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By R. F. Mehl, C. S. Barrett, A. H. Geisler

The complicated nature of the property changes that accompany age-hardening has made it necessary to reconsider and to elaborate the simple dispersion theory.l It has been apparent for some time that more direct information is needed concerning the atomic mechanism of precipitation from solid solution if the theory of age-hardening is to be developed past a purely qualitative stage.‡ Fortunately, in recent years information has been developed which allows us to trace in detail the lattice changes accompanying the process of precipitation from solid solution. This information relates chiefly to the sequence of the several stages of lattice alteration by which the matrix lattice is transformed to the equilibrium precipitate lattice, and permits reasonable inferences to he drawn concerning the states of internal strain that accompany these stages. This information is most complete for the solid solution of copper in aluminum. The equilibrium precipitate is the 0 phase, "CuAl2." This forms in plates, parallel to the {100} matrix planes. The atom pattern and atom spacing on the plane in 0 lying parallel to this plane are roughly similar to those opposite it in the matrix.3 The formation of 0, however, is preceded by the formation of a transition lattice 0': which again lies parallel to the matrix {100} plane, but in this case the matching of atom pattern and spacing across the matrix-precipitate interface is nearly periect; thus there is lattice coherency across the interface and the interface is a plane of separation in only a very limited sense.'8 Particles of 0' may be recognized microscopically and form a well-defined Wid-manstatten figure.* The 0' lattice is recognized by the occurrence of diffraction lines on powder photo-grams or of spots on Laue photograms which may be analyzed in the usual ways to determine the lattice type and the lattice spacings. Very recent research 6, 7, 1 has shown, however, that streaks occur on the Laue photogram at an earlier point in time during the aging process. These streaks have been attributed to a preferential clustering of copper atoms into small platelike elements of only a few atoms in thickness and a lew hundred atoms in diameter, probably of the composition of " CuA12," which may be designated as Guinier-Preston zones or aggregates.1 It is difficult if not impossible to determine the lattice type and lattice spacing in these aggregates. It is possible1 that these aggregates are in fact ?' in a high State of dispersion; the inclination to argue this is strong, as we shall see later. Never-

Jan 1, 1941

By David LeCount Evans

Not only E. B. Mayo but also W. C. Lacy, who apparently urged the preparation of this analysis, is to be commended. Regional thinking of this type is needed to assure future success in the never-ending search for new mineralized and petroliferous districts. As is usually the case, here is a regional study that will be read by the mining geologist alone. It is ironic that several of the trends established in this study have suggested themselves in northern mid-continent, detailed, and regional studies. These, where established, have offered new keys to petroleum exploration and have provided a possible basis for unraveling a number of broad generalities. The oil geologists, active in Colorado, Kansas, and Oklahoma, would find much food for thought in Mr. Mayo's projections.

Jan 6, 1959

By John G. Simmons

A tutorial account of the tunnel effect between metal electrodes separated by a thin insulating film is presented. Energy diagrams of metal-insulator -metal sandwiches are briefly discussed, and the isothermal and thermal J-V characteristics for symmetric and asymmetric tunnel junctions are derived from a generalized expression. Experimental data from tunnel junctions are presented, and it is shown how, correlation between theory and experiment permits a determination of some of the oxide properties. Finally, the barrier heights in AT-Al2O3-A1 junctions determined by various inr3estigators are discussed. The object of this paper is to give a tutorial account of the electric-tunnel effect between metal electrodes separated by a thin insulating film and to illustrate its utility in the study of metal-oxide interfaces. This paper will emphasize the theoretical aspects of the electric-tunnel effect: however, a brief account of the more recent experimental work will be presented. A more comprehensive experimental study of the tunnel effect will be presented in the following paper by Drs. Pollack and Morris, see p. 497. We will open with a discussion of the energy diagrams for metal-insulator-metal junctions and what we mean by the electric-tunnel effect. Following this is an account of the theoretical studies of Sommerfeld and Bethe, and Holm, and the recently reported calculations on symmetric and asymmetric junctions using the generalized formula. The theoretical presentation is concluded with calculations on the temperature dependence of the tunnel J-V characteristic. In the experimental section, it is shown how barrier heights and thicknesses are determined by comparing the experimental data with the theory. Finally, the results of various investigators on the determination of the barrier heights in Al-Al2O,-A1 systems are discussed. I) POTENTIAL BARRIERS BETWEEN CLOSELY SPACED ELECTRODES Since it is necessary to supply energy to a metal in order to observe electron emission from its surface, it is evident that the potential energy of an electron within a metal is lower than that of an electron at rest outside the metal. It follows, then, that the electron must undergo a change in potential as it crosses the metal-vacuum interface. In the Sommerfeld1 free-electron theory of metals it is assumed that the free electrons, the electrons responsible for the electrical characteristics of metals, move in a constant potential environment in the metal, and are contained within the metal by a potential barrier at the metal-vacuum interface. It will be evident that the idea of a constant potential environment is a very idealized model, since the potential energy of an electron is influenced by all of the atoms and the other electrons within the metal; however, its use is justified by the many excellent results it gives.2 Fig. l (a) is the energy diagram of the model envisaged by Sommerfeld; the metal is represented by a potential-energy well of depth V,; the vacuum level represents the energy of an electron at rest outside the metal. At 0°K the electrons, which exist in pairs in discrete energy levels, fill up the well to an energy ?, the Fermi level. The distance, Vo - ?, from the Fermi level to the vacuum level is known as the work function of the metal, and represents the minimum energy required to free electrons from the interior of the metal at 0°K.

Jan 1, 1965

By A. F. Crawley

The densities of some liquid Pb-Sb alloys up to 11 wt pct Sb and Pb-Sb-& alloys up to 10 pct Sb/10 pct Sh have been determined by a pycnometric technique over a temperature range of about 130°C above their melting points. The data given are accurate within 0.05 pct. Density is shown to vary linearly with temperature , and equations relating these quantities have been formulated. Molar volumes calculated from the density data indicate that volumetric deviations from ideal mixing are undetectable within the limits of experimental error. A continuing research program into some fundamental physical properties of liquid metals is being pursued at the Mines Branch, Department of Energy, Mines and Resources, Ottawa, Canada. This work has received support from the Canadian Zinc and Lead Research Committee in cooperation with the International Lead and Zinc Research Organization. This paper, which reports some density data for Pb-Sb and Pb-Sb-Sn alloys, follows previous work from this laboratory on lead, tin, and Pb-Sn alloys.' Of previous data from others, Greenaway2 and Sato and Munakata3 have reported results on Pb-Sb alloys. No previous work has been published on the ternary Pb-Sb-Sn alloys, reported here. EXPERIMENTAL METHOD Densities were measured by a pycnometric technique which has been described in detail and appraised for accuracy in earlier Mines Branch reports.475 Fig. 1 shows the densitometer with the pycnometer in position for a run. The pycnometer is also shown in some detail. The pycnometer of dense, high-purity graphite, about 14 cu cm in volume, was carefully machined to a uniform, smooth finish. The height was measured by a depth micrometer and the diameter by fitting precision gage blocks between steel balls.' In each case several readings were taken, and the final results were considered accurate within 0.01 pct. The resulting volumetric uncertainty together with small inaccuracies in the coefficients of linear expansion of graphite lead to a maximum systematic uncertainty in the method of ±0.03 pct. As shown in Fig. 1, the pycnometer lid is a threaded cap. Thus, the charge, a cylinder of the alloy, can easily be inserted and the solidified metal can readily be removed after a run. The dimensions of the cylindrical charge are chosen to ensure that, once molten, the metal will not only fill the pycnometer completely but will discharge an excess into the excess-metal float chamber. AS the temperature is increased above the melting point, the volume of metal in the excess chamber increases until the system has equilibrated at the desired temperature. At this point, the excess chamber is moved to one side by twisting the shaft F, leaving a fixed volume of liquid metal in the pycnometer. This volume of fluid is readily calculated using measured coefficients of linear expansion of the graphite which expands anisotropically. The associated weight of fluid is determined as the weight of the solidified metal removed after the furnace has cooled down. Alloys were prepared from 99.997 pct Pb, 99.999 pct Sn, and 99.999 pct Sb, being melted by an electric furnace in a graphite crucible and poured into graphite molds. Several density specimens of the same nominal size were machined from each ingot, and, by comparing specimen weights, relative differences in specimen composition resulting from segregation in the ingots could be detected. In this way, segregation was found to have occurred in Pb-Sb alloys at compositions beyond the eutectic (11.2 pct Sb) and this

Jan 1, 1969

By R. A. Burton, J. T. Hansford, D. A. T. Donohue

Substantial evidence indicates that many petroleum producing horizons contain naturally occurring, ordered fracture systems and that within a particular geologic zone, vertical fractures induced in wellbores often will be directed along a particular compass direction. Both conditions will seriously alter the fluid displacement behavior within reservoirs. In this study the effect of induced fracture orientation and length on sweep efficiency is determined for a five-spot pattern. In general, it is assumed that all wells are fractured and directed along the same compass direction. Using the electrical analog to steady state, two-dimensional fluid flow in porous media, boundary conditions are obtained from which flood fronts are tracked numerically. The numerical computations require a particle tracking routine for approximating flood front histories. It is shown that recovery is sensitive to the length and orientation of fractures for the pattern studied. with the proper design of fracture-pattern systems, recovery can be enhanced considerably. INTRODUCTION Hydraulic fracturing introduced in 1949l gave the industry a rather inexpensive means of increasing the fluid injection or production capacity of wells. It has been used with particular success to increase the production rate of wells completed in tight formations, such as in western pennsylvania2 where producers have fractured in depleted or near-depleted fields and observed economic responses. Once the natural energy declines in such a reservoir where all wells have been fractured, waterflooding is generally suggested as means of further increasing recovery. Of the dual objective sought in waterflooding — high injectivity and high breakthrough sweep efficiency — the former condition can be obtained if all wells in the flood pattern are fractured; the latter condition should depend on the nature of the fracture system. Considerable theoretical work has been published on the nature of fractures induced in boreholes.3-5 Although discussion persists concerning the possibility of forming a horizontal fracture at a given point within the wellbore, it is generally conceded that only vertical fractures will develop below a given depth, i.e., where the fracturing Pressure is less than the overburden load. Given the fact that fractures will be vertical in most cases of interest, it is also important to know whether there is order to fracture orientations within a given geological region. Kehle has suggested that in tectonically relaxed areas of uncomplicated geology, the stresses are fairly uniform and all fractures in the region should be parallel.5 Dunlap arrived at a similar conclusion in a theoretical investigation of localized stress conditions surrounding the borehole.6 He concluded that most vertical fractures are propagated in a preferred azimuthal direction. Fraser and Pettitt, in extending these theoretical suggestions to a specific field case, used an impression packer to record both a vertical fracture and the orientation of this fracture in the wellbore of a well in the Howard Glasscock field, Tex.7 Use of this information enhanced the waterflood recovery of the field. Anderson and Stahl also used impression packers on three fractured wells in the Allegheny field. N. Y.. and found that the fractures were oriented more or less along the same compass direction.8 Orientation of the fractures in this manner depends on the stress condition within the formation during fracturing. Elkins and Skov have demonstrated that a natural, oriented, vertical fracture system exists within the Spraberry field? Heck suggests

Jan 1, 1969

By C. S. Samis, J. C. Mitchell

Sodion activity data have been obtained for the Na-A1 system for sodium concentrations in aluminum between NN, = 25 . 10-and 300 x 10'. This concentration intert-a2 encompasses those sodium concentrations nor1)zally encountered in aluminum reduction cell operation. The sodium activity data were measured by a two-phase equilibration of sodium between a lead and an aluminam rich phase. The Na-Pb system was emplojed as a reference for the determination of the actiz7itj 0.f sodium. The activity of sodiin in aluminuwz exhibits large positi2.e deviations frorn ideality and a strong dependence, on concentration below NN, = 100 x 1K6. The inteated data indicate that the activity of aluminium is equal to its mole fraction over the range of miscibility of the Na-A1 sgstem. The data on the Na-A1 binary have been combined with experimental data on the cryolite-A1 system at 1025°C to obtain the activities of Na F and AlF, in liquid cryolite oz2er the cornposition 1-ange encountered in aluminum cell operation. The results are in agreement with activities calculated from the NaF-AlF, phase diagram. ALUMINUM is produced commercially by the electrolytic reduction of aluminum oxide dissolved in molten cryolite. There is considerable controversy over the actual mechanism of the discharge processes, but sodium potentials in the systems appear to play an important role in the reduction mechanism. The metal-salt reaction involving NaF and aluminum to produce A1F3 and sodium is responsible for the presence of sodium in the aluminum metal phase. Additional sodium may be produced from the simultaneous deposition of sodium and aluminum at the cathode as a result of a cathodic overvoltage. runert' has suggested that sodium gas at atmospheric pressure would be the result of reaction between cryolite and aluminum at 1000°C. Subsequent investigations have shown that production of sodium at atmospheric pressure does not occur. These later investigations can be conveniently separated into two categories. The first involves sodium, aluminum, and cryolite, in which the sodium activity was measured. The second includes a lead phase for sodium activity measurement. Jander and errmann,' studied the reaction: at 1090°C in alumina crucibles under an atmosphere of dry, oxygen-free nitrogen. The equilibrium constant for the reaction was expressed in terms of concentration. Their results in Fig. 1 show an increase in sodium content of the aluminum with increasing NaF/A1F3 weight ratio. Pearson and waddington3 performed similar experiments at 1000°C. Their results are included in Fig. 1. Dewing and ollinshead have measured the sodium content of aluminum as a function of the NF/AF, ratio at 1025"C, Fig. 1, and ewin' measured the sodium content of the aluminum in a system involving the solid reactants NaF, cryolite, and liquid aluminum. This reaction is different from those discussed above. Two solid phases, NaF and Na3A1F6, and a liquid aluminum phase were present. The sodium concentration in the aluminum was determined by the temperature. Dewing's measurements covered the temperature range 679" to 896°C. Omo, Matsushima, and 1t02" investigated the equilibrium 6NaF ential thermal analysis. Stokes and Frank6 determined sodium activities by

Jan 1, 1970

By J. E. Lawver, J. L. Wright, H. R. Kokat

Mesabi semitaconite and oxidized taconite ores that cannot be concentrated by froth flotation can be rendered amenable to flotation through partial concentration in a high-in tensity wet magnetic separator. Since 1964, a method for accomplishing this precon-centration has been under development at the Minnesota Mines Experiment Station, where several hundred tons of ore have been successfully processed. This paper is an analysis of the performance of the separators used at the Station. At present the United States is producing about 85 million tons of iron ore a year, and nearly 55 million tons of this comes from Minnesota. Nearly half of Minnesota's production is in the form of magnetite taconite pellets —the remainder being wash ore and gravity concentrates. As the demands of the blast furnace operators become more stringent - and they are becoming more so yearly — these demands are met by improved iron ore beneficiation technology. Furthermore, there is no doubt that as magnetite taconite, gravity ores, and wash ores are exhausted, new processes will be developed to produce a product comparable to magnetite taconite pellets from Minnesota's vast reserves of oxidized taconite and semitaconite. The magnetite taconite ores are rather easily bene-ficiated by conventional, low-intensity (500- to 1400-gauss) magnetic separators, followed, in some plants, by froth flotation of the magnetic concentrates.

Jan 1, 1969

By John T. Norton

In spite of the very general errlployment of nitride hardening, there is still considerable doubt as to the real nature of the mechanism involved. Experience has shown that the addition of small amounts of hardening elements to iron or steel results in a wide variety of desirable properties in a nitrided case. Perhaps the foremost of these elements is aluminum and in this investigation an attempt has been made to study the behavior of aluminum during the hardening process. It is believed that the establishment of a complete atomic picture of the metal at various stages of the process will indicate the relationships between the several kinds of atoms and their individual influences on the physical properties in a clear and direct fashion. A consideration of the problem suggests a surprising similarity between the mechanisms of nitride hardening and of age-hardening. It is now generally understood that age-hardening may take place by one of two distinct processes, the first involving the precipitation of a finely dispersed phase and the other being concerned with the modification of an existing phase. Following much the same line of reasoning, two theories of nitride hardening have been suggested. The first explanation, which has been generally discussed, particularly by Fry,' states in brief that the presence of aluminum causes the precipitation of aluminum nitride during nitriding and that this finely dispersed phase is the primary cause of hardening. The second explanation, which has not been published but which has been freely discussed by those interested in the problem, postulates the substitution of aluminum atoms for certain of the iron atoms in the several iron-nitrogen phases in the same manner that the substitutional iron-alurninurn solid solution is formed. The marked increase in hardness, as compared with the aluminum-free system, is attributed to the severe lattice distortion accompanying this replacement.

Jan 1, 1934

By Fred P. Dewey

Early last March Mr. Jerome Coldren, an old miner add prospector, undertook a prospecting tour through the western part of Kansas, and discovered a very peculiar bed of rock, which yielded a white metal on fusion with soda. Mr. W. D. Church, city chemist at Topeka, examined the metal and found it to contain nickel. This discovery created much excitement, and was at first doubted. Many samples of the material, from a range of twenty miles, were sent to the Smithsonian Institution for examination ; and in every instance a qualitative test showed the presence of nickel, although the amount appeared to vary greatly. The ore is quite different from any other nickel-ore. It consists of a quartzose conglomerate from bean-size down, with much decomposed material between the pebbles, and the whole cemented by a more or less manganiferous limonite. In the qualitative tests, the nickel appeared to vary with the manganese. In all the tests, simple treatment with HCI dissolved a great deal of AI2O3. The principal deposit is near the top of a small hill on the divide between Smoky Hill river and Butte creek. The surface-rock is the conglomerate, and, at varying distances, stains of the limonite appear and gradually increase ; so that the ore is simply the lower portion of a bed of conglomerate which has been heavily charged with the manganiferous limonite. Below the conglomerate is a layer of selenite; below this, a soft sandstone, containing well-preserved fossils, and below the sandstone, a shale. From 2 to 6 per cent. of nickel in selected samples has been reported by different chemists; but the following two analyses on large samples show the average composition of the material:

Jan 1, 1889

By P. S. Rudman

The solubility limit and the diffusivity of carbon in molybdenum have been obtained by duffising carbon into molybdenum rods from a Mo + Mo2C powder mixture. The solubility limit was taken as the long-time asymptotic limit of the rod composition. The diffusiv-ity was obtained from fractionally saturated rods from the rate of change of the average composition. Compositions were determined by chemical analysis. The solubility limit obtained is: WhILE the Mo-C system is important in refractory alloy technology neither the solubility limit nor the diffusivity of carbon in molybdenum is unambiguously known. In Fig. 1 the Mo-C phase diagram is presented. The heavy lines, the terminal solution solubility limit, and the eutectic temperature are results of the present investigation and will be discussed in detail later. However, it is readily seen that the previously published solubility limit determinations, Few and Manning1 and Fromm and ROy2 differ by up to an order of magnitude. The general form of Fig. 1, the Mo2C field, and a eu- tectic temperature -2200°C are due to an early Investigation by Sykes et a1.3 Although they did not determine the solubility limit, they did establish that the maximum at the eutectic temperature was about 1000 ppm. The only other prior data found on the solubility limit is from a lattice-parameter study by Speiser et a1 .,4 from which it can be concluded that the maximum solubility is greater than 1800 ppm. There does not appear to be any data oh the diffusivity of carbon in molybdenum. However, Samsonov and Epik5 have determined, from the rate of growth of an MozC layer, the diffusivity of carbon in Mo2C, and this has been erroneously interpreted, for example by ~c~eil,' as applicable to diffusion of carbon in molybdenum.

Jan 1, 1968

By William M. Bowron

Thirty years ago, when I stood on the cliff of red fossil iron-ore, on Red mountain, Jefferson county, Ala., I asked what were the geological relations of this remarkable deposit. In reply I was told that it was a limestone, colored and saturated by some unknown but wholly external influences, and that at a reasonable distance from the surface the color would disappear. I could find no satisfactory explanation, either of the nature of this wonderful external permeating influence, or of the cause of such a ferrous impregnation selecting this one particular bed of limestone, to the exclusion of the higher and lower beds of the same material which are not even stained. I. The Present Theory. Referring to this subject, Dana says :' "The clays, clayey sandstones and limestones of the Clinton epoch, through New York and the Appalachians, show that the mud-flats and sand-banks, and hence the shallow seas of the coast region, still continued.... The beds of argillaceous iron-ore, which spread so widely through New York and some of the other States, west and south, could not have been formed in an open sea; for clayey iron-deposits do not accumulate under such circumstances. They are proof of extensive marshes, and, therefore, of land near the sea-level. The fragments of crinoids and shells found in these beds are evidence that they were, in part at least, salt-water marshes, and that the tides sometimes reached them." At first, this explanation seemed satisfactory, but the more I studied the ore the less satisfying the explanation became. 1. In the ore itself, I found associated with the small particles of rounded matter (now consisting of iron oxide in which organic structure, if ever present, has become lost, though the

Jan 1, 1906

By R. F. W. Pease, R. A. Ploc

A scanning electron microscope with a resolving power better then 100Å has been developed for the direct examination of surfaces. This instrument was used to study iron undergoing oxidation at 500°C. It was found that the electron current in the scanning electron microscope was low enough (about 10-atrzp) to have no observable effect on the growth of the oxide. "Armco " iron, when oxidized, exhibited an oxide film whose thickness and whiskey population varied with pain orientation; but purer iron, when oxidized, exhibited no such pain dependence and whisker occurrence appeared to be caused by impurities. UNTIL recently most surfaces of opaque specimens could either be studied with a light microscope or, if higher resolution was required, by viewing a replica of the surface in a transmission electron microscope. Direct electron microscopy of a surface has, in general, proved difficult owing to excessive foreshortening and the poor image quality obtained. The scanning electron microscope, however, offers an alternative method of directly viewing a surface without these disadvantages. At low magnification it offers a much larger depth of focus than the light microscope, and at high magnifications it offers much higher resolution (about 100Å). PRINCIPLE OF THE SCANNING ELECTRON MICROSCOPE A schematic diagram is shown in Fig. 1. The electron optical system consists of a gun followed by a series of lenses which focus the electron beam onto the surface of the specimen. The beam is scanned in a rectangular raster across the specimen surface and, by amplifying the secondary electron current from the 'pecimen, a picture of the specimen surface is built UP sequentially on the face of the display cathode-ray tube. The magnification of such a system is given by the ratio of the scan amplitude on the display cathode-ray tube to

Jan 1, 1965

By HOWARD I. YOUNG

F. W. SPERR, Houghton, Mich.-Why does 10 to 20 per cent. of the ore formation have to he lost? It is not clear to me why it should not all be taken out, from the conditions as I saw them underground this afternoon. H. I. YOUNG.-The grade of our ore is so low that we cannot stand the expense of timbering to support the roof, which, in a sheet-ground mine, would be from 25 to 50 per cent. of our total mining cost at present. After the orebody is mined out, we can often recover 10 to 20 per cent. of the material that is left. F. W. SPERR.-I think it should be a very simple mining engineering problem to mine all of that mineral without the use of a stick of timber. Similar work has been done in the mines of Grand Rapids Plaster Co. The usual operation in deposits of this kind is to open up and excavate as far as the roof will stand; when it caves, start in and dig somewhere else. But in the case I referred to they learned that by working the ground more systematically and leaving in a sufficient amount of pillar, they could later draw those pillars and get them all, and avoid uncon¬trolled breakages which would be likely to occur if they tried to hold up the overburden permanently. From the point of view of safety and also from the financial point of view, I contend that it is better to keep the caving under control and make it do what you want it to do, rather than to take out what you can conveniently for the time being and after a while be compelled to let the overburden do what it pleases.

Jan 1, 1918

By Lo-Ching Chang, J. Chipman

C. B. POST*—Just what are you showing that has not been shown by fixing the attention on molecular species and choosing the molecular species to give you a perfect solution? J. CHIPMAN (authors' reply)—In general a fairly satisfactory thermody-uamic treatment of slag-metal equilibria can be worked out on the basis of assumed molecular species in the slag. This has been the method used by Shenck and more recently by White. Winkler and I also used it in studying dephosphoriza-tion. Darken and Gurry found that it did not fit satisfactorily in the case of their data on iron oxides. The ionic formulas used here conform to the data much better and probably correspond somewhat more closely with the actual structure of the slags. C. B. POST—It does seem to be similar to you? J. CHIPMAN—It is alternative, and may lead to a more complete understanding. C. B. POST—Have you had a chance to talk to glass technologists on this? Have they been using this type of set-up for glass solutions? J. CHIPMAN—Yes, and the ionic formulas have given them a little better understanding of what liquid glass is like. C. B. POST—Nelson Taylor always said we were going- about slag reactions from the wrong viewpoint when using molecular species. Evidently the glass technologists use ionic species exclusively when dealing with liquid glass reactions. J. CHIPMAN—I agree that it seems more rational and more accurate to use ionic rather than molecular formulas. We should be cautious, however, and not suppose that we really understand the structure of a slag just because we are able to fit its reactions by ionic equations.

Jan 1, 1950

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

Notched and unnotched tensile specimens of wrought and recrystallized, oxygmted and hydro-genated tantalum and columbium were tested over a range of temperatures selected to encompass the ductile-to-brittle transition. Increasing the oxygen content of tantalum and columbium increased their strength, and raised their ductility transition temperature, but did not cause a marked deterioration of notch properties below that of commercially pure material. The adverse effects of oxygen were more pronounced for recrystallized structures than for wrought material. The effects of hydrogen are complicated by strain aging or slow strain rate hydrogen embrittlement at -105°F. However, in general, hydrogen had only a minor effect an strength, but markedly increased the effective transition tem-terature and caused a deterioration of notch properties . BCC metals including the refractory metals in Groups Va and VIa (V, Cb, Ta and Cr, Mo, W) can be expected to undergo a ductile-to-brittle transition and exhibit brittle fractures at low temperatures.' Notch embrittlement is associated with this phenomenon, and can be a serious design problem. Table I compares the tensile transition behavior and notch sensitivity of commercially pure Group Va and VIa refractory metals. The Group VIa refractory metals have considerably higher transition temperatures, and become notch sensitive at higher temperatures, than do the Group Va refractory metals. In addition, the Group VIa refractory metals are sensitive to metallurgical structure. Recrystallized structures generally have higher transition temperatures than wrought material of the same composition. The relatively poor transition behavior of the recrystallized structures of these metals is generally attributed to the segregation of interstitial impurity atoms at grain boundaries. Pronounced sensitivity to structure is not evident with commercially pure Group Va refractory metals, however. Since these metals have higher solubilities for interstitial elements than do the Group VIa metals ,4 it can be expected that higher total interstitial concentrations are necessary to develop a comparable degree of grain boundary segregation and to produce a similar sensitivity of transition temperature to structure. Increasing only the concentration of interstitial atoms in solution would tend to increase the flow stress of a metal in relation to its cleavage fracture stress and thereby raise its transition temperature, but would not be expected to cause a marked sensitivity of transition temperature to structure. A research program has been conducted at the Battelle Memorial Institute to evaluate the effects of interstitial oxygen and hydrogen on the transition behavior and notch sensitivity of tantalum and columbium, and to evaluate the effects of structure on "contaminated" material. EXPERIMENTAL PROCEDURES Notched and unnotched tensile specimens of oxygenated and hydrogenated tantalum and columbium with both wrought and recrystallized structures were tested over a range of temperatures selected to encompass the ductile-to-brittle transition Oxygen levels selected for study in both tantalum and columbium were nominally 500 and 1000 ppm, whereas nominal hydrogen contents were 150 and 500 ppm in tantalum and 150 and 300 ppm in columbium. Oxygen and hydrogen additions were made directly to 6-in. lengths of 1/2-in.-diam electron beam melted wrought bar stock, in a Sieverts Apparatus. Subsequent high-temperature annealing was required for homogenization of the oxygenated material, but was not necessary in the case of hydrogenated stock. The oxygenated and hydrogenated bars were then swaged to 1/4-in.-diam rods. Tensile specimen blanks were cut from the 1/4-in.-diam rods and annealed to achieve stress-re-

Jan 1, 1963

By G. A. Alers, J. H. Bechtold, R. W. Armstrong

The plastic flow of .molybdenum was studied in compression at temperatures below the ductile-to-brittle transition in tension. It was found that molybdenum is ductile in compression at all temperatures down to —196°C. The yield strength continues to increase with decreased test temperature below the tensile ductile-to-brittle transition temperature range. Difficulty was encountered in correlating the experimental data obtained with existing theories of plastic flow. THE body-centered-cubic metals as a group show a rapid and very large increase in yield strength with decreasing test temperature.' It is of fundamental importance to the understanding of the mechanism of plastic flow that this general characteristic be examined carefully. Unfortunately, brittle fracture in low-temperature tensile tests prohibits the measurement of flow properties at very low temperatures. By using compression tests, fracture can be suppressed and the plastic flow of the bcc metals can be studied far below their tensile ductile-to-brittle transition temperatures. Molybdenum was chosen for this experiment and plastic-flow data were obtained down to —196°C.

Jan 1, 1959

By D. R. Wieland, A. N. Barron, A. R. Hendrickson

A definite relationship has been found between the reactivity of flowing hydrochloric acid and its shear rate in a carbonate fracture. Both flow velocity and fracture width affect the acid reaction rate. Laboratory studies were conducted on acid reactivity at different flow velocities through horizontal-linear fractures, using 15 per cent hydrochloric acid at 80' F and approximately 1,100 psi. Fracture width varied from 0.02 to 0.20 in. These data provide a new basis from which the spending time and penetration of the acid can be estimated. Equations were derived expressing the relationship between injection rate, fracture width, acid concentration, time and fracture height, for linear and radial fracture systems. Because the penetration of the acid before spending is closely related to the extent of productivity increase resulting from an acidizing treatment, these data provide a valuable insight into some of the controlling factors that must be taken into consideration during treatment preplanning. INTRODUCTION Acidizing of carbonate reservoirs to improve production characteristics has been widely practiced since 1932. Originally, it was assumed that the acid uniformly penetrated natural formation pores and flow channels, enlarging them and thereby increasing their flow capacity. Little consideration was given to the reaction rate of the acid, or how far it would penetrate away from the wellbore into the formation, before spending. It has been shown recently' that, unless fractures are present in the rock, very little penetration is attained before spending, and the benefits of the acidizing treatment are largely confined to the immediate vicinity of the well-bore. Therefore, acid treatments may be classified into two categories: (1) matrix acidizing, in which the acid flows through multiple: formation pores; and (2) fracture acidizing, in which the bulk of the acid travels through fractures in the rock, whether natural or induced. When acidizing treatments are conducted at pressures of sufficient magnitude to open and extend such fractures, it is often desirable to inject a propping agent to hold the fracture open after the treating pressure has been released, thus providing a highly conductive flow channel through the rock. In some cases where acid attack produces surface irregularities, the resulting flow passages can be sufficient to provide high conductivity without use of a propping agent. During injection, the acid dissolves the carbonate rock with which it comes in contact until it is spent. Deeper penetration of the spent acid into the formation produces no appreciable benefit (if no propping agent is used) because the unetched fracture faces will rejoin when treating pressures are released and the fracture will "heal", with negligible resultant conductivity. The spending time of the acid thus becomes important in determining how far from the wellbore the improved-conductivity zone extends. The spending time of acid after injection into carbonate rock depends on the rate at which the acid reacts with the rock. This in turn is controlled by a number of factors, as previously reported. 2-4 These include temperature, pressure, acid concentration, rock composition, injection rate and the area-volume relationship between the acid solution volume and the surface area of the formation flow channels through which it penetrates. Thus, in matrix acidizing, where an extremely large area is exposed to the acid, spending is rapid. In contrast, spending time is prolonged in open fractures, where the area-volume ratio is much lower. Thus, greatest penetration of the acid before spending will be achieved in acid-fracturing treatments where fractures are held open by hydraulic pressure. Perkins and Kern5 have presented equations for fracture-width determinations which, for hard formations such as limestone or dolomite, indicate that high injection rates and viscous fluids are required to create wide fractures. Increasing the injection rate will, in itself, produce faster reaction rates. Because this type of reaction can be considered to be first-order diffusion-controlled, '-' the rate of movement of fluid past the rock surface affects the thickness of the diffusion layer, in turn affecting the reaction rate. Staudt, et al,10 report the results of tests in which a rotating marble cylinder was immersed in acid, and the weight loss at different speeds determined. Such test conditions, however, are not truly indicative of the situation in a formation during an acid-fracturing treatment. This paper reports reaction-rate data obtained under

By G. E. Karantzavelos

A novel two-stage froth flotation process for the recovery of pure magnesite from low grade ores is described. The process consists of a first-stage, magnesite flotation step where a rougher magnesite concentrate is floated with amine collectors. The first-stage froth concentrate is then repulped in fresh water, and quartenary ammonium salt and fuel oil are added to float the remaining impurities. The results from laboratory batch tests show that a high-grade magnesite concentrate assaying 0.99-0.20% Si02 and 2.84-0.46%a Ca0 can be produced. Regulation of the variables controlling magnesite froth flotation also allows the variation of the ratio % Ca0: % SiO2, between the acceptable limits 0.32 to 5.79. This ratio is important to the quality of dead-burned magnesite.

Jan 1, 1985

Sykes, W. P.-Effect of Temperature, Deformation, Grain Size, and Rate of Loading on Mechanical Properties of Metals. Discussed by Zay Jeffries, W. H. Bassett, F. E. Carter 3 Evans, Geo. Watkin.-Alaskan Coal Fields. Discussed by P. N. Moore, H. H. Stoek, G. S. Rice, H. Emerson 4 Eavenson, Howard N.-Run-off and Mine Drainage. Discussed by J. R. Campbell, Andrew B. Crichton, J. B. Warriner, R. V. Norris, H. G. Moulton, H. B. Wright 7 Andrews, Allen, and Garcia, John A.-Skip Hoisting for Coal Mines. Discussed by R. V. Norris, Geo. S. Rice, H. N. Eavenson, E. A. Holbrook, Robert Obert, Andrews Allen, T. M. Chance 12 Rice, Geo. S.-Coal-pillar Drawing Methods in Europe. Discussed by Carl Scholz, D. Harrington; H. 1. Smith 16 Knapp, Arthur.-Modified Oil .well Depletion Curves. Discussed by Roswell H. Johnson 21 Alvey, Glenn H., and Alden W. Foster.-Barrel-day Values. Discussed by Roswell H. Johnson 22 Matteson, W. G.-Secondary Intrusive Origin of Gulf Coastal Plain Salt Domes. Discussed by Eugene Coste, E. W. Shaw, Joseph E. Pogue, F. G. Clapp, E. DeGoIyer, W. G. Matteson, H. W. Hixon, R. Van A. Mills 23 Reger, David B,-Carbon Ratio of Coals in West Virginia Oil Fields. Discussed by J. T. Singewald, Jr 33

Jan 5, 1921

By G. Kimmel, A. Bar-Or

The rate of nucleation and the rates of both lateral and longitudinal growth of martensite plates (needles) in b—a transformation were determined as a function of temperature, in various U-Cr alloys. The activation energies for nucleation and both modes of growth were calculated from the experimental results. The identical values for lateral and longitudinal growth clearly indicate that both are controlled by the WHITE,' Mott and Hines and Holdeen3 showed that characteristic martensite plates (needles) appear in U-Cr alloys during the transformation 8 —0 in the lower temperature range (up to -300°C). Holden pointed out that the rate of growth of the individual martensite plates under isothermal conditions is same mechanism. Lomer's suggestion that single-atom movement over subatomic distances controls the specially slow growth of martensite receives further support from the present kinetic study, which shows that the growth rate can be described quantitatively by known formulas for the growth rate in processes involving single-atom movement. very slow, and suggested that this is due to the slowness of the relief of the stresses engendered during the growth of the individual plates. lomer4 attributed the slow growth to the complexity of the atomic adjustment at the growing interface b/(u. In the present work the rates of nucleation and growth of martensite plates in U-Cr alloys were studied by direct observation, in order to elucidate the mechanism which controls their characteristic slow growth.

Jan 1, 1968