates demand and the

Jan 1, 1936

By Joseph E. Pouge

For the purposes of this analysis it is assumed that the petroleum industry has undergone a basic economic change whereby the degree of competition present in its operation is reduced by the collective control of production brought about by statme-directed proration. Formerly freely competitive in all its parts, the industry is now fully competitive only in its marketing, its manufacturing and transportation, its search for new oil supplies, its drilling operations (with some qualifications), and its capital movements. The practical problem before the industry in its new status is the maintenance of equilibrium, with planned control of crude-oil production (proration) substituted for competition and price as the regulatory mechanism at one point in the supply-demand system. It is further assumed that proration has become so firmly established in the legal and operating framework of the business that it may be looked upon as an institution. The purpose of this paper is to call attention to the effect of unregulated drilling upon the orderly functioning of proration. Economic Structure of Petroleum Industry The economic structure of the petroleum industry, under the current form of proration, may be visualized, in simplified form, as shown in Fig. 1. This diagram is designed to indicate the existing mechanism whereby supply and demand are equated. Demand is created largely by conditions external to the oil business, whereas supply is conditioned by a series of stages incidental to the discovery, development and production of a resource. The time elements involved in changes in demand and supply are of an entirely different order, the demand factor being much more flexible and "quicker" than the supply factors. It should be observed, also, that the position of price, formerly between "demand" and "supply," has been moved to a sidewise location where it still affects demand but influences current supply only through its bearing upon proration, drilling and search. Proration has been substituted for price as a throttle at the well head, but at this point only. The mechanism now works in this fashion: a declining price stimulates demand and the

Jan 1, 1936

By L. Russell Van Wert

DURING an investigation in which the solubility relations of the phases in Muntz metal (60 per cent. copper, 40 per cent. zinc) were under study, certain phenomena that had no immediate connection with the main problem were observed, which were thought sufficiently interesting to study further. Because of lack of time, only a preliminary survey was made of two of these; namely, the cleavage structure developed under certain conditions in a 60:40 brass and abnormal grain growth in this alloy. CLEAVAGE STRUCTURE IN HEAT-TREATED MUNTZ METAL Carpenter noted many years ago that cold-working a brass of the Muntz metal type, which had been quenched previously from within the beta field, results in a partial breakdown of the supersaturated beta solution and the precipitation of the solute (the alpha solution) in the cleavage planes of the beta grains. This manner of rejection of a solute from a metastable solid solution is not peculiar to this particular alloy, for among others, it occurs in the cold-working of certain austenitic steels; for example, the austenitic nickel steels. In these ferrous alloys, cold deformation produces a partial decomposition of the austenite, with the formation of martensitic "needles" and zigzags in the austenitic poly-hedra. It is interesting to note that while the two solid solutions-austenite and quenched Muntz metal- are metastable and in their mode of decomposition behave quite alike when deformed in the cold, the metastability of each results from a different cause; viz., that of the austenite from the fact that it is a supercooled solution (its solvent, gamma iron, at ordinary temperatures is below its normal stable range) whereas the metastability of the quenched Muntz metal is the result of supersaturation.

Jan 1, 1929

Some 15 years ago, Dr. Adolf Schmidt, director of the Magnetic Observatory in Potsdam, Germany, developed an instrument, which was a modification of Lloyds balance, for the measurement of the vertical component of the earth&apos;s magnetism in the field. There was a keen demand for this because (1) it was desirable to have a field instrument that would measure the component of the earth&apos;s magnetism which stands in the closest and simplest relation to the configuration of the subterranean magnetic formations-the vertical component; (2) it was desirable to have an instrument that was not only more sensitive but also more reliable than the existing vertical magnetometers (the dip needle, for instance). The application of the magnetometer in oil geology demanded such an instrument, because the magnetic disturbances produced by most types of magnetic formations associated with the occurrence of oil (salt domes, faults, anticlines with crystalline core, etc.) are too small to be detected with the ordinary dip needle. The writer can prove, by some investigations recently made for the U. S. Bureau of Mines, that these instruments may be used also to very great advantage in mining, because they are capable of measuring anomalies which are as great as twice the normal strength of the earth&apos;s magnetic field. Even for such anomalies, the field balance is more advantageous than the dip needle. First, the instrument rests on a firm support and can be adjusted in the proper azimuth, which insures measurement of the vertical intensity only, without a part of the horizontal intensity, which is very important for the interpretation. The readings give the vertical intensity in linear terms and not as a function of an angle; and the field balance is insensitive to temperature when used with scale values that are adequate for the determination of large anomalies. In another phase of mining, the gold placer work, the field balance has also shown excellent results for which the dip needle is not adequate. What has been said about the dip needle holds also, though to a lesser extent, for two other types of vertical variometers recently used, the Tiberg balance and the Thomson-Thalen magnetometer.

Jan 1, 1929

The Sub-committee on Coal Mining, since its appointment, has been collecting data about subsidences in coal mines in this country, and thinks that almost all of the available data about occurrences of this sort in bituminous mines has been collected. Similar data is being compiled for the anthracite regions, which it is hoped will be ready for the 1927 meeting. As most of the bituminous seams are nearly level, the records obtained give the problem in its simplest form, without complications due to the pitch of the seam. Copies of the questionnaire, Appendix A, were mailed to all of the coal operators&apos; associations, to most of the large operating companies and to many engineers, with the request that any data on the subject be returned to the committee, or that advice of any subsidences known be given: the replies to most of the questionnaires were general, although some specific cases were given. Many of the companies were unable to reply to all questions, as they lacked the necessary data, but in nearly every case where accuratc data was available, it was cheerfully furnished, and any additional information requested was secured. All specific cases of subsidence were followed up by correspondence, and in several cases by personal inspection. Figs. 1 to 31 were made from the information furnished. Table 1 gives measurements of elevations taken in one case at intervals from October, 1913, to May, 1918. With one exception, where the evidence cannot be released on account of a lawsuit, it is believed that the cases submitted with this report include practically all that have happened in bituminous coal mining in this country of which actual measurements were secured. Some of these have been published by Young and Stoek,l and some have been secured from other publications. In collecting these data, the subcommittee had the Engineering Societies Library extend its bibliography to date; this list is given in Appendix B. To assist in the study of the problem, all of the subsidence literature in English was examined for cases in which spccific measurements were given, and the essential data for each case are shown in Appendix C.

Jan 1, 1927

By M. T. Hepworth, T. P. Papazoglou

Hydrogen diffusion in hcp and bcc titanium in the temperature range 610° to 900°C was measured by reacting cylindrical specimens of high-purity titanium at constant temperature with small constant pressures of hydrogen of the order of a few Torr. In the range 0 to 6.7 at. pct H in hcp titanium, the diffusion coefficient D in sq cm per sec is given by: where T is in °K and R in cal per g-atom OK. Only three measurements of diffusivity in bcc titanium were made: at 900&apos; : the diffusivity in ß titanium was found to be 1.8 x 10-4 sq crn per sec. McQUILLAN1 has studied the constitution of the Ti-H system and reported the concentration of hydrogen as a function of pressure of hydrogen and temperature. He found hydrogen absorption was reversible and rapid at temperatures above 500°C in both crystallographic modifications, the a (hcp) phase and the ß (bcc) phase, with the latter phase stabilized by hydrogen additions. Wasilewski and Kehl 2 measured the diffusivity of hydrogen in hcp and bcc Ti-H alloys. For bcc alloys, they reacted cylindrical specimens of titanium with hydrogen gas at 1 atm pressure. They measured the rate of absorption of hydrogen isothermally on specimens ranging from zero hydrogen content when above the transformation temperature to hydrogen contents sufficient to stabilize the bcc phase when below the transformation temperature. By integrating Fick&apos;s second law for a cylindrical geometry, assuming a diffusion coefficient independent of composition, they calculated diffusivities as a function of temperature. In the range 650" to 1000°C their results in bcc titanium yielded the expression: where D is in sq cm per sec, T in OK, and R the gas constant in cal per g-atom-OK. Their studies on the hcp a phase were conducted by exposing long cylindrical titanium specimens to hydrogen at a sufficiently high pressure to establish a surface layer of fl phase 80 to 120 u thick for the duration of an isothermal experiment. Concentration profiles were then determined by hydrogen analysis from chips obtained upon machining quenched specimens. The diffusivity of hydrogen was then calculated yielding the expression: The present investigation was undertaken principally to redetermine the diffusivity data on a titanium by a direct absorption from the gas phase at sufficiently low hydrogen pressures to avoid the presence of a surface bcc phase and also to check the diffusivity data at low hydrogen concentrations in the bcc stmcture. EXPERIMENTAL PROCEDURE High-purity electrolytic sponge titanium (99.9 pct) of BHN 91 was arc-melted, forged, rolled, and machined into cylinders of final hardness, upon annealing, of BHN 92. Cylindrical specimens of two sets of dimensions were used: 1.524 by 2.931 cm and 1.905 by 3.663 cm diam and length, respectively. The experimental apparatus used for annealing specimens and for admitting known amounts of hydrogen at constant pressure is shown in Fig. 1. In a typical experiment, a specimen was lightly abraded with fine-grain silicon carbide, washed with water and detergent, and then thoroughly degreased with reagent-grade tri-chlorethylene and acetone. The specimen was suspended by a Chrome1 wire in the center of a quartz furnace tube, without contact with the tube, and heated to 925°C (as measured by a thermocouple adjacent to the specimen, outside the tube) for a period of at least 4 hr under a vacuum of from 10-6 to -7 Torr as measured by an ionization gage. The furnace temperature was then adjusted to the temperature chosen for the particular diffusion study and the specimen allowed to equilibrate thermally. Hydrogen was then ad-

Jan 1, 1969

By R. A. Swalin, B. W. Roberts

ONSIDERABLE controversy has centered about the existence of an order-disorder transformation in alloys in the composition vicinity of 75 atomic pct Ni and 25 atomic pct Cr. All the evidence to date for such a transformation is of a rather indirect nature, since direct X-ray confirmation is difficult to obtain as a result of the small difference in X-ray scattering factors between nickel and chromium. As a result, superlattice lines would be very faint if present. Several investigators1-5 have observed anomalies in the electrical resistivity vs temperature curves of alloys in the vicinity of 25 atomic pct Cr. The observed change is characterized by a rather broad resistivity peak at about 540°C. A discontinuous drop in resistivity is normally associated with ordering. However, Taylor and Hin-ton4 have rationalized that the discrepancy could conceivably be caused by changes in the Brillouin zones upon ordering. The same investigators measured the specific heat as a function of temperature and have also observed anomalies in the vicinity of 540°C. Nordheim and Grant5 have proposed, because of the absence of superlattice lines and the absence of a discontinuity in the resistivity vs temperature curve, that long-range order is improbable and that the results could be better explained by short-range ordering. To date, however, the question has not been resolved satisfactorily. Neutron diffraction techniques provide a method for partially resolving the question since nickel and chromium have considerably different atomic scattering factors in the case of neutrons and, therefore, superlattice peaks, if ordering occurs, should be readily discernable. The results of a neutron diffraction investigation* coupled with a dilatometric in- vestigation are reported here. An alloy containing 28.0 atomic pct Cr was prepared from carbonyl nickel and electrolytic chromium in the form of a 1-in. diam x 10-in. ingot. Melting was done in an alumina crucible and casting in a graphite mold. The ingot was homogenized at 1250°C for seven days, after which a 5-in. long piece was cut into shavings in order to obtain a suitable neutron diffraction sample. Hardness samples and samples suitable for dilatometric analysis (% in. diam x 2 in.) were prepared from the remainlng piece. The neutron diffraction sample, along with a hardness sample, was annealed at 501°C for seven days, at which time the temperature was lowered to 479°C and held at this temperature for twenty-four more days. The hardness was observed to increase from 133 to 147 Vhn during the course of the annealing treatment, in qualitative agreement with Nordheim and Grant." Neutron diffraction traces taken at room temperature and at 42 °K are shown in Fig. 1. The insert shows the trace taken at room temperature with short counting times and thus only fair statistical accuracy. No evidence for superstructure reflections of Cu3Au-type ordering is observed. The statistical accuracy of the 4.2°K trace was improved by using longer counting periods. Several weak intensities are observed at small angles, including an aluminum reflection from the cryostat assembly and a very

Jan 1, 1958

By Lewis Reeve

As part of a program of investigation of the properties of electric arc welds carried out in the laboratories of the A. 0. Smith Corporation, considerable work has been done on the determination of the oxygen, nitrogen and hydrogen content of different types of weld metal, employing for this purpose the so-called "vacuum fusion method." It is the purpose of this paper to describe certain improvements that have been introduced in this method of determining the gas content of metals, with particular references to the steel specimens examined in this investigation. The method and apparatus used at the beginning of the investigation were essentially those of the Bureau of Standards as described by Vacher and Jordan.&apos; Later a number of changes were introduced which resulted in more rapid evacuation of the graphite crucibles employed and which enabled larger volumes of gas to be dealt with than could be handled conveniently in the Bureau of Standards equipment. In addition, the analyzing of the gases evolved from a melt in the same apparatus as collected was abandoned in favor of analysis outside the equipment using standard methods of gas analysis. The time required for gas analysis in the apparatus itself, as described by the Bureau of Standards, was found to be considerable, and during this time the rest of the equipment was tied up, preventing its use for the analysis of further steel samples. As a result of the modifications introduced, the time required for the analysis of a steel sample for gas content was reduced from about 8 hours to less than 3 hours. Subsequently, the whole procedure of melting the sample and collecting the gases evolved was modified so as to enable a distinction to be drawn between the easily reducible oxides such as iron oxide and the more stable oxides such as silica and alumina. At the same time evidence was obtained indicating the probable existence in the steels of other nitrides than those of iron alone and making possible their quantitative etermination.

Jan 1, 1934

By R. A. Oriani

The partial molal volume of hydrogen is one of the parameters that describe the elastic interaction between the solute and the stress fields about inclusions, dislocations, and cracks. As such the partial molal volume is probably of importance in the elucidation of phenomena such as hydrogen embrittlement and hydrogen yield point. A knowledge of this quantity would also be helpful in thinking about the state of dissolved hydrogen in iron. However, because of the very low lattice solubility of hydrogen in iron the usual ways of determining the lattice expansion are not practicable. It is therefore of interest to apply the thermodynamics of stressed bodies to two sets of measurements of the effect of elastic stress upon the permeability of hydrogen in order to deduce a value of the partial molal volume, VH, of hydrogen dissolved in a iron. Beck ..&apos; and previously de Kazinczy, observed that a uniaxial tensile stress increases the permeability of hydrogen in iron and in various steels. Beck et 01. employed Armco iron and A.I.S.I. 4340 steel, whereas de Kazinczy used a steel the composition of which was 0.13 C, 0.23 Si, 0.46 Mn, 0.006 P, and 0.038 S. Upon releasing the stress the permeability increment disappeared if the stress was below the elastic limit. Both investigators employed cathodic charging to introduce the hydrogen. de Kazinczy measured the permeation through a thin-walled tube by collecting the gas, whereas Beck et al. measured the permeation through sheets of various thicknesses by a very sensitive electrochemical technique. Both investigators measured the steady-state permeation at constant rate of hydrogen ion discharge, and Beck measured in addition the hydrogen diffusivity by a time-lag technique which is independent of the boundary conditions. Beck et al. and de Kazinczy found a linear relationship between log (J,/Jo) and the stress, where Ju/Jo is the ratio of the flux of hydrogen when the metal is under uniaxial tensile stress, a, to the flux under zero stress, for the same temperature and charging current. Beck et al. found in addition that the diffusivity of hydrogen is not changed by stress. Both investigators concluded that the observed change in permeability is due to an increase in hydrogen concentration, and furthermore that the increase in concentration is due directly to the thermodynamic effect of stress upon concentration. Accepting this assessment of the situation for reasons given below, one may use the equation3j4 in order to evaluate I/H, the partial molal volume of hydrogen. This equation is valid for the domain of a/E «¦ 1 (where E is the Young&apos;s modulus) and under the assumption that hydrogen expands the lattice isotrop-ically. From the data of Beck el al, one calculates V7H - 2.0 cu cm per g-atom, and from those of de Kazinczy one obtains 1.8 cu cm per g-atom. That the increase of concentration with stress is indeed of thermodynamic origin is attested to by the facts that the experimental results conform to the thermodynamic relation, Eq. [I], and that the results are the same whether a pure iron1 or each of two different steels172 is used. Neither of these facts wou1.d necessarily be expected if the effect of stress were, rather, to increase the ratio kn/k, of the kinetic factors of the following competing reactions: H(ads) — H (dissolved) Such a change of kinetics at the surface could be an alternative explanation of the effect of stress on the permeability. Although this writer does not deem this explanation to be the correct one for the reasons given above, it must be admitted that unambiguous proof that the phenomenon has a thermodynamic origin does not yet exist. Two kinds of experiments may be suggested. One is to plate a variety of metals on the input surface of the steel and repeat the stress experiment at a variety of hydrogen charging currents. The other is to employ somewhat thicker specimens in order to be able to apply uniaxial compressive stress. Eq. [I] shows that ln(c,/c,) depends on the sign of the stress, but it is difficult to see a physical basis for which k2/kl would depend on the sign of a. The present value of V^ in a iron agrees with phragmen&apos;s5 estimate, which he based on comparisons with the lattice expansion by hydrogen of titanium, zir-

Jan 1, 1967