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By M. King Hubbert

THE growth of human knowledge is an evolutionary process. Historically our separate sciences came into existence as people became interested in various apparently unrelated domains of phenomena, and in this manner we acquired the sciences of physics, chemistry, astronomy, biology and geology. As various of these sciences became established, cognizance of them came to be taken by the universities and in this manner there arose the traditional departments of physics, astronomy, chemistry, biology and geology of our American universities. As there was no particular rationality in the boundaries separating the various sciences, in the university departments the jurisdiction of each has assumed quite arbitrary limits. In the domain of earth phenomena the first science to grow up was that of geology, which arose originally from the activities of the collectors science dealing with directly observable terrestrial phenomena for which elementary rational explanations were offered. The traditional treatment of phenomena by the science of geology has rarely been with more than an elementary regard for the fact that these phenomena were also phenomena of physics and chemistry. Since the latter part of the nineteenth century, a new approach to terrestrial phenomena has been emerging and becoming of so great a significance that it can no longer be ignored. This approach has been made by people trained primarily in the sciences of physics and chemistry, who have investigated terrestrial phenomena as constituting phenomena of their respective sciences. In this manner we have acquired the so-called "borderland sciences" of geophysics, the physics of the earth, and of geochemistry, the chemistry of the earth. Neither of these fields is new, having arisen chiefly at the hands of European investigators during the latter part of the nineteenth century. The European universities have long since given official recognition at least to geophysics, by the establishment of departments or institutes of geophysics, which are on a par with the university departments of the other sciences.

Jan 1, 1938

By W. M. Peirce, R. K. Waring

Zinc of high purity offers definite advantages in certain fields. A process by which zinc of 99.99 + per cent purity is produced by pyro-metallurgical methods is described in this paper. The process consists of a fractional distillation following the primary reduction; this fractional distillation employs the principles of rectification for the separation of lead and other high-boiling impurities and cadmium and other low-boiling impurities. Theoretical Considerations Involved in Production of High-purity Zinc by Distillation Fractional distillation, fractional condensation, and rectification are recognized methods of separating mixtures of liquids. In the field of organic liquids these methods are widely used but not commonly to effect as complete a separation of liquids as is done in the problem under consideration. Zinc boils at 905" C., cadmium at 778" C. and lead at about 1620" C. Zinc may contain from several hundredths of one per cent to over one per cent each of cadmium and lead, and the problem is to reduce these impurities to a few thousandths of one per cent. For lead and zinc, the spread in boiling points is substantial, 715° C., while for zinc and cadmium it is only 127" C. The basic limitation of any separation by distillation may be found from the relation between the equilibrium composition of the vapor and the liquid for all mixtures of the two substances involved. If a mixture of constant boiling point is found, or if a stable compound that vaporizes without dissociation occurs, there is a definite theoretical limit to the degree of separation that is possible when operating at atmospheric pressure with respect to that mixture. Otherwise, any degree of separation is theoretically possible. The equilibrium composition of vapor in contact with liquid mixtures of zinc and cadmiurn at the boiling point has been determined experi-

Jan 1, 1937

By Richard I. Petritz

A brief review of today's processing of integvated circuits is given. The major trends in the development of advanced integvated electronics are identified as 1) the broadening of the integvated circuit concept to a large class of circuit function, 2) the processing of more complex circuits within relatively small chips of silicon, and 3) the processing of very large electronic functions on complete slices of silicon. This latter trend, called array technology, is then developed in detail. Emphasis is given to defining the key tech-nological problems. Current progress being made is illustrated. THIS paper will endeavor to identify the major trends in advanced integrated electronics technology. One of these, array technology, will be developed in some detail. The array technology discussion will identify the key problem areas. Since it is the scope of the entire meeting' to present specific progress in the science and technology of integrated electronics, we shall indicate general directions being explored rather than discuss comprehensively solutions to the problems. In order to set the stage for the discussion of future trends in integrated-electronics technology, let us briefly compare the processes by which circuits are fabricated through discrete-device technology with that of integrated circuits technology. The reader is referred to the December 1964 issue of Proceedings of IEEE2 for a comprehensive review of integrated electronics. The article3 by Jay Lathrop is an excellent discussion of integrated-circuits technology. A discussion of the history of semiconductor technology is contained in Ref. 4. A) Current Status of Integrated Electronics. Fig. 1 (top) shows the process by which circuits are constructed from discrete devices. Key points are: 1) Slices containing large numbers of transistors or diodes are processed separately. 2) The slices are scribed into small chips (on the order of 15 mils on a side is about as small as can be conveniently handled) each chip containing one transistor. 3) Each device is specified separately—circuit -function specs are derived largely from device specs. 4) Circuits are formed by connecting together the discrete devices. 5) The number of circuit connections required is approximately equal to the number of devices. 6) There are potentially many more discrete devices per inch2 of semiconductor—only our lack of ability to handle them in discrete form prevents us from going to several orders of magnitude higher density iin Fig. 1, 400,000 transistors are discussed at 1.5 mils on a side). The bottom part of Fig. 1 illustrates the integrated circuit process. Key points are: 1) On the same slice of silicon, transistors, diodes, and resistors are processed grouped to do a complete circuit function. 2) While still in slice form, the components are interconnected into circuit functions by an evaporation process, eliminating the need for separate interconnection steps later. Dramatic improvements in cost and reliability are realized. With a simple flash of metalization thousands of interconnections are reliably made. 3) The slices are scribed into chips which contain complete circuit functions. 4) The circuit functions are specified-not each component in the circuit. This important point was missed by some of the early opponents to integrated circuitry. They argued that, with device yields at x pct, integrated circuit yields would be pct, where n is the required number of devices to make a circuit. This argument leads to extremely low yields for integrated circuits. The fallacy of the argument is that in integrated circuits each device is not specified separately. Furthermore, since a device is forever integrated into a specific circuit function, it need meet only the requirements for that particular function. Discrete devices, on the other hand, are tightly specified so that they can be applied to a variety of circuit functions. 5) Extremely high packing densities are achievable because one need only make the basic devices as large as the circuit demands. Their size is not dictated by handling requirements. A current example

Jan 1, 1967

By Lawrence Adler

In-situ rock has well-recognized rupture and yielding responses. Attention is called to an intermediate response, granulation, which consists of an evenly distributed, small-scale crumbling accompanied by swelling. Granulation results in a negative slope for the inelastic portion of the stress-strain curve as successive interlocks are destroyed, and the load-carrying capacity of the material is reduced. Volumetric swelling with softening also takes place. The prerequisites for such a response are moderate confinement and a uniformly distributed defect pattern. Since rock masses, as well as rock as an intact material, have such patterns in their jointing and texture, respectively, granulation is characteristic of them. The presence of granulation can be demonstrated for a very wide scale, ranging from laboratory testing to regional geologic phenomena. The response of an engineered structure is considered in detail. Granulation appears to be dependent upon internal moments, the formation of which can be controlled by engineering design. The practical implications of such control can be significant in optimizing underground instability and in improving excavation techniques. Rock is usually considered to behave inelastically under high load, by fracturing as a brittle material, or by yielding as a ductile material, ignoring time dependency. These responses, which are characteristic of metallic behavior, appear idealized in Fig. 1, where linear-elasticity approximates the initial behavior. However, another major deformation mechanism peculiar to rock has long been recognized in geology, the granulation of an interlocked material. Granulation consists of a uniformly distributed fracturing and crumbling of the material, accompanied by swelling and softening. Predictably, the associated inelastic portion of the load-deformation curve has a negative slope,

Jan 1, 1971

By G. R. Love, C. C. Koch

The changes in superconducting properties with aging time have been studied ,for the pecipitation reaction in a Tc-30 at. pct V alloy. Superconducting critical temperature, upper critical field, and relative critical current density were determined by ac susceptibility techniques. Aging produces changes in critical temperature of both matrix and precipitate which can be rationalized by compositional effects. maximum flux pinning (critical current density) occurs at a time during aging when subgrain boundaries are completely decorated with precipitates and the subgrain centers remain precipitate -free. The particular effectiveness as barriers to flux motion of planar defects which enclose regions of low deject density is discussed. THE precipitation of a second phase can dramatically modify the superconducting properties of type I1 super-conductors. According to Livingston and Schadler1 one might expect changes in the primary, secondary, and tertiary superconducting properties of the material. Changes in matrix chemistry caused by precipitation can alter the fundamental superconducting parameters; critical temperature, Tc, and thermody-namic critical field, Hc. The concimitant changes in electron mean free path (reflected in normal state resistivity) can affect the critical fields Hc 1, IIc2, Hc3. Finally, the presence of precipitate particles may hinder the motion of flux lines and may considerably improve the current-carrying capacity in high-field superconductors. The influence of precipitation on superconducting properties has been studied in a number of systems.2 Magnetization measurements have been used to study the influence of precipitates on flux pinning in lead-base alloys by Livingston3 and Evetts et al4 In these alloys precipitates induced magnetic hysteresis and flux trapping. The amount of hysteresis increased with the volume fraction of precipitate and decreased with coarsening of the precipitate. Jn an Al-Zn alloy5 and an A1-Ag alloy6 the initial precipitate size was presumably smaller than a coherence length and coarsening increased magnetic hysteresis5 and critical current density.6 The influence of precipitation on superconducting properties has also been studied in several of the commercially interesting Ti-Nb7-10 and zr-Nb11 alloys. The maximum in critical current density for these alloys was confined to a narrow range of either isothermal aging time" or isochronal aging temperature7 during the precipitation reaction. Thus, experimental evidence and theoretical considerations suggest there is an optimum precipitate size, spacing, and density, and a critical composition with respect to the matrix for flux pinning. What these "optimum" values might be and the relative importance of each is still not clear, although a few generalizations can be made. It is generally accepted1' that particle sizes smaller than the coherence length or larger than the inter-flux line spacing are poor pinning centers. In high Hc2 materials, precipitate sizes for maximum values of critical current density lie in the range of 50 to 2000Å,9,7 and there are indications that increasing dissimilarity between precipitate and matrix produces increasing pinning force.13 Because of several interesting features of the aging reaction in a Tc-30 pct V alloy, we have chosen to study the influence of precipitation on the superconducting properties of this alloy. The physical metallurgy14 and a survey of the superconducting properties" of the Tc-V alloy system have been reported. The Tc-V phase diagram is presented in Fig. 1. At 1500°C the Tc-30 pct V alloy is in the single phase 6 field. Samples quenched from the 6-phase field have a CsCl structure X-ray diffraction pattern at room temperature and it has been proposed that the 6 structure is closely related to the bcc lattice.14 When held isothermally below the eutectoid temperature, 115O°C, the 6 phase decomposes into the CsCl and hcp phases.

Jan 1, 1970

By E. J. Schmitz

The mining of the Triassic coals of the Richmond basin has been carried on, upon a larger or smaller scale, for more than a hundred years. Notwithstanding the close proximity of the field to a large city and to tide-water, assuring both a good home-market and cheap transportation, and notwithstanding the good quality of the fuel and the great thickness of the principal bed developed and worked, operations in this field have been conducted with but limited success. The basin comprises about 189 square miles, being from 24 to 31½ miles in length by 5½ to 10 miles in width. Not much more than one-tenth of this area has been explored in a practical and efficient way, and not over 1200 acres have been worked near and along the outcrops or edges of the coal. The practical mistakes which have been committed undoubtedly in a number of the mine-operations of the past, do not alone explain the unsatisfactory success and progress of the industry of this field ; nor can it be ascribed to the lack of local enterprise. Other reasons have to be looked for; and, as a principal one, the irregularity and the faulted conditions of the coal deposits must be pointed out. As a second cause, the indifference of the State government, which leaves the development of the field entirely to private enterprise, instead of aiding it by systematical and practical geological investigations, deserves to be mentioned. Nothing has been done by the State since the excellent work done more than fifty years ago by Professor Rogers, who could not at that time enter into the details of such

Jan 1, 1895

By S. Brunauer

The hydration of portland cement is treated as a chemical reaction and the changes in matter, in energy and the rate of change of the process are discussed, Portland cement is a mixture of four major and at least as many important minor constituents. In the hydration process, the four major compounds (trical-cium silicate, dicalcium silicate, tricalcium alumi-nate and tetracalcium aluminoferrite), plus gypsum and water form five or six new compounds. In spite o the great complexity of the reaction, considerable progress has been made in its understanding, primarily with the help of such research tools as X-ray diffraction and electron microscopy. The rate of the reaction can be followed by direct and indirect methods of measurements. The effects o composition, particle size (or specific surface), temperature and water-cement ratio on the rates of hydration are discussed. The hydration of portland cement is a chemical reaction accompanied by such highly important physical phenomena as heat evolution, setting and hardening. It is a vast and complex subject, on which hundreds of papers have been published. At the time of the writing of this paper, in October 1962, a two-volume book, which alone contains dozens of papers pertaining to cement hydration appeared in print.' The present paper deals with a few aspects of this vast subject, and the selection was not easy. The work reported here deals with some of the most recent investigations in the field. In any chemical reaction, the physical chemist is primarily interested in three things: changes in matter, changes in energy and the rate of change of the process or the speed of the reaction. This is true also of the chemical reaction between portland cement and water, and all three aspects of the reaction will be discussed. These three aspects are of vital interest to the engineer as well. Portland cement is not a cementing material — the hydration products, the new materials which form in the reaction, have the cementing action. The energy changes manifest themselves in a considerable evolution of heat, which may be useful or harmful. It is useful, for example, in winter concreting, but in very large concrete structures like dams, a large evolution of heat, which cannot be easily dissipated, may produce distress in the structure. Primarily for such a purpose was the Type IV or low heat portland cement developed. The speed of the chemical reaction is important because it determines the time of setting and hardening. The initial reaction must be slow enough to permit placing of the concrete before setting occurs. On the other hand, after the placing of concrete it is often highly desirable to obtain as rapid chemical reaction as possible. For this purpose the Type 111 or high early strength portland cement was developed. CHANGES IN MATTER Portland Cement: In a basic investigation, before one begins to study a reaction, one either knows the quantities and compositions of the starting materials, the reactants, or one determines them. This is obvious; the chemist expresses the changes in matter that occur in a reaction by a chemical equation, which has the quantities and compositions of the reactants on the left side of the equation and the quantities and compositions of the reaction products on the right side. The first question is then what to put on the left side of the equation in the reaction between portland cement and water? It is not very easy to answer this question. Portland cement is not a single chemical compound but a mixture of many compounds. Four of these are considered the major compounds, and at least four of the minor compounds also play important roles in the hydration reaction. In order to avoid complicating matters, the present discussion will be restricted primarily to the four major compounds, which constitute usually more than 90% of a portland cement. The relative amounts of these compounds vary from cement to cement. Actually not only the amounts but the compositions of these constituents also vary to some extent, but the variation in composition of the individual components will be neglected for simplicity.

Jan 1, 1963

By R. T. Southin

Cast ingots of 99.99 pct purity A1 and aluminum/copper alloys containing up to 2 pct Cu have been found to contain four zones rather than the three previously accepted, i.e., chill, colummar, and equiaxed zones. The fourth zone consists of a coarse dendritic layer across the top surface of the ingot which is open to the atmosphere. It is also found that the grains in the equiaxed region have a "cornet" shape, with a head which is coarsely dendritic and a tail which grew with the same structure as the columnar grains. Experiments using mechanical barriers, and others involving the elimination of the surface dendrile layer, have indicated that nucleation of the equiaxed zone is caused by the showering of dendritic particles from this surface dendrite layer. These particles are the dendritic heads found in the comet grains. A mechanism of nucleation and growth of these comet grains is put forward. Experiments with a number of other metals and alloys suggests that these conclusions may apply generally to ingots cast without the addition of nucleating agents, and solidified under normal conditions. THE macrostructure of cast ingots may contain the following three zones: i) a peripheral zone of fine equiaxed grains, commonly called the chill zone; ii) a zone of columnar grains extending inwards from the chill zone; iii) a central zone of equiaxed grains; these are normally larger than the chill grains. All three zones are not necessarily present in any particular ingot since their existence and magnitude depend upon the casting conditions and composition of the cast material. The mode of formation of zones i and ii is fairly well understood. However, the cause of the central equiaxed zone remains a matter of conjecture. Previous theories put forward to explain the mechanism of nucleation in the equiaxed zone have been examined by Chalmers1 and Winegard.2 At the time when the present work was carried out the most re -cent hypothesis was that due to Chalmers,1 who recognized more fully than previous workers that conditions in this zone during solidification were not conducive to nucleation. In his hypothesis, he suggested that nuclei were formed near the mould wall during the very early stages of solidification, and that they can drift into the central zone by convective motion. This was supported by evidence from experiments using mechanical barriers to stop the drift of nuclei. A similar hypothesis had previously been put forward by Genders.3 More recently, Jackson et al. 4 have observed that dendrite arms in organic compounds can melt off during solidification. They have postulated that this occurs in metals and alloys, and that the dendrite arms which have been freed from the main dendrite act as nuclei for the equiaxed zone. In the present work, critical metallographic examination has shown that there is a fourth zone in the macrostructure of cast ingots which is a dendritic layer over the top surface of the ingot. It is also shown that there is a relationship between this zone and nucleation of the equiaxed zone. EXPERIMENTAL DETAILS The alloys examined were prepared from super -purity aluminum of 99.99 pct min purity (spectro-graphically detected impurities of Cu, Fe, Si, and Mg) and copper of 99.98 pct min purity (spectrographically detected impurities of Si, Zn, As, Fe, Pb, Bi, Ni, Sn, Mn, Ag, Cr, and Al). Three compositions of ingots were examined, containing 0.0, 0.1, and 2 pct Cu, respectively. The alloys were melted in an alumina-lined salamander crucible using a medium-frequency electric induction furnace; when the appropriate casting temperature was reached, the alloys were cast without degassing or fluxing treatment. The mould used was made of electrode graphite and had the following dimensions: external diameter 6 in., height 9 in., with a mould cavity 8 in. deep and a diameter tapering from 5 in. at the top to 4 in. at the bottom. Casting temperatures used were generally in the order of 70" to 90°C above the liquidus and the mould was at room temperature before casting. Inserts kere placed in the mould cavity in some experiments. These consisted of either an 18-g stainless-steel tube of 2 in. diam held axially in the mould i in. off the bottom and extending 1 in. out of the top of the mould or a "trap-door" barrier of stainless-steel gauze of 24-mesh held horizontally in the mould 31/2 in. down from the top. The construction of this insert is shown in Fig. 1. All inserts were preheated prior to casting to prevent chilling. RESULTS The macrostructures of ingots of the three compositions are described, in terms of the three generally recognized zones, in Table I, and illustrated in Figs. 2(a) to (c). The most interesting observation in this table is that relating to the shape of the equiaxed grains, which were not in fact equiaxed but of almost tear-drop shape. Closer examination of these grains showed that each consisted of a head which had a coarse dendritic structure and a tail which always grew in the opposite direction to heat flow, and which had the same structure as that of the columnar material of the ingot concerned; i.e., in the pure aluminum and 0.1 pct Cu alloy it was cellular and in the 2 pct Cu alloy it was cellular-dendritic. Identification of original cast grains was greatly hampered in the super-purity aluminum ingots, and to a lesser degree in the 0.1 pct Cu alloy,

Jan 1, 1968

By R. H. Richards

IN nearly all ore-dressing operations it is a common practice to discharge mixtures of fine ore and water through spigots; for example, from classifier pockets, from jig hutches, from settling tanks, etc. As a, general rule it is desirable to regulate the composition, i.e., the ratio of water to sand, of such discharged products; and this can usually be done by varying the size of the orifice or spigot through which the material is discharged. Thus it is that problems similar to the following are frequently encountered: With a given quantity of solids per unit time, of a given specific gravity, to be discharged with water under a given head, and with a given ratio of water to solid, what must be the size of the spigot opening? If the spigot is to be open continuously, there are, aside from its form, but three factors governing the rate at which it will discharge a mixture of sand and water, namely: the head of water above the spigot; the area of the spigot opening; and the viscosity of the material to be discharged. The term viscosity, as used here, means the ratio of the volume of pure water that will flow through a given orifice under a given head in a given time to the volume of the material under consideration that will flow through the same orifice in the same time under the same conditions. While the actual viscosity of water containing sand in suspension is not increased by the presence of the sand, nevertheless the volume-rate at which such a mixture will flow through an orifice is less than that at which pure water will flow, by reason of the friction of the particles of sand against each other and against the sides of the orifice. In other words, the flow is retarded as it would be by increased viscosity; and therefore, for the purpose in view, we may speak of the viscosity of a mixture of ore grains and water as defined above. The head of water above the spigot is generally fixed by the form and design of the classifier or tank to which the spigot is attached. So, with the head known, in order to determine the size of the spigot required it is necessary to know the viscosity of the desired mixture, and the coefficient of discharge of

Jan 1, 1915

Discussion of the paper of E. C. HARDER, presented at the Pittsburgh meeting, October, 1914, and printed in Bulletin No. 94, October, 1914, pp. 2573 to 2586. I. C. WHITE, Morgantown, W. Va.-I have seen some of the great iron-ore deposits described in this paper. -One of these in the State of Minas Geraes appears to be an immense mountain of iron ore about 2,000 ft. in height. All over its surface from bottom to top may be seen large masses of rich iron ore, varying in weight from a few pounds to several tons, and from all that one can judge without exploitation, the quantity of available ore is certainly very large in this particular mountain. Whether it will prove a mere surface deposit or shell, like the famous Iron Mountain of Missouri, is for future exploration to determine. The question of transportation is the main factor in determining the availability for exportation of these Brazilian iron ores. There is no coal in Brazil that can be manufactured into coke without expensive previous treatment, since the best of the raw coal in the States of Rio Grande do Sul, Santa Catharina, and Parana, contains about 35 per cent. of ash, of which about 6 per cent. is sulphur, and coal of this composition cannot be utilized in iron smelting without purification. When I was chief of the Brazilian Coal Commission in 1904 to 1906, I had a cargo of this coal shipped to Balk, Germany, and treated in the great coal-testing plant of the Humboldt Engineering Works, located just across the Rhine from Cologne. It was found that by crushing and washing the Brazilian coal, it yielded 33 per cent. of briquetting coal, containing only 10 to 12 per cent. of ash (of which 1 per cent. was sulphur), and 42 per cent. of slack coal, with 25 per cent. of ash and low in sulphur, so that about 33 per cent. of the Brazilian coal could be converted into coke of fair quality, as shown by the following average of three analyses, using air-dried coal, of briquets made from the Barro Branco coal bed, State of Santa Catharina: Moisture 1.56 Volatile matter 31.66 Fixed carbon 56.73 Ash : 10.05 Total 100.00 Sulphur 1.34 Phosphorus 0.003 B.t.u 13,395

Jan 4, 1915

By R. C. Patterson

In view of the circumstance that very few important changes have been made within the last 15 or 20 years in the equipment of rod and wire mills, the description of a new process introduced by Grenville Mellen, of LleweIIyn Park, N. J., to take the place of the present laborious system of producing rods of lead, zinc, brass, copper, aluminum, etc., may be interesting to members of the Institute. This new process consists in the production of cast rods at one operation in a small continuous casting machine. The hot liquid metal is transferred from the melting crucibles directly into an endless chain of mold blocks in the machine, where solidification takes place, and the rod comes out continuously in a solid form at one end as long as the molten metal is supplied. The operation of these mold blocks so as to produce a solid rod of uniform structure constitutes an important part of Mr. Mellen's invention. The machine (Figs. 1 and 2), 12 ft. in height over all, 2 by 3 ft. in horizontal cross-sectional area, and 6,000 Ib. in weight, has a framework of cast iron, holding in position two endless chains of mold blocks, which are made in sections and join in center alignment. The mold orifice is made up of these mold sections, into which the liquid metal flows. The molding chains are composed of steel blocks, grooved on one face to form the molding cavity, and linked together with flexible joints. Each block is carried on four rollers which guide the chain around the end sprockets and carry it in its course through the machine. The accuracy of alignment requisite to the production of a perfect rod in the mold groove formed by these sections is secured by careful machine work, and by building the four ways, down which the alignment takes place, so that two of the sides are fixed permanently, whiIe the opposite sides are held to their position by spring pressure. The guides carrying the molds, while in casting position, are water-cooled square tubes. The length of this machine is somewhat indeterminate. A certain amount of both time and cooling surface is required to solidify the metal jn the mold; and one may either use a long molding chain and run it fast, or a shorter chain and run it correspondingly slower. We have found,

Jan 1, 1916

By H. I. Aaronson, H. A. Domian, G. M. Pound

Zener's two-parameter theory of the y a reaction in Fe-X alloys is extended to encornpass austenite-stabilizing as well as fewite-stabilizing elements, and is then cottzbitzed with statistical thermodynamic theories of Fe-C alloys to permit development of a ther-modynamic description of the proeutectoid fewite reaction in Fe-C-X alloys. Equilibrium tielines are calculated for tile a + y rep'on from experimental data and frort extrapolations of the y/y +a equilibrium surface. Sectzovs of the y/y + 0 surface are calculaled for the tzetastable sstuation LYL u-kich alloyrtg eleitzents do not partition betzseen azrstenite andfer-rite. The finding that the metastable y/a + y curves Lie close to their equilibriuwz counterparts when X = Si, .Vo, Co, Al, and Cu but well below them when X = A/ln or Ari pr-elides a thermodunamic explanation for the expcri1?7e?ztally obserted absence of partition during the proeutec toid ferrite reartlon in the fortner alloys and for the occurrence of partition at hzgher ternperatures in the latter alloys. Cotarison ofno- patitzoa free-energy changes and y/y i a curr,es in Fe-C-X alloys with the equilibrium 11al1es of these quantities in Fe-C alloys furnishes additional qualitative insight into the irqluence of allojling elements upon the kinetics of the proeutectoicl ferrite reaction. THE introduction of a substitutional alloying element, X, appreciably complicates calculation of the thermodynamics of the formation of proeutectoid ferrite from austenite. As noted in the preceding paper,' the positional entropy of the interstitial species is the principal component of the free energy of an interstitial solid solution with which theory has so far been able to deal. One would expect, however, that other components of the free energy of this type of solid solution may be significantly altered by the addition of a substitutional alloying element. Even if the assumptions are made, by analogy to the case of Fe-C alloys,' that changes in the positional entropy of carbon represent a significant part of the thermodynamic effects of an alloying element, and that the remaining effects can be taken into account by fitting the equations developed on this basis to experimental data on Fe-C-X phase diagrams or on the activities of carbon in alloyed austenite and ferrite, the experimental information available on either of these quantities is not yet sufficiently accurate or extensive, respectively, to make such an approach useful. An attempt made by Zener on the former basis to explain the effects of alloying elements on the thermodynamics of Fe-C alloys in terms of a temperature-independent "free-energy change" (actually enthalpy hane') required to transfer 1 mole of an alloying element from austenite to ferrite, in which the "free-energy change" was determined by fitting the theoretical relationships developed to Fe-C-X phase diagrams, thus proved inadequate in part because of deficiencies in the available ternary-phase-diagram data.= Other difficulties of a more fundamental nature, however, also indicated the desirability of a different approach to the problem.3y4y6 zener6 subsequently proposed that the free-energy change associated with y — a transformation in pure iron can be decomposed into magnetic and nonmagnetic components. Alloying elements were assumed to affect those components separately. One parameter was used to describe the quantitative effect exerted on each component. These parameters were evaluated from Ms (martensite-start) temperature data and from other experimental information usually either readily available or measurable with acceptable accuracy. Zener applied this treatment only to the calculation of Fe-X phase diagrams in which X is a ferrite-stabilizing element. In the present study, this treatment is extended to include austenite-stabilizing elements, and then combined with treatments previously considered for Fe-C alloys1 to permit calculation of the thermodynamic quantities of interest in the austenite - proeutectoid ferrite transformation in Fe-C-X alloys, where a number of representative, and commonly used alloying elements are chosen for X, including Si, Mn, Co, Mo, Al, Cr, and Cu. The results are used to explain important features of the partition of alloying elements between austenite and proeutectoid ferrite, as reported in a companion paper7 on the basis of electron-probe analysis, and to provide some additional understanding of the influence of alloying elements upon the kinetics of nucleation and growth of proeutectoid ferrite. Portions of this treatment6 have been clarified in the course of a review by Kaufman and Cohen.3 The consolidated summary of these developments with which this section is begun provides a basis for further clarification of the treatment, from which extension to include austenite- as well as ferrite-stabilizing elements is a natural consequence. The division of the free-energy change associated with the 7 - a transformation in pure iron, into two independent components is formally stated as:

Jan 1, 1967

By E. Gybbon Spilsbury

Everybody who has had his attention turned to the gold-deposits of the Southern States, is acquainted with the undisputed fact of the existence, at least in the Carolinas and Georgia, of enormous areas of gold-bearing rocks. Long before the discovery of the precious metal in California, gold-mining on a very extensive scale mas a well-estab-

Jan 1, 1887

By S. E. Bronisz, Dana L. Douglass

a Uranium was deformed by cold rolling, and the effects of this plustic deformation on the microstruc-ture of the metal were observed by the technique of transmission elecbon microscopy. The recrystalli-zation of selected cold-wmked samples was also studied by this method. The samples were prepared for examination by electrolytic thinning in a standard metallographic electrolyte which has not been previously reported as being used in producing thin foils of uranium. The microstructural changes observed in the a uranium were generally similar to those seen by optical microscopy. The changes in the microstructure of a uranium following cold work and recrystallization treatments have been the subjects of several studies employing optical and X-ray techniques.12-19 These studies indicated that twinning was the redominant mode of deformation at room temperature20 and that the regions of high energy associated with the deformation twins were preferred sites for the initiation of recrystallization.15,18, Recently several workers have prepared thin foils of uranium suitable for examination by transmission electron microscopy.'-lo The foils thus prepared have been used to study fission fragment damage; a particular dislocation reaction,' and gas precipitation." At this laboratory the microstructural changes occurring during the cold working and recrystallizing of a uranium samples have been studied by using transmission electron-microscopy techniques. The foils used in this work were electrolytically thinned in a polishing bath not reported previously in the literature as being used for this purpose. EXPERIMENTAL PROCEDURE The uranium used in this investigation was depleted a uranium sheet 4 mils thick. The results of a spectrochemical analysis of this material are shown in Table I. The as-received uranium was cut into strips, 1 in. wide by 5 in. long, and annealed in vacuo at 600°C for 2-1/2 hr. The resulting microstructure consisted of relatively uniform, equiaxed grains having diameters of 10 to 50 p. Cold Working. The cold-worked samples were prepared by rolling several of the annealed uranium strips to various thicknesses. The strips were reduced 3.5 ± 0.5, 6.0 ± 0.6, 10.0 ± 0.5, 19.5 ± 1.0, and 28.5 ± 2.0 pct in thickness. It was not possible to achieve these reductions with a single pass through the rolling mill, so the strips were turned end for end during the rolling procedure. The cold-rolled strips were stored in dry ice until samples from them could be thinned and examined (within 24 hr after rolling). Annealing. The samples used in studying the re-crystallization behavior of a uranium were obtained by annealing sections of the strips which had been reduced 10.0 and 28.5 pct. These samples were sealed in evacuated Pyrex capsules and were annealed in a tube furnace at temperatures from 200" to 600°C and for times from 1/2 to 2 hr, see Table l. Thinning: The samples from the rolling and heat treatments were prepared for examination in the electron microscope by electropolishing in a bath composed of 25 g chromic acid, 133 ml glacial acetic acid, and 25 ml water. This electrolyte has been used and recommended for preparing specimens for optical metallography It was necessary to mask the edges of the sample with a stop-off paint in order to prevent preferential attack in these areas. The paint used was made by dissolving polystyrene in benzene. The electrolytic cell consisted of a cylindrical stainless-steel cathode placed in a beaker containing the electrolyte, with the sample as the anode positioned at the cell axis. The temperature of the electrolyte was held below 15°C by cooling with liquid

Jan 1, 1963

By K. M. Kolobova, E. Z. Kurmayev, A. Z. Menshikov, S. A. Nemnonov, V. A. Trapeznikov

The present work represents a review of our intestigations into the X-ray spectra of solids, which have been carried out by us along two lines of upproach: 1) St@ of the electronic structure of high -rnelting compounds of transition metals; 2) stzddy of the interatomic binding forces by the fine structure of absorption spectra under varying temperature and concentration conditions. With this in mind, int>estigations hare been made into the emission and absorption spectra of the K-series of atoms of transition elements in alloys and compounds. In the problem concerned with the electronic structure of high-melting compounds of transition metals, considerable importance is attached to the question of ascertaining the role played by 3d4sp electrons of metal and 2p electrons of metalloid in the formation of chemical bonds and of giving, on the strength of this data, an explanation of the properties which seem to be contradictory at first sight: good conductivity inherent in metals and high brittleness and high-melting characteristics typical of covalent compounds. Over the last few decades this question has attracted the attention of many investigators whose studies were devoted to this type of compound. Many works, both of theoretical1-3 and experimental4- l5 nature , have contributed much to the elucidation of the physical character of the phenomenon referred to. Alongside the investigations in the field of electric resistance, Hall effect, paramagnetic susceptibility, electronic heat capacity, and the temperature of transformation into a superconducting state, we should particularly emphasize the studies on X-ray spectra, which have played a significant role in the development of the zonal theory for high-melting compounds. This fact has become highly evident after the theoretical calculation of the energy spectrum has been made and the density of states curve in Tic, TiN, and Ti0 has been plotted by Ern and Switendick3 who used the method of augmented plane waves. Correlation of the results of the theoretical calculation of the band structure in the compounds listed above with the data obtained by X-ray spectroscopy studies showed that X-ray spectra can be a source of valuable information on the electronic structure of high-melting compounds within a wide range of ener- gies. It is well known that X-ray emission spectra basically give a direct picture of the occupied excited states above the Fermi level of a solid (valence band, conduction band) and that the absorption spectra (region of initial absorption) give a similar picture of states corresponding to the unoccupied levels near the Fermi surface. Full information on the density distribution of electronic states by energies can be obtained by combining the emission and absorption spectra. Such an opportunity arises from investigation

Jan 1, 1970

By Albert F. Hill

The manufacture of structural shapes in steel of uniform quality, which shall command the full confidence of the engineer, is a problem in practical metallurgy which is beginning to attract much attention in this country. The progress of the past fern years in the improvement of plant and processes has placed it within the power of the steel-maker to supply a material of such chemical composition as will meet the requirements; but this solves only in part the difficulties of the constractor. It is well understood that the influence of shop manipulations is a most decisive one upon the mechanical properties of the finished product; in many cases so great, in fact, as to cause an entire transformation in the character of the material, and to render it unfit for the service for which it was intended. On the other hand, mechanical treatment is frequently resorted to as an efficient corrective of certain undesirable properties, which may be due either to chemical composition or previous manipulation. This understood and accepted, it is evident that careful investigation of the effects of mechanical treatment is fully as necessary to the successful use of steel in engineering structures, as the investigation of the influence exerted by its chemical composition. All structural material has to undergo more or less mechanical treatment, such as shearing, punching, upsetting, etc. Each of these operations produces effects which are far more marked and decisive in steel than they are in iron, and means must therefore be adopted to counteract, or at least to modify, these effects before the material is permitted to enter the structure. The fact that both shearing and punching affect the tenacity and elasticity of steel has long been recognized; bat, through more recent investigations, it has been established that these effects are purely local, and are therefore susceptible of correction by other and simpler means than annealing. The importance of this discovery to the use of steel in structures is very great. The impracticability of

Jan 1, 1883

By J. B. Umpleby

The function of gas in the development and production of oil has far-reaching consequences that should be emphasized. The technical aspects of the subject have recently had a great deal of attention but less thought has been given to fundamental concepts underlying oil and gas law and the many customs and practices that have grown up in the industry. I shall review briefly the advance in knowledge of the subject and attempt to relate these concepts to legislative, judicial and operating problems. Early writers on oil and gas in Pennsylvania noted their close association in oil pools and their contemporaneous decline in output; also, that as gas pressure decreases so does production, that new offset wells reduce the output of existing wells, and even that tubing a well lengthens its flowing life. Expanding gas was deduced as the principal expulsive force. These fundamental observations had been made at least as early as 1880.1 They were treated, however, as academic considerations and did not greatly influence law or practice for many years except to instill into all operators an urgent desire to hasten offset drilling in order to obtain as much of the flush as possible. The most noteworthy later advance in knowledge came in 1926 when Beecher and Parkhurst published their paper on Effects of Dissolved Gas upon the Viscosity and Surface Tension of OiL.² This paper added to the old idea of an expelling force the concept of a modifying agent that actually changes the physical characteristics of the oil and facilitates its movement through the pore spaces of the reservoir rock. Largely since the publication of this paper, intensive study and concerted effort have been given to means of using to a maximum, in producing oil, these combined properties of gas. This is shown clearly by the number of papers dealing with the subject, and the new and revived terms now widely used to express thought, such as the expressions gas energy, reservoir pressure, reservoir energy, gas-oil ratio, bottom-hole pressure, beaning, tapered tubing and back-pressure. These terms, some of which are

Jan 1, 1932

By J. M. McDowell

A study has been made to deter~r~irre how the behavior of a water drivee reservoir changes as a function of the permeability of the formation and as a function of the size of the aquifer. The effect of pressure maintenance programs on the rote of nat11rn1 water influx is also studied, (IS well as the influence on the influx of the position of water injection we1ls with reference to the oil-water contact. The results are determined by the use of an electrical reservoir analyzer and are plotted as families of curves of pressure, natural water influx, and water injection vs time or cumulalive production. Two size aquifers are studided. One is limited with a 36-inile radius, and the, other approximates an infinite reservoir. The field remains the same in all respects for the completed. study except that the permeability is changed to agree with that assumed for the aquifer. 1 N TR ODUCTI ON this study was undertaken in -dcr to determine how the pres- sure decline and water influx of a water drive field would change as a function of the rate of fluid withdrawals, as a function of the permeability of the formation, and as a function of the size of the aquifer. The effect of pressure maintenance programs on the rate of natural water influx was also studied as was the position of water injection wells with reference to the oil-water contact. The information has been determined by the use of an electrical reservoir analyzer1, sometimes referred to as a Carter type analyzer. This instrument is an analog type computer which can be set up to represent a water-drive oil field. It can reproduce the past performance of the field in terms of analogous electrical quantities when the proper circuit analog of resistors and condensers has been determined, also, it can determine the future behavior for any method of production which may be selected, or permit the comparison among several different methods. Although most applications of the reservoir analyzer"" have been to thc study of specific field performance, it is intended to use the analyzer here to help understand how various reservoir characteristics effect the final performance of the field and to sec under what conditions water injection will be of benefit and to what extent. Within the oil industry the performance of water-drive reservoirs was first described analytically by LV. Hurst' and M. Muskat2 for certain types of boundary conditions. The solutions of the equations developed involved products of exponential functions and Bessel functions. Later publications by Hurst4 and van Ever-clingen" and the hooks of Muskat6 gave further information on reservoirs with other boundary conditions. They also presented rather extensive curves and tables to help evaluate the analytical expressions involved. A rccent series of publications by Chatas. bascd on the work of Hurst and van Everdingen, gives quite complete charts and tables of data to evaluate the pressure decline or water influx in infinite or limited radial reservoirs. and in linear reservoirs. The curves in all of these publications are given in dimensionless form

Jan 1, 1956

By J. L. Shafer, Christopher L. Caenepeel, Martha L. White

Often an in situ leach is the only practical economic method for copper recovery from small low grade oxide deposits. The decision to develop a copper property by an in situ blast and leach is strongly dependent on ore grade, tonnage, hydrology, and the copper extraction and acid consumption rates. The inherent leachability of the ore will in part determine the desired amount of fracturing of the ore deposit by the blast in order to obtain a copper extraction rate that is economical. For the last several years Occidental Research Corp. (ORC), has undertaken a modest effort to address the question of how to best identify and determine the information necessary to predict and control the operation of an in situ leach for the economic recovery of copper. Modelling of the Leaching Process During the past 10 years the activity in the mathematical modelling of the leaching of copper sulfides in copper dumps and heaps has increased dramatically. The modelling of copper oxide leaching has not received as much attention. The acid leaching of non-sulfide copper minerals while chemically less complex, compared to sulfides, does generate a vertical acid concentration gradient in the ore heap being leached due to the acid-base nature of the reaction. This is generally not observed in sulfide deposits that are biologically active, due to the buffering action of opposing reactions involving the generation of sulfuric acid from sulfide minerals and acid consuming host rock. Thus, the objective of ORC 's copper oxide modelling efforts is to determine the leaching parameters which will account for this vertical acid concentration gradient. Knowledge of this gradient will result in the correct choice of the feed acid concentration to the top of the ore dump or heap, such that the effluent will have the desired pH.

Jan 1, 1980

By George Rice

THE A.I.M.E. Ground Movement and Subsidence Committee, pro-posed in 1920, held its first technical meeting in February 1923, under the able chairmanship of Mr. H. G. Moulton. The following list of papers and discussions, indicating the scope of the problems and relation to various conditions and method of mining, were given at that meeting by the distinguished mining engineers: J. Parke Channing, on Subsidence at Miami, Arizona; Howard N. Eavenson, on Mining an Upper Bitu-minous Seam after a Lower Seam Has Been Extracted; J. J. Rutledge, on Subsidence in Two Oklahoma Coal Mines; Benjamin F. Tillson, on Caving Cracks at the Franklin Mine, New Jersey; Dr. F. W. McNair, on the Dome Theory; William Kelly, on disadvantageous effects in Mining and Back-filling Working Upward a Steep-Pitching Iron-ore Bed; Eli T. Conner, on the good results of Back-Filling by Hydraulic Means in Preventing Destructive Subsidence in the Anthracite District; Thomas H. Claggett, on the merit of Systematic Pillar Drawing in Preventing Cracks in an Upper Seam; Henry H. Otto, successful results in the anthracite district in Mining Lower Seams before Upper Seams; Douglas Bunting, on Leading Factors Incident to Successful Mining of an Overlying Seam; Edwin Ludlow, on there being "less damage to buildings when there was complete removal of coal with complete packing than when room and pillar is used without extracting the pillars"; Edward O'Toole on "bumps" in eastern Kentucky mines, which he thought were the result of geologic stresses: H. A. Buehler, on Upheaval of Surface in an Illinois Case in Advance of the Face; and R. Dawson Hall, on The Mechanics of Subsidence from Mining. The author of this paper discussed various Winds of problems of ground movement and subsidence in both metal mining and coal mining; the production of great landslides by workings near an outcrop, as at Turtle Mountain, Alberta, Canada; and general

Jan 1, 1939