Search Documents

By George G. Binder Jr., James W. Lacey, Arthur L. Draper

An experimental investigation of miscible fluid displacement has been made in linear porous media under highly adverse mobility ratio conditions. Various refined oils were displaced at field rates by liquid propane in both horizontal and vertical models 9 to 36 ft in length. In horizontal tests, mixed zones or transition zones form between the two liquids early in the displace-lents. Initially, the zones grow rapidly. III 2-in. diameter models, the mixed regions become nearly stable zones from 6- to 20-ft long. From then on these quasi-stable zones apparently grow only by molecular diffusion. The lenghts of the quasi-stable zones appear to be almost independent of the core material in which displacement;; are made and increase with increasing rates of injection and oil/solvent viscosity ratios. The lengths of the quasi-stable zones. measured in 2-in. diameter models at viscosity ratios and injection rates anticipated in the field indicate that essentially piston-like displacements of oil by solvent would occur. However, the mixed zone lengths increase markedly as the model diameter increases. In vertical displacements controlled by gravity drainage, only short trans-sition zones form. The entire lenghts of these zones can be accounted for by molecular diffusion. Therefore, in reservoirs having characteristics allowing a high degree of gravity drainage, nearly complete oil recovery should be attainable by miscible fluid displacement. INTRODUCTION The oil industry is faced with an ever increasing cost for finding new oil reservoirs. This, coupled with the fact that conventional methods of oil recovery usually leave from 1 to 3 bbl of oil in the ground for every barrel produced, has aroused considerable interest in developing more efficient methods. An integral part of the mechanism of many of these new methods of recovery is a miscible fluid displacement in which oil is displaced by a much less viscous materiai such as liquid propane. A numher of irlvestigators have explored the mechanics of miscible fluid displace-ment,'.2.1.'."." but in the experiments reported many of the important factors have been varied only over a limited range far removed from norma1 oilfield values. This paper presents the results of an experimental study of oil displacement by liquid propane at field rates from linear, natural-sandstone models of various sizes. Both horizontal and vertical flow tests were made. EXPERIMENTAL APPARATUS AND PROCEDURE Refined oils with viscosities varying over a wide range were displaced at several rates by liquid Propane from both horizontal and vertical flow systems. The behavior of the displacement was observed by propane-oil analyses of the effluent and, when possible, by differential pressure measurements along the cores. A schematic flow diagram of the apParatus used to conduct the experirents is shown in Fig. 1. The cores used in the tests were 9-ft lengths cut from natural consolidated sandstone and turned to the desired diameter. These were cast in steel tubing with a low melting point (160°F) alloy which expands on solidification. Flanges welded to the ends of the steel pipes permitted sealing the ends or butting one core to another. Pressure seals were maintained with O-rings. The cores were cleaned by flushing

By M. G. Benz, J. F. Elliott

A new type of solution calorimeter has been constructed to measure heats of mixing, enthalpy increments, and heats of fusion, formation, and reaction at temperatures above 1000°C. With it, measurements hove been made of the partial molar heats of mixing joy tin in the Cu-Sn system from 0 to 13 at. pet Sn at 1127°C and fir nickel in the Cu-Ni system from 0 to 9 at, pet Ni at 1200°C. The integral molar heat of mixing for the Cu-Sn system is strongly negative with a calculated minimum value corresponding to the composition Cu3Sn. The integrnl molar heat of mixing for the Czi-Ni system is slightly positive at these temperatures. These integral molar values have been measured with a probable error less than 30 cal per g-atom at an atom fraction of nickel or tin equal to 0.1. The estimated probable error for the Cu-Sn system is approximately 450 cal for a measured heat of solution of approximately 9000 cal. For the Cu-Ni system it is approximately 700 cal for a measured heat of' solution of approximately 60 cal. A new type of heat of solution calorimeter was designed and constructed to provide a more accurate experimental method for determining heat effects at high temperatures, (T > 1000°C). With it, partial molar heats of mixing, enthalpy increments, heats of fusion, and heats of formation and reaction for metal systems can be measured directly. Previously it has been necessary to rely upon the use of the dropping calorimeter or the van't Hoff equation applied to equilibrium data for this information. For the most part equilibrium data are scarce and difficult to obtain in many cases, and it has been necessary to rely upon the "method of mixtures" for the desired enthalpy measurements. An earlier study1 provides a prototype for this work. The "method of mixtures" as outlined by K. K. kelley,2 "consists of dropping the substance under investigation from a furnace, with controlled and measured temperature, into a calorimeter operating at or near room temperature.'' In this manner the change in the total heat content (enthalpy) of the substance between the temperature of the furnace and that of the calorimeter is determined. In order to determine high-temperature heats of mixing, enthalpy increments, and heats of fusion, formation, and reaction, it is necessary to take the difference between two such measurements, one before and one after the occurrence of the enthalpy change being studied. The desired enthalpy change is then the small difference between two large numbers. Small errors in the large numbers are included as large errors in this small difference. It is this difficulty that must be avoided for accurate measurement of the desired functions. The procedure with the new solution calorimeter consists of dropping the substance under investigation from a furnace, with controlled and measured temperature, into a solution calorimeter operating in the temperature range of 1000o to 1200°C. Measurements in the range of 1200" to 1600°C are planned for the future. By selection of the composition and

Jan 1, 1964

By A. E. Jenkins, O. C. Roberts, D. G. C. Robertson

Using an inverted-cone coil at 450 kHz, it has been possible to levitate iron (FeS), cobalt (CoS), and nickel (NiS) sulfides. Important nontransition metal sulfides such as ZnS, PbS, and Cu2S have proven impossible to levitate although Cu-Fe-S ternary alloys containing 30 wt pct S and up to 10 wt pct Cu, and Cu-Co-S and Cu-Ni-S ternary alloys containing 30 wt pct Cu have been levitated. The levitation technique has been used in preliminary experiments on the vaporization from liquid sulfides and the reaction of liquid metal-sulfur alloys with oxidizing atmospheres. The course of the reactions with pure oxygen were followed using highspeed photography and two-color pyrometry. ELECTROMAGNETIC levitation is now established as a basic laboratory technique in high-temperature research but its application has been restricted mainly to metals and alloys. Applications have included alloy preparation,' metal purification,2'3 determination of liquid metal densities and emissivities,4,5 and studies of metal supercooling,4 alloy thermodynamics,6 and vaporization phenomena.7-9 The application of the technique to compounds has not been considered previously. The successful investigation of the reactions between dilute iron alloys and oxidizing atmospheres10'1 has prompted the current physico-chemical studies involving levitated metal sulfide drops and flowing inert or oxidizing atmospheres. This paper presents the results of such a study and provides a basis for future studies involving a wide range of other compounds of metallurgical interest. The successful levitation of many metal sulfides and mattes provides a method of studying the oxidation reactions fundamental to flash-smelting and similar pyrometallurgi-cal operations under closely controlled laboratory conditions. In addition the system allows the use of a controlled atmosphere (e.g., a gas stream of a certain H2/H2S ratio) with a particular chemical potential to study the relevant thermodynamic equilibria or the mass transfer processes between the atmosphere and the levitated drop under conditions where the hydrodynamics of the system can be closely defined. The optimum frequency for the levitation melting of metals in an inverted-cone coil type inductor is within the radio frequency range 400 to 500 kHz. At frequencies lower than 10 kHz the rate of heat generation is usually insufficient to melt the levitated charge' or where melting is achieved, "dripping" from the charge is encountered.'' At frequencies above 2 mHz the levitation force decreases. Metals, alloys and preheated elemental semiconductors such as germanium and silicon, have been levitated but the levitation of only a few metal compounds has been reported. Jostsons13 and the authors have levitated liquid titanium-oxygen alloys containing 50 at. pct 0 while clark14 has reported the levitation of mixtures of FeS and MnS for short periods. With a "cold crucible" inductor sterling15 has melted ferrites by preheating them by induction in a 4 mHz field and melting at a lower frequency. However this second type of inductor has been designed purely for the melting of materials without contamination; there is only a small gas film between the charge and the inductor and the electromagnetic levitation effect is of secondary importance. For this reason further discussion will be restricted to the use of the coil type inductor. The assessment of the suitability of a particular metal compound for levitation is based upon the following two criteria: i) thermal stability, and ii) physical "levitability". In this paper these two criteria will be considered separately. The thermal stability of a solid or liquid metal compound with respect to a gaseous environment depends upon its chemical reactivity with that environment or, in the case of an inert atmosphere considered here, its volatility. The physical criterion as to whether or not a particular compound can be levitated is based upon a comparison between those physical properties of the compound determining "levitability" which are defined by the fundamental equations of levitation theory as developed by Okress et a1.,16 and the properties of the metals. Since it is not practical to cover the vast field of metal compounds, further discussion will concentrate on the metal sulfides but the treatment would be applicable to any metal compound. THE THERMAL STABILITY OF METAL SULFIDES The temperatures usually encountered during levitation in inert atmospheres cover the range 1400" to 2000°C. The stabilities of the condensed states of the sulfides under these conditions are considered in relation to the periodic classification by reference to Table I. Two general classes of sulfides emerge. The solid sulfides of elements of group IIB and of groups further to the right are volatile while those sulfides of group IB and of groups further to the left are nonvolatile solids. The sulfides described as volatile may be dismissed as unsuitable for levitation. The stabilities of the more favorable nonvolatile sulfides under the anticipated conditions must be studied more closely From Table I it is seen that the alkali metal sulfides exist as liquids in the temperature range of in-

Jan 1, 1970

By R. J. Wasilewski

The variation of elastic modulus with terrzperature between -150° and 600°C has been investigated. Compounds close to equiatomic cornposition exhibit very low modulus values and very high damping near room temperature. The modulus rises steeply with both decreasing and increasing temperature. The modulus minimum and the high damping are believed to be connected with a martensitic transformation of TiNi. In bulk material this transition takes place slightly above room temperature quite rapidly and reversibly, with a hysteresis of some 30°C, depending on the Ti:Ni ratio. Oxygen impurity affects the reaction time. THE inter metallic compound TiNi has been reported to exist in an ordered CsCl (B2) structure,l-6 the homogeneity range varying rather markedly with temperature.7 Some investigators reported this compound to decompose peritectoidally to Ti2Ni and TiNi, between 650° and 800°C,3 or below,',g the latter workers also suggesting the decomposition to be strain-sensitive. Purdy and Parr were the first to report a structural transformation to a new, possibly hexagonal, structure at 36°C,7 a temperature indubitably too low to allow the significant amount of diffusion necessary for a peritectoid reaction. Mechanical-property investigations of compositions close to TiNi just above room temperature have qualitatively shown remarkable anomalies, particularly with respect to clamping,' and to a "memory" effect, that is, plastically deformed material returning to its original shape on being heated through the "decomposition" temperature.9 The original explanation of this effect—based on the apparent experimental observation of Ti2Ni or TiNi, formation in the material subjected to tensile or compressive stresses, respectivelp—does not appear plausible. It appeared more probable that the change involved may be a martensitic, diffusionless structural transformation, similar to those observed in other B2 structures such as 0 brass,'' AuCd,ll and AuZn.12 The existence of such transformation has been established recently,', although the symmetry of the low-temperature structure is not yet known. The present paper describes the elastic modulus and damping behavior of polycrystalline TiNi in both structures. EXPERIMENTAL METHOD 1) Specimens. All the specimens to be investigated were prepared from premelted electrolytic nickel and iodide titanium by nonconsumable arc melting and casting in a water-cooled copper mold. The cast billets were canned in mild steel, extruded, and swaged to approximately 0.375 in. diam. The cans were then removed by pickling or machining. Preliminary material balance checks indicated no significant weight losses on melting (less than 5 mg on a 50-g button); hence nominal compositions have been used throughout. In agreement with previously reported observations7 no single-phase material was obtained at—or close to—Ti 1.00 Ni1.00 a small amount of finely divided second phase always being present. It was found that most of the oxygen impurity was associated with this minor phase, which was identified as oxygen-bearing Ti2Ni—possibly Ti,Ni,O. The amount of this phase—at any given Ti:Ni composi-

Jan 1, 1965

By P. Marier, T. R. Ingraham

When anhydrous cupric sulfate is heated in a stream of nonreactive gas, cupric oxysulfate is formed. When this reaction is complete, the cupric oxysulfate then decomposes to cupric oxide, which is the normal end product of reaction. The kinetics of each of these reactions has been studied using pellets prepared from finely divided cupric sulfate and from finely divided cupric oxysulfate. In each case, the reactant-product interface within the pellet is well-defined, and by normalizing the decrease in inter facial area with the weight fraction of the pellet decomposed it has been shown that the interface migrates into the pellet at a uniform rate at constant temperature. The activation energy estirnated for the decomposition of cupric sulfate is 57 ± 7 kcal per mole and that for cupric oxysulfate is 67 ± 8 kcal per mole. The rate of interfacial reaction is flow-sensitive, increasing with increasing flow of a sweep gas in the range from 50 to 2000 cu cm per min. The rate of decomposition is retarded by sulphur trioxide in the sweep gas. The relationship between sulfur trioxide Partial pressure and rate is consistent with the Langmuir Adsorption Isotherm governing the retention of sulfur trioxide in the interfacial layer. MOST of the work reported on the thermal decomposition of cupric sulfate and of cupric oxysulfate is related to the thermodynamics of the individual decompositions.'-4 No information is available on the rates of the individual reactions, on their activation energies, or on the effects of gas flow or of partial pressure of sulfur trioxide on the reaction rates. Some dubious conclusions based on relative reaction rates have been drawn from studies on the oxidation of sulfides. For example, on the basis of the products observed in a quenched system, it has been suggested5" that, when copper sulfide is roasted, the cupric oxide which is formed arises from the decomposition of either cupric sulfate or cupric oxysulfate. This is very difficult to reconcile with the thermodynamics of the C-S-O System,3 which support the probability that both cuprous oxide and cupric oxide precede cupric oxysulfate and cupric sulfate in the sequence of products formed during the oxidation of cuprous sulfide. In this paper the individual sulfate decomposition reactions will be examined and suggestions will be advanced for the mechanism of reaction. This will be based on the effects on reaction rate of changes in interfacial area, flow rate, and back-pressure of sulfur trioxide. EXPERIMENTAL Materials. The copper source material used in all experiments was Fisher Certified Reagent Grade anhydrous cupric sulfate, for which the following analysis was supplied by the manufacturer: chloride, 0.002 pct; alkalies and earths, 0.2 pct; insoluble, 0.002 pct; iron, 0.020 pct. Cupric oxysulfate was prepared by roasting cupric sulfate for 48 hr, with frequent rabbling, in an open tray in a muffle furnace maintained at 725°C. At this temperature, cupric sulfate develops about 0.16 atm pressure of combined sulfur trioxide, sulfur dioxide, and oxygen. Cupric oxysulfate develops only about 0.05 atm pressure, and is stable until

Jan 1, 1965

By H. L. Gilbert, H. A. Johansen, R. G. Nelson

High purity electrolytic chromium plate has been hydrogen-reduced and arc-melted under inert atmosphere to give sound ingots. These ingots may be hot forged to break the as-cast structure and then worked at 500°C to finished form. An intermediate and final high temperature anneal gives best ductility and grain refinement. HE increasing interest in refractory metals for I use in high temperature gas turbines, jets, and rockets has led to great efforts in exploiting the fifth and sixth groups of transition elements. Much of the interest has centered upon production of metals that can be worked and fabricated by normal means to produce various engine parts or components having the high temperature characteristics of oxidation resistance and high creep strength required for such uses. If these pure elements do not exhibit all of the desired characteristics, it may be possible to obtain a high purity alloy that will. Since, in all cases, development of these transition elements has depended to a large extent upon removal of oxygen and nitrogen as a means for producing ductile metal, the hypothesis has been accepted that oxygen is the normal embrittling material in a high grade electrolytic chromium metal. Various methods have been employed in an effort to remove this oxygen by direct or indirect attack.' Many workers have endeavored to produce pure chromium through reduction of the oxide by carbon or active metals, while others have recommended fusion electrolysis of chromium salts or reduction of these salts by active metals, such as sodium or calcium. Hydrogen reduction of the oxide or chloride and thermal dissociation of the iodide have been reported to give high purity metal. Experimental Work The U. S. Bureau of Mines, Northwest Electro-development Laboratory, has systematically re-examined the more promising methods and developed two which produce metal having ductility at temperatures lower than heretofore described. It has been found' that oxide-free chromium chlorides in a NaCl-KCl carrier salt may be mag- nesium-reduced and the byproduct salts distilled off in vacuo to give a high purity chromium sponge. Fusion analysis conducted under the supervision of W. W. Horton of Knolls Atomic Power Laboratory showed the oxygen and nitrogen both to be below 10 parts per million on a selected sample. A small amount of carbon is carried over in the final metal from the chlorination and reduction steps which are carried out in graphite crucibles. This trace of carbon is not detrimental to hot ductility. A more practical method for producing ductile metal is through hydrogen reduction of high purity electrolytic chromium. Normal electrolytic chromium will, if "developed" for a few minutes at 1100°C in high vacuum, be found by the method of Adcock:; to contain about 1 pct chromium sesquioxide (Cr2O3). This small amount of oxygen may be effectively reduced by hydrogen.2, 4 The method employed was to crush electrolytic chromium plate in a gyratory crusher to pass 60-mesh; finer crushing appears to offer no advantage. A nitric acid leach removed the iron picked up during crushing. The leached powder was rinsed until neutral with distilled water and vacuum-dried.

Jan 1, 1954

By C. E. Westley, R. R. Beebe

Recent works by Plaksh et al.,1,2 Glembotsky,3 and others have renewed interest in the effects of oxidation on the surface activity of the sulfides. Since considerable supporting data are available on galena-potassium ethyl xanthate, this system is being studied at South Dakota School of Mines and Technology by contact angle measurement, using the technique of McGlashan and McLeod.4 The contact-angle method is well adapted to investigation of the influence of small amounts of oxygen on the establishment of a stable contact angle on galena in potassium ethyl xanthate solution. Samples of massive galena containing less than 0.001 pct Cu, 0.001 pct Ag, and 0.01 pct Zn are mounted in castable plastic and ground and polished manually in a glove box containing the desired proportions of oxygen and purified nitrogen. Oxygen and nitrogen contents of the test atmosphere are determined with an Orsatt analyzer. In this way a reproducible surface is created in contact with whatever oxygen concentration is desired. Water and all reagents are prepared and stored in the test atmosphere. An absorbent is used to control carbon dioxide that might be present. Final polishing is done with levigated alumina on a glass plate. The prepared sample is placed in the test solution and transferred to the contact angle apparatus in a sealed box, and the test is conducted while both sample and solution are maintained under a slight positive pressure of the test atmosphere. Table I gives the results of contact angle measurements made at various 02-Nz concentrations.5 Each value of contact angle is the average of at least six individual measurements made with different bubbles at different locations on the sample surface. A period of 20 to 25 min has been found by preliminary tests to be sufficient to permit develop- ment of maximum angle, and all measurements are made after at least this much time has elapsed. Exposure of prepared samples to pure water under the test atmosphere before exposure to the xanthate results in a small but measureable and consistent reduction in contact angle. This is particularly true in the oxygen-deficient atmospheres; for example, at 2.2 pct O2 such water contact reduces the average angle about 8" from that obtained by immediate testing in xanthate. The general trend of increasing contact angle with increasing oxygen concentration corresponds to the results of Plaksin et a12 The absence of diminish-ment of contact angle at very high oxygen concentration has been attributed to the high concentration of xanthate per unit of galena surface: At oxygen concentrations below 1 pct (the limit of accuracy of the Orsatt analyzer), no contact angle is obtained. Furthermore, no contact angle is obtained at any oxygen concentration in the absence of xanthate. This result seems to be in disagreement with those cited by Plaksin.1 Further work on the interaction of galena and potassium ethyl xanthate or a similar collector as influenced by oxygen is contemplated. The true nature of the interrelation is as yet unknown. For example, it is not known whether the governing oxygen reaction is with the mineral, with the reagent, or with both.

Jan 1, 1961

By H. Biloni, R. Morando

The surface structure and substructure of Al-Cu alloys solidified as conventional ingots and under particular conditions such as those used by Bower and Flemings are studied. The influence of lampblack coating on the mold walls is especially considered and the results compared with those obtained in copper and graphite molds where no coatings exist. When high heat extraction conditions exist the observations show that mechanism of copious nucleation is responsible for most of the chill zone. When the heat extraction through the mold walls is low, a coarse grain structure with dendritic morphology arises, with a size that depends on the degree of convection present, analogous to that analyzed by Bower and Flemings. In both cases the effect of the convection on the macroscopic and microscopic appearance is discussed. The ingot macrostructure consists of one or more of three zones: "chill zone", "columnar zone", and central "equiaxed zone". The mechanism of the columnar-equiaxed transition has been subject of considerable interest and at present at least three theories exist about the formation of the equiaxed region: 1) the constitutional supercooling theory1 maintains that the equiaxed crystals nucleate after the columnar zone has formed, as a result of the constitutional supercooling of the remaining liquid; 2) chalmers2 pointed out, however, that there were several objections to this proposal, and that consideration should be given to the possibility that all the crystals, equiaxed as well as columnar, originated during the initial chilling of the liquid layer in contact with the mold; 3) Jackson et aL3 and O'Hara and ~iller~ suggested that a remelting mechanism of the dendrite arms is responsible for the formation of the equiaxed region. After the work of Cole and Bolling and other authors6 it became evident that convection (natural, reduced, or forced) plays a very important role in the transition from columnar to equiaxed and on the size of the resultant equiaxed structure. Until recently the accepted explanation of the chill zone was that it occurs as a result of copious nucleation in the liquid layer in contact with the mold walls.798 The columnar region is a subsequent result of the growth of favorably oriented grains and, as a result of a selection mechanism studied by Walton and Chalmers,9 elongated grains with marked texture are formed. Recently, however, Bower and Flemings" using an ingenious laboratory experiment introduced the idea that the "copious nucleation" mechanism is not responsible for the formation of the chill zone and that the presence of convection, introducing some form of "crystal multiplication", plays a decisive role in the formation of the chill zone. Unfortunately, it is important to consider that for their conclusions Bower and Flemings extrapolated the results obtained in their special experiments to the case of conventional ingots, and that these authors only analyzed the macrostructures of the specimens. Let us consider the work by Biloni and chalmers" concerning predendritic solidification. These authors were able to show that a study of the segregation substructure of A1-Cu gives information about the nucleation and growth of crystals formed in contact with a cold surface. A spherical predendritic region characterizes the first part of every grain nucleated in contact with the surface as a result of the chill effect. The aim of this paper is to elucidate through the observation of the segregation substructure the conditions under which (in the Bower and Flemings type of experiments and in conventional ingots) either the nucleation or the multiplication mechanism gives rise to the structure in contact with the mold walls. I) EXPERIMENTAL TECHNIQUES The experiments were performed on two alloys: Al-1 wt pct Cu and A1-5 wt pct Cu. The purity of the aluminum was 99.99 pct and the copper 99.999 pct. The results obtained with both alloys were similar. In the Bower and Flemings type of experiments the apparatus employed to obtain rapid solidification against a surface was similar to that used by those authors. The liquid was drawn by partial vacuum into the thin section mold cavity. Plate casts were 5 cm wide and usually 7.5 cm high. The thicknesses of the cast were 0.1 and 0.3 cm. Two different materials were used for the mold, copper and nuclear-grade graphite. The internal mold surfaces were polished and left uncoated for some experiments. In other experiments, the copper or graphite surface was coated with a thin film of lampblack material. In some of these particular experiments one of the mold walls was left with an uncoated region (usually in the form of a cross). The conventional ingots were cast in graphite or copper molds. In different experiments the mold walls were sometimes uncoated or coated with lampblack material. The results obtained in conventional and Bower and Flemings copper molds were compared with those obtained with copper molds coated with a very thin film of graphite; the results obtained were essentially similar. The size of the conventional ingots was 5 cm diam and 7 cm high in all cases. The cast surfaces produced by the Bower and Flemings type of experiments and conventional methods were observed macroscopically and microscopically without any metallographic preparation. As Biloni and Chalmers showed," the observation of the chill surface can give considerable information about the structure and segregation substructure.

Jan 1, 1969

By J. S. Marsh, T. B. Winkler

THE past year, the first full one of peacetime production, proved that the process of beating swords into plowshares has increased in complexity in step with civilization. Further, judging by various remarks of our distaff departments, the crystal balls of certain radio and magazine oracles must have been cloudy, because we have been in formed from time to time that coveted items such as automobiles and refrigerators did not appear in great abundance. This seemingly extraneous matter is really not out of place here, however; the steel producer and the fabricator exist in a sort of symbiosis: the making of consumer goods produces scrap which is returned to the steelmaker who makes more steel, and so on and so forth. Thus, no abundance of automobiles, no abundance of scrap from this normal source; and other sources had been picked pretty clean during the war. To be short, so was scrap. Since the economy of the steel industry lean; as heavily upon iron from scrap as upon iron from ore, the statement on transformation of swords to plowshares follows. But this is not the whole story: after all, ingot production was a record for a peace year!

Jan 1, 1947

By AIME AIME

CHARLIE WARNER, Chairman of the Petroleum Division, is no stranger to the problems of the oil industry or to those of the Petroleum Division, after more than 25 years of experience in locating and producing oil and more than 22 years of membership in the Institute. He was born at Jefferson, N. Y.. April 27, 1894, and educated in the public schools of New York State and at Cornell University where he studied geology and allied sciences from 1913 to 1917 and received a B.A. degree. Immediately upon completion of this training, he was employed by the Empire Gas & Fuel Co. as a field geologist in Oklahoma and Kansas. Two years later he became district geologist for the Emerald Oil Co. in Oklahoma and Kansas, and in 1920 he rejoined the Empire Gas & Fuel Co. in the capacity of district geologist in Oklahoma. In September of 1921 he began his association with the Houston Oil Co. of Texas. He was district manager for the company in the Mid-Continent area until 1932 when he was transferred to the head office at Houston, where he became superintendent of the land and lease department in 1934 and was elected a director of the company in 1941. In these capacities, and also as petroleum engineer for the company, he keeps in intimate touch with all phases of field activity and with the regulation of the industry by State and Federal agencies.

Jan 1, 1943

By Harry H. Power

WORK of the Committee on Education of the Petroleum Division has been under way for approximately-one year. Although some progress has been made, further activities of the Committee are necessary in order to discuss mutual problems more thoroughly by a unified group interested primarily in this field of specialization.

Jan 1, 1944

By J. Blodget Britton

To the question, " Do the Pennsylvania anthracites contain phosphorus?" asked at the last meeting of the Institute during the discussion on the metallurgical value of Western lignites, I can now give a definite answer. Through the kindness of a gentleman connected with the Philadelphia and Reading Railroad, and another connected with one of the principal ironworks on the Lehigh, there was sent to the Ironmasters' Laboratory a number of samples of the coals now largely shipped from the Schuylkill and Lehigh regions. Seventeen of these I examined for their contents of ash and phosphorus, and obtained results as follows : Ash. Phosphorus. No. 1, . 4.10 .0063 2, . . . . 7.97 .0209 113, . 5.53 .0049 114, . . . . . . . 6.55 .0056 . 5, . 5.39 .0761 . . . . . . . 11 6, 14.15 .0593 7, . 10 43 ,0049 rl 8, . . . . . . . 5.29 .0354 9, . . . . . . . 3.01 .0042 6L10, . . . . . . 3.03 .0042 1 1 . 275 .0014 12, . 2.82 ,0111 l'13, . .3.69 trace L1 14, . . .2.35 trace 15, . . . . . . . 7.22 .0014 16, . . . . . . . 3.49 .0167 17, . 4.63 trace

By W. R. Shimer

In his valuable report on Finishing Temperatures and Properties of Rails,l Dr. G. X. Burgess, Chief of the Division of Metallurgy, U. S. Bureau of Standards, has begun a line of investigation which should be continued by those interested in the subject, and who have proper facilities for carrying out the work. For the past year or more the Bethlehem Steel Co. has been conducting experiments to learn the effect of rail finishing temperatures on their physical properties and microstructure and the results are here given for the consideration of those interested in the rail situation. Considerable differences of opinion have been expressed by various authorities, in the past, as to the effect of large or small grain size and high or low finishing temperatures of steel rails on their physical properties and wearing qualities. Low finishing temperatures and, therefore, low shrinkage, have been advocated on the theory that the wearing qualities would be improved. Others have recommended high finishing temperatures. The generally accepted cause for rail failures, due to the development of transverse fissures, is excessive wheel pressure on hard rails. One of the causes advanced for hard rails has been that they contain too high percentages of carbon and manganese; another that the rails were finished at too low a temperature, i.e., at or near the critical point. In the experiments herein described the rails were rolled from reheated blooms. All the rail blooms were charged hot in a reheating furnace and brought up to about the original ingot-rolling temperature before rolling into rails. These rails gave better results in deflection, withstood a greater number of drops before breaking, and showed greater ductility than rails of identically the same composition and section which were rolled direct from the ingot. Rails rolled from reheated blooms, finished at somewhat higher temperatures than when rolled direct from the ingot, have a different microstructure, which the writer does not believe is due so much to the difference in finishing temperatures, as to the difference in

Jan 1, 1915

By J. L. Gregg, C. W. Kuttner

ReceNtly there has been considerable interest in the production and use of extra hard alloys composed primarily of tungsten and carbon. Dr. Hoyt's recent paper1 gives a good description of these alloys and describes their performance when used as tools. There are a number of these alloys on the market sold under various trade names, and it is the purpose of this paper to describe the results of an investigation of the structure of five of these alloys by means of microscopic and X-ray methods. The samples studied were in the form of small tools or wiredrawing dies, which were either purchased or supplied as samples. They were in some cases not supplied by the original makers but were furnished by the agents in this country, and we wish to call attention to the fact that they may not be truly representative of the materials supplied under the various trade names No performance data are given and no inference as to the inferiority of one alloy as against any other is made. K. Schröter2 recently described methods for polishing alloys of this type for microscopic examination and has presented photomicrographs of several alloys. However, he did not identify their constituents or describe methods for their identification. Constituents and Their Identification As far back as 1915 attempts were made to utilize tungsten carbides commercially, but the great brittleness of these carbides made these first attempts unsuccessful. Later, successful dies were made by sintering the powdered carbides with small amounts of iron, nickel, or cobalt. Due to the high melting points of the tungsten carbides (2600" to 2800" C.), it is difficult to melt the carbides without volatilizing almost quantitatively the added element of the iron group. Inasmuch as the added metal does not exceed 20 per cent. and is usually present in much smaller amounts, some understanding of the tungsten-carbon equilibrium dia-

Jan 1, 1929

By C. W. Kuttner, J. L. Gregg

ReceNtly there has been considerable interest in the production and use of extra hard alloys composed primarily of tungsten and carbon. Dr. Hoyt's recent paper1 gives a good description of these alloys and describes their performance when used as tools. There are a number of these alloys on the market sold under various trade names, and it is the purpose of this paper to describe the results of an investigation of the structure of five of these alloys by means of microscopic and X-ray methods. The samples studied were in the form of small tools or wiredrawing dies, which were either purchased or supplied as samples. They were in some cases not supplied by the original makers but were furnished by the agents in this country, and we wish to call attention to the fact that they may not be truly representative of the materials supplied under the various trade names No performance data are given and no inference as to the inferiority of one alloy as against any other is made. K. Schröter2 recently described methods for polishing alloys of this type for microscopic examination and has presented photomicrographs of several alloys. However, he did not identify their constituents or describe methods for their identification. Constituents and Their Identification As far back as 1915 attempts were made to utilize tungsten carbides commercially, but the great brittleness of these carbides made these first attempts unsuccessful. Later, successful dies were made by sintering the powdered carbides with small amounts of iron, nickel, or cobalt. Due to the high melting points of the tungsten carbides (2600" to 2800" C.), it is difficult to melt the carbides without volatilizing almost quantitatively the added element of the iron group. Inasmuch as the added metal does not exceed 20 per cent. and is usually present in much smaller amounts, some understanding of the tungsten-carbon equilibrium dia-

Jan 1, 1929

By C. H. Mathewson, P.W. Bakararian

The greatcr part of the literature on the plastic behavior of magnesium dates back to that active period of research in crystal mechanics immediately following the widespread preparation of isolated metallic crystals large enough for the application of conventional methods of mechanical testing. These investigations, performed on single crystals, revealed an analogy between zinc and magnesium with respect to their fundamental mode of deformation. in the operation of glide and twinning, respectively, on crystallographically similar planes. Mathewson and Phillips (1928)' by geometrical analysis identified the plane in magnesium as the twinning plane. Schiebold and Siebel (1931) confirmed this twinning planc, established the basal plane as the plane of slip, and a digonal axis I as the slip direction. They also rcported twin formation in a secondary role on the {IOI} plane. Schmid (1931)³ summarized and discussed the earlier evidence and presented the results of his own experiments on the effect of temperature and small amounts of soluble elements. From X-ray studies on extended wire single crystals, he concluded that slip along the basal plane in the direction of the digonal axis I closest to the stress direction was the sole slip system operating at atmospheric temperature. This conclusion was based on experiments with crystals of many different orientations relative to the stress axis. Special attention was directed to the basal plane and the digonal axis I, as the plane and direction of greatest atomic density. Determinations of resolved shear stress at the onset of plastic yielding-—i.e., the critical resolved shear stress—were also made; the average of these calculations showing 82.9 grams per sq. mm. This value varied only slightly up to 300°C. at which temperature it was found to decrease to 70.5 grams per sq. mm. The extension of his crystals at temperatures above 225°C. further disclosed the presence of new slip systems. After the origince specimens of circular section had been

Jan 1, 1943

By C. H. Mathewson, P. W. Bakararian

The greatcr part of the literature on the plastic behavior of magnesium dates back to that active period of research in crystal mechanics immediately following the widespread preparation of isolated metallic crystals large enough for the application of conventional methods of mechanical testing. These investigations, performed on single crystals, revealed an analogy between zinc and magnesium with respect to their fundamental mode of deformation. in the operation of glide and twinning, respectively, on crystallographically similar planes. Mathewson and Phillips (1928)' by geometrical analysis identified the plane in magnesium as the twinning plane. Schiebold and Siebel (1931) confirmed this twinning planc, established the basal plane as the plane of slip, and a digonal axis I as the slip direction. They also rcported twin formation in a secondary role on the {IOI} plane. Schmid (1931)³ summarized and discussed the earlier evidence and presented the results of his own experiments on the effect of temperature and small amounts of soluble elements. From X-ray studies on extended wire single crystals, he concluded that slip along the basal plane in the direction of the digonal axis I closest to the stress direction was the sole slip system operating at atmospheric temperature. This conclusion was based on experiments with crystals of many different orientations relative to the stress axis. Special attention was directed to the basal plane and the digonal axis I, as the plane and direction of greatest atomic density. Determinations of resolved shear stress at the onset of plastic yielding-—i.e., the critical resolved shear stress—were also made; the average of these calculations showing 82.9 grams per sq. mm. This value varied only slightly up to 300°C. at which temperature it was found to decrease to 70.5 grams per sq. mm. The extension of his crystals at temperatures above 225°C. further disclosed the presence of new slip systems. After the origince specimens of circular section had been

Jan 1, 1943

By John T. Norton, Robert J. Anderson

The purpose of this paper is to report evidence, regarding metal structures, that is contradictory to the amorphous-metal hypothesis of Beilby, and particularly evidence that is opposed to the proposition that a vitreous amorphous layer is produced by polishing a piece of metal. According to the theory of Beilby, which has been developed by Rosenhain and others, polishing a piece of metal greatly affects the condition of the metal at or near the surface polished, making that surface entirely different in character from the metal beneath. A vitreous amorphous surface film is said to be formed. The polishing process, on the basis of Beilby's explanation, is well known and does not require discussion here, but it is advisable to seek the precise meaning of the term "amorphous." According to Beilby, "amorphous means non-crystalline in the most intimate sense of the word; the molecules arc not marshalled in crystalline order and orientation." According to Rosenhain, the amorphous condition is that assumed by a metal when the crystalline arrangement is completely broken up so that the atoms exist in a state of disorderly arrangement similar to that which exists in the liquid state. Thus, from the point of view of the phase rule, the "amorphous phase" is regarded as being identical with the liquid phase. Amorphous metal is often likened to an undercooled liquid. A crystalline substance is one in which the atoms are arranged in space according to some definite repeating geometrical pattern. The existence of amorphous metal has not been definitely proved. The evidence offered here that amorphous metal probably does not exist is of a direct nature and is afforded by x-ray diffraction effects given by a number of metals and alloys when polished, cold-worked, and annealed. Considerable of the experimental work was carried out with substantially pure aluminum and the aluminum alloy duralumin, but many of the observations made on these materials were checked by similar observations on copper, iron, tin, zinc, lead, mild steels, and

Jan 1, 1925

By F. Osmond

When a metal (whether a simple substance, an alloy, or a compound) presents, in each of the smallest parts to which it can be redueed by mechanical division, a constant chemical composition, it is defined as chemically homogeneous. But chemical hombgeneity by no means necessitates mechanical homogeneity. There are no perfectly amorphous metals. Crystalline forces, on the one hand, and tensions or compressions, on the other band, determined by icequalities of temperature in the mass during heating or cooling, give rise in every metal to the formation of geometric elements of structure. These elements may, moreover, assume perfect crystalline forms, with their planes of cleavage; or embryonic crystalline forms, segregated in the midst of. a paste of confused organization; or pseudo-crystalline forms of expansion and contraction, like those produced in the drying of gelatinous precipitates or (most frequently) these different forms associated. 111 either case the adhesions between two adjoining structural elements, respectively homogeneous, may be very different from the interior cohesion of each of these elements. The mechanical properties of this complex aggregate cannot be simple, and, when it is submitted to strains sufficient to produce deformation, the results may be very different according to the type of structure or the manner in which it is affected by the strains. It may be fairly said that a metal does not present a single resistance to tension, or a single resistance to compression, etc., but in fact, at least theoretically, as many resistances to tension, compression, etc., as it may possess coexistent features of structure; only, in any single test, it is the weakest of the resistances involved which makes itself evident. For further explanation, let us imagine a cylinder A B (Fig. I), formed of two similar halves A and B, placed together upon their common base x y. Such a system evidently presents no resistance to axial tension, while it would resist axial compression like a single

Jan 1, 1894

By R. M. Brick

The etched mierostructures of cold-worked alpha brasses, after reductions in excess of about 20 per cent, exhibit dark lines or markings, which have been termed "deformation bands," "etch bands," and "strain markings." The terms will be used synonymously in this report. The markings are similar in their general appearance to etch figures found in cold-worked iron, aluminum and other cubic metals but in certain respects may differ noticeably. At reductions of from about 20 to 50 per cent in brass, they appear as straight dark lines of irregular spacing and at random directions in different grains, but apparently intimately associated with definite crystallographic planes, usually {ill), in each crystal. At higher reductions, the markings on the rolling plane tend to appear in a direction transverse to the rolling direction in all crystals but may bend away at considerable angles, particularly near grain boundaries. Samans,1 on the basis of X-ray and micrographic studies of two single crystals of brass, rolled to a 50 per cent reduction, showed that the lines of deformation were the edges of thin mechanical twins parallel to octahedral planes. Barrett and Levenson2-4 have made comprehensive studies of the deformation of iron and of aluminum. They show that in these two metals the deformation markings originate by division of the original homogeneous crystal into banded areas differing in orientation by an amount that increases with the degree of deformation. The markings thus cannot be twin bands, and Barrett, in a review of this subject,2 attributed Samans' results on brass to an accidental choice of deformation that left the bands in approximately a twinned relationship. On the other hand, Mathewson6 has suggested that in some cases mechanical twinning offers a better rationalization of the coverage of some (111) pole figures of worked brass than the assumption of band rotation into symmetry positions. Considering next a deformed and annealed alpha brass, the most striking aspect of its microstructure is the multiplicity of twin bands.

Jan 1, 1940