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By Marsh S. Watson, Robert A. Howard

The effect of depth of formation penetration by casing perforations has been studied by means of an electrolytic model. It is found that the relative productivity of perforated casing is profoundly affected by the depth to which the formation is penetrated. The first in. of penetration i: of especial importance. A scaling equation which was shown to agree with experimental results at zero penetration is used to calculate the relative productivity of a waled down casing with scaled down perforations. INTRODUCTION In an earlier piper' the authors showed that the point sink representation of casing perforations is inade- quate. It was Pointed out at that time that while the electrolytic model results were a marked improvement over point-sink calculations, they still left a great deal to be desired in that the electrolytic model represented a case not realizable in practice, namely, a clean hole through the casing but undisturbed formation on the other side of the casing. Obviously, to be effective, the perforation must penetrate a finite distance into the producing formation. It was the purpose of the present investigation to find how the relative productivity of perforated casing varies with depth of penetration. The term "depth of penetration" as used in this paper refers to the distance which the perforation penetrates the producing formation. The amount of casing and cement penetrated is not taken into account, a fact which is discussed more fully later. The "casing radius," therefore, is to be interpreted as the radius of the boundary between cement and formation wall. in cases where the casing is not in contact with the formation wall. APPARATUS The electrolytic model experimental setup was identical with that described in the previous paper' except that the platinum electrodes were now allowed to project from the lucite cylinder by varying amounts. When fewer than eight electrodes were used, the unused ones were covered with a coat of insulating material to minimize disturbances to the current flow-lines. Comparison runs made with the unused electrodes uninsulated, however, showed that the values of Q/Q0 so obtained did not vary by more than the experimental error from the values obtained with the unused electrodes insulated RESULTS The variation of relative productivity* with perforation density is shown for various penetration depths from 0 to 4.03 in. in Fig. 1. It will be seen that even one in. of penetration into the formation results in a huge increase in the relative productivity. Moreover, as-the depth of penetration increases, it becomes less and less advantageous to use large perforation densities, 80 pel. cent of open hole productivity being obtained with only three 0.5-in. diameter holes per foot when the penetration is 4.03 in.

Jan 1, 1950

By Jr. W. L . Phillips

The deformation and fracture characteristics of lithium-fluoride single crystals stressed in compression at room temperature have been studied. In as-cleaved specimens the stress-strain curves were variable; two types of {110} fractures were observed in the vicinity of kink bands. The stress-strain curves of annealed crystals were reproducible; {100} cracks formed which propagated along the (100) and (110) planes. The deformation and fracture characteristics were affected by quenching and X-ray irradiation. STUDY of the mechanical behavior of nonmetallic materials has received considerable impetus in recent years because of the need to overcome the problem of brittleness before the refractory properties of nonmetallics can be fully exploited. Ionic crystals provide a convenient and simplified starting point from which to study the deformation and fracture processes in nonmetallic materials. Early investigations of the mechanical behavior of non-metals were restricted largely to determinations of the crystallographic indices of the cleavage and fracture planes and the glide and twinning elements. Until recently, only occasional systematic studies of the deformation characteristics of non-metals have been made; and investigations of the forces necessary to initiate plastic deformation and the factors which affect the flow characteristics have been restricted largely to studies of sodium chloride'-7 , magnesium oxides-l3 and lithium fluoride. 14-22 Fracture studies on alkali halide and metal oxide single crystals have been limited despite the fact that these materials have a number of advantages for fracture studies. Because they are transparent, the cracks which form can be viewed in three dimensions instead of in two dimensions as in metals. Also, they exhibit stress birefringence under polarized illumination, which enables the internal stress pattern and, therefore, the distribution of dislocations to be examined in the vicinity of the fracture. Early workers1-4 have shown that ionic crystals with a cubic structure fracture in tension along the (100) plane normal to the applied stress. These fractures were brittle at room temperature and propagated very rapidly across the cross section of the crystal. More recently, Stokes, Johnston, and Lil0 have studied crack formation in compressed magnesium-oxide single crystals. They found that the cracks, which were observed after about 3 pct strain, formed in the region of a kink band and lay on conjugate (110) slip planes instead of the usual(100) cleavage plane. Two different types of cracks were noted: stroh23 and secondary. The Stroh cracks did not exist merely on the surface but extended through the specimen in the form of tiny slits. A secondary

Jan 1, 1962

By Walter H. Bucher

THIS symposium is designed to lay the basis for a general discussion of the place of geophysics in the training of geologists. As there is danger that in the ensuing debate individual interests may be given emphasis out of proportion to their place, we shall do well to view the whole field of geological inquiry in order to see the problem in true perspective. THE NATURE OF GEOLOGICAL INQUIRY "Basic" and "Complex" Sciences It is convenient to divide all science into two major divisions, the basic and the complex sciences. The basic sciences separate out from reality such entities as "substances" and "movements," describe their behavior in terms of arbitrary units of measurement and derive from them by progressive abstractions concepts and patterns of behavior that exist between them, so-called general "laws" and "properties" of nature. The complex sciences, on the other hand, deal, with little or no abstraction, with those objects of reality that are accessible to man in the atmosphere, the hydrosphere, the lithosphere and the biosphere.† Their work comprises two types of inquiry. One is concerned with abstractions to the extent of dealing with types rather than individuals-that is, with such things as plants, animals, protoplasm; clouds, streams, glaciers; volcanoes and mountain ranges. It comprises the search for general properties and patterns of behavior or "laws" that characterize the objects and their reactions to each other. These properties and laws apply always, everywhere. They are independent of the stream of time. We may call the results of this sort of inquiry timeless knowledge. The other type of inquiry is concerned with the objects themselves-that is, with this animal and that plant; this river system and that mountain chain; this glacier and that valley. Like all concrete objects in nature, they are subject to change with the passage of time, especially when it is measured in years, centuries, eons. The characteristics by which we recognize them -indeed, their very existence are dependent on their position at this point in the stream of time. This we may call time-bound knowledge. The so-called descriptive sciences are all bound to the past of which the objects of their study are the product and through which alone their present properties can be understood. They are historical sciences. This obvious fact is easily overlooked, which leads to serious misunderstanding, as we shall see later. Dynamic Geology With this broad picture in mind, let us now examine the nature of geological inquiry, defining, for the purposes of this discussion, geology as the science of rocks. Air is not a rock; water is. Meteorology and climatology are, correspondingly, gen-

Jan 1, 1941

By R. W. Gurry

IN the course of a series of measurements of the rate of diffusion of carbon in austenite at about 960°C. (1760°F.) and 1110°C. (2030°F.), it became necessary to determine carbon concentration when austenite is saturated with graphite, because of indications that the hitherto accepted value of the solubility of graphite in this temperature range is too low. Specimens of carbonyl iron were saturated at temperature in a hydrogen-toluene atmosphere which was in equilibrium with graphite. The carbon content of the steel was measured either by combustion or by the loss of weight after substantially complete decarburization in an atmosphere of hydrogen saturated at room temperature with water vapor. The absence of carbide or graphite as a phase at temperature was demonstrated by microscopic examination of saturated specimens that had been drastically quenched. The mean result of concordant measurements is that gamma iron saturated with respect to graphite contains 1.39 per cent carbon at 957°C. (1755°F.) and 1.89 per cent at 1110°C. (2030°°F.). These two values, plotted along with what appears from the literature to be the best value (0.69 per cent) at the iron-graphite eutectoid temperature (738°C. or 1360°F.), yield a curve that is almost linear, and which, continued upward through a short interval, leads to a limiting solubility of 1.98 per cent at the iron-graphite eutectic temperature1135°C. (2095°F.) instead of the commonly accepted value of about 1.7 per cent. EXPERIMENTAL PROCEDURE The samples of carbonyl iron, with the exception of those for microscopic examination, were cylinders 3.8 cm. long, 0.475 cm. in diameter. They were placed in a graphite holder and suspended in a vertical furnace, the temperature of which was controlled precisely by means of the resistance of the platinum winding.1 In the empty furnace the range of temperature over a distance of 4 cm, at the heat center was 9°C. (16°F.) but at a given location the temperature remained within ±0.5°C. (0.9°F.); it was measured by inserting a platinum-rhodium couple calibrated at the melting point of palladium, 1555°C. Since the presence of the sample probably improved the uniformity of temperature, it was decided to consider the average temperature of the sample to be 3°C. lower than the maximum measured in the empty furnace with the same setting of the controller. Data were obtained in the vicinity of two temperatures, 960°C. (1760°F.) and 1110°C. (2030°F.). The samples for microscopic examination, 2.2 cm. long, 0.475 cm. in diameter, were suspended individually on pure iron wire; for these no temperature correction was applied. The carburizing gas passed into the furnace was dry, oxygen-free hydrogen saturated at room temperature with

Jan 1, 1942

By D. C. Porterfield

ProUuction of crude oil in Venezuela increased from 186,134,000 bbl. in 1940 to 2~8,131,ooo bbl. in 1941, or 22.6 per cent, to establish a new all-time high for the country. While the average production for the year was 625,000 bbl. per day, production during the month of December 1941 averaged 751,000 bbl. per day, and during the last week of the year, 766,000 bbl. per day. Production from the Lake Maracaibo basin averaged 454,000 bbl. per day during the year, or 72 per cent of the total for the country, compared with 73 per cent of the total produced in 1940. Drilling during the year was approximately on the same scale as in 1940, with 438 wells completed in 1941 as compared with 429 the year before. Exploratory completions decreased from 18 in 1940 to 6 in 1941. Of the drilling operations in 1941, 56 per cent was concentrated in the Lake Maracaibo basin and 44 per cent in eastern Venezuela, success being 98 per cent in the Lake basin and 83 per cent in the east. Successful completions for the country as a whole amounted to 92 per cent of the total wells drilled. Exploratory drilling in 1941 resulted in the discovery of three new fields, all in eastern Venezuela; viz., Guara, about II km. to the northeast of the Oficina field but on a separate structure; Santa Rosa, which is east of El Roble field on a structure forming a part of the major Santa -Ana- San Joaquin-El Roble uplift; and Santa Barbara, which is southwest of the Jusepin field on an extension of the main Jusepin anticline. At the close of the year three wildcats were drilling, all of which showed prospects of obtaining production; that is, Mercedes No, 2 in central Guarico, Las Ollas No. I on the Anzoategui-Guarico border near the town of Zaraza, and Quiamare No. I in Anzoategui northeast of the town of San Mateo. In spite of heavy withdrawals and the resultant natural decline in the potentials of older producing areas, new drilling during the year increased the potential production of the country from an estimated 780,000 bbl. per day at the end of 1940 to an estimated 810,000 bbl. per day at the end of 1941, or approximately 4 per cent. Since domestic consumption of petroleum products is insignificant compared with total production, exports of crude and products during the year increased in line with production. Crude exports totaled 196,800,000 bbl., compared with 158,400,-000 bbl. in 1940, and exports of products were 26,100,000 bbl., compared with 21,900,000 bbl. the year before. Exports of crude from Venezuela to the United States amounted to 36,500,000 bbl. In addition, about 2,200,000 bbl. was imported in bond into the United States for transfer to Canada. Total refining capacity of the country in 1941 was approximately 125,000 bbl. per day, including a crude-conversion plant with a capacity of 32,000 bbl. per day, capable of making fuel oil only. Three plants with a capacity of 121,000 bbl. Per

Jan 1, 1945

By Gilbert H. Cody

The present article calls attention to the activities of a committee on coal research of the sister society of Economic Geologists. The field of coal geology crosses the boundary between the two societies and joint meetings are as applicable here as in the metallic and other nonfuel fields of mining and natural resources recovery. The six fields of coal geology are briefly described and some of the ways in which they touch on coal mining, preparation, and recovery briefly indicated.

Jan 2, 1950

By D. C. Hilty, W. Crafts

L. S. Darken—Laboratory investigation of deoxidizing and other steelmaking reactions is usually centered, at least first, on the determination of the equilibrium or equilibria involved. This seems a reasonable procedure since equilibrium, if attained, depends only on composition, temperature, and pressure; hence conclusions derived from data on small experimental quantities are applicable to a heat of steel providing eauilibrium is attained in both cases. A knowledge of equilibrium serves as a useful framework even though we may know that practical conditions do not correspond to complete equilibrium. On the other hand, nonequilibrium or rate phenomena depend on a wider variety of conditions and are more difficult to interpret; conclusions applicable to laboratory conditions may or may not apply to larger scale phenomena. Hence the attainment or nonattainment of true equilibrium in the experiments here reported is of critical importance in evaluating their significance. Since some of the statements in this paper and in the closely related preceding one (on aluminum deoxidation) imply some doubt on this matter, I should first like to ask the authors whether their conditions are intended and believed to represent equilibrium. I should like to point out three considerations which seem to cast considerable doubt on the achievement of equilibrium, at least of the particular equilibrium under consideration. 1. In the experiments on manganese deoxidation the authors point out that they could not maintain the manganese-oxide slag on top of the metal in their rotating crucible, and hence they substantially dispensed with this slag. This leads to serious trouble in the interpretation of the results, for any equilibrium is, of course, a particular specific equilibrium—in this case Mn + O = MnO The experimental deletion of the upper layer of manganese oxide means that if equilibrium is attained at all it is attained between the metal and the MnO which has soaked into or adhered to the crucible (under the metal) and has dissolved substantial amounts of the crucible material including impurities. These impurities may constitute a significant portion of the slag by virtue of the small total amount of slag, even though the crucible is relatively pure. Hence there would seem to be a strong presumption that the equilibrium (if attained) involves not a pure MnO (or MnO — FeO) slag but one saturated with alumina and containing perhaps considerable impurities which substantially lower the concentration and activity of MnO, causing the above reaction to proceed to the right further than it would in the absence of alumina and impurities. Hence it is not surprising that manganese here appears as a better deoxidizer than found by other investigators. The present results may represent equilibrium with a slag of unknown composition which seems unlikely to be particularly related to plant experience. 2. The curves representing the observed silicon deoxidation (figs. 3, 4, and 5) are all drawn with a discontinuity in slope at about 0.02 pct oxygen. This point is interpreted as corresponding to the three-phase equilibrium, metal, slag, solid silica. The type of construction shown in these figures (though apparently fitting the data) is contrary to a fundamental principle of heterogeneous equilibrium as pertains to the construction of phase diagrams. According to this principle, the two solubility curves (each of the two portions of the curves in figs. 3, 4, and 5) must intersect in such manner that their (metastable) extensions must lie outside the homogeneous field rather than inside as in these figures. In other words, the "point" in these curves should be aimed in the opposite direction, if it is to be interpreted as corresponding to the three-phase equilibrium. The construction adopted is in violation of the second law of thermodynamics. This matter is discussed in detail in several texts and also by Lipson and Wilson.&apos;" The same criticism applies to the later figures representing conditions for manganese additions. The occurrence of this discontinuity or break at 0.02 pct oxygen casts further doubt on its interpretation. The earlier investigation of this system by Korber and Oelsen is in substantial agreement with the several recent findings of Chipman and coworkers that the oxygen content of iron in equilibrium with silica and silica-saturated iron oxide slag is about one third to one half that (0.24 pct at 1600") of iron saturated with pure iron oxide; thus there seems reliable evidence that iron saturated with silica and iron silicate slag at 1600" contains about 0.1 pct oxygen, or certainly much more than the 0.02 pct proposed in this paper. 3. In the quarternary system iron-silicon-manganese-oxygen one of the equilibria involved may be written 2 Mn + SiO2 (solid) = 2 MnO <slag> + Si The activity of SiO, is constant (if equilibrium is attained) by virtue of its presence as a substantially pure solid. At not too low metallic manganese content, the activity of MnO in the slag is constant by virtue of the fact that the slag is substantially pure manganese silicate saturated with silica and hence of constant composition. Thus the equilibrium constant for the above reaction is asi/a2Mn. Barring unanticipated large changes in the activity coefficients, the equilibrium constant may be adequately approximated for the composition range covered as [% Si]/[% Mn]2. Thus a plot of log [% Mn] against log [% Si] would be expected to be linear with a slope of one half as found by Kijrber and Oelsen. In the present investigation the slope (shown in fig. 15) is found to be one. It is difficult to believe that this finding represents a correct equilibrium determination, since it is at odds both with prior experimental investigation and with. theory. In view of the above points it seems that, although this paper reports many interesting findings, there is room for considerable skepticism as to the attainment of equilibrium and as to the conclusions drawn. N. A. Gokcen—The authors consider that Si% x O2% product is constant. This product is a function of the asi X a0 activity of Si02. The true constant is -------------. If the asio2 slags of this investigation were always saturated with SiO2 then Si% X O2% product would be constant,

Jan 1, 1951

By K. F. G. Hosking

I read Professor Gaudin&apos;s paper with great interest and pleasure because for some time I have held that the chemical aspect of comminution is a subject of considerable importance to the mineral dresser and deserves to be thoroughly investigated. It does seem appropriate, however, to emphasize the fact that "fresh" edges and corners produced by the grinding of solids display enhanced reactivity has been recognized and utilized in the development of certain mineral identification techniques. Some of these techniques are worth noting, not only because they might facilitate research in the aspect of mineral dressing under discussion, but also because they emphasize the fact that many mineral species commonly regarded as being very inert can display a surprising reactivity when in the freshly ground state. In 1951 Isakov6 published a number of tests for the components of certain mineral species which depend essentially on grinding in a mortar a mixture of the material under investigation with a solid reagent. Thus when stibnite, 4(Sb2S3), is ground with sodium or potassium hydroxide. the antimony is revealed by a momentary development of a yellow color which changes in air to orange-red. Other antimony minerals need a preliminary treatment before the test can be carried out. This consists of grinding with aluminium sulfate, ferric sulfate or potassium bisulfate, and breathing upon the resultant mixture. I have employed a similar technique to determine the approximate magnesia content of certain limestones.&apos; The method depends essentially on the fact that when a sample of limestone is ground under controlled conditions with solutions of sodium hydroxide and Titan yellow the color of the final product is, within limits, a function of the amount of magnesia present. I have also shown that the components of a wide range of minerals can be identified by applying chemicals to their streaks on portions of vitrified, unglazed floor tiles, etc. Under such circumstances the diversity of the reactions which take place in the cold (because of the reactivity of fresh corners and edges) is surprising. Thus, for example, if a garnierite, (Ni,Mg)3Si2O5(OH)1, streak is treated first with a drop of 0.880 ammonia and then with a drop of a 1 pct alcoholic dimethyl-glyoxime it immediately becomes red, indicating the presence of nickel.&apos; Stevens and Carron9 have evolved a simple field test for distinguishing minerals by "abrasion pH." A soft nonabsorbent mineral is scratched in a drop of water on a streak plate until a milky suspension is formed. A piece of pH indicator paper is dipped into the suspension, after which it is removed and the maximum deviation from neutrality noted. When a hard mineral or one which absorbs water is being tested, fragments are first ground for 1 min with a few drops of water in a mortar to make a heavy suspension. The importance of the findings of such tests to mineral dressing may be judged by the abrasion pH values, Table 11, recorded by Stevens and Carron for certain species usually regarded as comparatively inert. The combined results Of the above researches clearly indicate that comminution is capable of altering the pH of a pulp and of causing the chemical nature of the surfaces of some of the components to be profoundly changed&apos; Depending On circumstances such surface alterations may have a beneficial or an adverse effect if these products are subsequently subjected to flotation. The tests also suggest that by grinding "inert" minerals with appropriate solid or liquid reagents "reactive" surfaces may be developed which might facilitate separations by flotation. It is an interesting and instructive problem to determine the reactions that are likely to take place when dry solid substances are subjected to comminution and to the unavoidable heat liberated during the process. To do this it is theoretically necessary to know the free energy values of the reactants and possible resultants, but unfortunately there is a dearth of such data! However, the heats of formation of many substances are known, and generally speaking, if in a reaction of the type AB + CD = AD + CB the sum of the heats of formation of AB and CD is less than that of AD and CB the reaction will probably proceed to the right. Thus, according to a note I have (the author of which I cannot name) if PbS (black) is warmed with CdSO, (white), PbSO., (white) and CdS (yellow) are formed, and that the reaction does, in fact, take place is indicated by the change in color of the mixture. The reaction is expected, as the sum of the heats of formation of PbS and CdSO, is less than that of PbSO, and CdS (as shown below). PbS + CdSO4 = PbSO4 + CdS 22.2 + 218.0 < 216.2 + 33.9 Finally, certain other aspects of the chemistry of comminution, which are neither mentioned by Professor Gaudin nor referred to by me are to be found in a paper by Welsh" and in the printed discussion thereof. A. M. Gaudin (author&apos;s reply)—The observations contributed by Dr. Hosking are indeed welcome, as they add to our experimental knowledge of a topic which is believed to be of the first importance. In connection with the experiments cited it should be kept in mind that oxidation, hydration, and carbonation at various rates should always be deemed to be possibilities when grinding is done in water or in air, even in "industrially dry" air. Special precautions might lead to sufficient minimizing of these reactions and to the assertion, instead, of deliberately-created reactions. The author wishes to thank Dr. Hosking for his contribution.

Jan 1, 1957

By John V. Beall

Tsumeb has added a chapter to its absorbing history with the beginning of copper smelting operations this month. This development will be followed shortly by another one when lead smelting and refining plants go on the line next year. In our own milieu these events would be common- place enough (although a new lead smelter certainly would be cause for wonder), but in the sparsely settled remote regions of northern South West Africa they are a dramatic industrial expansion. They are also, however, a sound businesslike extension of policies which have marked the tenure of Tsumeb Corp. Ltd. The historical data given in Table I are a drab listing of factual bones without the corporeal splendor which should surround the denouement of the Tsumeb bonanza. When Sir Francis Galton traversed the country, his was an expedition which was in keeping with the then blooming era of heroic explorations. The Otavi highlands in the interior were unexplored and the reception of the natives uncertain. While the exploratory work was in progress during the turn of the century the Hottentots and Hereros were successively in open bloody rebellion. The suppression of these uprisings, particularly the Hereros, by German soldiers so decimated the tribes that a labor shortage ensued for many years, hampering the development of the colony. To these troubles may be added difficulties In obtaining mining supplies. However, there should have been no shortage of meat from wild game judging by conditions prevailing even today.

Jan 12, 1962

By Toshihisa Adachi, Shosei Serata, Shunsuke Sakurai

Many different methods of measuring the in-situ stress field have been developed in recent years. They are all based on the assumption of elasticity without allowing any viscoelastic deformation. By using the high resolution strain-measuring technique recently developed in the laboratory at Serata Geomechanics, many rocks were found to be viscoelastic. The viscoelasticity of rock media was found to be dependent upon the resolution of the strain measurement. The higher the resolution of the strain measurement, the greater number of rocks could be identified as viscoelastic. All rocks eventually exhibit viscoelastic deformation under high stresses relative to the strength of the material. Therefore, the conventional methods of elasticity become less reliable with increase of ground stress. In deep underground formations, even hard rocks become viscoelastic. At the same time, many ground formations near the surface are actually viscoelastic. A new method was developed in the laboratory to determine the in-situ stress field in viscoelastic rock media. Rocks in general exhibit a small amount of viscoelastic creep whenever mean stress and octahedral shearing stress are changed substantially from their initial states. Such changes take place around a borehole immediately following the drilling although they are short-lived. We developed a viscoelastic method of determining the in-situ stress field by relating the time-dependent behavior of the borehole with the tensor properties and stress field of the underground. In developing the viscoelastic relation, only isotropic and homogeneous

Jan 1, 1970

By Strathmore R. B. Cooke, Paul B. Queneau

The kinetics of the dissolution of scheelite in basic solutions of carbonate and fluoride were investigated. Work was also done with solutions of alkali metal chloride, hydroxide, phosphate, and mixtures of phosphate and fluoride. The study was conducted at 90 psig and at temperatures ranging from 100" to 155"C, and both natural and synthetic scheelite single crystals were used. The interaction of scheelite with carbonate solutions generally followed a parabolic rate law, and resulted in the formation of calcite crystals on the attached surface. The transport of the CO3 through the calcite to the scheelite surface was probably rate -controlling between 115" and 135°C. Positive deviations from Parabolic behavior were observed at 100" and 155?C, presumably due to the calcite grain growth, and to the formation of a noncoherent calcite layer, respectively. The leaching of scheelite with alkaline fluoride solution produced a calcium fluoride reaction-product which covered the surface as a sheet-like layer. Below 110°C the dissolution rate was parabolic; at 115" and 135°C it was linear. In the linear region, the periphery of the calcium fluoride layer lifted from the sample. Only the lower layers, braced by the scheelite substratum, remained unbroken. This bound layer, approximately constant in thickness, limited the rate at which the fluoride could attack the scheelite. The phosphate and phosphate-fluoride leaches dissolved scheelite at a linear rate; solid reaction products were respectively hydroxyapatite and fluorapatite. Sodium hydroxide and chloride were not effective leachants, and did not produce observable solid reaction products. THE feasibility of pressure leaching of scheelite pulps with basic solutions containing either carbonate or fluoride ions, as indicated by the following equations, has been established by previous investigators:1-3 200°C CaWO4s + CO37q - CaCO3s+WO4aq [1] 200°C CaWO4s + 2Faq ^ CaF2s+WO4aq [2] It is to be noted that a commercial process employing reaction [I] is in use at Union Carbide&apos;s operation near Bishop, Calif. In the earlier work referred to, it was apparent that the precipitation of the solid reaction-product on the scheelite particles sharply reduced contact of the leachant with the scheelite. We have extended this work by studying the kinetics of dissolution employing single crystals of scheelite of known exposed surface area. In addition, the effectiveness of solutions of phosphate, of phosphate with fluoride, and of chloride and hydroxide as leachants for scheelite have been investigated. EXPERIMENTAL Apparatus. The low-pressure autoclave used in this wo (100 psig maximum) is essentially that of J. Halpern4 as modified by F. A. Forward.5 Constructed entirely of 316 stainless steel, its maximum capacity is 4000 ml. The temperature in the autoclave was regulated to *0.5?C by a Wheelco thermocouple controller. A 4-in. diam, three-bladed impeller, circulated solution upward against the sample, and a strobo-scope permitted holding the stirring rate to *15 rpm. A check valve and a "pop" type safety valve were installed, a sample holder was fixed to an externally adjustable rod, and a water-cooled condenser was placed in series with the sampling valve. The stainless steel sample holder, Fig. 1, held the epoxy-mounted sample (f) five mm above the impeller. Tightening the tapered sleeve (d) positioned the epoxy-resin specimen-mount by forcing it back against the spacer (c). The mount (e) was 1 in. diam. Sample Description and Preparation. Both synthetic and natural scheelite crystals were leached. The former were single crystals of 99.95 pct purity which were leached approximately perpendicular to the "c" axis; they were supplied by the Gallard-Schlesinger Chemical Manufacturing Corp. The natural crystals, supplied by Minerals Unlimited, were transparent, analyzed 99.8 pct CaWO4, and in ultraviolet illumination exhibited the characteristic blue glow of substantially molybdenum-free scheelite. To permit exposure of an essentially constant surface area of scheelite to the leachant, the samples were mounted in Scotchcast Brand Resin No. 250 (Minnesota Mining and Manufacturing Co.). The mount-

Jan 1, 1970

By J. C. Fisher, J. H. Hollomon, David Turnbull

Understanding of the diffusion problem has recently been furthered by the analysis of Birchenall and Meh1.l They pursued the problem of the variation of the diffusion coefficient with composition for non-ideal solid solutions. Their analysis follows the tradition of Wagner,l Jost, Dehlinger, and Darken & who assumed the net flux of diffusing material to be proportional to the gradient of a quantity related to free energy. The basic assumption in Birchenall and Mehl&apos;s formulation of the problem is that the net flux of diffusing material is proportional to a thermodynamic activity gradient. To estimate the applicability of the derived relations, they corrected the diffusion coefficients of carbon in austenite by utilizing Smith&apos;s6 activity data for carbon, and the diffusion coefficients for zinc in copper with activity data computed from the vapor pressure measurements of Har-greaves.&apos; The corrected coefficients for carbon were virtually independent of carbon concentration. For the diffusion of zinc in copper a moderate variation of diffusion coefficient with concentration remained after the correction. The problem of diffusion can be formulated in another way than that used by Birchenall and Mehl. The method is that of chemical rate theory and has been used by Eyring and his coworkers8,9 as well as by Eyring and Zwolinskilo in a discussion to Birchenall and Mehl&apos;s paper. As yet the method has not been applied to substitu-tional solid solutions. On the basis of their assumptions, Eyring and Zwolinski derived a relation between the diffusion coefficient and activity that is identical with that of Dehlinger and Darken but which does not correct for the variation of the diffusion coefficient with concentration as well as does the relation derived by Birchenall and Mehl. It was thought that the theory of diffusion would be more complete if the inconsistency between the two analyses could be rationalized and if diffusion in substitu-tional alloys were analyzed on the basis of the concepts of the chemical rate theory. Chemical Rate Theory According to the theory of absolute reaction ratess the reaction +..... +X, Eq I is viewed as taking place in two steps. First the reactants A1, A², . . . A; combine to form an activated complex M with which they are in equilibrium: A1 + A1+ . . . + A=M. Eq 2 Second the activated complex decomposes to give the products XI, XZ, . . . Xi: M?X, + X²+ . . . +Xi Eq g It has been showns that the number of activated complexes decomposing per unit volume per unit time is given by the expressiont kT -h CM † The transmission coefficient has been taken as unity.

Jan 1, 1949

By David Turnbull, J. H. Hollomon, J. C. Fisher

Understanding of the diffusion problem has recently been furthered by the analysis of Birchenall and Meh1.l They pursued the problem of the variation of the diffusion coefficient with composition for non-ideal solid solutions. Their analysis follows the tradition of Wagner,l Jost, Dehlinger, and Darken & who assumed the net flux of diffusing material to be proportional to the gradient of a quantity related to free energy. The basic assumption in Birchenall and Mehl&apos;s formulation of the problem is that the net flux of diffusing material is proportional to a thermodynamic activity gradient. To estimate the applicability of the derived relations, they corrected the diffusion coefficients of carbon in austenite by utilizing Smith&apos;s6 activity data for carbon, and the diffusion coefficients for zinc in copper with activity data computed from the vapor pressure measurements of Har-greaves.&apos; The corrected coefficients for carbon were virtually independent of carbon concentration. For the diffusion of zinc in copper a moderate variation of diffusion coefficient with concentration remained after the correction. The problem of diffusion can be formulated in another way than that used by Birchenall and Mehl. The method is that of chemical rate theory and has been used by Eyring and his coworkers8,9 as well as by Eyring and Zwolinskilo in a discussion to Birchenall and Mehl&apos;s paper. As yet the method has not been applied to substitu-tional solid solutions. On the basis of their assumptions, Eyring and Zwolinski derived a relation between the diffusion coefficient and activity that is identical with that of Dehlinger and Darken but which does not correct for the variation of the diffusion coefficient with concentration as well as does the relation derived by Birchenall and Mehl. It was thought that the theory of diffusion would be more complete if the inconsistency between the two analyses could be rationalized and if diffusion in substitu-tional alloys were analyzed on the basis of the concepts of the chemical rate theory. Chemical Rate Theory According to the theory of absolute reaction ratess the reaction +..... +X, Eq I is viewed as taking place in two steps. First the reactants A1, A², . . . A; combine to form an activated complex M with which they are in equilibrium: A1 + A1+ . . . + A=M. Eq 2 Second the activated complex decomposes to give the products XI, XZ, . . . Xi: M?X, + X²+ . . . +Xi Eq g It has been showns that the number of activated complexes decomposing per unit volume per unit time is given by the expressiont kT -h CM † The transmission coefficient has been taken as unity.

Jan 1, 1949

By S. F. Bartram, G. A. Chase

COMPUTED X-ray diffraction powder patterns of YNi3, YNi5, and CbBe3 are available on request from either author.

Jan 1, 1968

By Clemens Jones

The difficulties attending the reduction of ferric sulphate in the determination of metallic iron by the method of Marguerite, are often serious, and affect time, patience and accuracy. They depend upon the condition and purity of the zinc used, the state of saturation of the solution, acidity, and temperature. D. J. Caruegie (Chem. News, lvii., No. 1481), says that ferric solutions are instantaneously reduced by the use of zinc-dust. But there are obvious objections to its employment in quantitative work. Dr.

Jan 1, 1889

By L. D. Jaffe

From the limited experimental data in the literature, preliminary values were derived for the thermal diffusivity of titanium alloys and for the quenching severity of various mediums used in heat treating them. The thermal diffusivity, under quenching conditions, was found to be approximately 0.006 sq in. per sec. The quenching severity H for brine is approximately 8, for water 4, for oil 0.9, for air 0.08, and for argon 0.02 in. -&apos; The quenching severity of the Jominy-Boegehold end quench water jet against titanium alloys appeared effectively infinite. Using these results, graphs were prepared showing ideal round sizes and Jominy positions having cooled conditions equivalent to those at the center and surface of titanium alloy rounds, plates, and sheets quenched in various media. THE importance of proper quenching of steel parts has long been recognized, and much quantitative work has been done on the subject. Recently, it has become evident that for titanium alloys, too, the rate of cooling from high temperature is important in obtaining high strength and hardness. Maximum hardness and strength may not be attained in the as-quenched condition but rather after a subsequent tempering or aging treatment. Nevertheless, if cooling from temperatures near the ß transus is too slow, for the hardenability of the alloy used, a soft a-ß structure will be produced which will not harden on subsequent aging.&apos;-" The quenching of parts of practical interest can usually be approximated by simple shapes, such as cylinders (rounds) and plates (or sheets) of various thickness and combinations of these. A standard that has been used extensively for comparison purposes is the center of an ideal round: a cylinder quenched in a medium that instantly cools its surface to room temperature." For steel, considerable practical use has been made of the Jominy-Boegehold end quench hardenability specimen,".&apos; and its value for titanium alloys is becoming evident. It therefore appeared worthwhile to attempt comparison of cooling conditions in titanium alloy rounds and plates of various sizes quenched in various media with cooling conditions in ideal round and Jominy quenches. These comparisons are based upon measurements reported in the literature. Quenching Severity of Jominy Water Jet and of Brine As one starting point, there were available the data of Phillips and Tobin8 for positions on a Jominy specimen having the same hardness as the centers of round bars of various size quenched in 5 pct NaOH brine, shown in Table I. The Jominy speci- men is a round bar, normally 1 in. diam and 4 in. long, quenched by a water jet at one end and air cooled on the other surfaces.&apos; After quenching, hardness is measured vs distance from the quenched end on longitudinal flats ground 0.015 to 0.10 in. deep. The data of Table I were based on a subsized specimen of 3/4 in. diam. Since the positions tested are close to the jet quenched end, cooling there may be taken as due solely to the jet, and air cooling can be neglected. These positions are then equivalent to various locations near one surface of an 8 in. plate jet quenched on both sides. Assuming that the thermal diffusivity is constant and that Newton&apos;s law of cooling holds, temperature vs time curves at corresponding positions in Jominy specimen and round bar then may be calculated for various assumed quenching severities of the water jet and of the brine. Cooling curves are generally taken to be metallurgically equivalent when they show the same time to reach a temperature halfway between the initial (heat treating) temperature and the final (quenching medium) temperature.5 On this basis, using Russell&apos;s tables,9 upplemented by heat flow tables derived in similar fashion by the author for positions near the surface of severely quenched plates, it was found that the experimentally observed equivalence, Table I, was best matched if the quenching severity H of the Jominy water jet was taken as infinite (H = co). This means that the jet quenched surface should be considered as instantly cooled to the temperature of the water

Jan 1, 1956

By G. M. Schwartz, J. N. Gundersen

Utilization of magnetite-bearing taconite from the great Mesabi range of Minnesota is fast becoming a major industry in the state. The planning and early development stages of taconite processing projects have been de-scribed1-3 and an excellent discussion has appeared recently4 concerning the current mining, crushing, concentrating, and pelletizing techniques of the Reserve Mining Co., whose operations lie entirely within the Eastern Mesabi district. The present paper will deal only with some of the geological aspects of taconite utilization in the district, with emphasis placed upon some of the common mineralogical and textural features of the tacon-ites currently being mined or stripped and how these factors generally affect the potential recovery of the iron from the metamorphosed Biwabik iron-formation. The generalized geologic setting of the Eastern Mesabi district is presented in Fig. 1. The small circles on the geologic map, adapted from Grout and Broderick,3 mark the location of drill holes that were available for inspection during this study through the courtesy of Reserve Mining and Erie Mining Cos. The cores from these holes were divided into stratigraphic units and examined for their mineral content. Typical mineral associations and grain fabrics were also determined from hundreds of thin and polished sections. Available metallurgical tests made it possible to determine the probable response of a given variety of taconite to magnetic concentration. The longitudinal section of Fig. 1, projected along the strike of the iron formation, presents the simple stratigraphy of the area. It also shows the uniformly thick nature of the iron formation members in the district as well as a somewhat abrupt thickening of the formation to the west of the probable fault. The stratigraphy of these precambrian rocks has been described5-&apos; elsewhere and need only be briefly reviewed. Historically, the oldest rocks unit, the Giants Range granite (Algoman) was covered by the Animikie group of sediments (Middle Huronian?), consisting of the Pokegama, Biwabik, and Virginia formations. Outcrops of the Pokegama quartzite are locally distributed along the northern limit of the Biwabik iron formation, but they are too limited to depict on the geologic map of Fig. 1. The effects of the intrusion of several small diabase sills within the Virginia and Biwabik formations are obscure because all of these rocks have been subsequently highly metamorphosed, mainly by the Duluth gabbro. The emplacement of the transgressing Duluth gabbro (Middle Keweenawan) and that of numerous peg-matitic veins in the iron formation8 has resulted in extensive contact and metasomatic metamorphism which has locally reconstituted the previously existing minerals of the Biwabik formation, in large part quartz and magnetite, into a wide variety of silicate mineral assemblages9 that have a profound effect upon the re coverability of the remaining magnetite. The entire region has subsequently been eroded and largely buried beneath Pleistocene glacial deposits. Structurally, the strike of the gently dipping Animikie group generally parallels the elongate outcrop pattern of the Biwabik iron formation on the map of Fig. 1. The Animikie group most commonly dips from 5" to 15" to the south-southeast. In this area, the Duluth gabbro pluton is somewhat sill-like, dipping about 30" to the southeast. Projecting these present structures upward, it seems probable that the gabbro once extended over the underlying Animikie group in the Eastern Mesabi district. SELECTION AND PRESENTATION OF DATA Because of the locally intense metamorphic activity in the district, mineralogical variations within the magnetite-bearing taconites are commonly abrupt, both vertically and laterally. Consequently it is difficult to select a single hole or small group of holes whose cores will be entirely representative of all of the district. Two holes have been selected, however, that in a general way represent mineralogical and textural variations that are likely to be encountered in both the eastern and western parts of the district. These recently drilled holes were chosen for discussion because it was possible to log the core and then to place the sample intervals at stratigraphic boundaries prior to preparation of the core for magnetic tube tests.

Jan 1, 1961

By R. Chanchani

Single and mixed mineral flotation behavior and the mechanisms for the loss of selectivity in 1:1 and 95:5 apatite: dolomite mineral mixtures are presented. Loss of selectivity in mixed mineral systems is attributed to depletion of oleate ions available for adsorption by bulk precipitation with calcium and magnesium ions dissolved from dolomite. Flotation after two-stage conditioning was found to be a potential technique to separate dolomite from apatite. This method involves conditioning at pH 10 followed by reconditioning at a lower pH. The results indicate that selective flotation of dolomite, a minor mineral in south Florida phosphate deposits, could be obtained by reconditioning at pH below 4.5. Higher selectivity was observed for mixed minerals as compared to that of single minerals.

Jan 1, 1986

HENRY M. HOWE, Bedford Hills, N. T. (communication to the Secretary?).-The authors valuable results as to the effects of the air-hardening temperature on high-speed steel may be summed up thus: Influence of Rising Air-Hardening Temperature on. High-Speed Steel Air-hardening microstructure Cutting Properties temperature S Austenite Grain Free Carbide Grains Boundaries Too low Small or Narrow Maximum Too soft undeveloped Intermediate, Well-developed Intermediate Little or even Best correct none Too high Coarse hide, even with Minimum . Weak, brittle, three-rayed crumbling stars Here the suggestion is that as the air-hardening temperature rises it causes two prominent effects, one helpful and the other harmful, the increase of the former exceeding that; of the latter up to a certain point, at which the steel is most useful, and then in turn being outrun by it. The first is the progressive dissolving of the free carbide in the austenite, increasing the stability of the red-hard state. The second is the progressive coarsening of the grains, and thickening of the intergranular cement, developing at last into spandril-like three-rayed stars of the 1,288° specimen. (2,350° F.) of Plate D, thus giving clear proof of incipient fusion, that is of crossing the solidus. This causes intergranular weakness. The individual grains may have great red-hardness, but they do not cohere. They approach the condition of a bag of emery grains.

Jan 6, 1917

By D. O. Ehrenburg, R. J. Watson

During the earlier period of electrical prospecting, the search for orebodies was by far the most important application of this method of geophysical prospecting. In the past few years, however, increasing attention has been paid to the possibilities of this method in the investigation of subsurface structures. Not only have fault zones been located, but attempts have been made to determine the depth to certain strata and thus contouring on some bed which proves to be a good "electrical marker." Many workers have published the results of field tests showing how their particular interpretations have agreed with the actual field conditions, but very few have stated their method of interpretation. Weaver, Hummel and Stefanesco and Schlumbergerl have given a more theoretical discussion of the resistivity methods. Hummel and Stefan-esco and Schlumberger have published mathematical solutions for the flow of electricity in a medium involving four layers. In this paper the authors present a solution for the flow of electricity in a medium of any number of horizontal strata. By means of this solution, curves showing the relationship between the apparent resistivity and the electrode spacing can be computed for ideal cases. Point-source in an Infinite Homogeneous Medium In resistivity measurements the current is conveyed to the earth by means of two electrodes, which can be mathematically treated as point-sources of equal and opposite strength. A point-source of strength I is defined as a point at which electricity is being generated at the constant rate of I coulombs per second, or I

Jan 1, 1932