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By Arhtur T. Allen

THE Kingsport formation, a part of the Knox dolomite of Ordovician age, is composed of 538 ft of dolomite and limestone. Numerous bands, layers and nodules of chert, arenaceous and shale zones are present. The characteristics displayed by these features have been useful in mapping, prospecting and mining. Perhaps a better understanding of the origin of these zones will increase their usefulness.

Jan 1, 1947

By J. Gurland

THE microstructure of sintered carbides consists of particles of metal carbides, such as WC and TiC, embedded in a metallic binder which is usually a cobalt—or nickel-rich solid solution. One of the important factors influencing the strength of the alloys is the degree of dispersion of the carbide particles in the binder matrix. While it is generally accepted

Jan 1, 1960

By Howard A. Smith

Of late considerable experimental and theoretical interest has been shown in the rates of transformation from a single phase, usually a supercooled solid solution, into one or more phases. Such reactions may involve both diffusion and transformation of the major constituent, as in iron alloys, or it may simply involve diffusion, as in superstructure formation and in age-hardening systems. Most of the work has been confined to ferrous alloy1-9† although two investigations have been made on copper alloys10*". That such work may be of considerable practical importance has been demonstrated by Bain12, by the workers at the Kaiser Wilhelm Institut fur Eisen-for~chung'13, 14, and by the everyday use of precipitation and age-hardening principles15. Experiments in this country have generally followed Davenport and Bain's technique of rapid supercooling followed by isothermal treatment. In Germany16, 17 the work has been extended to the study of the influence of accurately controlled and measured rates of cooling. The work on steel indicates that there are two subcritical temperature ranges where reaction starts sooner after quenching and proceeds at a more rapid rate than at other temperatures. At suberitical temperatures above Ar" (temperature of martensite formation) where reaction is dependent upon atomic migration there is a period of time of which the length depends upon the alloy content and the temperature, before which no reaction has been detected. Davenport and Bain' find that different sorts of atoms in solid solution in gamma iron affect the length of this " prereaction" period differently, manganese probably being the most effective in lengthening it. It is very difficult to believe that nothing occurs within these "prereaction" regions, for if this were so there is no reason why any reaction at all should be observed. In the light of experimental facts and theoretical considerations it is certainly

Jan 1, 1935

By R. H. Fillnow, D. J. Mac

IT has been demonstrated that alloys in systems structurally analogous to steel undergo reactions during heat treatment similar to those of steel, and yet very little work has been done on such systems, particularly from the standpoint of isothermal transformation. The literature shows that most of the isothermal work has been done on copper-alu-minum alloys.'-3 One paper has been reported on a eutectoid copper-silicon alloy,' and one on iron-nitrogen alloys.' There are no published reports of previous investigations on the isothermal transformation of a eutectoid beryllium bronze. At least two papers have been reported on isothermal age-hardening phenomena in beryllium-copper alloys of lower beryllium content.5,6 No information on eutectoid transformations in this alloy is given in Rimbach's book, "Beryllium." ' This paper reports the results of an investigation on the isothermal transformation characteristics of a eutectoid beryllium bronze. Materials Used and Procedure The eutectoid beryllium bronze used in this investigation was centrifugally cast at the Ampco Metal Co., Inc.. Milwaukee. Wis. A master beryl-lium-copier alloy, purchased from the Brush Beryllium Co., was used to make the beryllium addition to the copper. The alloy was melted under a protective carbon cover and Centrifugally cast into a graphite mold preheated to 920°F. Some trouble with segregation of beryllium in the melt was encountered but was eliminated by violent stirring during melting and pouring. Since very thin .specimens were used for the various heat treatments, only one casting of the four prepared was necessary for the complete isothermal study, thus eliminating any discrepancies caused by a change in composition. The analysis of this casting was 94.035 pct copper and 5.965 pct beryllium. A slight trace of iron was found. The castings were sawed into specimens approximately 3/32 in. in thickness. The specimens were first given an "austenitizing" heat treatment at 788°C, well within the single phase beta region, in a vertical tube furnace. The specimens were then quenched individually into an adjacent molten salt bath and held there for a definite time, after which they were quenched into water at room temperature. Temperature was held to ± 2°C in the salt bath. No homogenizing treatment was given the specimens other than the soak at 788°C. Despite the fact that this was a cast alloy, no evidence of segregation or coring was found in the microstructure of any specimen, either as cast or as heat-treated. Upon completion of the heat treatment, the speci-mens were subjected to metallographic examination

Jan 1, 1951

By Howard A. Smith

Of late considerable experimental and theoretical interest has been shown in the rates of transformation from a single phase, usually a supercooled solid solution, into one or more phases. Such reactions may involve both diffusion and transformation of the major constituent, as in iron alloys, or it may simply involve diffusion, as in superstructure formation and in age-hardening systems. Most of the work has been confined to ferrous alloy1-9† although two investigations have been made on copper alloys10*". That such work may be of considerable practical importance has been demonstrated by Bain12, by the workers at the Kaiser Wilhelm Institut fur Eisen-for~chung'13, 14, and by the everyday use of precipitation and age-hardening principles15. Experiments in this country have generally followed Davenport and Bain's technique of rapid supercooling followed by isothermal treatment. In Germany16, 17 the work has been extended to the study of the influence of accurately controlled and measured rates of cooling. The work on steel indicates that there are two subcritical temperature ranges where reaction starts sooner after quenching and proceeds at a more rapid rate than at other temperatures. At suberitical temperatures above Ar" (temperature of martensite formation) where reaction is dependent upon atomic migration there is a period of time of which the length depends upon the alloy content and the temperature, before which no reaction has been detected. Davenport and Bain' find that different sorts of atoms in solid solution in gamma iron affect the length of this " prereaction" period differently, manganese probably being the most effective in lengthening it. It is very difficult to believe that nothing occurs within these "prereaction" regions, for if this were so there is no reason why any reaction at all should be observed. In the light of experimental facts and theoretical considerations it is certainly

Jan 1, 1935

By Hans Von Höfer

Apart from the hypothesis of a cosmic origin (which failed of acceptance because it was not adequately supported by facts), the only important controversy concerning the origin of petroleum has been, for a long time, between the advocates of inorganic and of organic origin respectively. Each of these theories has had a long history of development, and is still being perfected, under the influence of two causes: (1) the increasingly extensive and thorough study of the oil-fields (of which new examples are periodically discovered and opened); and (2) the progress of synthetic experiments devoted to this question. Moreover, the advance in our physical and chemical knowledge of the properties of this peculiar natural product has necessarily modified all criticism of conflicting views. I. The Hypothesis of Inorganic Origin That the nation of an inorganic origin of petroleum, first set forth by Berthelot in 1866, and afterward ingeniously developed and formulated by Mendelejeff, should thus have proceeded chiefly from chemists, is quite natural; for the question was one of possible chemical processes in the earth's interior, and of imagined chemical reactions to be verified by ex-periment. Hypotheses of this kind were suggested by many chemists, of whom two, P. Sabatier and J. H. Senderens, may be specially named by reason of their highly interesting chemical experiments. Among geologists, Mendelejeff's hypothesis was received at first with much interest and favor; for it rested on the assumption of a central terrestrial mass of iron carbide, and the geologists had good reasons for adopting that assumption. Yet comparatively few of them attempted to furnish geological proofs of the hypothesis: the majority either silently believed in it, or for one or another reason rejected it altogether. An apparently weighty support of Mendelejeff's view was furnished by the American, G. F. Becker, who found in the oil-regions of the United States important and abnormal disturbances of the isogons of terrestrial magnetism, and inferred that in these regions the central iron mass must

Jan 1, 1915

By Nicholas J. Grant, John S. Benjamin

A series of composite alloys containing a high volume of NiAl, Ni3Ah or CoAl, bonded with 0 to 40 vol pct of a ductile metal phase, were prepared by powder blending and hot extrusion. The binder metals were of four types: pure nickel or cobalt, near saturated solid solutions of aluminum in nickel and cobalt, type 316 stainless steel, and niobium. Sound extrusions were obtained in almost all instances. Studied or measured were the following: interaction between the alunzinides and the binders, room-temperature modulus of rupture values, 1500° and 1800°F stress rupture properties, hardness, structure, and oxidation resistance. Stable structures can be produced for 1800°F exposure, with interesting high-temperature strength and good high-temperature ductility. Oxidation resistance was excellent. A large number of experimental investigations have been made of the role of structure on the properties of cermets and composite materials. Gurland,1 Kreimer et al.,2 and Gurland and Bardzil3 have indicated the preferred particle size in carbide base cermets to be about 1 µ, with a hard phase content of 60 to 80 vol pct. The optimum ductile binder thickness was noted to be 0.3 to 0.6 µ.1 Complete separation of the hard phase particles by the binder is important in reducing the severity of brittle fracture.' The purpose of the present study was to produce structures comparable to the conventional cermets, using a series of relatively close-packed intermetal-lic compounds rather than carbides as the refractory hard phase, and to study the effects of binder content and composition on both high- and low-temperature properties. The selected intermetallic compounds were particularly of interest because of the potential they offered in yielding room-temperature ductility. The highly symmetrical structures are known to possess high-temperature ductility and room-temperature toughness. Based on a ductile binder, the alloys were prepared by the powder-metallurgy route to avoid melting and subsequent alloying of the matrix, and were extruded at relatively low temperatures. It was expected that the composite alloy would retain useful ductility. In contrast, infiltration and high-temperature sintering led to alloying of the matrix and to decreased ductility. The systems Ni-A1 and Co-A1 were selected for this study. In the Ni-A1 system the compounds NiA1, having an ordered bcc B2 structure, and Ni3Al(?1), having an ordered fcc L12 structure, were chosen. In the system Co-A1 the intermetallic compound CoAl with an ordered bcc B2 structure was used. ALLOY PREPARATION The intermetallic compounds, see Table I, were prepared by using master alloys of Ni-A1 and CO-A1, with additions of either cobalt or nickel to achieve the desired compositions. The master alloy in crushed, homogenized form, was melted with pure nickel or cobalt in an inert atmosphere, cold copper crucible, nonconsumable tungsten arc furnace. The resultant intermetallic compounds were homogenized at 2192°C in argon, crushed, and dry ball-milled in a stainless mill to -100 and -325 mesh for the Ni-A1 compounds and to -325 mesh for the CoAl compound. Finer fractions were separated for some of the composite alloys. Several ductile binders were utilized. These included Inco B nickel, 5µ ; pure cobalt, 5 µ, from Sher-ritt Gordon Mines, Ltd.; fine (-325 mesh) niobium hydride powder; fine (15 µ) type 316 stainless-steel powder; and near-saturated Ni-A1 and Co-A1 solid-solution alloys, also in fine powder form. The niobium hydride was decomposed above about 700°C in processing of the compacts in vacuum to produce niobium powder. The Ni-7.1 pct A1 and the Co-5.3 pct A1 solid-solution alloys were prepared from pure nickel or cobalt and pure aluminum by nonconsumable tungsten arc melting under an inert atmosphere. The ingots were homogenized, lathe-turned to fine chips, and dry ball-milled in air to -325 mesh powder. These solid-solution alloys are designated NiSS and CoSS; see Table I. Subsequently the hard and ductile phases were dry ball-milled as a blend. Experiments clearly established the need to coat the hard particles with the ductile binder to optimize subsequent hot compaction by extrusion. Ordinary dry mixing usually resulted in nonhomogeneous alloys which were quite brittle. Conventional cermets are consolidated by liquid phase sinteiing or infiltration, which resulis in undesirable and uncontrolled alloying of the binder phase. For this study, a loose (unsintered) powder-extrusion process was emploved, minimizing reactions between binder and hard particle, thereby permitting much greater control of composition and structure. The constituent powders were first mixed in the desired

Jan 1, 1967

By E. R. Borcherdt

METHODS and equipment are subject to study in the Butte district at all times in order that advantage may be taken of any new developments that might serve to increase efficiency and lower costs. Detailed time studies of each operation involved in the entire mining process have been of invaluable assistance in analyzing the individual operation for possible improvement. In other words, the fact that a practice has been in vogue for many years does not exempt it from change provided an easier and cheaper method can be found. EXPLORATION Ore occurs in the Butte district in such manner that structures must be drifted on, no matter how small or unimportant they appear when intersected by a crosscut. Parallel structures also add to the crosscut requirements. This prospecting work, which formerly was done entirely by drifting and crosscutting, is now being supplemented by diamond drilling, to aid in greatly decreasing the amount of waste. In long-shot prospecting, or in second or third class prospecting, where the chances of developing commercial ore are not very great, diamond drilling is of particular value. In prospecting where chances of encountering commercial ore are certain or where crosscuts can be used later for haulage or ventilation, drilling obviously is not applicable. Improvement in drilling machines and bits has contributed greatly to the present success of diamond drilling. STOPING For many years square-set filled sloping was the principal mining method used in the Butte district. Later timbered and untimbered rill stopes were used, also some horizontal cut-and-fill sloping where both ore and walls were particularly strong. Because of the amount of timber required for square-set stoping, and the relatively low production per scope unit, experiments with horizontal cut-and-fill scopes were begun in ore bodies of which many had fairly weak walls. It was felt that increase in the speed of the stoping operation, followed closely by filling, to avoid weight being produced by permitting ore and walls to remain insufficiently supported over comparatively long periods, would maintain the walls and backs in safe condition without the use of timber and without ore dilution from wall slough. Cycles of drilling, scraping ore, and filling were devised, which have materially increased stope production and decreased timber consumption, so that both stope labor and supply costs were lowered appreciably without materially affecting grade control. In the larger mines of the district, where wide veins favor this stoping method, half of the total production is now being mined by horizontal cut-and-fill stopes (Fig. I). The increase of the filling rate demanded by the increased stoping rate was the greatest obstacle encountered in the accelerated stoping operations. Finally this problem was solved by replacing the time-honored method of transferring filling waste by small cars, which were hoisted or lowered in the auxiliary shaft, by a transfer

Jan 1, 1941

By Reinhardt Thiessen

In the general study of coal, all evidence points in the one direction —that coals had their origin in a manner analogous to that of peat. The best method of studying coal, whether it concerns its chemistry, composition, or physical condition, is to study peat. The essentials in a study of peat are a knowledge of the chemistry of plants, knowledge of decay and of the transformation process of plant-substances into peat. A number of facts must be emphasized, namely, (1) peat is formed under wet conditions only; (2) plants grow in the place where peat is formed; (3) all the plant substances go into the bog; and (4) all the plant substances are subjected to a series of phases of decay which are (a) in the air completely above the water level but in relatively moist conditions; (b) above the water level, but covered by debris; and (c) completely submerged by both water and debris. Plant Chemistry Plant chemistry as a whole is remarkably well understood. The number of compounds composing plants is large, and it is not possible here to give even a comprehensive outline, but a classification into definite groups is possible; this is as follows: Carbohydrates; glucosides; pigments; tannins; acids, alcohols and ketones, etc., and their salts; essential oils; resins; vegetable bases; proteins; enzymes. Plant substances may also be grouped according to the role they play in the life of the plant, such as: Framework materials, living materials, food materials, protecting materials, waste materials. While this classification groups them well for. certain purposes, it does not group them exactly chemically; but in a consideration of the composition of coal, this is an excellent classification for our purpose here.

Jan 1, 1925

Jan 1, 1943

Jan 1, 1943

By A. C. Fieldner

IN the Wall Street journal for March 1, 1941, was a tabulation of the construction under way or under negotiation by thirteen iron and steel companies for a predicted increase in annual coke production of 3,165,600 tons. That even this figure was short of the mark is indicated by other plans, then being considered, for a later expansion of 2,610,000 tons additional. Considerable progress has already been made on thin program, for approximately 500 new ovens were put in operation in 1941. and well over 200 should be completed in 1942. These figures include a number of units that replace older and obsolete equipment.

Jan 1, 1942

By J. R. Dunn

Planning quarry operations and control of the quality of rock materials at Hudson Cement Co. at East Kingston, N. Y., are special problems because of multiple uses for the stone and the great structural complexity of the rocks. Problems have been largely solved by detailed geologic work. These geologic studies have paid dividends in long and short range planning, in assessment of reserves, in vastly reduced cost of chemical analyses, and in reduced drilling costs. Limestones of the Hudson Valley outcrop along the Hudson River from Albany to Kingston. Old established cement companies are located just south of Catskill and just east and southeast of Hudson, N. Y. The new Atlantic Cement plant is being constructed at Ravena. Hudson Cement located at East Kingston, is a newcomer and is closest to the New York metropolitan area (Plate I).

Jan 11, 1961

By F. T. Havard

The present truce in litigation between Western smelting and ranching interests gives opportunity for a summary of the results achieved by metallurgists in condensing fume and de-acidifying furnace-gases. In the absence of complete records of past experiments, there ha's been a good deal of unliecessary duplication of attempts and failures. Yet, especially uilder the recent policy of our large corporations, looking to the economic recovery of the values of by- and waste products, . original and, in some cases, effective measures have been developed by American metallurgists. In the case of Bliss us. the Anaconda Copper Mining Co., the Montana Suprenle Court, recognizing the progressive efforts made to render the flue-gases innocuous, and the value to the community of the smelting company's operations, refused to hamper its work, and returned a verdict in favor of the defendant. In the trial, the experimental farms of the company ill the so-called "aff'ected region" were proved to be thriving perfectly, showing that immunity was guaranteed to vegetation and stock by tlle wide distribution of the sulyhurous acid gas in the dry air of Montana. Indeed, L. S. Austin has proved that by the time the fume is 4,000 ft, distant from the stack, the percentage of sulphurous acid has been diminished from 2.28 to 0.00045; and Angus Smith has shown that rain must contain 40 parts per million of free acid before vegetation is affected. The arsenic in the stack-gases is but a very small part of the original content of the ore, of which 80 per cent. and over is rejected in the coilcentrator and furnace waste-products or recovered in the flues, Nevertheless, neither the peace in Montana nor the armistice

Jan 1, 1911

By G. H. Kesler, J. E. Oberele, C. E. Dryden, J. H. Oxley

Heat-transfer rates were measured in a model of a multifilament vapor-deposition bulb fo the preparation of high-purzty metals. Local transfer coefficients for heat transfer frow the filaments to the circuates process stream were determined as a functiol of gas flow rates and bulb, inlet, and filament, geowzetvies. These results a-e then convertted to n mass-t7,ansfer basis to provide a method of correlating vapor-deposition rates and to predict the performance of commercial urzits. The firm1 cor?,elating equation for mass transfer was found to be- wheve k, is the mass-transfer coefficient; D, is bze gas difficsivity : P is the system pressure; R is the gas constant; T is the gas temperature; Df, DB, and Di ave tlze diameters of the filament, bulb, and inlet, respectively; k is the gas conductivity; C, is the specific heat of the gas, M is the wzolecular zleight of the gas; Npr . N,,, NRe a7'e the Prandtl, Schmidt, and Reynolds numbem of the system, respectively; LB is the height of the bulb; and SB and Sf are the total suyiace area of the bulb and filaments, respectively. ONE of the more conventional methods of preparing very high-purity metals is the vapor deposition of the metal upon heated filaments. The reactions which can be employed in such a process generally fall into two classes: 1) Pyrolysis of a volatile metal compound. Generally because of their instabilities, metal iodides are used; however, other metal halides and hydrides have been employed. These processes are frequently carried out under vacuum conditions, and the filaments are maintained at high temperatures. 2) Hydrogen reduction of a volatile metal compound. A metal chloride is normally the preferred feed for these processes, but other halides are sometimes used under special conditions. These hydro- gen-reduction processes are usually operated at atmospheric pressure. Many of the current processes for the production of semiconductor materials are actually vapor-deposition processes. However, the vapor-deposition process itself is relatively old, and almost all metals can be prepared in a state of very high purity by the use of vapor-deposition techniques. Loonam has recently given an excellent review of the iodide process for metal deposition,' and Owen has started some detailed studies with a carbonyl system.' A more general treatment of all vapor-deposition processes has been outlined by Powell, Campbell, and Gonser.3 Despite the fact that vapor-deposition techniques have been employed since 1890, there is a surprising lack of fundamental information regarding the transport characteristics of even the simplest deposition system, the heated filament. The purpose of the investigation described in this paper was to extend some of the earlier data obtained at Battelle to predict deposition rates and the uniformity of deposition in large-diameter, multifilament deposition bulbs under forced convection conditions.4'5 A number of other investigators have already presented a simplified treatment of the deposition process under non-flow conditions, i.e., pure diffusion.6"9 To obtain information on the transport characteristics of a deposition bulb, a model of a typical plant deposition unit was constructed, and local heat-transfer coefficients from the filaments to a circulating air stream were determined under various conditions of air-flow rates and bulb, inlet, and filament geometries. These results were then converted to a mass-transfer basis, and consequently provided a method to correlate experimental vapor-deposition rates and to design commercial deposition units. EXPERIMENTAL WORK Description of Model. The apparatus which was used in this work was a scaled model of one type of deposition bulb. It was constructed of Lucite and was easily altered to give several combinations of diameter of bulb liner, inlet size and location, number of filaments, and outlet geometry. The model is shown in Figs. 1 and 2. The bulb shell was made octagonal for convenience in construction and observation, and the bulb liners were cylindrical. Air, introduced through one of several different jet inlets, was used as the test fluid in these model studies. Filaments for deposition of metal were simulated by metal rods 1/4-in. in diam. Two of the rods could be heated by passing electrical current through them ¦ while the remaining rods could not be heated. This procedure minimized the amount of heat which was

Jan 1, 1962

By A. K. Mukherjee, J. E. Dorn, J. D. Mole

Investigations were carried out on the effect of polyslip on the strain hardening of aluminum single crystals. The orientations investigated were those lor which the tensile axis was in the [001], [111], [112], and [012] directions plus another for which the Schmid angles for {111}(110) slip were 1 deg. The experimental data were analyzed on a model based on the intersection of dislocations with particular emphasis on the effect of polyslip on the activation volume for inter-section. It is shown that the rate of strain hardening inreases for those orientations wherein attractive dislocation intersections occur and that those orientations which produce the greater number of such intersections exhibit the greater strain hardening. Good correlation of the data is obtained with the concept that attractive junctions, as proposed by Saada, Play an important role in accounting for the rate of strain hardening. EXISTING concepts on the nature and cause of strain hardening in fcc metals have been deduced principally from experiments on the deformation of single crystals under single slip. The effect of crystal orientation on the shapes of the stress-strain curves for single slip have been summarized by seegerl and more recently by Clarebrough and Hargreaves.2 Tensile specimens whose axes fall near the center of the [001]-[011] line of the standard triangle of the stereographic projection exhibit the longest range of easy glide (Stage I) and the lowest rates of linear hardening (Stage 11) whereas specimens whose axes lie near fie [001]-[111] line of the standard triangle have limited or no easy-glide range and exhibit somewhat higher linear strain-hardening rates. Specimens whose axes lie near the [001] or the [ill] poles do not exhibit easy glide and have the highest rates of linear hardening. Kocks3 has shown that the highest rates of linear hardening Occur under Polyslip when the tensile axis coincides with the [111] or the [ 001] pole. Since the rate of strain hardening is sensitive to specimen orientation and the incidence of polyslip, these relationships might help to discriminate between various dislocation models for strain hardening in fcc metals. Previous attempts to analyze the effect of orientation on strain hardening,1"3 however, did not provide a unique answer to this problem. Consequently the present investigation was undertaken wherein additional data, particularly that for the effect of polyslip on the activation volume for intersection, was also determined in order to provide more complete information on the details of strain hardening. Whereas analyses of these data reveal that several recommended models for strain hardening are at variance with the facts, good correlation of the data is obtained with the concept that attractive junctions4 play an important role in accounting for the rate of strain hardening. I) EXPERIMENTAL APPROACH seegerl demonstrated that slip in fcc crystals at low temperatures is dependent on thermally activated intersection of glide dislocations with forest dislocations. This has been confirmed by tests on single crystals of aluminum by Mitra, Osborne and Dorn5 and on polycrystalline aluminum by Mitra and Darn.' Thus in accord with Seeger's theory, the shear strain rate, ?, below a critical temperature, T, is where .V is the number of points of contact per unit volume between forest dislocations and glide dislocations, A is the area swept out per successful intersection, b is the Burgers vector, v is the frequency of vibration of the segment of the glide dislocation undertaking intersection, U is the activation energy for intersection, k is Boltzmann's constant, and T is the absolute temperature. For aluminum, which has an extremely high staeking-fault energy, the constriction energy is negligibly small and therefore the activation energy decreases practically linearly with the stress according to as will be recomfirmed later, where Uo is jog energy at the absolute zero, G and Go are the shear moduli at the test temperature T and O°K, respectively, L is the spacing of the forest dislocations, t is the applied shear stress for slip, and tGo is the stress field that must be surmounted athermally.

Jan 1, 1965

By N. Mungan, F. W. Smith, J. L. Thompson

Adsorption of polymers and transport, rheology and oil recovery efficiency of their solutions were studied in the laboratory to evaluate the use of polymers in waterflood-ing. While a tenfold mobility reduction was obtained with polymer concentrations as low as 0.05 per cent by weight, the mobility reduction depended on the type of polymer, molecular weight, salinity and pH of water, crude oil and capillary properties of the porous media. Choice of a suitable polymer and a workable concentration will have to be tailored for each application. Little reduction in the residual oil saturation can be expected from polymer flooding. Improvement in the volumetric sweep efficiency is possible hut the extent of the improvement can best be evaluated by properly designed field testing. Some aspects of the field use of polymer floods are discussed. INTRODUCTION Waterflooding is a simple, inexpensive secondary recovery method and is being used widely. Innumerable laboratory studies have been made to unravel the fundamentals of the displacement of oil by water and to find the ways of most efficient oil recovery. These studies and a great many field case histories have revealed that the prime cause of poor oil recovery is the inefficient and incomplete sweep of reservoir volume by the injected water. Sweep efficiency is affected by many factors of which the mobility ratio is an important one. Mobility ratio M is defined here as the ratio of water to oil mobilities: M = (k»/y,r)/(k,JJJJ........(1) In Eq. I, the permeabilities are the effective permeabilities and depend on fluid saturations and, hence, change during the different depletion stages in a flood. A wide practice is to use the effective water permeability at residual oil saturation and the effective oil permeability at interstitial water saturation in Eq. 1. If the mobility ratio is greater than one, the mobility ratio is unfavorable and water, being more mobile than oil, would finger through the oil zone resulting in poor oil recovery efficiency. If the mobility ratio is favorable (one or less) the displacement of oil by water occurs more or less in a pistonlike fashion. In some waterfloods. the mobility ratio is unfavorable and any additives by which the mobility of water can be decreased would favor more efficient oil recovery. The thing to bear in mind, however, is whether or not the improvement in oil recovery is sufficient to more than pay out the cost of the additives needed. For example, materials like sugars, alcohols and glycerine reduce water mobility by thickening the water, but the cost of material requirement precludes any field application. For an additive to be useful in water-flooding, it must bring about a large reduction in water mobility at low concentrations; it must be adsorbed only negligibly; and it must not completely plug up the formation. Some synthetic organic polymers have shown promise of meeting these requirements and have been used in the field.'-W owever, no in-depth studies of the rheological, adsorption and oil displacement characteristics of polymer solutions have been reported. The present work is a study of these properties. EXPERIMENTAL In this work, concentrations are given on a weight per volume basis; 0.5 per cent concentration means 0.5 gm of polymer is dissolved in enough water (or NaCl solution) to make 100 ml. A bactericide, usually 0.1 to 0.2 per cent by volume of 38 per cent formaldehyde solution, was used in the polymer solutions. The NaCl solution was 30,000 ppm. Some properties of the polymers studied are given in Table I. Physical properties of all cores used are in Table 2. Flow behavior of polymer solutions was studied by three consecutive flow tests in cores. First, water (or brine) was injected at constant rate of about 1 ft/D to obtain the water mobility. Then, filtered polymer solution (prepared in water or brine) was flowed through the core. Since the rate was constant, increase in the pressure drop across the core reflects decrease in the mobility. Finally, the core was flooded with water (or brine) to study recovery of mobility. The Alundum cores which were used in

Jan 1, 1967

By W. J. Moore, E. M. Swiggard, H. Shenker

Beryllium is the most soluble of the double-acceptor impurities in germanium; the solubility is at least 1 x 10 19 atoms cm3. Photoconductive, optical, and electrical measurements were made on a set of Ge:Be samples grown without other intentionally added imp~ivities. The excited-states spectrum of beryllium in germanium was determined both in zero field and in magnetic fields up to 30 kc. It was found that the absorption 0-f lines in the vicinity of the G line increased markedly with increasing magnetic field. The ioniza-tion energy of neutral beryllium in germanium was determined to be 24.3 * 0.1 mez: using the excited-states spectrum. An infrared detector using a Ge:Be element was found to have a normalized detectivity D* (50 p, 1000 cps, 1 cps) of 9 X ldO cm-~ps"~-w-'. The Ge:Be sambles exhibited low-field breakdown and inibzirity band conduction effects at low temperatures. WHILE the properties of most dopants in germanium have been thoroughly investigated, the properties of beryllium in germanium have had relatively little attention. Much of the work that has been done' has been concerned with the properties of singly ionized beryllium in germanium. The purpose of the present work was to determine the photoconductive and electrical properties of beryllium-doped germanium (Ge:~e) with a small concentration of other electrically active impurities. Ge:Be is of special interest since beryllium is the most soluble of the known double-acceptor impurities in germanium. MATERIALS PREPARATION A set of &:Be crystals with beryllium concentrations between 5 x 1013 and 1x 10'' cmm3 and without other intentionally added impurities was grown in a hydrogen atmosphere by the horizontal zone-refining techniques described by Swiggard and Shenker.2 The segregation coefficient of beryllium in germanium was found to be about 0.07 and its maximum solubility was found to be greater than 1 x 10'' atoms cm-3 which is in agreement with previous results.' Most of the crystals were found to have a small net concentration of shallow acceptors; for example, a crystal having a beryllium concentration of 1.1 X 1016 cm-3 was found to have a net concentration of shallow acceptors of less than 1.5 X 1013 cm-3. Ingots designed to have a beryllium concentration of 1 x 1017 cm-3 or less exhibited a loss of electrically active beryllium. That is, the beryllium concentration was lower than expected and the decrease of the beryllium concentration along the length of the ingot was much larger than expected. It is hypothesized that this effect is due to the oxidation of the beryllium by the residual oxygen in the system. This effect is similar to but not as severe as the effect observed with boron in germani~m.3, 4 OPTICAL ABSORPTION SPECTRUM The excited-states spectrum of neutral beryllium atoms in germanium was studied by measuring the infrared optical absorption spectrum. A typical spectrum is shown in Fig. 1; the labeling of the absorption lines follows that of Fisher and Fan.* The spacings between the observed lines and the D line are nearly equal to the corresponding spacings for the other ac -ceptors in germanium.5-7 By the use of the theoretical result67' that the neutral impurity ionization energy is 2.53 mev larger than the energy of the D line, the ionization energy of neutral beryllium in germanium was determined to be 24.3 * 0.1 mev at 4.2"K. This method yields a more precise value of the impurity ionization energy than the usual Hall effect method.' The absorption spectrum of Ge:Be was also measured as a function of magnetic field using a magnetic field parallel to the incident radiation and using unpolarized radiation. A typical spectrum taken at 30 kG is shown in Fig. 2. An unexpected observation is that the absorption of the lines in the vicinity of the G line (there is a strong possibility that some of these lines may be associated with lines other than the G line) increases with magnetic field. RESISTIVITY AND HALL DATA Measurements of Hall voltage vs temperature were made on several of the samples. The thermal activa-

Jan 1, 1968

By Ralph Hultgren, Prodyot Roy

Manganese vapor pressures from 1250° to 1500°K were measured by conventional Knudsen and torsion-effusion methods in twelve Fe-Mn alloys with compositions from 9 to 80 at. pct Mn. The Knudsen re-sults agveed approximately with previous measurements found in the literature which indicated the solutions were nearly ideal. However, except for the higher manganese compositions, the initial torsion readings indicated much (up to 50 pct) higher vapor presszcres than the Knudsen method. These high readings decreased steadily with time. The results are interpreted as due to depletion of surface concentration of manganese during evaporation. Thus the initial torsion readings are the most nearly correct and Knudsen methods on alloys are to be regarded with suspicion unless it can be demonstrated that diffusion rates are rapid enough to replenish surface concentrations depleted by evaporation. For the lowest manganese contents and highest temperatures, depletion causes initial torsion readings to be too low. FEW thermodynamic data are available for alloys of the high-melting transition metals due primarily to experimental difficulties at the high temperatures involved. Measurement of vapor pressure is one of the most promising techniques to be applied to this problem. From the vapor pressure of a component of an alloy phase, its activity or its partial molar Gibbs energy can be directly calculated. From measurements over a sufficient range of temperatures and compositions the partial and integral Gibbs energies, enthalpies, and entropies may be determined through Gibbs-Duhem integration. For solid phases of variable composition, which commonly are found in alloys, measured vapor pressures are low because of depletion of the surface concentration of the more volatile component as it is selectively vaporized. Diffusion from the interior tends to restore the depleted concentration. The seriousness of the effect depends on the relative rates of diffusion and vaporization. Although depletion has been recognized as a factor,' direct measurements of its rate are lacking and quantitative estimates of its effect on measurements are uncertain. In the present work the vapor pressures above a series of Fe-Mn alloys have been measured by the torsion-effusion method. This method permits a measurement of the vapor pressure of manganese as soon as the sample comes to temperature and continuously throughout the run. The rate of decline of the apparent vapor pressure measures the rate of depletion and the torsion reading at zero time should be correct. At high manganese concentrations (70 and 80 at. pct Mn), the torsion reading remained nearly constant; surface depletion was negligible. There was a slow drop in measured pressure due to bulk loss of manganese from the sample. However, for lower manganese contents, especially at high temperatures, the depletion effect was considerable and the apparent vapor pressure decreased steadily with time. For these alloys the Knudsen method should give pressures which are too low. The measurement of pressure in the Knudsen method cannot be made until enough manganese has been vaporized to be weighable. The Knudsen result is therefore an integrated average between the initial and final vapor pressures. To verify this, conventional Knudsen measurements were also made with results in approximate agreement with previously published Knudsen measurements for these alloys. As expected, for the lower manganese contents the initial torsion readings of pressure were as much as 50 pct higher than the Knudsen. THE APPARATUS The apparatus, shown in Fig. 1, is capable of operating to temperatures up to 2000°K. A vacuum of 5 x 10"6 mm Hg can be maintained. Temperatures were measured to +3° by a W-Re thermocouple placed in the dummy cell, N. The torsion cell consisted of two alumina crucibles with holes in their covers. They were placed in the molybdenum holder shown suspended from the torsion wire. Rectangular torsion wires (1 by 4 mm) were found to have superior sensitivity and less residual distortion than circular (2-mm-diameter) wires. The precision of angular measurement was found to be *0.025 deg; the variation is no doubt due to temperature fluctuation and vibration. For the Knudsen experiments the alumina cell was set on the support, N. SAMPLE PREPARATION 800-g samples were prepared by melting together electrolytic iron and electrolytic manganese and pouring the melt into a water-cooled copper mold. Melting and pouring were done under a helium at-

Jan 1, 1965

By R. F. Hehemann, D. J. Cometto, G. L. Houze

The w transformation in the Zr-Nb system was studied using X-ray diffraction, dilatometric, re-sistornetric, hardness, and metallographic techniques. w forms in a diffusionless, completely reaersible manner on quenching and in a diffusion-controlled manner- on aging. The temperature at which w begins to form on quenching was determined as a Junction of composition and was found to decrease with increasing solute content. w formed bv aging establishes a metastable equilibrium with an enriched ß phase. The ß/w + ß transus has been determined for this metastable equilibrium and employed to rationalize retrogression and reversion phenomena observed in these alloys. The decomposition mechanism is discussed in terms of a gradual or continuous transformation from ß to the w state. BETA- stabilizing alloying elements lower the MS temperature of the martensitic bcc (ß) to hcp (a') transformation in zirconium and titanium alloys. In certain titanium alloys, a lower symmetry modification of the martensitic structure, termed (a"), also has been reported.1,2 These martensitic transformations are suppressed when the amount of the ß-stabilizing element exceeds a critical level. However, the high-temperature ß phase cannot be quenched to room temperature without change. At alloy contents just above the critical level, |ß trans-forms to the w phase when cooled rapidly.3-6 The amount of w in quenched alloys is reduced by increasing alloy content, and this phase virtually disappears above a critical composition.5 In addition to the transformation during cooling, w also can be formed by aging ß at temperatures below approximately 500°C, and significant alloy enrichment of retained 13 accompanies the isothermal transformation.1-8 The structure of LC is closely related to that of the ß from which it forms.9-15 The bcc (ß) lattice can be generated using a hexagonal cell with three atoms located at (000) and ±(2/3, 1/3, 1/3). This cell has an axial ratio of 0.612 and is oriented with respect to the cubic cell such that (0001)H (111)C and [1120]H [101]C. Consequently, there are four possible orientations of the hexagonal cell, associated with the four (111) planes of the bee lattice. Formally w can be obtained from 0 by allowing the two atoms at the ±(2/3, 1/3, 1/3) positions to approach the coordinates ±(2/3, 1/3, 1/2) and there are four equally probable orientations of w for each 0 grain. In titanium alloys w retains the cubic axial ratio of 0.612" and hence also can be indexed as triply cubic, but this is not the case for aged Zr-Nb alloys where w is clearly hexagonal with an axial ratio of 0.622." The lattice parameters and atomic positions of w depend on thermal history and alloy content. The atomic positions (000), ±(2/3, 1/3, 1/2) provide reasonable agreement between calculated and observed diffracted intensities for w in the fully aged condition.10,14 In the quenched condition, on the other hand, the atoms appear to be displaced from the central plane12,13,15 and assume positions ±(2/3, 1/3, Z = 0.42-0.48) rather than ±(2/3, 1/3, 1/2). This results in a structure with trigonal rather than hexagonal symmetry. The readily detectable parameter and axial-ratio changes of w in Zr-Nb alloys make this system especially attractive for studying the structural changes that occur in the formation and aging of w. Particular attention in this investigation has been directed to the relationship between the structure of w in the quenched and aged conditions, and to certain aspects of the reaction kinetics. MATERIALS AND PROCEDURE Zr-5, 12, 17.5, and 25 pct Nb alloys were prepared by a double arc-melting practice, encased in stainless-steel cans and hot-rolled to 1/8-in.-thick sheet.* Charged weights have been employed for the niobium contents and interstitial analyses are reported in Table I. Dilatometric, X-ray diffraction (filtered CuK, and MoK, radiation), metallographic, and hardness techniques have been employed to follow the transformations during isothermal and quench-aging heat treatments. In quenched specimens, the electrical resistivity also was studied. Betatizing was conducted for 1 hr at 900°C. With the exception of the isothermal dilatometric studies, samples were

Jan 1, 1965