Search Documents

By B. Russell, J. R. Tuffley

The stability regions of the normal sulfate and the various basic sulfates of lead in 02-SO2 and PhS-SO2 gas atmospheres were calculated from available thermodynamic data over the temperature range 600o to 1200oC. Roasting experiments were carried out on samples of synthetic lead sulfide at various temperatures and for various roasting times. Compounds in the oxidized surface layers were identified by X-my techniques. The order in which the various reactions occurred was determined by considering the experimental results in conjunction with the thermodynamic calculations. The results of these investigations were applied to the sintering of lead sulfide concentrates, and the extent to which each of the various reactions occurred in a sinter bed was determined. PRODUCTS which may be formed during the roasting of PbS are PbS04, PbSO4. PbO, PbSO4 . 2PbO, PbSO4 . 4PbO, PbO, and Pb.1, 2 The formation of some sulfates has been studied by a number of investigators3-' whose experiments have mostly been confined to the temperature range between 500" and 850°C. Culver, Gray, and spooner3 were able to isolate the reactions which formed PbSO4 and PbSO4. PbO by carefully controlling the compositions of the roasting gases. The kinetics of these reactions were studied within the temperature range 673" to 807°C. Gardner4 and Merrick5 also studied the kinetics of oxidation of PbS. Gardner disregarded the existence of basic sulfates and, as a result, misinterpreted some of his experimental data. Merrick recognized that most of the products of oxidation were mixtures of basic sulfates, but was unable to identify the individual components. Hoschek6 oxidized PbS in air at temperatures up to 800°C. The products were analyzed after roasting had proceeded for some minutes, but no attempt was made to follow the reactions in the initial stages. Consequently, no roasting mechanism was derived. He also showed that PbSO4 and PbSO4 - 4PbO decomposed slowly in air at temperatures in the region of 800°C. The stability regions of sulfates in the temperature range 500" to 850°C have been only partially determined, while practically no information is available for higher temperatures. In the lead sintering process, PbS concentrates are roasted at temperatures within the range 1000o to 1200°C. In order to investigate sulfate formation, it is necessary to determine the effects of temperature and gas composition upon the various oxidation reactions and upon the regions of stability of the various lead sulfates. Kellogg and Basu2 introduced an equilibrium diagram similar to those in Figs. 1 to 3 which provides a convenient medium for represent-

Jan 1, 1964

By C. F. Weinaug, P. M. Blair

Many difference equations used to approximate reservoir flow problems treat the phase pressures implicitly but not the mobility-density coefficients. Such difference equations are neither wholly explicit nor implicit, but might be described as mixed. Mixed equations are relatively easy to apply. But the associated time truncation error is relatively large, and when used to solve problems characterized by high flow rates, these equations may be unstable for practical size time steps. This paper outlines the development of a completely implicit difference analogue for reservoir simulation, along with a Newtonian iterative method for solving the resulting nonlinear set of algebraic equations that arise at each time step. While this implicit equation requires two to three times more work than does the mixed equation, it is shown to markedly decrease the time truncation error and to yield a stable solution for much larger time steps than does the mixed equation. INTRODUCTION Calculation of multiphase, multidimensional flow in porous media is generally accomplished by numerical methods that involve approximating systems of partial differential equations by systems of partial difference equations. The early development of difference equation techniques was directed toward the solution of linear differential systems. However, the equations of multiphase fluid flow through porous media are highly nonlinear in that mobility and density often are strong functions of pressure and saturation. Thus, solution of the flow problems by difference equations involves solving sets of algebraic equations whose coefficients change from step to step of the calculations. Current practice is to evaluate most coefficients at the beginning of a time step and then to apply difference methods well suited for solving linear problems. At least two major difficulties arise from the use of this practice. First, evaluation of coefficients at the old time level and evaluation of pressures at the new time level results in larger time truncation errors near displacement fronts than if all quantities in the distance derivative were evaluated at the same time level. Second, evaluation of mobility coefficients at old time levels results in an unstable difference equation in regions of high flow rate. The first of these difficulties often results in optimistic recovery behind the displacement front, and the second requires the use of small time steps or special techniques in solving coning problems1 or problems of gas percolation.2 Evaluation of all quantities in the distance differences at the new time level results in a completely implicit difference system. Such a difference system has a lower time truncation error than equations in which mobilities are evaluated at the old level and pressures evaluated at the new level. The algebraic equations resulting from the fully implicit difference equation are, in this case, nonlinear and require some iterative method for their solution. This paper develops fully implicit difference equations for two-phase flow in porous media, describes their solution by Newtonian iteration, and gives examples of problems more easily solved by the new method than by previous methods. EVOLUTION OF DIFFERENCE EQUATIONS FOR NONLINEAR PROCESSES The completely implicit difference equation used in these calculations results from evolution beginning with explicit difference equations, proceeding through what we will call "mixed" equations, and arriving now at a completely implicit equation. Let us illustrate the evolution by considering different analogs of the nonlinear equation

Jan 1, 1970

By Chas Fettke

DURING the summer of 1916, while on a visit to the United States Agricultural Experiment Station at Mayaguez, Porto Rico, the writers were told by D. W. May, the director, that an occurrence of manganese ore had been reported from the mesa southeast of Mayaguez. A visit to the locality showed that the mesa is covered by a mantle of bright red soil resting upon serpentine. Here and there over its surface concretionary masses of limonite have been washed out of this soil. These were FIG. I.-MAYAGUEZ FROM NORTHWEST END OF MESA. apparently mistaken for manganese ore. On account of the similarity of this occurrence to the extensive iron deposits of northeastern Cuba, it was thought that a brief description based upon a two days' reconnaissance survey of the area would be of scientific interest. Mayaguez is on the west coast of Porto Rico, at Mayaguez Bay, which is the third in importance of the harbors of the island. The city itself is about ¾ mile inland on the low-lying plain at the mouth of the

Jan 3, 1918

By J. Brett, S. Friedman

A study of the diffusion of nickel into both fibrous and recrystallized 0.065-in.-diam silica-alumina doped tungsten wire at 1200°C has been conducted. The diffusion profiles were determined by chemical dissolulion of successive circumferential layers and spectro-photometric determination of nickel in the etchant. It was shown that the diffusion of nickel into tungsten is markedly structure-sensitive. No significant amount of nickel could be introduced at 1200°C into tungsten which had first been recrystallized at temperatures of 2300°C, leading to an upper limit estimate for the bulk diffusivity of nickel in tungsten of 10-11 sq cm per sec at 1200°C. However, nickel did diffuse into initially fibrous wires, caused re crystallization, and was alsays present at the advancing recrystallization front. The accumulation of nickel in an initially fibrous region ceases when the recrystallization front arrives. The characteristics of the resulting diffusion profiles are explained in terms of the relation between diffusion processes and micro structural changes. WHILE it is well-known that the presence of nickel and certain other metals causes low-temperature recrystallization of the cold-worked fibrous structure of doped tungsten,''' the character of the phenomenon is not well understood. Recently it was shown that the recrystallization reaction can be induced at low temperatures by the presence of solid nickel on the surface of doped wire, but not by exposure to nickel vapors.3 Once recrystallization was initiated, a continued source of nickel was required for propagation of the recrystallization front. The phenomenon appeared to be a complicated solid-state reaction since, in addition to the change in structure of the tungsten from fibrous to equiaxed grains, diffusion of nickel from the surface into the recrystallized and fibrous structures was occurring with possible chemical reaction between nickel and tungsten at the surface and interaction of nickel with the dopants which ordinarily stabilize the fibrous structure within the wire. The objective of the present work was to study the diffusion of nickel into fibrous and recrystallized tungsten structures in order to clarify the relationship of the diffusion process to nickel-induced recrystallization. Studies of interdiffusion in the Ni-W system4"7 have been principally concerned with the mobility of tungsten in nickel. Information on diffusion of nickel in tungsten is meager, and there seem to be no studies of the mobility of nickel in tungsten which elucidate the structural aspects of the phenomenon. The present experiments were designed to determine the diffusivity of nickel at 1200°C in fibrous tungsten, in large-grained tungsten prerecrystallized at high tem- perature, and in tungsten recrystallized at 1200°C due to the presence of nickel. Although the concentration profiles were determined in these experiments, unexpected changes in boundary conditions or complex diffusion paths complicated the analysis of these profiles so that the interpretation could not be readily expressed in terms of simple diffusivities. EXPERIMENTAL PROCEDURE The experiments were conducted on Sylvania 0.065-in.-diam silica-alumina doped commercial tungsten wire, hereafter designated as ordinary doped wire. A special lot of 0.065-in.-diam silica-alumina doped low-nickel wire was also used. Impurity analyses of the wire are given in Table I. The experimental design is shown in Fig. 1. All heat treatments were conducted in vacuum. Two groups of ordinary doped wire were prepared for diffusion with nickel. One group in the as-received (fibrous) condition was elec-tropolished, nickel-plated, and annealed at 1200°C for 20 and 40 hr, or was exposed to nickel vapor at 1200°C for 20 and 40 hr. The second group was recrystallized to an equiaxed grain structure at 2300°C for 3 hr, electropolished, nickel-plated, or exposed to nickel vapor for anneals at 1200°C for 20 and 40 hr.

Jan 1, 1969

By Clarence Zener

Contents Page General Principles................................................................. 551 Equilibrium Diagrams......................................................... 551 Nucleation................................................................... 553 Kinetics of Phase-boundary Propagation......................................... 553 Kinetics of Growth of New Phase............................................... 556 Spheroidization............................................................... 560 Pure Iron-carbon System........................................................... 561 Formation of Pearlite.......................................................... 561 Interlamellar Spacing........................................................ 562 Pearlite C-curve............................................................. 563 Bainite Formation............................................................. 565 Formation of Martensite....................................................... 570 Loss of Tetragonality of Martensite.............................................. 570 Effect of Alloys upon Decomposition of Austenite..................................... 572 Pearlite...................................................................... 572 Bainite and Martensite......................................................... 574 Time-temperature-transformation Curves............................................. 576 Appendix A............................................................. ......... 579 Appendix B....................................................................... 580 Appendix C....................................................................... 580 The present investigation started in an attempt to understand certain details of the decomposition of austenite, and of the effect of alloying elements thereon. As the investigation proceeded it became apparent that not only these details, but all the general features of austenite decomposition, could be understood in terms of fundamental physical principles. Since the direct applicability of these physical principles has not been previously recognized, it was decided to incorporate the original results of the investigation into a review of the general subject of the kinetics of austenite decomposition. This review constitutes the present article. An extended summary of the results is given on pages 576 to 579. This article, which deals with the kinetics of phase transformations, may appropriately be considered as a sequel to two recent articles1,2 from this laboratory on the equilibrium relations in medium alloy steels.

Jan 1, 1947

By Richard O. Carlson

Ions of p31 and B 11 were implanted in natural insulating diamond macles. The thin (-0.4µ) layers showed sheet resistances of 107 to 1011 ohm per sq and activation energies of 0.17 to 0.34 ev above room temperature. However, no Hall effect could be measured, indicating that mobilities were less than I to 10 sq cm per (v-sec). Such low mobilities may be due to excessive scattering due to radiation damage in the bombarded layer or to very high concentrations of active compensating impurities. Annealing did not materially change the room -temperature properties, but the temperature was limited to -800°C by surface graphitization, the latter process probably being accelerated by lattice damage in our diamonds arising from the ion bombardment. A weak n-type thermoelectric power was detected after p31 irradiation, but it cannot be presumed that we have made the phosphorus ions active as donors in diamond. The natural diamonds have a high and uncontrolled concentration of impurities and, when coupled with the radiation damage and graphitization problems, would appear to seriously limit the quality of semiconductor that we can presently achieve by ion implantation in diamond. ALTHOUGH diamonds are usually thought of as insulating in terms of their electrical conductivity, it was found about 15 years ago that natural semiconducting diamonds do occur rarely, and these were designated as type IIb diamonds. These p-type semiconducting diamonds were found to be dominated by an impurity level 0.37 ev from the valence band. Evidence today based on correlation of the concentration of acceptor states from Hall effect measurements with the impurity concentrations determined by neutron activation analysis point to aluminum as the dominant acceptor impurity.' The compensating donor is believed to be nitrogen, which has a donor level 1.6 ev above the valence band.' However, only a small fraction of the total nitrogen content in the diamond is electrically active. An infrared absorption band at 7.8 p and ultraviolet absorption near 4 ev have been associated with nitrogen, the former providing a quantitative measure of nitrogen content.3 The nitrogen content is -l020 cm-3 in insulating or type I diamonds, but is less than 10'' in natural semiconducting diamonds. Much of this nitrogen is distributed in platelets oriented in (100) planes and not atomically dispersed in the diamond lattice.4 Semiconducting diamonds have been deliberately formed by incorporating impurities into the graphite charge in the high-pressure apparatus used to form diamonds.5 These manufactured semiconducting diamonds are always p-type, and while some show the 0.37 ev level due to aluminum, most such samples have been ascribed to impurity banding effects.6 The best natural or manufactured semiconducting diamonds have hole mobilities near 1500 sq cm per (v-sec) at room temperature, and those with the 0.37-ev level can be analyzed to reveal an acceptor concentration of 3 to 8 X 1016 cm-3 and a donor concentration 3 to 10 times lower.' NO bulk n-type diamonds have ever been reported, but the electron mobility has been measured as 1900 sq cm per (v-sec) by irradiating a diamond with ultraviolet to excite electrons out of the deep nitrogen donor level or other levels.7 New hope for the formation of n-type diamond has emerged from the ion-implantation method whereby desired impurities are introduced into a crystal lattice by bombardment with a high-energy beam of the impurity ion. It was found in the case of silicon that the usual donors such as phosphorus and arsenic and acceptors such as boron and gallium could be implanted into silicon. Wentorf and arrow' produced semiconducting layers on diamonds by an ionic bombardment in a glow discharge at potentials of about 2 kv. The observed typeness from thermoelectric probing seemed to depend on the atmosphere gas (nitrogen, argon, or hydrogen) rather than on the electrode material, but the nature of the conduction process in the thin damaged surface layer is completely unknown. A Russian group under Vavilov has attempted high-energy ion implantation in natural diamonds using boron and lithium ions9 and later also phosphorus, aluminum, and carbon ions.10 Their papers claim n-type layers from lithium, phosphorus, and carbon implant and a p-type layer from boron and aluminum implant, though the methods of type determination are not described in detail. Under government contract support, the Ion Physics Corp. has studied ion implantation in several semiconductors. While the bulk of their study1' was devoted to the irradiation of silicon, they did carry out a short study on boron and phosphorus implantation into natural diamonds. They did observe surface conducting layers but did not determine the typeness of the layers. For our experiments, phosphorus and boron were chosen as the dopant ions because of their respective donor and acceptor behavior in germanium and silicon. Moreover, they are the lightest mass dopants of the shallow level donors and acceptors from columns 111 and V of the Periodic Table (excluding nitrogen which is already present in diamond), and will have the largest depth penetration into the diamond lattice. EXPERIMENTAL Diamonds. As the target diamonds for our ion implantation study, we chose commercially available macles, which are flat, twinned diamond crystals. By scanning through the stock of a wholesale distributor

Jan 1, 1970

By Armando M. Lago

Secular and cyclical patterns of postwar sources and uses of funds of the mineral sector are analyzed. A simultaneous equation behavior model of sources and uses of funds is developed for both mining firms and integrated producers, and these models were put through the task of predicting the financial and expenditure be-havior of mineral corporations in response to mergers and changes in investment tax credits and depletion allowances. Finally, the quantitative analysis methodology is applied to the analysis of optimum capital structure of mining corporations. The postwar changes that have occurred in the expenditure and financial behavior of mineral corporations are reviewed, particularly the relative importance of factors that affect the industry's supply and demand for funds. This quantitative statistical investigation of factors affecting sources and uses of funds of mineral corporations is achieved through the formulation of a simultaneous equation model of sources and uses of funds. After a description of the study sample, the postwar cyclical and secular financial behavior of mineral corporations is analyzed in detail. An econometric model of mineral corporate financial behavior is formulated. This model is then estimated and reviewed. Policy issues regarding depletion allowances, investment tax credits, and industrial organization of the mineral sector are discussed. Finally, the optimum financial structure of mining firms is discussed and the effect of corporate financial structure on the mining corporations' average cost of capital is analyzed.

Jan 1, 1971

By H. Hubert

The first attempts at direct utilization of blast-furnace gas in engines were made in 1895. For a considerable time the gas had been burnt in Cowper stoves for heating the blast for the furnace, and under the boilers which supplied steam to the blowing-engines, and others serving the furnaces. It was natural, therefore, that the idea of directly employing it in gas-engines should have occurred simultaneously to several engineers, notably to Lurmann and to Lencauchez, who had pointed out the blast-furnace as a powerful gas-producer. Nevertheless, nowhere had any attempt been made to apply it to this purpose up to the end of 1894, when Thwaite proposed it to Mr. James Riley, of the Glasgom Iron & Steel Company. About the same time investigations were being made in Belgium and in Germany, independently of Thwaite's experiments, which were not generally known on the Continent. The industrial world, which up to that time had hardly favored the idea, had thus been gradually prepared to receive it. The gas-engine, long restricted to small sizes and dependent upon the use of an expensive fuel obtainable only in large centers, now began to make headway. At the Paris Exhibition of 1889 two engines of 100 h.p. were shown and excited much interest among engineers. One had four cylinders, and was made at the celebrated works of the Deutz Company, and the other was a single-cylinder engine, exhibited by two French designers, Messrs. Delamare-Deboutteville and Malandin. In the meanwhile the design of gas-producers had made important progress, completely freeing the new engine from its

Jan 1, 1907

By R. W. Shearman, F. Weston Starratt

A new center for mining and metallurgical research is developing at Sterling Forest, N. Y., under the auspices of Union Carbide Corp. Here is to be located the Union Carbide Nuclear and Ore Research Laboratories. In truth, history has repeated itself; the Sterling Forest area in the days of the Revolutionary War, and for many years thereafter, was the mining and metallurgical center of the US. For in these Ramapo hills along the New York-New Jersey border, iron ore was mined, pig lion was cast, and the weapons of war and the plowshares of peace were forged. Before embarking on an historical pilgrimage to yesteryear-a brief description of Sterling Forest. Located in Orange County, N. Y., near Tuxedo, immediately north of the New York-New Jersey State line, and just west of the Erie Railroad and the New York State Thruway, Sterling Forest is approximately 35 mi from New York City. Title was acquired in 1956 from the Harriman family by City Investing Co. Its President, Robert W. Dowling, has established himself as a city planner, having conceived such projects as Pittsburgh's Gateway Center and Philadelphia's Penn Center. A unique, self-contained community -is planned that will contain light industry and centers for research and engineering. Colonies of homes will be interspersed throughout the 20,000 acres of forest land, lakes, and rolling hills. Culture will not be neglected, for Sterling Forest will be the new home for the annual Empire State Music Festival The Sterling Forest Gardens, 125 acres of landscaped woodland and streams, will become the "world's largest permanent floral showplace" The Sterling Forest International Research Building was opened earlier this year, and designed to provide all facilities needed by small growth research companies. The first major company to acquire land to construct research buildings at Sterling Forest is Union Carbide. 1763 ... Discovery of iron ore In turning back the pages of history, a fascinating story can be told of special interest to the metallurgist, the mining engineer, and perhaps even the sociologist. For, where new communities are planned today, older communities had been born, matured, and died. In these hills had lived the. iron miners, the blacksmiths, the lumbermen, the masons, and the teamsters that had given America its start in heavy industry. This was the area where the forests were crisscrossed with many wood roads that brought logs to the charcoal pits, and iron ore to the furnaces. Men make history. Our story brings forth many names of men known as ironmasters, or as industrial leaders-Hasenclever, Faesch, Erskine, Townsend, Ryerson, Parrott, Cooper, Hewitt, Jay Cooke, and Harriman. The name Sterling is derived from a Scotch Lord, the Fifth Earl of Stirling (in its earlier spelling). Lord Stirling was one of seven Englishmen granted a patent of land in the Ramapo hills by Queen Anne in 1707, known as the Cheesecock Patent. He sent an agent, Cornelius Board, to America in 1730, with the express purpose of looking for copper deposits. While he found no copper in his travels up and down the Ramapo Valley, he did find iron ore in two localities: first, in the vicinity of what is now Ringwood, N. J.; second, five miles to the north. There he constructed a forge and furnace at the edge of a lake in 1736, naming the land Stirling Property, after his patron. In 1740, the Ogden family in Newark bought land from Board at Ringwood and began smelting of iron in 1741. The Ringwood story Soon, a genius in the person of Peter Hasenclever appeared on the scene. He was attracted by an advertisement in the New York Mercury for March 5, 1764, in which David Ogden of Newark offered

Jan 1, 1961

By Philip B. Bucky

[ ] FOREWORD THIS symposium brings together points of view, experiences and ideas on rock bursts from a goodly portion of the globe. Some conceptions, particularly those regarding the necessity of depth, have been fairly well shattered, as we find that they are present in the water tunnels of New York, on the surface at marble quarries in Vermont, and in the coal mines of the United States, as well as in the deep mines of the South African and Kolar gold fields, and in the nickel, copper and gold mines of Canada. Their occurrence under such a variety of conditions is, therefore, a challenge,

Jan 1, 1942

By G. S. Cole, G. F. Bolling

A series of Al-Cu alloys has been cast from constant superheat to solidify either with a hot top or with a free liquid/air interface. All the other variables which affect relative fluid motions were kept constant except the imposition of slow rotations m oscillations of the mold. Depending upon the exact circumstances, evi-dence could be found for the nucleation of equiaxed grains from dendrite bits detached from the columnar zone, or from the free surface, or from solid bits induced at pouring; a special experiment showed the solute buildup during ingot solidification and by inference the reality of constitutional supercooling. All methods of grain nucleation are thus supported. When solidification is arranged in a static mold the columnar- to-equiaxed transition occurs by one of these nucleation paths, subject to the natural decay of temperature gradients which promotes nucleation or the survival of nuclei. But when solidification is forced under special fluid flows it may display odd transitions. In one of these the equiaxed zone is synihesized from. dendrite bits detached from the solid/liquid interface. These survive under the concurrent lowering of temperature gradients and eventually cause transition by impeding columnar growth. GRAIN structure control is desired because real experience shows that specific properties are associated with specific cast grain structures. But since control is thus a matter of need and does not require understanding, much of casting remains art. For example, the manipulation of relative fluid motions in simple ingots provides a control of grain structure development,1-4 but theoretical insight is not required in order to broaden its potential applicability. Fortunately, however, once a variable like fluid flow is recognized it can also provide paths toward new insight. New observations using this variable have provided an insight which is curious. All the theories or descriptions of the columnar-to-equiaxed transition (CET) seem to be supported as long as the appropriate experiment is carried out. In order to develop this idea, let us ignore segregation, the chill zone (until a later section of this paper), and the origin and development of the columnar zone.= The details of questioning how equiaxed material forms in a casting may be divided in two. The first part is simply a questioning of the origin for equi-axed grains: are there fresh nuclei from heterogeneous nucleation, or dendrite bits broken off or melted from the columnar zone or elsewhere,6 or other solid bits surviving from the outset of freezing? The second is more complex, a questioning of the CET: does columnar growth slow down and allow the dominance of equiaxed grains, however they are formed, or do equi-axed grains take over and force columnar growth to stop? This "chicken-or-the-egg" second question can be quite useful, especially because it allows us to delineate the ordinary or NATURAL EQUIAXED ZONE and the induced or SYNTHETIC EQUIAXED ZONE. A natural equiaxed zone occurs if solidification proceeds in the absence of disturbances or extraneous forces such as ultrasonics, stirrings, and so forth. Both the CET theory proposed by Winegard and Chal-mers, 7requiring constitutional supercooling, and the CET theory suggested by Chalmers,8 requiring nuclea-tion only on pouring, pertain to the natural equiaxed zone. The best collating evidence to date for both these theories is contained in the work by Biloni and Chal-mers;9,10 the former theory7 is supported by special versions of the unidirectional growth experiment performed by Plaskett and winegardl1 and the latter theory' is supported in detail for the solidification of small ingots. An equiaxed zone can be synthesized when disturbances caused by forced fluid flows2-4 or other artificial means9,10 break off or melt off dendrite tips from an advancing solid/liquid interface,* if (and only if) temperature gradients in the melt are (forcibly) reduced enough to ensure the survival of these bits of dendrites, 2'3 Willful disturbances even so trivial as those produced by rapping a mold might be included here; as will be shown for example, this follows Southin's suggestion that the free liquid/air interface

Jan 1, 1970

By Kurt Stock

The war caused a demand for enormous quantities of high-grade zinc, which were not available and could not be produced from pure ores in sufficient amounts and in the time required. Redistillation of virgin spelter on a large scale was practiced to supply this demand; this paper gives a full description of the process used by the Oklahoma smelters of the Bartlesville Zinc Co. As the redistillation of zinc has become of historical interest only, having been superseded by the electrolytic process, it was deemed advisable to give expression to this phase of the metallurgy of zinc that, in the past, had never gone beyond laboratory experimentation. THE grades of spelter demanded by the consuming industries were not definitely established until the American Society for Testing Materials undertook to fix specifications, based on the varying percentages of the common impurities (lead, iron, and cadmium) as follows: TOTAL, NOT LEAD, IRON, CADMIUM, OVER. PER PER CENT. PER CENT. PER CENT. CENT. A. High grade 0.07 0.03 0.05 0.10 B. Intermediate 0.20 0.03 0.50 0.50 C. Brass special 0.75 0.04 0.75 1.20 D. Prime western 1.50 0.08 The question which grade was the best for certain purposes and why was left unanswered. The conservatism of the zinc-smelting industry and the unwillingness of the spelter-consuming industries to engage in research work prevented the full benefits being obtained that such standardization promised. The custom smelters, producing spelter in pigs or plates, found it impossible to adhere closely to the established limits on account of the variety of ores treated; and the smelters with long-established and known brands, or those manufacturing their metal into marketable products, like sheet zinc, did not have to abide by the newly established grades based on chemical percentages.

Jan 7, 1924

By Strathmore R. B. Cooke, Iwao Iwasaki, C. S. Chang

The effects of aeration on an aqueous suspension of pyrrhotite were studied and their results correlated with flotation tests using xanthates as collectors. The effects of copper activation and of pH variation were determined and possible mechanisms postulated. PYRRHOTITE has long been considered a gangue mineral to be eliminated as tailing in the treatment of various sulphide ores. However, in recent years the world-wide lack of sulphur resources has called attention to this mineral as a potential source of both sulphur and iron. Its importance as an economic mineral, however, has not been particularly emphasized. For this reason very little is known about its response to flotation, except that it can be depressed easily in alkaline circuit, by long aeration,1,2 addition of oxidizing agents,3 or by starch.' The object of this work was to study the floatabil-ity of pyrrhotite. This includes the effect of oxidation by aeration, of copper activation, and of change in pH. Preparation of the Pyrrhotite Sample: It was desirable that the highest grade of pyrrhotite obtainable be used for this experiment, since the presence of other minerals could affect the surface properties.5 However, no pyrrhotite was available as crystals, and massive deposits of hydrothermal origin commonly contain considerable amounts of chalcopyrite. Pyrrhotite concentrate was, therefore, prepared from a sulphide deposit occurring near Aitkin, Minn. The deposit is of pyrometamorphic nature consistirlg mainly of pyrrhotite and pyrite with graphite, silicates, and carbonates as gangue. The ore, already crushed through 3 mesh when received, was screened at 65 mesh and the undersize discarded. The oversize was crushed through rolls, and then stage-ground dry in an Abbe porcelain mill, the —65 mesh portion being screened out after every 15 min of grinding until all the material passed through this size. The ground product was then concentrated with a drum-type dry magnetic separator. The rougher concentrate was cleaned twice and then demagnetized. The final product was split in a Jones splitter and stored in air-tight bottles. Microscopic examination of the concentrate showed that it was relatively clean and free of pyrite, locked particles, and gangue. By means of the krypton gas adsorption method," the specific surface was determined to be 3000 cm2 per g. The chemical and screen analyses of the final concentrate are given in Tables I and II respectively. It is a well-recognized fact that the oxidation of some sulphide ores during stockpiling, grinding, and conditioning affects their flotation behavior. The problem of oxidation may become serious in the case of pyrrhotite, since this is known to be more easily oxidized than many other sulphides. To ascertain the extent of oxidation, an experiment was carried out by aerating an aqueous suspension of pyrrhotite with air, oxygen, and nitrogen as follows. A 300-g sample of pyrrhotite in 2700 ml of water was agitated and simultaneously aerated in a Fager-gren-type laboratory flotation machine. A Precision wet test meter was connected to the air inlet valve, the flow rate of the gas being kept constant at 0.3 cu ft per min throughout the experiment. Samples of approximately 30 ml each were taken from the cell at 0, 4, 10, 20, 35, 60, and 90 min. After the pH was taken, each sample was filtered and the filtrate was analyzed for total iron and sulphur. The iron was determined colorimetrically by the thioglycolate method using a green filter.' The filtrate was oxidized with bromine to convert all of the soluble sulphur compounds into sulphate and this was determined with a Parr turbidimeter." When aeration tests were made in alkaline circuit, calcium hydroxide or sodium hydroxide was added at regular intervals to maintain a constant pH. A similar procedure was followed in an experiment to determine the abstraction of copper. ion by pyrrhotite. In this case various quantities of cupric chloride were added. The filtrate from each sample taken was analyzed for copper, total iron, and sulphur. The carbamate method with a green filter was used for the copper analysis,' since this method could tolerate a considerable amount of iron in the solution. A pneumatic cell, made from a 350-ml fritted glass Buechner funnel, was used for this experiment. The detail of the assemblage has been described elsewhere." In the present work a stainless steel baffle was inserted in the cell. This baffle overcame the tendency for the coarse pyrrhotite particles to be swirled around the wall of the cell and thus fail to collect in the froth. A 50-g sample of pyrrhotite was added to the cell which contained 260 ml of water. When pretreat-ment of the sample was desired, reagents, such as activator and pH regulator, were then added and the pulp was conditioned for a specified conditioning time. Prior to the addition of the collector approximately 15 ml of the solution were removed for pH measurement and for iron and sulphur analyses. Copper when used as activator was also determined. Collector and frother were then added and the pulp was conditioned for an additional 2 min. Air was admitted to the cell and the froth removed. The separation required from 4 to 6 min, depending on the characteristics of the froth. The float and non-float products were filtered, dried, weighed, and assayed for iron.

Jan 1, 1955

By W. L. Fink, R. S. Archer

This paper describes results obtained on aluminum-beryllium alloys and aluminum-beryllium-copper alloys in the preparation of which aluminum of 99.95 per cent. purity was used. The constitution and structure of the high purity binary alloys are given. The aluminum-beryllium eutectic occurs at 0.87 per cent. beryllium and 645° C. The solid solubility of beryllium in aluminum at 631° C. is 0.05 per cent, beryllium, and at room temperature is less than 0.013 per cent. beryllium. The densities of the alloys are substantially the same as the values calculated on the assumption that the densities of the elements are not changed by alloying. All of the alloys age-harden at room temperature after a solution heat treatment, and the chill cast aluminum-beryllium-copper alloys age-harden at room temperature without a prior solution heat treatment. Hardness and tensile properties are given. Salt spray corrosion tests on sheet specimens are described. It is shown that beryllium docs not lower the corrosion resistance of aluminum to salt spray provided the alloy has received a solution heat treatment. Commercial Possibilities of Beryllium Alloys Beryllium has certain properties such as low density, high hardness, good corrosion resistance, low thermal expansion and fairly good electrical conductivity, which would indicate that it is worthy of consideration as an ingredient of light alloys. It was not until recently, however, that beryllium could be produced with sufficient ease to encourage research along this line. The production of beryllium by electrolysis from a fluoride bath has now developed to the stage where it could be used commercially if there were sufficient demand for the element. Claims made in certain newspapers and technical articles in regard to thc strength and corrosion resistance of thc aluminum-beryllium alloys are not justified by experimental results. Moreover, beryllium is an expensive metal ($200 a pound at the time this work was done) and, on account of the nature of its ore and the consequent difficulty of its extraction, it will in all probability continue to be a relatively expensive metal, although the cost would undoubtedly be a great deal less than $200 a

By K. C. Strebig, C. W. Schultz, A. A. Selim

The effect of some organic additives in diamond drilling of quartzite was investigated in the laboratory. The drill was designed to measure the rate of penetration, the thrust, and the torque and to record each as a function of the distance drilled. A statistical plan was followed throughout the investigation and an equation representing the bit performance was derived from the mathematical theory of reliability. The drilling torque was found to increase with the use of additives while the sliding coefficient of friction and the wear coefficient decreased. The energy per unit volume consumed was found to increase with the use of additives. A hypothesis explaining the effects achieved with the additives is given. INTRODUCTION For some time researchers have attempted to increase drilling efficiency by adding certain agents to the flushing medium. Much of this interest is the result of the observations of Rehbinder, Shreiner and Zhigach1 They postulated that "...in processes for the mechanical destruction of solids, a region of increased crack formation is created in the deformed layers adjoining that surface of destruction, forming the predestmction zone. The surrounding medium (for example, a liquid) which wets a given solid will penetrate the embryo microcracks of the predestruc-tion zone. Increasing the molecular affinity of this liquid for the surface of the solid considerably facilitates the deformation and destruction by softening the solid in the zone of increased crack formation. In this manner, the hardness or strength of the deformed body is decreased by the influence of the penetration of the liquid into the predestraction zone." This is known as the "Rehbinder effect". Rehbinder's work has prompted many investigators to examine the effect of additives on the mechanical destruction of rocks. Engelmann, Terichow and Selim reported that the maximum penetration of the rock by a diamond point in a solution environment was at the isoelectric point of the solution.* Robinson reported that his results did not appear to support the theory of Rehbinder.3 Joris and .McLaren suggested that additives with surface tension lower than water will be more efficient in cooling the diamonds.4 Their effectiveness in removing the fine cuttings from the face of the bit will also improve the efficiency of the system. They reported an improvement in impregnated bit life and penetration rates with the use of soluble oil additives. In contrast, Long and Agnew, drilling with surface set bits, reported that lubricating agents increase bit temperature and wear.5 A significant change was reported6 in the mechanical properties of rock with polar additives. It was concluded that this change in the mechanical properties of the rock in the presence of the additive is due to the rock hydrophilic properties. Ethylene glycol, glycerine and anionic detergent were selected for this investigation because their surface tension is lower than that of water. The surface tension of these additives for the concentrations studied was 42 to 75 percent of the surface tension of water. A low surface tension additive would wet the surface of the diamonds more easily and hence would be more effective in cooling the diamonds. Another characteristic of these low surface tension additives is their effectiveness in removing the cuttings and preventing the flocculation of the formed particles in the drilling process. This article summarizes the results of an investigation performed at the laboratories of USBM, Twin Cities Mining Research Center. The objective of the investigation was to study the over-all effects of some organic additives on the performance of diamond impregnated bits in atmospheric drilling conditions only and not in downhole pressured conditions.

Jan 1, 1970

By M. A. Jones

Performance of a pilot flood in eastern Kansas indicates improved recovery and accelerated production resulting from mobility ratio control obtained by adding a high moleculur weight polymer to injected water. Ultimate pilot flood recovery of the 75-cp reservoir oil is anticipated to he 350 bbllacre-ft during the six-year flood life. Cumulative recovery to date totals 242 bbl/acre-ft after 30 months of injection. Reservoir parameters and flood performance are disc~rssed in detail to provide a case history relating to the feasibility of polymer flooding. INTRODUCTION The Vernon Polymer flood of the Brazos Oil & Gas Co., located in Sec. 2, 24 S., 16 E., Woodson County, Kans., was begun in late Oct., 1963. Injection of a 500 ppm solution of Pusher* polymer was initiated in a 15-acre pilot to determine feasibility of improving oil recovery by mobility ratio control. Performance to date and the anticipated recovery of 115,000 bbl from the 329 acre-ft pilot indicate efficient displacement of the viscous reservoir oil. Dependence of flood recovery on the displacing fluid-displaced oil mobility ratio has long been recognized. Displacement efficiency of the reservoir oil decreases with increasing mobility ratio. Therefore, economic reduction of this parameter is an attractive approach to improving oil recovery. particularly from viscous oil reservoirs where mobility ratios are often quite high. Waterflood mobility ratios can be controlled by dilute solutions of certain polymers'; which provide a displacing fluid with considerably reduced mobility. Reservoir parameters and flood performance are emphasized in this paper to provide data relating to polymer flood applicability. THEORY The polymer used in the Vernon pilot exhibits the property of unusually high resistance to flow through porous media.'.' A small concentration in injected water effects a mobility reduction considerably beyond that predicted from increases in bulk viscosity as measured in a capillary or rotating cup viscosimeter. Water mobility in the subject flood is reduced by a factor of 7.55 with the addition of 500 ppm Pusher chemical to injected water while the bulk viscosity is increased from 1.03 to only 1.40 cp at 75F. The exact flow mechanism causing resistance to flow has not been established; however, it is observed only in tortuous flow systems and appears to be influenced by brine properties, rock properties and oil saturation. Consequently, mobility reduction is estimated from flow studies for a given sample of reservoir rock and is expressed in terms of a "resistance factor".' This parameter is defined as the ratio of brine mobility to polymer solution mobility measured at residual oil saturation: RF= ?m/?p= (km/µm)/(kp/µp)M.......(1) where RF = resistance factor (dimensionless) k*. and A, = mobility of water and polymer solution, respectively k,,, and k,, = water and polymer permeability, respectively (darcies) µie and µp = viscosity of water and polymer, respectively (poise). Eq. 1 is similar to the expression commonly used to relate the relative mobility of the water bank at residual oil saturation to oil-bank mobility at irreducible water saturation: where M =mobility ratio of water to oil (dimension-less) A, = mobility of oil k, = permeability to oil (darcies) )i* = oil viscosity (poise). From Eqs. 1 and 2 it is apparent that the polymer-solution-to-oil-mobility ratio can be approximated by dividing the brine-to-oil ratio by the resistance factor RF: Mpn=M10/RF...........(3) where M,-, = mobility ratio of polymer solution to oil (dimensionless). This simplified presentation assumes no dilution of the polymer solution by connate water. Also, the presence of a connate water bank separating the polymer solution from the displaced oil is not considered. Displacement of oil by waterflooding is increasingly dominated by viscous forces as the viscosity of the oil displaced increases. When the oil mobility is less than that of the injected water, the oil-water interface is not a piston-like front.3,' Instead, instabilities occur at the flood front in the form of viscous fingers which tend to penetrate the less mobile oil bank. The magnitude of these protrusions, or the degree of channeling, increases

Jan 1, 1967

By Waldemar Lindgren

No one would maintain that all ore deposits or all deposits of useful minerals have been formed by the same processes. Generally they have originated by special processes of concentration but these may be of many different kinds. Some deposits have their origin in chemical or biochemical processes of concentration in rivers, lakes or seas, others developed on land by means of chemical reactions of surface waters on various forms of rocks. Certain insoluble substances remained behind; others were dissolved and precipitated in favorable places. This action proceeded in the realm of the oxidizing surface waters or in the deeper zones to which the waters from the surface could find their way. Examples of the latter kind may be found in the extensive copper and vanadium deposits of some sedimentary beds or in the lead and zinc deposits of certain broad limestone strata. In these instances the evidence for any other mode of origin would seem to be very weak indeed.' Nor does it seem possible to deny that circulating waters may form deposits of the more common metals along fissures after having dissolved many constituents from paths traversed. Another very large class has been formed by magnetic processes of concentration. The last 40 years have been a period of intense activity in the investigation and description of a vast number of deposits; all modern methods have been employed and the result is an accumulation of data, difficult or impossible to master. It has been a period similar to that in petrography. The generalizations, the able deductions, have lagged behind. Evidently several geologists have become weary of this "infinite detail" and a mistrust of the microscope seems to have arisen. Although this feeling of being swamped in microscopic detail is a painful experience, nevertheless only through the detail in combination with the large features, and only by utilizing all the related sciences shall we

Jan 1, 1927

By J. W. Lacey, F. H. Brinkman, J. E. Faris

This paper presents an analysis of the high-pressure, gas-driven LPG-slug process, based on fluid flow tests in areal models. Two types of tests were made. One series was made in low-pressure models which permitted observation of fluid movement. Three completely misci-ble analog fluids were used. A second series of tests was made in high-pressure models using methane, propane and a light refined oil saturated with methane at room temperature and 1,550 psig. Under the test conditions of room temperature and a pressure level of 1,550 psig, the phase diagram for the fluids used is similar to those for many of the field systems where the process is considered for use. A method for using these laboratory data to calculate field performance of the process is outlined. As a result of this work, it is concluded that small banks of LPG (5 per cent HV or less) are not effective in increasing oil recovery in horizontal reservoirs. Znstead, where small banks are used, the driving gas quickly penetrates the LPG bank because of fingering and channeling; and from this point on, the process behaves essentially as an immiscible gas-injection project. The validity of this conclusion was substantiated by: (1) laboratory studies of the effect of rate, model size and mobility ratio on miscible displacement in areal models; and (2) calculation of field recovery, which compared closely with actual field recovery. INTRODUCTION Field applications and pilot tests of the gas-driven, LPG-bank, oil-recovery process are on the increase. Most of these tests are employing small banks (2% to 5 per cent hydrocarbon volume) of LPG, which is miscible with both the driving gas and the oil in place, in an effort to attain an effective yet economical miscible displacement of oil by gas. The expectation of miscible displacement with small banks is based on the concepts that: (1) lengths of solvent-oil mixed zones, measured during miscible displacements in long slim cores, are representative of those that will occur in the field; and (2) areal sweep efficiencies5 measured in electrolytic model studies are applicable to miscible displacement in reservoirs. Our experimental evidence indicates that the mixed-zone lengths and sweep efficiencies mentioned are not applicable to miscible displacement in reservoirs. In this paper we present an evaluation of the gas-driven, LPG-bank oil-recovery process based on fluid flow experiments in areal models. These results are used to predict the performance of a field pilot test of this process, and the results are compared with the actual test results. THE EFFECTIVENESS OF LPG BANKS The effectiveness of LPG banks of various sizes in accomplishing miscible displacement of oil by gas was determined by displacement tests in a model representing one-quarter of a confined five-spot pattern. The model, 12 X 12 X 1/4 in. in size, was packed uniformly with glass beads. It was operated at a pressure of 1,550 psig and at room temperature; the fluids used were methane, propane and refined oil saturated with methane at 1,550 psig. The saturated oil had a viscosity of 1.2 cp at room temperature. The results of these tests are shown in Fig. 1, where recovery is plotted as a function of the volume of fluid injected for: (1) an immiscible-gas drive with an oil-to-gas viscosity ratio of 85; (2) three sizes of LPG banks; and (3) two completely miscible displacements with mobility ratios of 85:1 and 10:1. (The miscible displacement data plotted are the averages of several tests.) The results show that a 2½ per cent bank of LPG does not increase oil recovery over that obtained by immiscible-gas drive. The 7 and 17 per cent banks are, respectively, about 30 and 50 per cent effective (with reference to the M = 85 miscible-displacement curve) in increasing oil recovery at the point where 2½ hydrocarbon volumes (HV) of fluid have been injected. The percentage effectiveness of the banks at a given volume of fluid injected is defined as Recovery by Bank — Recovery by Gas Drive Recovery by Miscible Recovery by Flooding Gas Drive We conclude from these results that banks of LPG smaller than about 5 per cent HV in an individual stratum will cause from little to no increase in oil recovery. This finding was substantiated by work in low-pressure models, which permitted visual observation of fluid movements. In these tests, three completely miscible fluids having the same viscosity ratios as those used in

By Henry Lloyd Smyth, J. Ralph Finlay

The most important area of the so-called Keewatin rocks of northern Minnesota is that which runs westerly from Lake Saganaga, near the national boundary, and finally disappears beneath the drift (or has not been farther traced), in the neighborhood of Vermilion Lake. With this belt we have a general acquaintance, extending back some four years. During the past year we have had the opportunity of studying in considerable detail a small part of it, embracing an area of about 12 square miles on the south and east shores of Vermilion Lake. In this paper we desire to record our observations and conclusions, which seem to us important. II.—Literature. Outside the Minnesota Geological Survey, the list of the investigators who have studied the geology of the Vermilion Lake area is not long. Whittlesey, in 1876,* mentioned the occurrence, in the area about Vermilion Lake, of rocks resembling the Canadian Laurentian. Chester,? in 1884, described the iron-ore at Vermilion Lake as occurring in connection with jasper and quartzite, intimately bedded with the country-rock, chiefly sericite schist, and standing in a nearly vertical attitude. The Vermilion iron-bearing rocks, and those of the Mesabi range, he says, are of the same age.

Jan 1, 1896

By O. B. Bucklen, P. G. Meikle

INTRODUCTION The trend in the coal industry for many years has been to make every- thing "bigger and faster." This also held true for loading and storage facilities. Where once a million ton per year mine was rare, three to five million ton per year mines are not uncommon today in the bituminous industry. This greatly increased production, made possible through mechanization, required greatly improved loading facilities just to get the coal away from the mine. Also, there is a trend toward combining production from more than one mine and cleaning it in a single preparation plant. In addition to increased loading capacity, this frequently necessitates raw coal storage and blending facilities. The development of the unit train with its attendant economics, more than any other factor, has contributed to the widespread construction of storage and high-speed loading facilities. In the export market, the construction of ever larger coal colliers has contributed to a need for faster and larger loading facilities. In this climate of rapidly changing technology, any written account is faced with the possibility of obsolescence before its appearance. Thus, this chapter seeks to define the common and current practice in coal loading and storage facilities with the full knowledge that this practice is an ever-moving target. FUNDAMENTALS OF COAL STORAGE Storage of coal is becoming an increasingly important part of coal handling systems at mines, particularly since the advent of the unit train concept in transportation. In order to take advantage of reduced transportation rates on trainload shipments of coal offered by unit train movement, operators have found that storage is an economic necessity. In unit train practice large predetermined quantities must be loaded in relatively short periods of time as opposed to conventional practice where coal is loaded at a speed dependent on the production capacity of the mine and/or the cleaning capacity of the preparation plant. Two surveys of storage practices at mines reveal several objectives for storage.1, 2 Raw and/or clean coal storage is generally practiced in order to accomplish one, or a combination, of the following objectives: 1. To improve plant efficiency by distributing plant feed over the entire operating time, or to allow a preparation rate different from the production rate. 2. To limit interruptions of supply, ie, allow mine and plant to function independently with delays in one not affecting the operation of the other.

Jan 1, 1968