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By O. D. Gonzalez, R. A. Oriani

The migration of hydrogen and of deuterium dissolved in a iron and in nickel induced by an applied electrical potential has been measured over a range of temperature. In all cases the intevstitial solute migrates to the cathode. The deduced charges of transport are positive, independent of or slightly dependent on temperature, and markedly larger for the beavier mass. These results are interpreted as showing predominating momenlum transfer between electron holes and the acticated complex of the elementary diffusion act. THE migration of components of a metallic system under the action of an applied electrical potential is called electromigration or electratransport. This phenomenon has been known since 1861 and is becoming of increasing interest to metal scientists because of the opportunity it offers to explore the connections between mass transport and electron transport. Until recently, reliable data have been very scarce because of the difficulties inherent in the measurements. In addition, theoretical understanding has been either nonexistent or rudimentary and at present this situation is only moderately improved. Whereas the prevalent notion had been (and is still widely held) that electromigration directly reflects the state of ionization of a component in its equilibrium state in the metal, it is now becoming clear that the major, if not the sole, factor is the momentum transfer between the charge carriers, themselves in motion because of the applied field, and the metallic components in their activated state. It becomes important therefore to obtain reliable data over a range of temperature on electrornigration in systems where only one component moves, that is, either in pure metals (vacancy motion) or in interstitial solid solutions. Our choice of systems was dictated by our measurements' of the Soret effect in solid solutions of hydrogen and deuterium in iron and nickel. Indeed, the main reason for making measurements on electromigration at all is that we suspected a mechanistic connection between thermal diffusion and electromigration. In our former paper' we proposed that what is common to both phenomena is the momentum transfer between the charge carriers in the metal and the atom as it jumps from one equilibrium position to another. In Soret diffusion, however, there is in addition the dissipation of the energy of the jumping atom via pho-nons. We have since found that similar ideas for this interconnection have been developed by Fiks.2 In the present paper we will discuss in more detail our understanding of the mechanism of electromigration itself, but we turn first to a presentation of the experiments and results. EXPERIMENTS AND RESULTS Let us consider a metallic system in which only one component, m , can diffuse at the temperature in question, and to which are applied simultaneously an electrical potential gradient, grad cp, and a chemical potential gradient, grad p,. One may write3 for the material flux Jm and the electronic charge flux Je by applying the condition, grad = 0, to Eq. [I] and evaluating grad(um/T) for the isothermal case and for activity coefficient independent of composition over the relevant composition range. ere, c is the concentration and D the diffusivity of the mobile component. The experimental technique that we have used to measure Z* for the isotopes of hydrogen individually dissolved in each of two transition metals has been developed from a method used by Wagner and Heller.4 (A somewhat similar method was also used by Herold.5) A wire or thin rod of the metal under study connects two volumes of gaseous hydrogen at identical pressures; hence grad um = 0. A direct current is made to pass through the specimen, serving to maintain the specimen at the desired temperature and also to produce the electromigration of the hydrogen dissolved in the metal in equilibrium with the gaseous hydrogen. Under these conditions, the flux of hydrogen from one volume to the other is given, from Eq. [I] for grad( um/T) =0by

Jan 1, 1968

By Klaus Schwerdtfeger

The equilibria in the Cr-N system have been investigated in the temperature range 1100° to 1310°C by reacting chromium powder with Nz-Hz gas mixtures. The solubility of nitrogen in chromium in equilibrium with chromium subsitvide ("Cr,N") is given by Chromium subnitride is nonstoichiotnetric; its nitrogen content is always less than that corresponding to the formula CrzN. The lattice paranzeters of quenched samples have been measured; c, and a. parameters are found to increase with increasing nitrogen content. The growth rate of the subnitride layer on chromium plates was measured by a thermogravimetric technique, using a silica spring balance. The self-diffu-sivity obtained from the theoretical analysis of the parabolic rate constant is found to decrease with increasing nitrogen content, i.e., with decreasing vacancy concentration in the nitrogen sublattice. The intrinsic nitrogen diffuivity is derived from another series of rate measurements using "CrzN" plates; the intrinsic diffusivity, DN = 3.2 X 10-a cmZ sec-' at 1200 C, is found to be essentially independent of- the subnitride composition. The concentration gradient was measured in a chromium subnitride layer by the X-ray method and found to be consistent with the derived diffusivity value. TWO chromium nitrides are known to exist:' the nonstoichiometric subnitride "CrzN" and the nitride CrN. In the present work the kinetics of the formation of chromium subnitride from chromium and nitrogen have been investigated at 1100" and 1200°C. In additional experiments the relevant equilibria have been measured. The data are used to evaluate the diffusivity of nitrogen in chromium subnitride. Since chromium nitrides are often found in chromium-containing steels, the results are expected to be helpful in the interpretation of the chemical reactions between chromium steels and nitrogen. Equilibria in the Cr-N system have been determined by several investigators.2"3 The rate of nitriding of chromium was measured by Arkharov et a1 .' in ammonia in the temperature range 800" to 1200°C. The parabolic rate law was observed. Due to the undefined nitrogen activity of the ammonia atmosphere, it is dif- ficult to interpret these rate data theoretically. An additional difficulty arises from the fact that the two-layer scale consisting of CrN and "Cr2N" was formed at the temperatures below 1030°C. The rate of nitriding of technical chromium (95 pct) was measured by Zaks in nitrogen at -1 atm in the temperature range 800" to 1300°C. EXPERIMENTAL METHODS The chromium samples were reacted with Nz-HZ gas mixtures in a vertical tube furnace, wound with Pt-10 pct Rh resistance wire. The gas-tight reaction tube was of high-purity recrystallized alumina. In nitrogen solubility measurements the nitrogen content of chromium was determined by the Kjeldahl method, on samples quenched in the cold part of the furnace. The nonstoichiometry of the subnitride and the nitriding rates were measured thermogravimetrically using a sensitive (+0.1 mg) silica spring balance. For the equilibrium measurements samples of 1 g of chromium powder contained in high-purity alumina crucibles were used. In order to remove most of the oxygen and nitrogen impurities from the chromium, the samples were initially annealed in purified hydrogen until a constant weight was obtained. The chromium plates (approximate dimensions 2 by 1 by 0.08 cm) used for the rate measurements were machined from ingots obtained by arc-melting of iodine-processed chromium. According to manufacturers' specifications the purity of the chromium powder was 99.9 pct Cr and that of the iodine-processed chromium 99.99 pct Cr. Our own spectroscopic analysis of the chromium powder yielded 0.02 pct Fe, 0.05 pct Mn, 0.05 pct Si, and 0.02 pct Ti as major impurities with all the other detectable elements below 0.005 pct. The nitrogen partial pressure of the gas phase was controlled by mixing prepurified hydrogen and nitrogen with constant pressure head capillary flowmeters. Oxygen and water vapor were removed from the mixed gas by passing it through columns of platinized asbestos (450°C) and anhydrone. The gas flowed upward in the furnace with flow rates of 300 to 500 cu cm per min (25"~). Gas tightness of the furnace system was ensured by pressure checks at regular intervals. The furnace temperature was controlled electronically in the usual manner. The reported temperatures were measured with a Pt/Pt-10 pct Rh thermocouple and are estimated to be accurate within ±$C The X-ray measurements were made with a Debye-Scherrer camera and a diffractometer using chromium radiation {\Ka = 2.29092A). EQUILIBRIUM MEASUREMENTS The experimental results of the equilibrium measurements are contained in Tables I to In. Fig. 1 shows the solubility of nitrogen in solid chromium in the temperature range 1100" to 1310°C. In Figs.

Jan 1, 1968

By Pei-Yung Huang, Carle R. Hayward

IN order to understand more fully the actual state of copper lost in copper reverberatory slags, a systematic study on the various reactions between certain metallurgically important copper compounds and synthetic copper reverberatory slags was undertaken by the authors in the Massachusetts Institute of Technology from 1942 to 1945.1 This paper, being only a part of the work completed, is published first because it furnishes the first experimental evidence of the formation of copper ferrite from reactions between cuprous oxide and copper reverberatory slags. CHOICE OF SLAG COMPOSITION The choice of the composition of the synthetic reverberatory slags to be used was much deliberated. Commercial copper reverberatory slags, neglecting minor constituents, average:2.3 45 to 47 pct FeO; 38 to 42 pct Si02; 5 to 6 pct CaO; 5 to 6 pct A1203. Since the ternary system CaO-FeO-SiO2 has been much more thoroughly studied4 and is much simpler than the quaternary system CaO-FeO-Si02-A1203, it was decided to use calcium oxide only instead of calcium oxide and alumina in the synthesis of the slags. Fortunately the composition of the average copper reverberatory slag with calcium oxide substituted for alumina lies in the region of the phase diagram clarified by the investigators. A survey of the phase diagram (Fig I) suggested two compositions: (I) the com¬position near the invariant point S, which is made up of 46 pct ferrous oxide, 37 pct silica and 17 pct calcium oxide; (2) the composition near the invariant point K with 45.5 pct ferrous oxide, 43 pct silica and 11.5 pct calcium oxide. Composition S has the advantage that the percentages of ferrous oxide and of silica almost exactly coincide with those of the average reverberatory slags, and that of the lowest melting point (1093° ± 3°C) in the whole ternary system. The calcium oxide content, however, obviously is high. Since we have already substituted calcium oxide for alumina, and since calcium oxide is more basic than alumina, the resulting slag is decidedly too basic. Composition K has a slightly higher melting point (1105° ± 3°C) and a higher silica content, but this is preferred because the slag is saturated with respect to tridymite and thus should not corrode siliceous refractories. Besides, it is less basic than composition S. The final slag composition, therefore, was chosen to

Jan 1, 1947

By H. W. Hitzrot

SEPARATING a mixture of particle sizes of material suspended in a liquid medium is by no means an exact science. Selecting machines for individual classifying operations is even more difficult. The plant operator's own background is of course invaluable, and considerable help may be obtained from technical articles, talks with sales engineers, and handbooks on ore dressing. These several sources of information, however, are difficult to marshal in proper perspective for the major decision on classification units that an operator may be called upon to make. To the present writer's knowledge this assembly of facts is not available in handbooks, and technical papers are scarce on classification equipment developed in the past five or six years. It is believed that this paper will be helpful to users of classification equipment at this particular period in the development of hydro-classification. For easy reference the following classification units now available and in use in metallurgical and industrial operations are listed below, with a brief description of each. Unit-type classifiers, bowl classifiers, and bowl desiltors are all rectangular tanks, slightly tilted, with reciprocating rakes or screws to remove settled sands. The unit-type classifier, Figs. 1 and 2, is available in widths from 14 in. to 20 ft and lengths up to 40 ft. The shallow bowl of the bowl classifier, Fig. 3, equipped with rotating rakes, is superimposed on the lower end of the tank. Reciprocating rake compartments for this design range from 18 in. to 20 ft wide. Bowl diameters vary from 4 to 28 ft. The flat-bottomed bowl of the desiltor, Fig. 4, of relatively large diameter, is equipped with rakes rotating outward and partly over a pit, which is created by extension of the rectangular tank into and under the bowl section. Bowl desiltors are available with reciprocating rake sections 4 to 20 ft wide and bowls from 20 to 50 ft in diam. The bowl desiltor is used for applications beyond the range of the bowl classifier. The hydroseparator, Figs. 5 and 6, is a circular tank equipped with slowly rotating rake arms, set on a slope, with interrupted rake or spiral blades to move the settled solids to a central discharge cone. Tank diameters vary from 4 to 250 ft. Tank depths at center are 2 to 3 ft for small units and up to 25 ft for larger units. Hydraulic classifiers of the sizer and super-sorter types, Figs. 7 and 8, are narrow, deep, rectangular tanks divided by vertical baffles into a series of pockets. Hydraulic water is added near the bottom of each pocket. Perforated constriction plates, spiral flow arrangements, or jets are used to disseminate the water under pressure (hydraulic water) throughout the bed of material in the pocket. Discharge valves on each pocket are operated automatically by a pneumatic mechanism, a pincer-type mechanism, or a pressure control and motor combination actuated by a hydrostatic tube within the pocket. Hydraulic classifiers are available in 4, 5, 6, and 8-pocket units of varying constriction plate areas to suit conditions. There is now a jet sizer of unit pocket design that can be made up in 1 to 25 sections or more to accommodate sizing requirements. The hydroscillator, Fig. 9, is a rectangular tank set on a slope of 3 to 4 in. per ft. A bowl is superimposed on the lower end. The bowl bottom is an oscillating rubber-covered disk, perforated to allow hydraulic water introduced beneath the disk to set up a teeter bed and thus produce an oversize or rake product exceptionally free of slimes, and material minus the mesh of separation. A shallow dam at the periphery of the bowl allows the coarse or oversize fraction to spill over and drop down into the tank compartment, where it is moved up the deck by reciprocating rakes. The material, minus the mesh of separation, overflows a circular and stationary weir which is several inches higher than the dam on the oscillating disk. It is carried off in a circular launder in the usual manner. These units are available in bowl diameters from 4 to 14 ft and with reciprocating rake compartment widths to suit the tons per hour to be handled. Centrifugal classifiers include the solid bowl centrifuge and the cyclone classifier. The solid bowl centrifuge, Fig. 10, consists of a truncated cone fixed to a horizontal shaft and rotating at high speed. An internal spiral rotating at slightly less speed continuously removes solids deposited on the inner surface of the cone, or bowl. Feed enters the cone by means of the hollow center shaft. Overflow leaves through ports at the large end of the cone, and oversize solids, moved by the spiral, exit through ports at the small end. Centrifugal classifiers of this type are available in cone diameters from 18 to 54 in. The cyclone classifier, Fig. 11, is a stationary cone having a cylindrical upper section and a lower cone section. Feed is introduced tangentially into the upper cylindrical section under pressure from a hydrostatic head or by means of a pump. Centrifugal force thus induced effects a classification within the cone, the fine sizes being carried off in the overflow through an opening at the top of the cylindrical section. Coarse solids at relatively high pulp density exit through a control valve at the apex of the lower cone section. Cyclone classifiers are available in 3, 6, 12, 14, 24, and 30-in. diam. The cone classifier, Fig. 12, is a steel-plate cone with sides usually about 60" from horizontal. It contains no rotating mechanism. Feed enters a feed-well at center and classification is effected by gravity and pulp density. Fines are carried off in the flow over a peripheral weir at the top of the cone. Settled solids exit through an opening at the apex. An apex valve actuated through levers and rods by the pulp density in the lower cone section is usually supplied. Diameters are usually maximum at 8 ft.

Jan 1, 1955

By T. E. Kihlgren

SYSTEMATIC data are presented on the relation of composition of nickel silvers to color, tarnish resistance, hardness and liquidus temperatures, for alloys containing up to 30 per cent nickel and 50 per cent zinc, further modified at certain nickel and zinc contents by 0 to 8 per cent of tin and 0 to 10 per cent of lead. Attention has also been directed, using a still more limited range of alloys, toward a study of tensile properties and such casting properties and characteristics as fluidity, shrinkage and pressure tightness. In some of these, rather broad ranges of composition are dealt with; in others, it has been expedient to focus attention on the Federal Specification 20 per cent nickel silver casting alloy, WWP-541. INTRODUCTION The demand for an alloy essentially white in color, which could be cast and worked by simple methods and which possessed strength and corrosion-resisting properties superior to the usual brasses, led to the discovery and early use of cupronickel alloys containing zinc, and some-times tin, lead and other metals. This type of alloy was generally known as German silver until the war, when the term "Nickel Silver" became generally accepted. The element principally responsible for the white color of the alloy and for its strength and corrosion resistance is nickel, which may constitute from 8 to 30 per cent of the alloy. The functions of the other elements will be described later. The manifold uses of nickel silver are largely due to its color, corrosion resistance, ease of casting, fabrication, joining and rather moderate cost. In many instances the alloy is finished by grinding and polishing while in others it may be finished with a silver or nickel plus chromium plate. Electroplates

Jan 1, 1935

By Walter Lawson

THE first plans were made in 1930 for the mining by open-pit methods of the low-grade disseminated ore body now known as the Morenci open pit. It was not until 1937, however, that final plans were completed and the decision reached to go ahead with the actual development. Many advances were made in open-pit mining equipment during that period of seven years, therefore the ways and means of attack actually used were very different from those originally contemplated. Diesel-operated bulldozers, big trucks, full-revolving electric shovels and electric churn drills constitute the major equipment finally purchased for this modern stripping operation. Neither the bulldozers nor the big trucks were considered in the early operating plans, for at that time bulldozers had not, been used in mining operations and the trucks as yet were undesigned. The full-revolving shovel and the churn drills were not new developments in open-pit equipment, but both had undergone remarkable manufacturing transition, emerging far more efficient and far more dependable than their predecessors. Even the ordinary drilling steel had been fundamentally changed. It was now threaded so that the dulled cutting bits could be detached and replaced, thus eliminating the costly transportation of long bars to the drill shop for resharpening. The decision to use trucks in the preliminary stripping operations was based on the desirability of this type of transportation to economi-cally prepare the pit for rail haulage, coupled with the success that the contractors had had with them on other big excavation jobs. There are at present no plans for the use of trucks beyond the preliminary work, inasmuch as rail haulage will give lower costs after roadbeds and benches are once established.

Jan 1, 1938

By J. J. Calaman, D. H. Fleming

DURING 1950 the jet-piercing process was used commercially in the piercing of primary blast-holes in magnetic taconite at the preliminary taconite plant of .the Erie Mining Co., Aurora, Minn. The Erie Mining Co. purchased a jet-piercing machine and associated equipment in 1949, and the machine has been in operation since its installation in the summer of that year. An overall view of the pit with the JPM-1 jet-piercing machine in operation is shown in Fig. 1. During three months of 1949 and continuously since February 1950, production piercing took place under all pit conditions. By the end of October 1950, a total of 15,000 linear ft of hole had been pierced in an open pit handling an average of 1200 to 1800 tons of crude a day in one 8-hr shift. While it is recognized that this output does not approach the millions of tons a year planned for the developing Minnesota taconite projects, the machine as a unit has been operating under conditions probably more adverse than those that eventually will be encountered in the large operations. This pilot operation has permitted evaluation of the piercing problem in the full-scale taconite plant. This paper describes jet-piercing process funda- mentals, important features of the latest jet-piercing burners and machine, actual piercing results obtained, and new developments that give promise of materially increasing overall process efficiency. To produce the blasthole, jet-piercing utilizes thermal energy, as contrasted with the application of mechanical energy in churn drills and jackham-mers. The heart of the process may be termed a tailored flame produced by a rocket-type burner, thermodynamically similar in every respect to that of the giant rockets being developed for military purposes. The heat release in the combustion chamber of the burner is about 50x10' Btu per cu ft per hr as compared with 5x10' for most modern steam generators.* Combustion of liquid petroleum fuels (kerosine, diesel oil, or No. 2 fuel oil) with gaseous oxygen in the burner chamber at pressures of 100 to 200 psi results in temperatures of about 4300°F. Expansion of the hot combustion gases through divergent nozzles produces high-temperature supersonic jets having measured velocities of about 6000 fps. Impinging the flame jets on rock causes a thin surface layer to expand and break away from the base as a result of the thermally induced stresses. This spalling action is aided further in chert and quartzite by the 0.82 pct volume change resulting from the 6 to p quartz inversion at 1066"F.t The dynamic action of the jets whisks the spalled rock

Jan 1, 1952

By O. R. Bergmann

Two approaches were taken to obtain direct experimental evidence jar the existence oj a jet in the explosion-cladding pvocess: 1) direct observation of the claddirg jwocess by rtzeans ojf kig-h-speed photography using a fvartziiy catnera and 2) use of a plated-surface experiment in contribution with clzetrzical analysis. The framing-camera records showed clearly the presence of a jet it1 the form of what appears to be a line spray. The jet velocity is considerably highev than the detonation velocity arid in vacuum it is almost twice as high as the detonatiou velocily. The results jrorrz the plated-surface experiment also corzfivtned the preseizce of- a jet. The artzoutlt o,f etzergy dissipated in the jetting process was foundd lo be consislent with the basic theovetical model o/ the cladding mechanism.. MaNY reports on metal working with explosives have appeared in the literature during the last few yearsThis paper describes experiments concern- ing the mechanism of the explosive metal-cladding process. It has become increasingly important as a unique method for bonding metals and a typical cladding arrangement is shown in Fig. 1. A theoretical analysis of the mechanism of explosive bonding and a description of the nature and types of bond zones obtained was given by Cowan and oltzman." A further discussion of the basic principles of the process, a detailed description of the different bond-zone types, and extensive information on the properties and the applications of explosively bonded metals was recently published by Holtzman and cowan. " The process is now in commercial use by E. I. du Pont de Nemours & Co. The concept of the existence of a jet during metal bonding with explosives forms a central part in the theoretical analysis of the cladding mechanism described by Cowan and Holtzman When a layer of explosive is detonated on a metal plate that is separated from a second metal plate by a small distance the metal plate in contact with the detonating explosive is accelerated by the detonation pressure. An angle is established between the undeflected and deflected portions of the plate. Subsequently the deflected portion of the first plate collides with the second metal plate.

Jan 1, 1967

By C. H. Mathewson

MICROSCOPIC. rnetallography has been exploited quite well enough to bring about a very general understanding that the typical metal or alloy is composed of minute crystalline particles blended into a coherent microstructural mosaic. One does not have to be a specialist in metallography to realize that the properties of such an aggregate are essentially a summation in appropriate form of individual effects derived from the shape, size, placement or orientation and cohesive characteristics of the component particles. It is clearly of great importance to consider the various forms of discontinuity which may occur at the boundaries between these crystalline particles. When a number of 'particles each possessing the same orderly arrangement of atoms are brought together into a close-fitting system of purely haphazard contacts, not unlike a handful of snowflakes compacted into a snowball, the particles are said to possess random orientation. There are no generally accepted views concerning the arrangement of the atoms or the constitutional reaction between atoms where one crystal meets another, but these contact regions are characterized by strength rather than weakness and it is customary to require the presence of many rather than few boundaries in preparing metal for useful service. Under certain circumstances all of the particles in a metal may be nearly alike in orientation. Other general tendencies of orientation may be associated with particular forms of mechanical and thermal treatment. In contrast with these cases of fortuitous or statistical diversity of orientation, we often find adjacent particles united along a plane which possesses a grouping of atoms belonging equally well to both structures. This, of course, determines a fixed relationship between the two orientations and it is always possible to derive one from the other by some form of rotation or reflection prescribed by the symmetry of the crystal structure under consideration. Particles united in this manner are known as twin crystals although the term refers to the form of association rather than the number of individuals concerned.

Jan 1, 1928

By C. S. Giggins, F. S. Pettit

The oxidation of Ni-Cr alloys in 0.1 atm of oxygen has been studied at temperatures between 800" and 1200°C. For alloys with 30 wt pct or more Cr, continuous layers of Cr2O3 are formed during oxidation. In the case of alloys with chromium concentrations between approximately 5 to 30 wt pct, external scales of Cr203 are formed over grain boundaries whereas internal precipitates of Cr2O3 and external layers of NiO are formed at other areas on the alloy surface. When such conditions are present on the alloy surface, chromium diffuses laterally from those areas covered with a continuous layer of Cr2O3 to areas where a Cr2O3 sub scale exists and it is possible for the sub-scale zone to become separated from the alloy by a continuous layer of Cr2O3. Whether such a state will be attained depends upon the initial grain size of the alloy and the oxidation time. When the concentration of chromium in the alloy is less than 5 pct, Cr2O3 is formed internally both at grain boundaries and within the interior of grains and the alloy is covered with an external layer of NiO. MECHANISMS which describe the growth of oxide scales on nickel-base superalloys are complex and the effects produced by the various elements in these alloys on the oxidation behavior of superalloys are not clearly understood. In order to determine the influence of the different elements on the oxidation behavior of superalloys, it is first necessary to examine the oxidation properties of binary nickel-base systems which contain the principal elements present in the superalloys and then progressively more complex systems until compositions typical of the superalloys are attained. Chromium is present in virtually all nickel-base superalloys and the purpose of the present studies was to examine the selective oxidation of chromium in Ni-Cr alloys. The oxidation characteristics of Ni-Cr alloys have been extensively studied1-" to date principally as a result of the high oxidation resistance exhibited by some of these alloys. Ni-20Cr* has long been known *All compositions are given as wcight percent unless specified otherwise. to be oxidation resistant and is commonly used as resistance heating elements for service temperatures up to 1100°C. This alloy cannot be used for extended periods of time at higher temperatures because of the apparent reaction of the external scale with oxygen to form gaseous CrO3. In spite of the considerable work cited above some important aspects of Ni-Cr oxidation still remain unresolved. Virtually all of the previous studies agree that small additions of chromium to nickel, e.g., <10 wt pct Cr, result in increased oxidation rates as compared to that of pure nickel, whereas larger additions, e.g., 20 to 30 wt pct Cr, form alloys with substantially lower oxidation rates. The controversial aspects of the oxidation mechanisms for these alloys that still remain unresolved are as follows: 1) A description of the oxidation mechanism for the low chromium alloys. 2) A description of the oxidation mechanism for the high chromium alloys, particularly with respect to the composition of the external scale which results in the lower oxidation rates. 3) The specific alloy compositions at which the oxidation mechanism changes from that obtained for low chromium contents to that of the high chromium alloys and the reason for this transition. EXPERIMENTAL The Ni-Cr alloys listed in Table I were prepared from high purity metals by nonconsumably arc melting and casting as buttons. These alloys were then given a preliminary annealing treatment in argon at 815°C for 100 hr to promote homogeneity. Each button was cut into 0.250 in. thick sections that were subsequently cold-rolled to 0.050 in. thicknesses and annealed in argon at 815°C for 48 hr to provide a twinned, equi-axed grain structure. The grain size for these alloys was not uniform and the limits, within which the average grain size lies, are given in Table I for the single-phase alloys. All the alloys were single phase with the exception of the Ni4OCr alloy in agreement with the Ni-Cr phase diagram.&apos;&apos; Rectangular specimens were cut from the sheet to provide surface areas of approximately 2.5 sq cm. Exact areas were determined with a micrometer after surface preparation was completed. All of the specimens except the Ni-40Cr alloy and pure chromium were polished through 600-grit Sic abrasive paper, ultrasonically agitated in ethylene trichloride, rinsed with ethyl alcohol, and electro-polished. The specimens were electropolished in a 10 vol pct H2SO4 (conc), 6 vol pct lactic acid, methyl alcohol solution at 70" to 80°C for 2 min at a current density of 0.8 to 1.2 amp per sq cm. This electro-polishing procedure did not produce acceptable surfaces on the Ni-40Cr alloy nor on pure chromium and the oxidation properties of these materials were obtained for specimens polished through 600-grit Sic

Jan 1, 1970

By G. A. Merkt

THE Isley furnace control, here presented as a novelty in furnace construction, is, in principle, one of the oldest methods of maintaining furnace heat for industrial purposes. Records unearthed in Egyptian tombs and the primitive methods of melting metal practiced by African tribes today indicate that fanning the fire and forcing the furnace by bellows have been an effective means of regulating heat for man&apos;s work during thousands of years. Even today, these cruder forms of mechanical draft production are still nn use within the borders of this most highly developed industrial land. Stacks, as we know them, are of com- paratively recent historical age but their attractive simplicity and seeming effectiveness have made them exceedingly popular. And so we find one of the most important types of furnace the world has even known, the open-hearth furnace, duly and more or less properly equipped with a chimney. The regenerative, or reversing, type of furnace, how-ever, required another mechanism between its hearth and the stack to provide a means for alternately con-necting one side and the other of its system of regen-erative chambers and flues to the stack and to a source of fuel and air supply respectively. Various types of reversing valves were developed, some of which are re-markably well designed for maximum efficiency and ease of installation as well as operation. However, this combination has a number of inherent faults which are so difficult to correct as to make efforts in the direction of improving over-all efficiency almost futile. These inherent difficulties are as follows: (1) The necessarily high temperature at which the gases must be delivered to the stack in order to make it operative. (2) The great temperature difference incidental to the reversal of flue gas and air and consequently the large variation in preheated air and fuel delivered to the furnace dur-ing the cycle. (3) The leakages and resistances created by the reversing apparatus and the complicated flues necessary. (4) The inadequate range of control af-forded by the natural draft system, especially under adverse atmospheric conditions.

Jan 12, 1927

By B. G. Klugh

The present paper represents a preliminary investigation of the ultimate structure of iron-bearing materials which have been subjected to heat treatment for the purpose of agglomerating the fines, or for chemical changes, or for both. Primarily, the object of this inquiry was to determine the relation of the microstructure of each of these materials to its specific susceptibility to the action in the blast-furnace. It is hoped that this small contribution will serve as a nucleus to a line of research that will throw some light upon the debated questions involved in blast-roasting. Thus far the investigation has been conducted along lines of analogy of known principles, rather than through the application of any well-defined system of microscopic petrography. This is obviously due to the fact that we are dealing with ma-terials which are the artificial products of a new art, rather than with the natural materials from which the essence of the pure science has been evolved. In the limited time allowed for this research, it has been conducted upon those materials the chemical content of which allows of their use commercially in the blast-furnace. The following microphotographs are arranged in the order of the degree of complete fusion to which the mass in question has been subjected, in effectively binding the particles together. A very notable fact here clearly demonstrated is that the degree of fusion to which the material has been subjected is inversely proportional to the reducibility of the product. The characteristic of the material under consideration to which reducibility is almost universally attributed call be progressively traced in the following arrangement, through the identity of the obvious microscopic constituent. Furthermore, the degree of fusion to which a bod? has been subjected is recorded in the presence of resultant products of fusion in that body. Such readjustment is generally apparent

Jan 1, 1914

By L. D. Clark, S. S. Saluja

A physical law, governing the rupture of rock by confined explosive charge correspondent to current expressions for determining weight of charge to rupture rock burden, W, was developed in the form Q = cVw3 by two early investigators performing unique experiments with ice. The coefficient C, is found by trial blast. Recent physical tests conducted with rock, synthetic materials and ice to establish the validity of the theory on which it and other related formulae are based indicated: (a) that failure under hydrodynamic impact pressure is by tension rather than shear as was assumed; (b) that the fundamental law of mechanics, enabling the determination of Q = cvw3, modified to the form P = R x Sa x Wb is valid when low velocity explosives are used; (c) that rock breakage under the action of low velocity explosives is entirely due to explosion gas pressure, as was believed; (d) that under the action of high velocity explosive it is due to the joint effects of scabbing and gas pressure; and that further possible modification could make the above equation also applicable to these joint mechanisms. shape could be easily frozen and because large loads would not be required. They found: (a) that the not unfamiliar shearing equation for metals was applicable to ice where P = load in lb; S = periphery of pressure surface, in.; W = burden, in.; K = modulus of rupture by shear in lb per in.2; and (b) that "the form of cavity produced by the application of gradual pressure is similar to that obtained by blasting in rock under similar conditions of free face and pressure surface!" This similarity in crater shapes leads to the conclusion that rock would rupture by shear, as did ice, and its behavior under the force of a blast could be governed by such a relationship as P = S x W x K. Three important interrelated empirical expressions were derived and rock, charging and spacing coefficients C,, C, and e were established and substantiated by trial blasts. In checking the accuracy of the main assumptions, duplication of the ice tests, substituting rock, suggested that K is not constant and that P = K x W x S, though valid for ice, does not necessarily hold for homogeneous limestone.&apos; Conclusions from this later work raised questions making continued investigation desirable because such conclusions do not destroy the practical value of the empirical equations or theory. Further study for the establishment of the relationship between load, burden and periphery of the pressure surface and possible application of these to the mechanism of rock blasting was undertaken by the authors of this paper. MECHANICAL TESTING - EXPERIMENTAL PROCEDURE Certain inconsistencies in the results of the aforementioned tests repeated on three types of limestone suggested these inconsistencies be attributed to rock inhomogeneity. It was also suspected that the loading speed, which could not be held uniform, may have contributed. The earlier work with both rock and ice

Jan 1, 1964

By W Lindlief, Cyril Stanley Smith

Several investigators, mainly concerned with the mechanical properties of the alloys, have studied the so-called aluminum bronzes after various quenching and reheating treatments. Of these works, perhaps the most complete is that of Bouldoires, who studied changes of length, electrical conductivity, thermoelectric force, hardness and micro-structure on tempering quenched alloys containing 5 to 20 per cent of aluminum, although the work of Carpenter and Edwards,² Curry13 Greenwood,4 Braesco,5 Matsuda,67 Grard8 and others has added much to our knowledge of the changes occurring during tempering. The so-called acicular ß decomposes on tempering at temperatures between 350" C. and the eutectoid, giving rise to a Widmanstätten structure of a needles in a matrix of 6 or fine a + 6, associated with an increase in hardness and almost complete loss of ductility. Matsuda studied the eutectoid transformation by means of dilatation and electrical conductivity measurements during cooling at different rates. He found that on cooling at the rate of 10" C. per minute there was a decrease in electrical resistance and in length instead of the usual increase which occurred with slow rates of cooling. On tempering the rapidly cooled samples, the increase commenced at about 400" C. and at 520" C. the resistance and length had reached the equilibrium values. These peculiarities he accounted for as being due to a transitional phase ß&apos; being formed, ß&apos; having an electrical resistance and volume less than either ß or a + 6. Obinata9 published some electrical conductivity curves for copper-aluminum alloys showing a double break at the eutectoid temperature,

Jan 1, 1933

By A. U. Seybolt

Since the time this topic was originally treated in 1954, more recent French3,1 work has been published making it advisable to repeat the earlier oxygen solubility experiments, but using iron of a higher purity. Upon repeating oxygen saturation experiments with zone-refined iron, it was found that the oxygen solid solubility was at least an order of magnitude less than previously observed. SINCE the publication of an earlier paper1 (1954) on this subject by the present author, several contributions on this topic have appeared. Meijering2 in 1955 attempted to reconcile recent conflicting solubility data, without reaching any definite conclusion. sifferlen3 (1955) found that iron of high purity appeared to absorb a quantity of oxygen (0.005 to 0.025 pct) approximately proportional to the structural imperfections present, such as polygonization and grain boundary area. However, he also indicated that purity itself was a significant factor. He concluded that very pure iron nearly free of lattice imperfections would have essentially zero oxygen solubility. His second paper4 (1957) supported this contention since a zone-melted iron containing initially 0.0007 pct O analyzed only 0.0006 pct 0 after prolonged soaking at 850°C with an FeO layer on the surface. Because of the discrepancy between the results of Ref. 1 and those of Sifferlen, it seemed desirable to attempt to resolve this disagreement. EXPERIMENTAL PROCEDURE AND MATERIALS The experimental method used by sifferlen3,1 was essentially the same as that of Ref. 1. In this technique thin iron strip with a surface layer of FeO is soaked for prolonged periods at an elevated temperature in order to saturate the iron with oxygen. After two days at temperatures near 800° to 900° C, one would expect that the iron would be in equilibrium with the surface FeO. In the work reported in Ref. 1 there was evidence that two days holding at 8000to 900°C was more than sufficiently long for saturation. Sifferlen used 48 hr at 850°C. Because of the evidence presented by Sifferlen that the apparent oxygen solubility is a function of iron purity, three grades of iron were used as indicated in Table 1. The Bureau of Standards wire was used only for resistivity tests, while the other two irons were used for saturation-analysis tests of the type described above.

Jan 1, 1960

By Raymond Edmundson

BARITE probably was first mined in the United States in 1845, when a small deposit was operated in Prince William County, Virginia1. The next state to produce barite was Missouri, and according to Weigel2, mining began about 1860. Virginia was the leading producer during the early period of barite mining, but by 1893, Missouri was producing almost an equal amount3. From this date, Virginia, although not the leading producer, furnished large quantities of crude barite until oper-ations gradually declined about 1907. Since 1910, there has been only one producer in Virginia. It is not known when barite was discovered in each of the Virginia areas (Fig. 1), but it is reliably reported that mining on a commercial scale began in Campbell-Pittsylvania counties about 1874; Smyth County in 1877; and in the Russell-Tazewell area about 1890. Barite is widely distributed in Virginia, occurring in nineteen counties. The localities that contain material of some economic value have been grouped into six areas (Fig. 1), each designated by the county or counties in which the barite is found. As many of the smaller areas show a similarity in geologic occurrence, they will be considered in this paper as two major groups; namely, Appalachian Valley and Piedmont Province. The first group, which includes the barite deposits of Russell, Tazewell, Smyth, Botetourt and Roanoke counties, lies northwest of the Blue Ridge and its foothills and southeast of the Appalachian plateaus. The other group includes deposits from the Blue Ridge on the west to the western margin of the Coastal Plain, in Campbell, Pittsylvania, Bedford, Grayson, and Fauquier counties.

Jan 1, 1936

By V. F. Swanson

A petrographic study was made of the type and sources of mineral contamination occurring in Florida phosphate rock products. Emphasis was placed on contaminants in the screened rock (+1 mm), since this portion of the product undergoes no physical beneficiation except for scrubbing to remove slimes. Since iron and aluminum contents of the finished product affect the salability, special emphasis was placed on identifying types and sources of these contaminants and relating chemical composition to visual characteristics. Wavellite derived from the overburden was the major aluminum contaminant with some aluminum being included as secondary clay balls. Iron occurred as phosphates in the overburden and as colloidal oxides included in the phosphate pebbles. Chert and limestone contamination derived from the Hawthorne formation underlying the phosphate matrix.

Jan 1, 1972

By W. L. Saunders

It has been estimated that the value of the mineral products of the United States is about $2,000,000,000 a year; that about $25,000,000 is expended annually for explosives and that about double this sum is paid in wages where blasting is done. The value of the mineral products does not adequately express the importance of the industry involved in the excavation of rock and ore because of the enormous sums of money expended in tunnel driving, in quarries, and in open-cut excavation generally. We know that the Catskill Aqueduct in the neighborhood of New York, which is now nearing completion, has cost some $165,000,000 and that about one-third of this may be rated as rock excavation. These illustrations are given in order to call attention to the great importance of an industry the extension and development of which in our industrial life depend so much upon the economics of rock drilling. Reference has been made to the new Catskill Aqueduct. There are three aqueducts leading into New York, each built at periods separated by some 20 years of time. The first one, known as the Old Aqueduct, conveys the waters of the Croton river to New York City in a manner which reminds one of the old Roman aqueducts, the ruins of which are still in evidence. The engineers who laid out these old conduits sought to direct their lines around the hills and into the valleys, at all times avoiding the rock. When it was necessary to cross a river or a deep ravine, a bridge or causeway was constructed. High Bridge, over the Harlem river, is an arched masonry viaduct differing in no essential features from the aqueducts of the Romans. When the second Croton Aqueduct was built, about the year 1890, the art of drilling rock had been so far perfected, and the use of explosives, through the invention of dynamite, had become so general, that this waterway was planned and executed on straight lines, following rather than avoiding the rock. The second Croton Aqueduct is a tunnel through rock, about 32 miles in length; material gneiss, almost as hard as granite. Its construction was made practicable by sinking

Jan 1, 1914

By F. B. Foley

A description of tests made by a committee of the Division of Engineering of the National Research Council to determine whether velocity of impact affects the formation of Neumann bands. FOREWORD Not infrequently, in the case of the failure of a metal structure, such as a bridge, tank, airplane, gun carriage, etc., a doubt arises whether the failure was due, among other causes, to the effect of an overburden or of an explosive maliciously or accidentally exploded in contact with it. As few means of discriminating between the effects of these causes have been known and these means were of a rough qualitative character, it was surprising to find in the record of an inquiry into the failure of a structure, the statement that, by observations on the Neumann bands in the structure, it was possible to determine the speed of breakage in the metal and to distinguish between a fracture caused by an explosion and one caused by an ordinary mechanical strain. Such a criterion, if well proved, was of value to the explosives experts of the Bureau of Mines, the Ordnance Department of the United States Army and the Bureau of Ordnance of the United States Navy, but search showed no record of it in the literature nor did any of the metallurgists and metallographers consulted know of any data on which such a criterion could be based having been assembled and critically studied. However, it was universally held that there was promise in the idea and that there existed unique facilities at the Bureau of Mines Experiment Station at Pittsburgh for the preparation, under definitely known conditions, of material for study by metal-lographers, and that material of value might also be obtained from the proving grounds of the Army and Navy. Therefore, with the approval of the Director of the Bureau of Mines and the Chiefs of Ordnance of the War and Navy Departments, the Chairman of the Division of Engineering of the National Research Council, on April 12, 1919, appointed a Committee on the Investigation of Neumann Bands, which has since been engaged in this study and which, after some slight change in its personnel, consists now of the following: Dr. William Campbell, Advisory Metallurgist, Bureau of Ordnance, Navy Department. F. B. Foley, Metallurgist, Bureau of Mines. S P. Howell, Explosives Engineer, Bureau of Mines. Comdr. O. M. Hustvedt, U. S. N., Bureau of Ordnance, Navy Department. Dr. Charles E. Munroe, Chief Explosives Chemist, Bureau of Mines.

Jan 9, 1922

By G. A. Croes, N. Schwarz

The dimensionless groups, to which the variables that govern the displacement of oil from reservoirs by liquids can be combined, are derived. Three types of displacement are considered, viz. cold-water drive, hot-water drive and solvent injection. The derivation of the dimerzsionless groups is carried out by means of the relevant basic equations (in-spectional analysis). The resulting sets of groups are afterwards completed by means of dimensional analysis. The form of the groups is given in such a way that they can be adapted to suit the various boundary conditions that are encountered in practice. The physical meaning of the groups is discussed. They have all been brought together on a chart, from which their mutual relation and their corresporzdence to related dimensionless groups in common use in other engineering sciences can be read off. The limitations of dimensionally scaled model experiments as a useful tool for studying liquid flow in porous media, as occurring in oil reservoirs, are discussed. The use of models to study fluid mechanics has an appeal for everyone endowed with natural curiosity. What active boy has not played with ship and airplane models, or crude models of dam and drainage systems Even in the most advanced technical engineering, such models play a fundamental and indispensable role. "And yet in few departments of the physical sciences is there a wider gap between theory and practice, between scientific knowledge and the state of art, than in the use of models to study hydrodynamic phenomena." Garrett Birkhoff1 INTRODUCTION Laboratory displacement experiments are extensively used to investigate, directly or indirectly, the production behavior of petroleum reservoirs. Such experiments are representative of the reservoirs as a whole, if they are carried out with models that are "properly scaled." The performance of oil reservoirs is governed by the values of a number of variables, which can be combined to dimensionless groups. Two general methods are available for the derivation of these groups. In the first of these, dimensional analysis, combination of the variables is done essentially by trial and error. Its only premise is knowledge of the complete set of relevant variables. In the second method, inspectional analysis, the dimensional homogeneity of the equations describing the behavior of the system to be studied is used. The resulting dimensionless groups can be divided into: (a) independent (variable) groups, such as dimensionless length, time, etc.; (b) dependent groups, giving the dimensionless form of the variables, such as recovery and pressure, that can, at least in principle, be measured during an experiment; (c) similarity groups, which are independent constant groups, such as ratio of length to height of the reservoir and ratio of

Jan 1, 1957