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By R. Maddin, N. Ujiiye

ALTHOUGH the cold-rolled texture for body-centered-cubic metals and alloys is well known (see, e.g., Barrett'), the pole figure representing the texture may be interpreted in two ways. It may be regarded as consisting of several ideal preferred orientations with an associated spread (a view which is shared among several investigators2), or it may be regarded as consisting of two sets of continuous preferred orientation also with an associated spread."." Recently, Chen and Maddin7 noted a stable (001) [loo] end orientation for molybdenum single crystals rolled at low rates of reduction provided the initial rolling. orientation" was close to the cube ori-

Jan 1, 1957

By M. T. Simnad, G. Derge, Ling Yang

A method is described for using radioactive tracer for the direct determination of ionic mobility in a molten electrolyte. The ionic mobility of Fe" in silica-saturated iron silicate is found to be 0.0009 (*0.0002) cm2 sec ' volt L at 1250°C. eLECTROCHEMICAL studies', ' of molten iron eE oxide and iron silicates have shown some ionic conductivity at all compositions. The current efficiency in electrolysis increases with the concentration of silica to a maximum of 90 pct at about 34 pet SiO,. In the silica-saturated melts the transport number of ferrous ions is near unity, indicating that

Jan 1, 1957

By O. N. Carlson, E. D. Gibson, D. W. Bare

SEVERAL investigators have recently contributed to a clarification of the controversy concerning the allotropy of chromium. Ross and Hume-Rothery1 and Vasyutinskii et a1.2 have reported high-temperature X-ray data on unalloyed chromium from which they have concluded that no allotropic transformation occurs in this metal. Bechtoldt and vacher3 in their investigation of the Cr-Ni alloy system found no evidence for a transformation in chromium and Smart and Haynes4 in critically analyzing the data presented to date concerning this system could find no evidence for a eutectoid reaction in this system. Wyder and Hoch5 in research concurrent with our

Jan 1, 1964

By A. Yazan, M. Sagheer

To meet the demands of the planned development of Turkish steel industry an Iron ore processing plant is under construction at Divrigi, Anatolia and is planned to be commissioned mid of 1978. The plant has been designed for an annual capacity of 4 million tons of crushed magnetitic ore. About 1.9 million tons of coarse concentrate of 25-2 mm size and 1.3 million tons of pellet feed concentrate will be produced by wet screening, dry magnetic concentration of coarse size fractions and wet magnetic concentration of fine size fraction. The fine magnetic concentrate will be reground and filtered to prepare the feed for the pelletizing plant.

Jan 1, 1978

By R. M. Schuller, J. J. Suloway, W. F. Childers, R. A. Griffin, S. J. Russell

Seven solid wastes from coal conversion processes were characterized chemically and mineralogically. The wastes included three Lurgi gasification ashes, two liquefaction residues (SRC and H-coal), a fly ash, and a water-quenched slag. Leachates generated from the solid wastes at various pH levels over the range 2.5 to 11.0 were analyzed for over 40 constituents. Results of the leachate analyses demonstrate the wide variation in constituent solubility for the solid wastes. To help assess the environmental impact of the disposal of these wastes, the leachates were also employed in soil attenuation studies and acute 96-hr static bioassays using young fathead minnows.

Jan 1, 1981

By C. W. Merrill

Minerals research by the U.S. Bureau of Mines embraces the mining and metallurgical problems of some 80 metals and nonmetals excluding the mineral fuels. It requires the energies and talents of about 1400 persons, almost half of whom are professionally trained in the physical sciences or engineering. Of approximately $13 million appropriated to the Bureau for minerals programs in Fiscal Year 1962, 76% has been allotted to technologic research and 24% to resources examination and appraisal. In addition, almost $2 million will be made available to the Bureau for minerals research from other Government sources and from private organizations that wish to utilize Bureau experience and capabilities in cooperative studies.

Jan 11, 1961

By Louis A. Rosales, Kanji Ono

The anomalous behavior of hydrogen in iron is examined and a new model is proposed It is postulated that hydrogen single and di-interstitials are in equilibrium with each other. When the binding enthalpy of the di-interstitial, B, is assumed to be about 10 kcal per mole, the predicted temperature dependence of the solubility agrees reasonably well with the reported data. Effective diffusiuity is calculated assuming the di-interstitials to be immobile. Since the number of mobile single interstitials is greatly reduced at lower temperatures, the effective diffusivity is decreased. A good agreement in the temperature dependence of diffusivity between theory and experiment is provided with B - 10 kcal per mole. The predicted diffusivity is also a function of total concentration of hydrogen and this appears to be Partly responsible for the large scatter in the reported data. HYDROGEN is known to form an interstitial solid solution with iron.''' At elevated temperatures, it has been well-established that hydrogen enters iron in the dissociated form and occupies the interstices, and that diffusion of hydrogen in iron is via the interstitial mechanism. The concentration, c, permeability, P, and diffusivity, D, of hydrogen in iron have been separately determined and are consistent with each other under the steady-state condition for temperatures above approximately 400°C; that is, the relationship P = c-D holds. At lower temperatures, however, anomalous behavior of hydrogen in iron has been observed by many investigators. The results of experimental studies4-'' of the diffusion of hydrogen in iron are summarized in Fig. 1, in which the values of D are plotted against the reciprocal temperature. Although there is an increasing divergence in observed values of D with decreasing temperature, the values of D at temperatures below approximately 200°C are definitely small as compared with the extrapolation from high-temperature data. The lines shown bracket the region containing the most probable data. The observed values of c6," are plotted against the reciprocal temperature in Fig. 2, where the dashed lines represent Geller and sun's'' most probable isobars at 1 and 100 atm. At high external hydrogen pressure and low temperatures, the values of c observed are higher than those expected from high temperature data. It is generally accepted that certain trapping mechanism is responsible for the anomalies, but the nature of the trapping mechanism has not been clarified. Various types of hydrogen traps were suggested in the literature, such as "rifts" in the lattice dislocations, voids, microcracks, and so forth. However, no quantitative account of the observed behavior has been given in terms of these trapping mechanisms. Formation of methane in hydrogen-charged steel was found by ~odgurski." This appears to explain the existence of the so-called "residual" hydrogen,4 but not the observed anomalies of hydrogen in iron. McNabb and Foster' proposed a mathematical analysis in terms of a trapping mechanism. However, the physical significance of the traps was not clarified. The necessity of evaluating five parameters in their theory made comparison with experiment difficult. In the present paper, a model is proposed in which the anomalous behavior of hydrogen is attributed to the formation of hydrogen di-interstitials at lower temperatures. In this model, it is postulated that single and di-interstitials are in equilibrium with each other. (The hydrogen di-interstitial is to be distinguished from a hydrogen molecule which may exist in voids.) It can then be shown that most of the anomalies can be explained by assuming that the di-interstitials are virtually immobile and that the binding enthalpy of the di-interstitial, B, is approximately 10 kcal per mole. Predictions of the theory agree with the available experimental data reasonably well. THEORY The basic postulate of the present analysis is that single and di-interstitials are in equilibrium with each

Jan 1, 1969

By D. S. Eppelsheimer, D. N. Williams

The compression texture of iodide titanium is determined and found to consist of a [0001] texture rotated 15° to 30° from the axis of compression. As the amount of reduction increases, the angle of rotation decreases. The 0001 rotation showed a slight preference for a <1010> rotation axis. RECENT investigation of the cold rolled texture of titanium&apos; has shown this metal to exhibit a new type of rolling texture. This texture can best be described as a (0001) [10i0] with the 0001 planes rotated approximately 30" to the transverse direction around a <10i0> rotation axis. Rather good results in explaining the cold rolled texture have been obtained by other workers&apos; by examination of the tension and compression textures. No information was found giving the tension texture of titanium. Generally the tension texture of a hexagonal close-packed metal is identical with its wire texture. The drawn texture of titanium has been investigatedh nd has been found to be predominately [10?0]. Since this is the common tension texture of hexagonal metals of low c/a ratio, the explanation of the difference between the rolling texture of titanium and the rolling texture of other hexagonal metals is not indicated by examination of the tension texture. Therefore, the compression texture of titanium should be particularly important in the explanation of the unusual transverse rotation of the 0001 planes found in the cold rolled texture. The compression texture of titanium was examined by Yen.",&apos; His results showed titanium to exhibit the usual [0001] texture up to 85 pct reduction. At higher reduction a double texture appeared in which the 0001 planes were rotated from 10" to 30" from the plane of compression. This change in the compression texture seemed unusual since the tendency for hexagonal close-packed metals is to approach the [0001] texture as the idea compression texture. Mechanical twinning generally occurs over a considerable range of reductions beginning at a rather low reduction. The samples used by Yen in his investigations were prepared by two methods. Compression in a testing machine was used up to a reduction of 85 pct. Compression by compression rolling was used at higher reductions. Since the change in texture occurred at the same reduction as the change in the method of compression, a connection between the two seemed likely. To check this possibility and to locate the position of the change in texture definitely, if it was found to exist, the compression texture of titanium was re-examined. An iodide titanium crystal bar (99.9 pct Ti) produced by the New Jersey Zinc Co. and donated by the Titanium Alloy Manufacturing Div. of the National Lead Co. was used in this investigation. Procedure The investigation of the compression texture was carried out in three steps; compression, specimen

Jan 1, 1953

ELECTROREFINING Canadian 1,023,691 -Removal of bismuth from slime filtrate in the Betts process refining of lead. The filtrate is subjected to electrolysis in a cell having an anode of crude lead and a cathode of refined lead under operating conditions to preferentially deposit bismuth on the cathode. The substantially bismuth-free filtrate is recycled for use in the process as the electrolyte for producing high-purity lead. S. Hirakawa and R. Oniwa, assigned to Mitsui Mining & Smelting Co., Ltd. Jan. 3, 1978. 8 pp. (204-73). Filed: 2-18-74 (192,810). Same: U.S. 4,026,776, dated May 31, 1977.

Jan 1, 1979

By George M. Bouton, Lawrence Ferguson

The experiments described in this publication were inspired by the Bell System&apos;s large interest in lead-alloy sheathed cables and by the wide range of fatigue and corroding conditions to which they are sometimes subjected in service. The first experiments consisted of operating specimens of lead + I per cent antimony telephone cable sheath alloy in a fatigue test while they were immersed in water taken from a manhole. Because of many published reports concerning corrosion-fatigue phenomena of various metals and alloys, a reduction in fatigue life was expected(1)2 Instead, however, the fatigue test ran on for many times the normal number of cycles an4 was finally stopped without failure. Because of this, the experiments were broadened to include the effect of many media on the fatigue properties of four lead alloys over a wide range of testing speeds and strains. One material, a viscous tacky polymerized isobutylene3 used in

Jan 1, 1945

By H. L. Gilbert, C. Travis Anderson, W. J. Kroll

IN a previous paper,1 the use of a split graphite tube resistor as a heater element for high-temperature furnaces has been described. The principal advantages of this type of construction are: I. The quadruple resistance or voltage compared with the top-bottom clamp resistor furnace. 2. Free expansion of the resistor. 3. The ease of protection from oxidation by air. 4. The firmness by which it may be held in the compact split clamp. This construction appeared to be well adapted for the fusion of high melting metals which require fusion in a vacuum. Zirconium metal had previously been melted at the Albany Laboratory of the Bureau of Mines in a vacuum arc furnace on a water-cooled plate, using a movable tungsten top electrode.2 When larger furnace capacities were desired, this type of construction proved to have its limitations as the largest tungsten rods available were about 7/8in. in diameter. The supply of direct current of high amperage for producing the . desired arc characteristics was also not available. Considerable difficulty was also found in compensating the atmospheric pressure on the flexible tubing of the movable electrode, at the same time keeping its movement sufficiently free to enable the striking of an arc on any part of the metal briquet. Among the various materials used for the electrodes in conducting experiments in the vacuum arc furnace was graphite. It was found that zirconium fused in a graphite cup with a carbon arc was contaminated to only 0.2 pct carbon. It was therefore decided to melt zirconium directly in graphite crucibles. A high-frequency furnace was first used in the attempt to melt the zirconium in graphite crucibles. The high-frequency heating coil was placed outside a silica tube which was evacuated by means of an oil diffusion pump backed up by a mechanical pump. The graphite crucible was thoroughly degassed at 1900°C before use. Considerable difficulty was experienced in operating at such temperatures in vacuo because, as shown by Zintl,3 carbon vapor formed and reacted with silica according to the reaction: Si02 + C = SiO + CO. The silicon monoxide which is volatile at these high temperatures reacted with the zirconium, thereby contaminating it with silicon and oxygen. The presence of carbon monoxide was detected by means of a gas discharge tube placed in the vacuum system as indicated by the pale blue glow of the tube as soon as carbon vapor started to react with the hot silica. The reaction between the carbon vapor and hot silica was avoided by the use of split cylindrical molybdenum shields which were inserted between the graphite crucible

Jan 1, 1948

By J. W. Leonard

This expanded and more detailed supplement to earlier published work1 is offered as a means to demonstrate the high empirical correlation which exists between the readily measured coal bench scale test parameters of volatile matter (d & a.f.), Hard-grove grindability index (HGI), Koppers cone bulk density (BD) and pulverization level (% passing a 1/8-in. screen) to the less readily measured full scale coke stability index. Thus, Fig. 1, 2 and 3 represent the correlated test data contained in Tables I, II and III respectively. Ninety-six coals are correlated so that 97% of the resultant cokes fall within two points and 100% fall within three points of the actual tested coke stability indices. The main generalizations which can be drawn from the correlation of these coals are as follows: 1) The coke stability indices for higher bulk density coals (46.0 BD to 50.6 BD) appear to be largely influenced by differing combinations of factors for coals above and below a pivotal point of approximately 36% to 37% volatile matter. Below this pivotal volatile matter coke stability index appears to be influenced largely as a result of changes to the coal volatile matter and pulverization level. While above this pivotal volatile matter coke stability indices appear to be dependent on the coal hardness, as measured by the HGI, and to some extent upon coal volatile matter. Pulverization appears to have little influence on the coke stabilities of the harder coals (52 HGI to 58 HGI) of greater than 36% to 37% volatile matter. 2) The coke stability indices for lower bulk density coals (41 BD to 45.9 BD) appears to be largely influenced by changes to coal volatile matter and pulverization level for softer coals above approximately 58 HGI. 3) The main empirical observation to be drawn from these results is that for coals above approximately 36% to 37% volatile matter the quantities of hard and soft constituents as measured by the HGI are important when defining coal rank for correlation to the coke stability index.

Jan 1, 1965

By J. H. Frye, D. L. McElroy, E. E. Stansbury

The rates of growth of pearlite in high-purity Fe-C alloys have been measured as a function of the transformation temperature. These and other data have been correlated in terms of a derived rate equation. Activation energies for the growth were found to be 24,200 cal per mol of austenite for the 0.78 pct C alloy and 27,600 cal per mol for the 0.93 pct C alloy. Theoretical implications are discussed. AN excellent review of the the theoretical and experimental studies on the mechanism and kinetics of the eutectoid reaction has been presented recently by Mehl and Dube.&apos; They have pointed out that these investigations have followed two lines of approach: 1—experimental studies and derivations of expressions for the overall transformation characteristics, and 2—derivation of expressions for the nucleation and growth rates in terms of fundamental processes. Investigations of the latter type have been concerned for the most part with the nature of the growth at the austenite-pearlite interface in plain carbon and alloy eutectoid steels. They discuss two theories of the rate of growth of pearlite from aus-tenite—those of Brandt and of Zener. Both derive rate equations which are based on the assumption that carbon diffusion is the controlling mechanism. Mehl and Dube,&apos; Zener,2 and Brandts. " have attempted to calculate growth rates by use of these equations together with thermodynamic and diffusion data. The results are encouraging, but agreement is not so good as to constitute verification of the theories. Furthermore, it Is not clear how these equations are to be used to study the effect of alloying elements which apparently exert little influence on carbon diffusion, but markedly decrease growth rates. It is not clear whether or not the addition to iron of an alloying element which does not diffuse during transformation can alter the rate of growth of body-centered from face-centered cubic iron. That it can greatly decrease the overall transformation rate has

Jan 1, 1954

By J. J. Reed

The mines of southeast Missouri&apos;s Lead Belt have been in operation since 1864, almost 100 years. During this period about 10 pct of the total ore available has been left in place as pillars, and this now represents the best ore reserve left to the older mines. St. Joseph Lead Co. has been investigating various plans of pillar recovery for several years. The example to be described is only one possible approach under a specific set of conditions. Conditions vary greatly in the different areas within the Lead Belt, and the same approach would be entirely inadequate in certain other areas, but there are important sections where this system is clearly applicable. Horizon mining is practiced in the Lead Belt, and stopes may vary from 10 ft to well over 100 ft high. Fig. 1 is a plan view of 6100 stope, the area to be discussed. For these mines this is a small stope, only 10 to 12 ft high. Before any plans were drawn up for pillar recovery, three independent estimates of the pillar grades were made by the mine superintendent, the mine captain, and the mine geologist. After these results were averaged, pillars indicated to be of economic grade were marked for removal as shown. At this stage several alternatives were considered: 1) retreat with caving, 2) concrete replacement pillars, and 3) systematic bolting and retreat. A retreating system with caving was not chosen because the roof was known to be too bad even to permit loading a blasted pillar before caving would begin. Concrete replacement pillars would have been too costly and would have required a large crew, bulky materials, and unwieldy equipment. Systematic bolting was chosen as being most acceptable for the following reasons: 1) Limited area and spans were involved. 2) Only minor modifications to the jumbo would be required for bolting. 3) Only a two-man bolting crew would be needed. 4) Only compact bolting materials would be required. 5) The bolting plan could be modified to allow

Jan 1, 1960

By B. H. Kear, B. J. Piearcey

The orientation and temperature dependence of the tensile and creep propevties oj Mav-M200 crystals halle been determined. Crystals oriented for single slip exhibit ,maximum ductility, minimum work hardening, and least creep resistance, whereas crystals in multiple slip orientations show nzinimu~n ductility, strongest work hardening, and greatest creep resistance. At 1400" and 1600°F there is a marked improzlenzent in creep strength for orientations approaching [001] and [111], indicating that interactions between dislocations gliding in intersecting octahedral slip systems play an important role in creep resistance. At 1800°F the creep strength is much less dependent on orientation, which is rationalized in terms of slip in cube planes as well as octahedral A frequent mode of failure in high-strength cast nickel-base superalloys is by intergranular fracture, particularly along those grain boundaries oriented transverse to the major stress axis. VerSnyder and ~uard&apos; demonstrated that this problem could be overcome by eliminating transverse grain boundaries through unidirectional solidification. Piearcey and versnyder2 made use of this principle in the development of unidirectionally solidified gas turbine blades and vanes, where the growth direction of the columnar grain structure coincides with the axis of principal stress under operating conditions. The present investigation was undertaken to determine if further improvement in properties may be obtained by eliminating grain boundaries altogether, so as to take advantage of the well-known dependence of mechanical properties of single crystals upon the orientation. 1) EXPERIMENTAL PROCEDURE Single crystals of Mar-M200* were grown from the melt under vacuum by a modified Bridgman method. The melt was poured into a preheated alumina mold, and crystal growth was promoted from one end by appropriate gradient cooling. Tensile and creep specimens (2 in. diam by $ in. gage length) were prepared by a series of operations involving electrical discharge machining, precision grinding, and electropolishing. The orientations of the specimens were determined by the Laue X-ray back-reflection method. Tensile tests were carried out in aWiedemann machine with furnace attachment, using a strain rate planes. In all orientations imzpvouement in the strength charactevistics of the material can be induced by heat treatment. Creep ad stress rupture data for (001) oriented crystals are compared with similar data obtailted previously joy random polycvystalline material, and also columnar grained material having a prejevved (001) orientation. The single-crystal )material exhibits both longer rupture life and lower minimum creep rate at all temperatuves, and the rupture elongation is comparable with that in the columnar grained material. From these results it is concluded that single crystals should and useful application in gas-turbine blades and tanes. The optimum orientation for a blade is considered to be with its axis of principal stvess parallel to (001) ou (111). of 0.0001 sec-&apos;. Load and extension were recorded directly on an X-Y recorder. The strain measuring device consisted of extension arms attached to the grips at one end and leading out of the furnace to an LVDT (linear variable differential transformer) at the other. Creep tests were performed using a standard constant load creep frame. 2) DISCUSSION OF RESULTS 2.1) Structure of Alloy. The structure and segregation in as-cast and heat-treated Mar-M200 has been described in detail else where.~ The main features are as follows: the as-cast material is heavily cored, due to pronounced dendritic segregation during solidification; the dendrites are rich in tungsten and cobalt whereas the interdendritic regions are rich in chromium, titanium, nickel, and carbon. The structure consists of -60 vol pct coherent precipitate of y&apos;, basically Ni3(A1,Ti), in a matrix of y (nickel-base solid solution), interspersed in the interdendritic regions with minor MC carbides and -y&apos; eutectic. The y&apos; particles, and y-y&apos; eutectic, contain more titanium, aluminum, and nickel, and less tungsten, cobalt, and chromium than the y matrix. Heat treatment partially removes segregation, eliminates the eutectic, refines the y&apos; dispersion in y, and gives additional partially coherent M23Cs carbide. An as-cast crystal, therefore, is composed primarily of two oriented phases (y + y&apos;), whereas the normally heat-treated crystal consists of three oriented phases (y + y&apos; + MZ3Cs). Typical electron transmission micrographs of the y + y&apos; structure are shown in Fig. 1. Crystals grown in the (100) orientation develop a simple unidirectional dendritic structure, Fig. 2, since (100) happens to be the preferred direction of growth for dendrites in this material. Crystals grown in the {110) and (111) orientations, however, tend to promote equal growth, generally in separate colonies, in the two and three geometrically favored (100) growth directions, respectively. In other orientations of growth, a single (100) dendrite direction generally pre-

Jan 1, 1968

By R. E. Ogilvie, A. R. Kaufmann, S. H. Gelles

The solid-solubility limits of iron in beryllium were determined between 850o and 1200oC by analysis of differential type multiphase diffusion couples, using an X-ray absorption technique. The maximum value of the solubility limit was found to be 0.92 ± 0.02 at. pct (5.46 wt pet) at the eutectic temperature 1225°C. The solubilities of nickel and beryllium were determined between 900°and 1200°C by the same technique and the maximum solubility was found to be 4.93 + 0.01 at. pct (25.2 wt pet) at the eutectoid temperature, 1065°C. A previously unreported high-temperature phase which decomposes eutectoidally at 1065 °C was found to exist in the beryllium-nickel system at a composition of approximately 8 at. pct Ni (36 wt pet) by diffision-couple analysis. The presence of this phase was confirmed by thermal analysis and metallo-graphic analysis of the structure resulting from the eutectoid decomposition. G. V. Raynor1 has treated the solid solubilities of some of the elements in beryllium on the basis of the "Hume-Rothery" rules2 which have been modified to include ionic size and ionic distortion effects. It was predicted that the solubility of iron and nickel in beryllium should be slightly less than that of copper. The lowering of the solubility, according to Raynor, is due to a more unfavorable relative valency effect and an ionic size effect. Kaufmann and corzine3 have compiled data on the solubilities of elements in beryllium and have discussed them in the light of the Raynor paper. These authors feel that, because the elements having the greatest solubility in beryllium systematically fall in the Group VIII and IB Columns of the periodic table, the electronic structure greatly influences the maximum solid solubility of elements in beryllium. The solubility of iron in beryllium was determined by Teitel and cohen4 as part of the study of the beryllium-iron phase diagram. The determination was carried out by X-ray and thermal analysis and according to the phase diagram presented, the maximum solubility of iron in beryllium is 0.41 at. pct (2.5 wt pct) at 1225oC. However, it is estimated that the uncertainty in the position of the a-beryllium primary solid-solution boundary is about 0.5 at. pct (3wtpct). Losana and Goria3 in studying the beryllium-nickel phase diagram, determined the solid solubility of nickel in beryllium by thermal analysis. They found the maximum solubility to be between 1.65 and 2.65 at. pct (10 to 15 wt pct) at 1240°C. This value decreased rapidly with decreasing temperature. In determining approximate ranges of solubilities for different elements in beryllium, Kaufmann, et al,8 reported a value of between 1.3 and 1.7 at. pct (7.9 to 10.1 wt pct) for the solubility of nickel in beryllium. The value was obtained by metallographic examination of quenched alloys and lattice-parameter measurements. However, the authors also noted a single-phase structure for a 1.7 at. pct Ni alloy (10 wt pct) on cooling from the liquid. This would indicate a higher solubility range than was reported. ~isch,&apos; in his X-ray studies of beryllium-copper, beryllium-nickel, and beryllium-iron intermetallic compounds, reports the disappearance of a second phase (Ni,Be2) in the beryllium primary solid solution at approximately 4 at. pct (20 wt pct). THEORY The analysis of concentration gradients in diffusion couples has proven to be a useful tool in determining phase equilibria.8-14 In this particular study the diffusion couples were chosen to straddle the expected composition range of the phase boundary, then heat treated at a given temperature and the concentration gradient evaluated. The composition of the phase boundary for a given temperature appears at a point of discontinuity of the composition gradient. Examples of typical phase diagrams and the concentration gradients which should be found in such systems are shown in Fig. 1. In the present work, gradients of the form of Fig. l(c) were obtained in diffusion couples made of pure beryllium and two-phase alloys of beryllium with either iron or nickel. The composition at the point where the gradient becomes discontinuous, Cs, corresponds to the solubility limit of either iron or nickel in beryllium. The analysis of the concentration gradients was carried out by an X-ra absorption method developed and applied by Ogilvie and later used by Moll13 and Hilliard.l4 It depends on the fact that the absorption of X-rays by matter is determined by the concentration and type of the various atomic species present. The relationship for the intensity, I, of a monochro-

Jan 1, 1960

By H. R. Ogden, E. S. Bartlett, A. G. Imgram

Unmodified disilicide coatirigs were applied to sheet-tensile specimens ofCb-Dg3 and Mo-TZM veJractovy- metal alloys. Coating thickness, degree of coating-substrate interdiffusion, and specimen geonzetry (notched and plain were included in the variables studied. Tensile tests were made to determine the ductile-lo-brittle transition temperature. The disilicide coating modestly increased the transition temperatlre of TZM, but had no effect on 043. Neither material condition (recrystallized or stress-velieved) nor specimen geometry (notched or unnotched) significantly altered the effects of coatings on the transilion temperatures of. the alloys. Cracks in the brittle coatings did not propagate into the substrate, and fracture modes appeared to be the same for both un-coated and coated specimens. MOST potential structural applications for refractory metals and alloys involve exposures to oxidizing environments at elevated temperatures. The general lack of oxidation resistance of these metals will require protective coatings to allow fulfillment of their potential. Currently preferred coatings for the oxidation protection of refractory metals are brittle intermetallic aluminides or silicides. These are typically formed on the surface of the refractory-metal substrate by a diffusion reaction between the substrate and a gaseous or liquid medium that is rich in aluminum or silicon. Because of the brittleness of these coatings, they will sustain no plastic deformation at low temperatures. They are frequently cracked by cooling from the coating temperature because of the thermal-expansion mismatch with the substrate alloy. Even if they survive cooling intact, they crack rather than sustain deformation under load at low temperatures. Thus, when a coated refractory metal is strained beyond the elastic limit of the coating at low temperatures, the mechanical environment of the substrate would include both static and dynamic cracks. These might be expected to influence the flow and fracture behavior of the substrate. This could be manifested in an altered fracture mode and/or an increase in the normal ductile-to-brittle transition temperature of the refractory-metal substrate. This paper presents the results of a research program that was conducted to determine the influence of the presence of a brittle surface coating on the low-strain-rate tensile behavior of typical refractory metals at low temperatures. EXPERIMENTAL PROCEDURES Material Preparation. Thirty-mil-thick sheets of molybdenum TZM alloy (Mo-0.5Ti-O.1Zr) and colum-bium D43 alloy (Cb-IOW-1Zr-O.1C) were obtained commercially. These alloys were selected as substrate materials representing two classes of materials important in current refractory-metal technology. The TZM was in the stress-relieved condition, and exhibited a heavily fibered grain structure. The D43 had been processed by the duPont "optimum" fabrication schedule,&apos; and exhibited slightly elongated grains typical of this process. Tensile specimens of two geometries were prepared from these materials: 1) plain specimens with 0.2-in.-wide 1.0-in.-long gage sections; 2) specimens similar to above, but with a 0.06-in.-diam hole drilled in the center of the gage section, providing a stress concentration factor, Kt, of 2.5. The "notch" geometry was selected to represent a typical condition of a rivet hole or other geometric discontinuities as might be encountered in various applications. Machined specimens were degreased, with a final rinse in acetone, prior to the application of coatings. Specimens of each substrate and configuration were pack-siliconizedin a particulate mixture of 80 pct A1203, 17 pct Si, and 3 pct NaF. Specimens were embedded in this mix (contained in graphite retorts) and coated in an electrically heated argon-atmosphere furnace under time-temperature conditions to effect nominal 1- and 3-mil-thick silicide coatings: Coating Thickness, mils Thermal Treatment 0.6 to 1.4 24 hr at 982°C 2.4 to 3.2 48 hr at 1093°C Coating kinetics were similar for both the TZM and D43 substrates. These treatments had little or no visible effect on the substrate microstructure as determined by optical metallography. The coatings on TZM were essentially single-phase unmodified disilicides, while those on D43 showed substantial evidence of modification by proportionate reaction with the respective substrate elements or phases, as shown in Fig. 1. It was recognized that these coatings might not be particularly desirable regarding protective capability. However, it was desired to circumvent possible inter -ferring chemical interaction with the substrate by pack additives such as chromium, titanium, boron, aluminum, and other elements that typify the better protective coatings for these materials.&apos; Thus, the results presented apply specifically to the simple silicide coatings investigated. They may not be rep-

Jan 1, 1967

By G. L. Chierici

Starting from Muskat&apos;s theory of water and gas coning, maximum permissible oil production rates without water and/or free-gas production have been determined, in a broad range of reservoir and well parameters, using the potentiometric model technique. The main assumptions made are as follows: (1) the reservoir rock is homogeneeous (either isotropic or anisotropic); (2) the volume of the aquifer underlying the oil zone is very small, so that it does not contribute to reservoir energy; and (3) the gas cap expands at a very low rate, so that it can be assumed to be in quasi-static conditions. The results obtained are presented in the form of diagrams which can be used for solving two types of problems: (1) given the reservoir and fluids characteristics, as well as the position and length of the perforated interval, determine the maximum oil production rate without water and/or free-gas production; and (2) given the reservoir and fluids characteristics only, determine the position and length of the perforated interval which optimize the maximum permissible oil production rate, without water and/or free-gas production. INTRODUCTION In oil reservoirs where the oil-bearing formation is underlain by an aquifer which does not participate in the production mechanism, water-coning is a limiting factor to the flow rates of producing wells. Production rates are usually kept to a value that will prevent the water from entering the wells. The entry of water into a well lowers its productivity by increasing the weigbt of the fluid column; moreover, the separation of water from the effluent, at the surface, may constitute a very difficult problem in cases of heavy viscous oils. A similar situation is encountered in oil reservoirs with a gas cap overlying the oil-saturated zone; here a downward gas cone is induced by the flow of oil towards the producing wells. Production rates must be low enough to prevent the gas from being produced; producing gas from the gas cap would be a waste of energy. Of course, water-coning and gas-coning phenomena can occur at the same time in the same reservoir if the oil-producing formation is both overlain by a gas zone and underlain by a water zone. Due to its relevant practical importance, the mechanism of coning was studied by many people.2,3,5-8 Defining the conditions for getting the maximum water-free and/or gas-free oil production rate is a difficult problem, often encountered under one of the following aspects: 1. Predict the maximum flow rate that can be assigned to a completed well without the simultaneous production of water and/or free-gas. 2. Define the optimum length and position of the interval to be perforated in a well, in order to obtain the maximum water and gas-free production rate. A systematic study of these problems was made by means of the electrical analog technique. The results of this study are presented here, under the form of a set of curves providing solutions for the above stated problems. These curves are valid only for homogeneous forrnations, either isotropic or anisotropic. Should the formation be non-homogeneous (by horizontal or vertical variation of permeability, shale diaphragms, fractures, etc.), a specific potentiometric study would be required for each specific case. Especially when shale diaphragms of some radial extension are present, the critical rates observed are much larger than would be expected from the diagrams. STATEMENT OF THE PROBLEM In the present study the aquifer is supposed to be of such limited volume that it does not contribute to the energy of the reservoir. Moreover, the gas cap is supposed to expand at such a low rate that the potential gradient in the gas cap is negligible. Under static conditions water-oil and gas-oil interfaces (T1 and T2) are both horizontal. When the reservoir production starts, below each well these interfaces take a cone-like shape (Fig. 1) having as an axis the axis of the well. This shape results from the equilibrium between potential gradients in the oil zone and gravitational forces due to density differences between oil and water and between oil and gas. Assuming the oil-bearing formation to be homogeneous and the oil to be incompressible, the analysis of the problem (see Appendix) shows that the oil-water and gas-oil interfaces are stable only if the oil production rate of the well is not higher than the following values.

Jan 1, 1965

By Fred C. Bond

COMPRESSION TESTS THE standard method of determining the crushing resistance of rocks consists of crushing prepared shapes under slow compression, and expressing the ultimate crushing resistance at the load causing failure in pounds per square inch of crossectional area perpendicular to the crushing force, with the height approximately equal to the diameter. One-inch cubes or cylindrical drill cores are commonly used. Cubes and drill cores are cut by a high-speed steel disk with diamond dust embedded in the edges, and running under a water spray. Such a saw will cut one square inch or more of hard stone per minute. An oiled, spherical, swivel compression block of small diameter should be used to equalize the pressure. Each sample is crushed between sheets of cardboard or blotting paper extending about one-half inch beyond the edges of the stone. A cloth is wrapped around it to prevent dangerous explosive shattering. It is probably preferable to place the swivel block below the specimen, with either a rigid head or another swivel block above. Whatever the arrangement, the conditions should be selected that will develop the maximum crushing strength of the specimen, even though its top and bottom planes may not be precisely parallel. The cardboard pads may be dispensed with if the ends of the specimens are polished smooth. The use of lead pads was discontinued because of the observed tendency to split the material. The samples are weighed and measured before breaking, and the density is calculated. Cubes that contain bedding planes or veinlets are usually placed with these vertical and parallel to the crushing force, in order to develop the maximum resistance possible. A number of compression tests were made on Canadian ores, by Forrest Nagler, of the Allis-Chalmers Manufacturing Co., and are listed alphabetically in Table 1. These tests were made on one inch cubes or on diamond-drill cores approximately one inch in diameter and one inch long. The drill cores represent virgin rock, while the cubes may have been previously weakened by explosives. Compression tests have been made in the Allis-Chalmers Milwaukee Laboratory on a number of ores and other materials. These are listed alphabetically in Table 2. In test No. 1339, on limestone from the Hanna Coal Co., comparison was made between 2 by 2-in. diamond-drill core segments and one-inch cubes cut from the cores in the same strata. Results for the cylinders are tabulated directly below those for the cubes. The bedding planes were normal to the compressive force in breaking the cylinders and parallel in breaking the cubes, which accounts for the lower strength obtained from the cylinders. The percentage of net linear compression at the ultimate pressure was measured in test No. 1055 for Fontana TVA quartzite as 0.30 for cube A, and 0.37 for cube D.

Jan 1, 1946

By James M. Stapleton

IT has long been recognized by blast- furnace men that correct top distribution of materials is very important in efficient and economical furnace operation. Thousands of experiments on top design, filling, sizing, and other operations have been carried out to improving furnace performance by securing uniform distribution. Many of these experiments have worked out satisfactorily and have been passed along to the industry. Many of them have been discarded and forgotten. It has been the custom to judge the results of such experimentation by the results shown in improved or lowered furnace efficiency. While the effect on furnace practice will have to continue to be the final criterion of experimental changes, it has always been a desire of blast-furnace men to ascertain the reason for failure or success. Efficiency in the blast furnace approaching the maximum can be measured in several ways: (I) by actual operating results as revealed in the coke rate and tonnage figures, and (2), in the degree to which the top gas approaches the limiting ratio of CO/C02 for the reduction of iron oxide by CO gas. This ratio is shown in the equilibrium curve in Fig. I for the system Fe-O-C and CO2-CO-C. The closer the top gases approach this limiting ratio (set at 1.08 by Martin1 because of the effect of limestone calcination) the more efficiently we may expect a furnace to operate. The fact that low CO/C02 ratios parallel eficient operating performance caused us to investigate the cause of good or poor distribution and the effect of filling and other changes on furnace operation. Heretofore it has been possible to take a sample of furnace gas (usually from the dust catcher) and from it determine how closely the reducing gases were to the ideal or limiting value as set by the equilibrium diagram. However, to find just where in the top area the distribution was distorted and the top-gas CO/CO2 ratios were distant from equilibrium values has been a difficult and expensive investigational procedure. In an effort to overcome this difficulty, apparatus was designed to take gas samples and temperatures across the top radius of the furnace. It was hoped that with the aid of this apparatus traverse sampling of the ascending gases could be simplified, and the cost of sampling substantially lowered. Routine experimenting could then be maintained and results checked with furnace operation. It must be emphasized that a traverse sampling is necessary for a true picture, as single samples at any one point are unreliable. This statement can be verified by an examination of Tables 3 to 6, showing results obtained at our furnaces in a large number of tests. APPARATUS The design of the equipment for taking the samples was governed by the need for providing a simple, routine test that could be performed fairly quickly without adversely affecting normal furnace operation.

Jan 1, 1943