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KNOWING the endpoint, or the equilibrium state, in steelmaking reactions is only part of the story. The rate at which the reactions proceed can be equally important. But the power of thermodynamics, which enables us to estimate the endpoint, is that a knowledge of the mechanism is not required. The methods of kinetics, however, are step-by-step analysis in which a knowledge of the detailed reaction mechanism is essential. As is evident from Chapter 16, a great deal of thermo- dynamic data for steelmaking are available and the underlying theory rests on a completely sound basis. This is far from the case with kinetic data and even kinetic theory. Nevertheless, it is worthwhile to examine the present state of knowledge, to see how far it may be applied to electric furnace reactions. KINETIC THEORY Heterogeneous Reactions. Classical kinetic theory and experimentation have been mainly concerned with homogeneous reactions taking place between different chemical species in a gas or liquid phase. The species are mixed together and the progress of the reaction can then be observed. This is possible because most experiments have been done at relatively low temperatures where the characteristic time for the mixing process is much shorter than the time for the chemical reaction to be completed. For example, in the homogeneous gas reaction, H2 (g) + I2 (g) 2HI (g) hydrogen and iodine may be added to opposite ends of a tube containing a diaphragm. When this is withdrawn, gaseous diffusion (and convection) mixes the two types of molecule almost completely before any hydrogen iodide molecules begin to appear. Such an experiment is inconceivable at more elevated temperatures, since the rate of the chemical process is so sensitive to temperature that reaction would be completed almost instantaneously wherever hydrogen and iodine came into contact; the rate of the mixing process would then determine the rate at which hydrogen iodide was formed. We should not, therefore, expect to observe many homogeneous reac-

Jan 1, 1964

Page Bronze Bearing Metals. By G. H. Clamer............... 162 Pennsylvania Railroad Anti-friction and Bell Metals. By F. M. Waring .. 166 The Tin-plate Industry. By D. M. BUck. Discussed by G. H. ClameR, J. W. RICHARDS............................ 168 The Aluminum Bronze Industry. By W. M. Corse............ 171 Bronzes, Bearing Metals, and Solders. By G. K. BURgess and R. W. Woodward. Discussed by G. H. Clamer, R. T. Roberts......... 175 Babbitts and Solder. By G. W. Thompson................ 184 The Cadmium Supply of the United States. By C. E. Siebenthal. Discussed by M. L. Lissberger, C. W. Hill, F. F. ColcoRd.......... 185 Solder, Its Use and Abuse. By M. L. LissbergeR............ 192 Bronze Bearing Metals G. H. ClameR,* Philadelphia, Pa.—Unfortunately, prior to the war no serious attention was given to the conservation of tin, notwithstanding that this country is practically dependent upon outside sources for its entire tin supply. Tin is of vital importance in many industries, but it is surprising how many and how excellent are its substitutes when we become acquainted with them. Tin has always been a relatively high-priced metal, and it is part of the human attitude to associate high prices with high standards; it is not until the price of a commodity becomes well-nigh prohibitive that we hunt for substitutes, because the idea of substitution seems always to involve an assumption that the substitute must necessarily be inferior. The history of the development of bearing bronzes is a striking example of this policy. In the early days, copper-tin alloys were almost universally used, the idea then being prevalent, which is still held by many, that a bearing to resist wear must be hard, and the harder the better. The favorite bronze bearing contained 90 per cent. copper and 10 per cent. tin; frequently, in service which was considered severe, even higher proportions of tin were used. Such hard alloys have great resistance to compression, but as a rule they had a very wide factor of safety in this

Jan 1, 1919

By Arthur Taggart

FLOTATION of ores is a practical utilization of the energy that resides in the surfaces of solids and liquids. The best known manifestation of this energy is called surface tension; an equally important, though less apparent, phenomenon is adsorption. This paper reviews some of the recent investigations of these phenomena, and gives the results of certain experiments performed by the authors. Surface tension is a manifestation of energy having its seat at the bounding surface between the adjacent phases of a multiphase system. Thus, at the interface between a liquid and a gas, or between two immiscible liquids, or between a solid and a gas or a liquid, there are forces capable of doing work, their magnitude depending on the nature of the adjacent phases and the extent of the bounding area. These surface forces are inappreciable when the ratio of surface to volume of the adjacent phases is small, but they become powerful when this ratio becomes large, as it does when one of the phases is highly dispersed. Froth flotation, which consists in buoying solids heavier than water to the surface of water by means of gas bubbles, utilizes the force of surface tension to attach the solid particles to the gas bubbles and again to maintain the floating mass of bubbles as a more or less persistent froth at the surface of a pulp for a sufficiently long time to allow its removal. It follows from the second law of thermodynamics that the potential energy of a system in equilibrium is a minimum. Therefore a multiphase system, tending toward equilibrium, will arrange itself in such a way that the total energy of the interfaces will be the least possible. This end can be accomplished in two ways: by a change in shape that will reduce the interfacial area; by a change in the nature of the surface layer in

Jan 8, 1922

By B. Ramaswami, Y. Nakada, U. F. Kocks

Compression tests were performed on single crystals of aluminum, silver, gold, and a Ag-10 pet Au alloy, with height-to-width ratios from 8:1 to 1:1. As this ratio decreased, so did the amount of easy glide until, for cubic specimens of all the pure materials, it was entirely absent. Heterogeneity of deformation is proposed to he a major contribution to the explanation of easy glide in slender specimens. For comparison, one single-crystal cube of zinc was tested and showed a behavior very similar to that in tension. Beyond easy glide, tension and compression curves are very similar. It is concluded that, in this range, neither grip effects nor orientation change influence the work-hardening characteristics to any significant extent. (121) and (100) crystals of all materials had similar stress-strain curves in tension and compression, except that the stress level of the flat portion of aluminum (109 crystals at high strains mas somewhat higher in compression. These results are at variance with previously proposed mechanisms of orientation dependence by both Hosford and Kocks. The compression tests themselves are described in detail and it is shown that they are essentially frictionless and produce single slip when the crystal is suitably oriented. DEFORMATION in uniaxial compression does not necessarily give the same result as deformation in uniaxial tension, essentially because the boundary conditions chosen are practically always different. 1) The shape and size of the specimens are usually different, and any genuine effect of size on work hardening should thus influence the result. 2) The grip constraints are usually different and can vary substantially for different kinds of tests. If the compression specimen is a thin plate and the friction on the platen is large, the grip contraints are more serious than in tension and lead, in the extreme, to uniaxial strain rather than uniaxial stress. If the specimen is roughly cubical and the friction is low, the specimen is less constrained than in tension inasmuch as displacements in the contact face are allowed. 3) The orientation change of single crystals is of opposite sign in tension and in compression; it is furthermore different in detail, because the relevant orientation in a squat specimen is the normal to the contact face, whereas that in a slender specimen is the generator of the side faces.' The considerable dependence of work hardening on the initial orientation in tension would suggest that the orientation change should also be very important. 4) Finally, localized deformation instabilities found in tension tests, such as necking and Lüders band propagation, are not possible in squat specimens. This is, for some investigations, a favorable consequence of the large grip influence. Even if one is not interested in any of the effects mentioned above, compression tests are often desirable just because the specimens needed are so much smaller and sturdier. For example, they have been very helpful in the investigation of latent hardening by means of alternate longitudinal and lateral compression of cubes,* and for testing

Jan 1, 1964

By Heihachi Kamura

In this research, the proper temperature for the reduction of iron ores by carbon monoxide was determined. Also, the difference of the rate of reduction on the sizes of ore under four mesh per linear inch was estimated, but no evidence could be found. Rates of reduction on the seven kinds of ore were compared with the results of the experiment, showing a close relation between reducibility and density of ore. Finally, the maximum size of ore that can be reduced in applicable length of time was determined. The author thinks that the process of production of steel may be replaced by low-temperature reduction of iron ores some time in the future. THE reduction of iron oxide, such as Fe203, to iron in the blast furnace is performed principally by carbon monoxide, but partly by solid carbon by the two following reactions: Fe203 + 3CO = 2Fe + 3CO2 2Fe203 + 3C = 4Fe + 3CO2 It is known that reduction by carbon monoxide takes place at a much lower temperature than reduction by carbon and that the reducing action of carbon monoxide progresses to the inside of the ore in lump form by gaseous diffusion. In the reduction by carbon, however, the reducing action takes place only at the contact surface of the ore and carbon, so that the more complete the reduction by carbon monoxide, the more efficient is the operation. However, the reduction does not progress as shown in the foregoing formula, because carbon dioxide acts oxidizingly on the metallic iron to such a degree that when the gaseous composition reaches a certain proportion of carbon dioxide to carbon monoxide, the reduction practically stops, even though the gases are moving slowly through the heated ore. The proportions of carbon monoxide and carbon dioxide in the gas depend on the kind of iron oxide and the temperature of reduction, also the duration of time in the reaction. The longer the time of the reaction, the higher the proportion of carbon dioxide obtained in the gas, but finally it will attain to a condition of equilibrium.

Jan 1, 1925

By Frank S. McKenna, Myron A. Pugacz, Clarence E. Jackson

The notched-bar impact test has proved worth while in certain applications as a test for control of the quality or the heat-treatment of steel. In view of the serious thought that even so simple a test as the tensile test has evoked during the past years, it is not surprising that the notched-bar impact test should have inspired much experimental work. The correlation of the great number of data has not been successful, although steady progress has been made toward a better understanding of this test. Progress has been made, especially, in the isolation of the effects of the many variables that control the results. The stress system imposed on a specimen with a notch is so complicated and unpredictable that no simple evaluation of the test has been possible. Because of this uncertainty, many engineers hesitate to use the notched-bar impact test, and this attitude may well continue until a better understanding of the effects of the variables in the test are available. Without doubt, any additional data that may be presented should be accompanied by as complete a description of the - details of test as possible, so that it may be added to the general fund of information that is to serve as the basis for the theory of the notched-bar impact test. The many factors that may control the test results have been pointed out repeatedly. The importance of the effect of the type and dimensions of the specimen has been recognized. Most of the work reported by American investigators has been limited to small-size (Charpy) specimens tested as a simple beam; two types of notches (Fig. I) have been commonly used. Considerable data have also been presented by many investigators using a small specimen tested as a cantilever beam; this commonly being called the Izod test. Here, however, a shear component of stress makes the stress system even more complex than that present in the simple beam type of test, hence a critical analysis is difficult. Much work has also been reported by investigators using the tension type of specimen. A second variable that must be controlled is the testing temperature. An indication that the tests were performed at room temperature is not sufficient, since in many steels a variation of a few degrees in the actual testing temperature may be sufficient to give an entirely different range of results. Other factors, such as the composition and condition of the material being tested and the speed of test, should also be considered. Many investigators have contributed data and theoretical discussions on the problems encountered in notched-bar test-

Jan 1, 1944

By Walter R. Crane

Operators of diamond drills have long been familiar with threadlike markings or riflings on cores but apparently have given but little serious thought to the conditions that are responsible for their production. The opinion generally held by those who have observed the phenomena is that the riflings are produced directly or indirectly by vibration, but so far as the writer is aware no systematic attempt has been made to demonstrate the fact. A careful search through the literature on diamond-drilling practice has been rewarded by only one reference to such markings of cores. J. N. Justice1 writes, "Of the peculiarities met with in the core, I will mention only one. The core from the "H" drill, at about 360 ft. came out rifled and pentagonal. The change from the circular to the pentagonal was sudden, and for 9 ft. this structure was maintained, when suddenly it returned to the circular. I have not been able to find any one who can explain the cause of this change of form. The drill men marveled at it and suggested vibration, six-stone bits, and several other hypotheses which need not be mentioned." The writer became interested in the matter of core riflings some 10 years ago while in the Flat River lead region of Missouri, where many remarkable examples of "rifled" cores were observed and collected. Since that time similar phenomena have been observed in various localities throughout the United States and Canada, and samples have been gotten together illustrating a large number of variations in form. After a careful study had been made of the material at hand it seemed desirable that certain data should be obtained from the experience of others regarding the normal action of diamond drills in forming cores, portions of which are occasionally rifled, before an attempt was made to draw any conclusions as to their cause. About 20 letters were addressed to diamond-drill companies, operators, and engineers actively engaged in drilling operations, with a

Jan 1, 1917

By Hsun Hu

Direct observations were made on the recrystalli-zntion of a cold-rolled (110) [001] crystal of 3 pct Si-Fe by annealing thin sections of the specimen inside the electron microscope during examination. Subgrain formation, presumably by polygonization, occurs rapidly, followed by a slow increase in the subgrain size before recrystallization can be detected. No migration of the subgrain boundaries was observed, and the formation of recrystallization nuclei by coalescence of subgrains is suggested. Re-c~ystallization characteristics of various texture components were individually examined. AS reported in a previous paper: orientations of the various deformation texture components in a 70 pct cold-rolled (110) [0011 crystal of 3 pct Si-Fe were completely confirmed by transmission electron diffraction patterns taken at various areas of the specimen. These orientations can be summarized as follows: Over most areas of the deformed crystal (111) planes are parallel to the surface. These areas correspond to either $- the two main defor: mation textures, the (111) [112] or the (111) [112].2-5 Within a few areas, (100) planes parallel to the surface are frequently found. These areas represent the minor deformation texture component, the (100) [Oll] type, which is derived from rotated Neumann bands.2'4'5 Only in very rare instances are (110) planes found parallel to the surface. This orientation corresponds to the very weak texture component of the (110) [001] type. In a pole figure, this (110) [0011 orientation is located within the orientation spread between the two main (111) [1121 type textures. Usually the electron diffraction patterns taken at various areas of the specimen are very simple ones, i.e., for any one area the pattern consists only of sharply defined spots of a single orientation. In some areas, however, more or less continuous rings of weaker intensities are superimposed on a simple pattern, indicating the presence of a wide range of additional orientations. In order to understand in detail the recrystallization of this cold-worked crystal, the recrywtallization characteristics of each of the various deformation texture components must be examined. This can best be done by using a high-temperature stage and transmission electron microscopy techniques, whereby small areas corresponding to the various texture components can be selected individually for examination. The present paper presents results obtained by this method. MATERIAL AND METHOD Specimens were prepared from a previously studied1 single crystal of a commercial grade 3 pct Si-Fe alloy with an initial orientation (110) [00l], cold-rolled 70 pct from 0.014 in. to 0.004 in. in thickness. Thin foils were prepared by electrolytic polishing as described in the earlier paper.' Specimens of this thin foil were then mounted in a high temperature stage similar to the one designed by Whelan.6 A direct current was used as the heating source. The temperature of the heating grid was calibrated by means of a Pt vs Pt-10 pct Rh thermocouple in a vacuum chamber (0.01 to 0.02µHg). Maximum variation within the temperature range of 250o to 000°C was about ± 25°C. After the desired areas were selected for examination, the specimen was heated to a low temperature for some time while the selected area was constantly watched. When no further change in structure and orientation could be observed, a higher temperature was applied. Photomicrographs and diffraction patterns were taken from time to time during examination, with the heater temporarily turned off* while the photographs were

Jan 1, 1962

By C. W. Hill

IN a previous article preliminary experiments were described, indicating the possibilities of a quantitative spectroscopic method for the determination of small amounts of lead in copper, which would be accurate and rapid, and could be carried out in the refining plant by one not skilled in chemical analysis. The present paper deals with the development of the method in the factory, giving the details of apparatus and its standardization, and presenting a comparison of the accuracy of the method with that of the standard electrolytic determination. (For variations and other applications of the method, the reader is referred to the first article.) FIG. 1.-STEPS IN THE ELIMINATION OF LEAD. (The lead line, at point 105.8 in the violet portion of the spectrum, is seen between the two copper Lines,-102.29 and -106.29, lying close to the latter. The crowded faint lines are due to the carbon are.) 1. OUTLINE OF METHOD A carefully weighed sample (0.4 gm.) of the copper to be tested is placed in a cavity in a graphite positive electrode. An arc capable of

Jan 10, 1918

By Byoung Whie Lee

In order to investigate the change in surface energy as a function of cold work ad environment, the contact angles between a liquid and the surface of elec-tropolislzed aluminum with various degrees of cold work were measured. Specinlens cut from aluminum rod (99.99 pct Al) were annealed at 600°C for 24 hr and then cold compressed parallel to the drawing di-rectzon of the rod in increments of approximately 10 pcl from 0 to 70 pct. The sections, taken transversely to the drawing direction, were mechanically and electro chemically polished. Contact angles between the sessile drop of distilled water, glycerin, and glycol and the specimen surface were measured optically. The differences in interfacial energy were calculated from the contact angle data. The effects of chemical washing and surface roughness of the specimen on the contact angle were also studied. The liquid contact angle was a linear function of the degree of cold working (D) ad changed markedly with differed liquids. THE plastic deformation of polycrystalline metals induces a preferred orientation in crystal structure. A preferred orientation changes the atomic density of a metal surface. This change in surface atomic density brings about the changes in surface interactions of the metals."' Also, the plastic deformation of metals raises the internal energy by increasing the stored energy.' Consequently, the total Helmholtz free energy of the metal increases and, in turn, the surface free energy of the metal. In order to study the effect of plastic deformation on solid surface phenomena, the liquid contact angle of a sessile drop made on cold compressed and elec-trochemically polished aluminum was measured. The preferred orientation in aluminum, due to uniaxial compression, is known to be [110] direction parallel to the compression axis. However, this description is only a first approximation of a rather complex orientation. In actuality, half the crystallites are more than 10 deg from this orientation, regardless of the amount of compression." For randomly oriented fcc crystals, the average surface atomic density can be calculated as follows: The number of atoms in a unit volume is 4/a3, where a is a lattice constant. Hence, the number of atoms per unit surface area is about (4/a3)2/3 = 2.52/a2 However, when the preferred orientation took place along [110] direction, the surface atomic density is as follows: The area of (110) plane of a unit cell, considering ridges and valleys, is BYOUNG WHlE LEE, Member AIME, is Research Metallurgist, Atomic Energy Research Institute of the Republic of Korea, Seoul, Korea. Manuscript submitted May 29, 1968. IMD 2 x J2- a x Ga = 6a2 Since this plane contains 4 atoms, the surface atomic density is 4i6a2 = 2.3/a2 Upon changing from random to preferred orientations, the surface atomic density decreases about 10 pct. The increase in the stored energy and the change in surface atomic density due to plastic deformation would certainly alter the surface tension of a metal. EXPERIMENT High purity aluminum rod of 6-mm diam (99.99 pct Al, obtained from Johnson, Matthey & Co., Ltd, London, England) was cut into sections approximately 1 cm long. The transverse cross section was mechanically polished. Then, the specimens were annealed in air at 600°C for 24 hr. Thus, eight annealed specimens were uniaxially compressed at room temperature from 0 to 70 pct of cold working with an increment of 10 pct. The extent of cold working was determined by the percentage of reduction in axial length to the original length. The specimens were further polished mechanically and, then, electrochemically with the Modern Battelle Type 1 electropolishing solution with a current density of 0.3 to 0.4 amp per sq cm and an electrode potential of 8 to 12 v at the solution temperature of 78" to 82°C for approxirr~ately 5 min. The Modern Whlte Diffusing Screen \t/ --------------- re Goniometer for Mercury Lamp ^-^ Sessile Drop ¦=• Condenser c=> Microscope l_*~_i bJ Mlcromster Filer with Protmcter Fig. 1—Schematic diagram of apparatus set-up for liquid contact angle measurement.

Jan 1, 1970

By E. W. Hough, B. B. Wood, M. J. Rzasa

An apparatus for the determination of fluid-fluid interfacial tension by the pendant drop method has been constructed. The apparatus is refined beyond those previously described in that the samples are introduced into an evacuated windowed cell without contacting air or mercury. Interfacial tension data are reported for the water-methane system between 74 and 280°F and 15 and 15,000 psi. The variation of wettability of the stainless-steel dropper tip with pressure and temperature was observed incidentally to the measurements. INTRODUCTION The most refined previous apparatus --for the determination of fluid-fluid interfacial tension at reservoir conditions was built by Hauser and Michaels.' These authors used the pendant drop method, previously investigated by Andreas, Hauser, and Tucker.' Recently, Fordham3 has made the pendant drop method an absolute one by numerical integration of the differential equation of drop shape. It is necessary to know the difference in density of the two fluids and the acceleration due to gravity in order to evaluate the interfacial tension from measurements of drop dimensions. Contact angle is not involved in the measurements by this method. Some precise tests of the method have been made at atmospheric pressure and 77°F by Douglas," who found agreement with established values to within about 0.1 per cent for water and air, cyclohexane and air, benzene and air, and benzene and water. No values of interfacial tension from the recent pendant drop apparatusJ have been published by Hauser and Michaels. However, values for the water-benzene and water-decane systems are given in Michaels' thesis5 or Dressures from 15 .to 10,000 psi and temperatures from 73 to 268ºF. Some determinations on gas-oil and gas-water systems in the range of 15 to 4,000 psi and 78 to 178°F have been made by Hozott,' by the drop-volume method. The capillary rise method has been used to investigate the interfacial tension in gas-oil systems at 88°F to several thousand psi by Swartz.7 Other determinations in gas-oil systems at pressures under 1,000 psia have been made by Jones: and Beecher and Parkhurst.9 The scarcity of data for pressures above 5.000 psi is apparent. APPARATUS An assembly drawing of the working section of the interfacial tenqion apparatus is given in Fig. 2. 'The endanant drop (A) is housed in a pressure chamber having glass windows (B). An agitator (6) is provided. The metal parts of the apparatus coming into contact with the sample are made of AISI: Type 316 steel. Drain grooves are provided around the whdows so that the sample in contact with the O-rings is not returned to the working section when the pressure is reduced. A schematic arrangement of the apparatus is given in Fig. 3. The working section containing the pendant drop (A) is filled by samples from bombs (B) with the aid of the vacuum system (C). The O-ring sealed pistons (D) used to separate the sample from the hydraulic fluid are shown together with the pressure production and measurement system (E). A front view of the apparatus is shown in Fig. 1. Most of the hydraulic system is at the top of the panel. The pump and displacement piston are at the lower right. The Variacs for the air bath heaters. the camera. and the vacuum gauge are a1so visible on the panel. The working section together with a window closure and a drop-forming tip closure are shown in Fig. 9. The carbon arc light source with filter is visible in the upper part of the picture. Two sides of the air bath with the impeller and a part of the convection shield can also be seen. The assembled air bath is shown in Fig. 10.

Jan 1, 1951

By George A. Moore, Donald P. Smith

In spite of many investigations of the occlusion of hydrogen in iron, the nature of the process and the reasons for the accompanying effects upon the metal are still open questions. This is in large part due to three causes: (1) the difficulty of obtaining iron of adequate purity as starting material; (2) the occurrence of allotropic transformations, which complicate the effects; and (3) the fact that the body-centered cubic modification does not lend itself readily to crystallographic investigation. The present paper attempts a critical review and correlation of the somewhat scattered and disconnected existing observations, and an experimental determination of the extent to which the conclusions that appear to follow from these are applicable to iron of really high purity, studied under well-defined conditions. Review Although only a comparatively few investigations have so far been made on the pure system iron-hydrogen, there is a much larger volume of literature which throws some light on the problem but falls short of a place in the systematic investigations, either because no attempt was made to measure equilibrium conditions or because the metal used was not iron or the gas not pure hydrogen. Such results have been variously dismissed in the past as of no importance, or as too complicated to try to explain; or they have been explained in terms of any of a dozen or more pictures, each of which is contradicted by data from other sources. The present importance of these data thus arises from their very mass and diversity, which present a picture of occlusion as a phenomenon whose variability cannot be ignored. We have attempted to organize the literature into groups comprising similar experiments or data leading to similar conclusions, thus of necessity sacrificing accuracy of historical order. Lattice Occlusion.—Throughout this discussion, the term "lattice occlusion" will be used to denote the formation of a simple solid solution of a gas in a metal lattice, usually of interstitial distribution. The word

Jan 1, 1939

By Lester W. Strock

METALLURGISTS handling lead and zinc ores have long been familiar with the spectrograph as a routine analytical tool, as its earliest regular use by American industry was in controlling impurities of zinc metal and its alloys. This application has been extended to other metal industries on an extensive scale, accompanied by refinements of procedure to such an extent that a large part of some metals produced, especially magnesium, aluminum and steel, are checked only by spectrographic methods for conformity to specifications. The spectrographic analysis of ores and other poorly conducting powdered solids presents difficulties not encountered with metallic samples, which can be arced or sparked as self-electrodes or can be readily dissolved, so that their solutions can be analyzed, as in the American Society for Testing Materials standard methods for zinc and zinc-base alloys. Spectra of powdered solid samples can be prepared by using carbon electrodes provided with a crater of suitable size, into which the sample is packed. Ore samples and many other powdered solid materials usually analyzed in the chemical and metallurgical laboratory are more complex and varied in composition than samples of metals produced in large tonnages. More preliminary work therefore is usually necessary in devising a spectrographic method for analyzing a given type of powdered sample than for analyzing metal samples, in order to use that method with confidence. The knowledge that the standard samples and unknowns produce equivalent line intensities at equal concentration is the fundamental basis of any quantitative spectrographic method. On the other hand, powdered samples have an advantage over metals in that any desired number of chemical compounds can be mixed dry in any desired ratio to produce a synthetic standard. Experience has shown, however, that spectra of elements in finely divided compounds introduced into a standard in preparing a synthetic ore sample do not always behave in the electric arc in a manner that produces spectral line intensities similar to those observed at the same concentration in a natural mineral. In ore samples minor elements frequently are contained in the crystal lattice of larger particles of an abundant ore mineral. Their dissociation and volatilization from the sample into the arc then proceeds differently in the standard and sample, with resultant differences in intensity. During the past 10 years I have devised and applied several quantitative spectrographic methods for determining various elements in rocks and minerals in connection with studies on their geochemistry,1 but the incentive has gradually changed since the summer of 1940 to the specific practical problem of searching for domestic sources of rare and strategic metals. The

Jan 1, 1945

By J. S. Aronofsky, A. S. Lee

Results and experimental procedures are presented covering a preliminary laboratory investigation of the compaction of reservoir rocks and its effect on porosity and permeability. "Egective" compressibility was measured by subjecting core material to an overburden load and reducing pore pressure. Preliminary results showed relatively high effective compressibilities which varied from 1.8 X 10-' pore volume/pore volume /lb / in.~ for limestones to 7.7 X 10-6 pore volume/pore volume/lb/in.' and even higher for sandstone reservoirs conmining large amounts of fine clay material. It appeared from the initiol results that the effective compressibility of the material could not be correlated directly with porosity and that other factors, such as the amount of clay material present might have to be taken into account. The work to date has indicated that effective compressibility factors will have to be measured for the particular reservoirs heing studied. Oil permeability of core materid was measured under various effective overburden loads from 0 to 8,000 psi. It has been found than reduction of permeability in clean sands was relatively small and the results agreed with published data. For sandstones containing large amounts of clay, preliminary tests indicated very large reductions in permeability with increasing effective overburden pressures. It is planned to continue laboratory work on this phase because of its importance in low-permeability reservoirs. INTRODUCTION During the past few years increasing interest has been shown in the differences obtained between conventional laboratory measurements on cores at atmospheric pressure and those when reservoir conditions are simulated. Since these data are used as the basis for calculations and the prediction of reservoir behavior, their evaluation under reservoir conditions is most important. The effect of the compressibility of the rock upon the reservoir behavior, as fluid pressure declines, is an important subject which has been insufficiently studied. The total pressure on any plane through a reservoir is the result of the grain-to-grain rock pressure due to the overburden and the pressure of the interstitial fluid on the plane. As reservoir fluid pressure declines, the net load on the rock phase must increase, and the result is the compaction of the rock structure which produces a decrease in pore volume. Simultaneously, the rock grains expand into the pore space as the fluid pressure declines. The result of these two effects is defined as the effective compressibility of the rock and is expressed in units of pore volume/original pore volume/psi. Work was started by Imperial in 1954 on the effects of pressure on the porosity of reservoir rock. These studies established effective compressibility factors for some limestones and dolomites. Since that time effective compressibilities have been obtained for other Canadian and some U. S. reservoir rocks. In conjunction with the study of porosity, an investigation has also been initiated to determine the effects of pressure on permeability. One outcrop and several reservoir sandstone cores have been tested to date. ROCK COMPRESSIBILITY Apparatus anD Procedure A diagram of the apparatus used in these studies is shown in Fig. 1. The equipment was constructed so that a uniform pressure, equivalent to the reservoir overburden, could be applied by the oil pump and transmitted on all sides of the core through the Lucite sheath. The sample was completely saturated by circulating brine through the mounted core. Pressure in

By Appendix by A. S. Goldoni, R. E. Tate, E. M. Cramer

The diffision coefficient for self-diffision of plutonium in the temperature range 350" to 440°C has been measured by using puZ3 as the tracer isotope. Autoradiopaphic techniques were used to inzlestigate the possibility of grain boundary diffusion, hut only evidence for volume diffusion was found. The least-squares fit of the data gives the .following equation for the diffision coefficient: The computer least-squares technique for fitting the nonlinear equations is outlined. DETERMINATION of the self-diffusion coefficient of the fcc 6 phase of plutonium is in principle a straightforward experimental task. However, the chemical reactivity, the intense @ activity, and the toxicity of plutonium put limitations on the experimental techniques. The technique selected included roll bonding for preparation of the diffusion couples and pulse-height analysis of the @-particle activity to determine the distribution of the PU tracer in the diffusion couples. EXPERIMENTAL PROCEDURE Couple Preparation. Cylinders about 0.5 in. in diam were cast from two special stocks of plutonium, one of which had been enriched in puZ3', as shown in the isotopic analyses listed in Table I. For each roll-bonded composite sheet, a cylinder 0.437 in. in diam and 0.190 in. thick was turned from each kind of plutonium on a lathe in a 98 pct He atmosphere. The two freshly machined cylinders were positioned face to face in a tube of commercially pure aluminum which had been sealed at one end by welding and the assembly was evacuated on a vacuum manifold overnight. The elapsed time between machining the faces of the plutonium cylinders and evacuating the loaded tube was about 15 min. After overnight evacuation of the assembly the indicated vacuum was 1 X 10"5 torr or better. The aluminum tube was then warmed and pinched off with a cold-welding tool. The pinched-off weld was also fusion-welded as an additional precaution against leakage of air into the evacuated assembly. The assembly was immediately heated for 30 min in a 250°C furnace and reduced in thickness by being passed through a rolling mill with rolls heated to 200°C. The rolling schedule (four passes of 100 mils each with a 10-min reheat after two passes) reduced the thickness of the assembly to 100 mils. The rolled assembly was allowed to cool normally in air. The rolled assembly was sheared at the edges and the aluminum peeled from the composite plutonium sheet. The elliptical sheet was about 0.060 in. thick and usually three 0.383-in.-diam disks could be punched from its central portion. The sheet was heated on a hot plate to the ductile low 0 range (140°C as measured by temperature-indicating pellets) before each disk was quickly punched. The quality of the bond in the disks was evaluated by metallographic examination of the scrap sheet adjoining the hole left by the punch. Only well-bonded specimens without oxide in the interface (as indicated by metallography) were considered satisfactory for further use. More than half of the specimens so examined contained sufficient oxide in the interface to be rejected. Diffusion Anneal. Each disk to be diffusion-annealed was wrapped in 1-mil-thick tantalum foil and sealed within a Pyrex capsule evacuated to 1 x 10~5 torr or better. This capsule was then sealed within another Pyrex capsule at a similar pressure. The diffusion anneals were carried out at temperatures between 350" and 440°C in Marshall furnaces adjusted to have a temperature gradient of not more than *1/2"C over a 5-in. length. This gradient was then further smoothed by using a nickel tube as a liner in the furnace. The liner was divided into three longitudinal cavities by a septum of nickel sheet to which two calibrated Chromel-Alumel thermocouples were attached. One thermocouple was used for controlling the furnace temperature by means of a Brown Pyrovane controller equipped with a Capaciline anticipation circuit; the second thermocouple was monitored twice daily with a Leeds and Northrup K-2 precision potentiometer.

Jan 1, 1964

By Wilfrid R. Foster

The industrial importance of the sillimanite group of minerals depends upon the beneficial properties exhibited by porcelains and refractories in which substantial amounts of these minerals are utilized as raw materials. The presence of "sillimanite" (now known to be the closely related mineral, mullite) in conventional porcelains and refractories has been known since before the turn of the century. As early as 1906 German investigators observed a direct correlation between the "sillimanite" content of a porcelain and its electrical and mechanical properties. Acting upon this discovery, U. S. Bureau of Standards investigators during World War I developed improved pyrometer tubes and spark plug porcelains, by increasing substantially the amount of "sillimanite" at the expense of quartz. The success of these experiments, first reported in 1918, at once aroused a lively interest in the location of natural sources of sillimanite and its related minerals. As a result of diligent search, the large andalusite deposits in California were discovered in 1919. Within the next several years large deposits of kyanite and sillimanite in India and kyanite in the United States had been reported. The search for these minerals in quantity, by both private and governmental agencies, has continued unabated during the ensuing forty years. A number of domestic deposits of kyanite have been worked during the past 30 years. Of these, only the Virginian and South Carolinian deposits are currently in substantial production. The only commercial andalusite production in the United States has been in California and Nevada. A dumortierite deposit in Nevada, known since 1917 but ignored for want of a commercial use, began production in 1925. A topaz occurrence in South Carolina has yielded a small production since about 1940. Domestic production of andalusite, dumortierite and topaz had virtually ceased by 1950. There has never been any commercial development of domestic sillimanite deposits. Kyanite has been mined almost continuously in India since about 1922. The remoteness of the large deposits of Indian sillimanite had caused it to be neglected until 1949. In that year sillimanite production began, and it has continued to the present. South African andalusite has been marketed from the 1930's until the present time. From 1944 to 1955 Kenya, British East Africa, was an important producer of kyanite. Commercial deposits of kyanite in Ontario, Canada should soon be in production. The first production of kyanite in Europe began in Austria in 1953. No commercial deposits of mullite are known anywhere in the world. It is of interest to note that synthetic mullite, which as "sillimanite" first elicited interest in the A12O3-rich aluminosilicate refractories, has enjoyed a marked increase in production in recent years. This is a result of the gradual depletion of known deposits of high-quality kyanite and related minerals."' Composition The sillimanite group includes kyanite, andalusite, and sillimanite, all having the same chemical composition (A12O3•SiO2) but different physical properties. Two other minerals, dumortierite and topaz, are also included in

Jan 1, 1960

By F. N. Rhines

DESPITE the large amount of study which has been devoted to the subject our present knowledge of the copper-oxygen system remains incomplete and unsatisfactory in many respects. This applies particu-larly to those regions in which solid metallic copper exists. The primary object of the present paper is the contribution of new information relative to the solid solubility of oxygen (or cuprous oxide) in copper at atmospheric pressure, together with certain observations in the low-pressure regions of the system. It seems appropriate also to present a brief summary of the outstanding previous work on the constitution of mixtures of copper with its lowest oxide in order to show the relation between the new facts and the system as a whole. The earliest recorded investigations of the copper-oxygen system are those of M. S. Lucas (1) § and of M. Chevillot(2) in 1819 and 1820. Lucas believed that liquid copper is capable of dissolving its oxide, but neither he nor Chevillot was able to furnish convincing proof of this property. It was not until 1866 that T. Graham° definitely established the existence of such a solubility. Nine years later W. Hampe(4) measured its extent and roughly outlined the copper-rich portion of the system. The first really precise examination of the constitutional relationship between copper and cuprous oxide, however, was that of E. Heyn(5) who in 1900 published a temperature-concentration diagram covering the range from 0 to 10 per cent of cuprous oxide at atmospheric pressure. Within these limits of composition cuprous oxide was found to dissolve in liquid copper, forming at 3.4 to 3.5 per cent a eutectic which melted at 1065° C. R. E. Slade and F. D. Farrow(6) extended these studies to mixtures of higher

Jan 1, 1934

By J. F. Butler

Boron nitride, BN, has been identified in boron low-carbon steels by means of light microscopy, electron microscopy and diffraction, and chemical analysis. This boron nitride is responsible for strain aging suppression in these steels through the removal of nitrogen from solution; however, small oxidizing potentials which result in deboronization In the austenitic temperature range also result in boron nitride decomposition and the subsequent occurrence of nitrogen strain aging. THE addition of boron to low-carbon steels is an effective means of eliminating the detrimental effects of strain aging;',' however, the mechanism by which boron suppresses strain aging has not been established. In studying the effect of heat treatment on the strain aging of boron low-carbon steels, Butler3 found that no detectable nitrogen was present in the ferrite solid solution after various heat treatments even though the total nitrogen analyses of the steels were 0.003 pct N. Apparently the function of boron in suppressing strain aging is the removal of nitrogen from solution to form a relatively stable second phase. A clue to the identity of this phase was found by Speight4 who extracted from an aluminum-killed boron steel an acid insoluble residue which contained boron and nitrogen in proportions corresponding to the compound, BN. Shyne and Morgan5 found that the addition of nitrogen to a hardenable boron steel lowered its hardenability in a manner which suggest-d the presence of nucleating particles (presumably BN) even at high austenitizing temperatures. Although this indirect evidence for the presence of boron nitride in boron steels has been found, the compound was not identified metallographically as a separate phase in these steels. Because boron has an affinity for oxygen comparable to that of silicon,5 boron steels must be thoroughly killed with aluminum in order to prevent the reaction of boron with oxygen.7 The affinity of boron for oxygen also is demonstrated through the ease of deboronization of a boron steel in an oxidizing atmosphere. Digges, Irish, and Carwile8 found that a mixture of wet natural gas and air caused both deboronixation and decarburization of a boron steel at 1900°F. The boron content rose at the surface of the steel due to the formation of boron oxide. Shyne and Morgan9 encountered deboronization at much lower oxygen potentials; loss of boron occurred in steels treated at 1750o F under argon purified to 0.0014 pct 0, even though decarburization did not occur. Boron oxide, B2O3, is much more stable than the nitride, BN, as is indicated by the standard free energies of formation at 980oC: -235 kcal per mol of B2O3 (liquid) and -28 kcal per mol of BN (crystal). It is evident that the oxygen potential must be kept low in the presence of BN in order to prevent its decomposition and the subsequent formation of B2O3' The purpose of the work described in this paper was to identify the nitride phase responsible for the removal of nitrogen from solution and to study its stability under oxidizing conditions. IDENTIFICATION OF BN In order to identify the phase containing boron and nitrogen, several alloys high in boron and nitrogen were made up in a small vacuum furnace. In alloys 3 and 4, Table I, electrolytic iron was used as a charge material. Boron additions were made in the form of 18 pct B ferro-boron after the iron was molten. In the case of alloy 3, the charge was solidified at this point; for alloy 4, nitrogen at 1 atm pressure was admitted over the melt before it was

Jan 1, 1962

By Willis T. Burns

I. Introduction.......................................... 703 II. History................................................ 703 III. General Description of Plant......................... 704 IV. AnoDes................................................. 711 V. Cathodes............................................... 714 VI. Electrolyte............................................ 718 VII. Electrolytic Slime..................................... 727 VIII. Power................................................. 728 IX. Operating Details..................................... 732 X. Furnace Refining...................................... 736 XI. Physical Testing oF Products.......................... 739 I. Introduction. These notes are submitted, not as a discussion of the modern practice of electrolytic-copper refining, but as the record of a refinery that was among the pioneers in the field and that is to-day, and has been for 17 years, operating under conditions not to be found in any similar plant in the country. I refer to the current density, which is at least 60 per cent. higher than that regularly employed elsewhere, and to the fact that the anodes treated are the direct product of the converter rather than of the reverberatory furnace. The writer has no knowledge of any other refinery treating anodes of this character. II. History. This refinery, now one of the oldest plants of its kind operating in this country, was built in 1892 by the Boston & Montana Consolidated Copper & Silver Mining CO. to refine the product of its Great Falls reduction works. The estimated capacity of the plant as designed was 65,000 lb. of cathodes per day at a current density of 16 amperes per square foot.

Jan 1, 1914

By N. C. Fick, R. L. Rickett

DESPITE the large volume of literature on alloys of iron and silicon,1 there is little published information dealing specifically with the constitution, at various temperatures, of the alloys containing less than 0.10 per cent carbon and from 0.5 to 4.5 per cent silicon that are used extensively in the electrical industry. Because such information was needed by those engaged in the production of these alloys in, sheet and strip form, the constitution was determined of a series of commercial silicon steels containing 0.05 to o.08 per cent carbon and 0.20 to 4.31 per cent silicon, over the temperature range 1300° to 2500°F. These alloys were all from regular production heats and of commercial quality. The results of, the tests are given in Fig. I and for comparison the constitution diagram of iron-silicon alloys with 0.01 to 0.02 per cent carbon, taken from the literature, is also presented. MATERIAL AND PROCEDURE All steels were hot-rolled to a thickness of 0.060 to 0.080 in. and used in this condition. Their chemical compositions, including over-all check analysis, and "center" analysis for carbon and silicon, are given in Table I. The so-called center analysis was determined on samples pickled to remove the outer surface and leave only the center third of the gauge thickness-the portion of the sample on which metallographic ratings were based. In most, but not all, of the alloys, slightly higher carbon was found at the center than when the whole strip was sampled; the two methods of sampling show relatively little difference in silicon. Two of the steels, A and E, contain relatively high phosphorus, while I and K are somewhat higher in manganese than the others. [ ] The procedure consisted essentially of heating specimens (about 1/16 by 3/8 by 3/4 in.), protected from oxidation or change in carbon content, at a temperature in the desired. range and for a selected period, after which they were quenched in iced brine; the degree of transformation that had then occurred was determined by metallographic examination. The soaking periods were selected after preliminary investigation had shown that a con-

Jan 1, 1946