Search Documents

By Joseph Kaye Wood

A metal is said to be overstrained when it is deformed beyond the elastic limit at a temperature well below the critical range, as in cold working. Quantitatively, overstrain might be considered as that part of the total elastic deformation of the piece of metal, left over after the external load is removed, that added to the permanent deformation due to plastic action will give the total permanent deformation. Ordinarily the effects of this phenomenon, which vary with the internal residual stress probably in accordance with Hooke's law, are more noticeable when the yield point of the metal is exceeded, but they probably also exist to a smaller degree when the load is just large enough to cause the least amount of permanent set. These effects, which we recognize as the result of overstrain, are as follows: 1. An apparent increase of the elastic limit in tension and a decrease of the elastic limit in compression, provided the external load is tensile. The reverse is true when the load is compressive. 2. An elastic after-effeet in which time and temperature are important factors. 3. A state of imperfect elasticity in which Hooke's straight line becomes slightly curved, giving rise to an hysteresis loop. 4. In addition to the apparent increase in the elastic limit, such properties as the hardness, ultimate strength, and resistance to fatigue failure are increased, provided the overstraining has not been carried far enough to make the metal brittle. 5. Correspondingly the ultimate elongation, reduction in area, magnetic quality, ratio of endurance limit (fatigue breaking stress) to elastic limit, and resistance to season cracking (in certain copper alloys) are decreased. The question naturally arises: how do these changes in the properties of a metal resulting from overstrain influence our method of design? The fact that most of the desirable qualities are increased makes overstraining a favorable process, from an engineering standpoint; but on the other hand, the loss of such qualities as perfect elasticity and complete

Jan 1, 1924

By L. Thomassen, N. Spooner, J. M. Thomas

NI-CR and some Ni-Cr-Fc alloys, when used as electrical resistance heating elements in reducing atmospheres, at times suffer rapid breakdowns due to so-called "green rot." These reducing atmospheres are most frequently used in bright annealing and heat-treating furnaces which are kept for long periods of time at 1500' to 1800°F. The green rot is a preferential oxidation of the chromium in the alloy to such an extent that the remaining metal frequently becomes ferromagnetic. The Curie point (magnetic transition point) at room temperature for a pure Ni-Cr alloy is known to be at about 7 pct Cr.¹ This represents a severe loss in chromium for one popular grade of resistance alloy, which is nominally 80 pct Ni-20 pct Cr. The formation of oxides along the grain boundaries makes the ribbon brittle and gives the fracture a green, earthy appearance—hence the name. The authors have studied this phenomenon, simulating the industrial conditions by heating resistance ribbons in various reducing atmospheres, such as moist hydrogen or the atmosphere specified in the ASTM test.² This atmosphere contains 16 pct H2, 10 pct CO, 4 pct C02, 1 pct CH1, 1.5 to 2.5 pct H2O, balance N2. Little success was had in producing severe corrosion with the commercial 80 pct Ni-20 pct Cr alloys. It had been noticed, however, that 90 pct Ni-10 pct Cr alloy wires deteriorated very rapidly when placed in the bottom of narrow thermocouple protection tubes. The bottoms of the tubes with the wires were heated in air. This took place both in porcelain tubes and in Inconel* tubes either with the cold end open or loosely stoppered with asbestos. On examination the wires showed microstructures which would be classified as green-rot corrosion. Subsequent investigations with various alloy wires confirmed the observation that corrosion occurred in some wires, including 80 pct Ni-20 pct Cr alloys, much more rapidly in such tubes than had occurred previously in test atmospheres mentioned above. When 90 pct Ni-10 pct Cr alloys are oxidized with an abundant air supply, the oxide coat consists of both nickel and chromium oxides. In this case thermodynamic equilibrium between the oxides is not established. However, when oxidized 90 pct Ni-10 pct Cr alloy specimens were heated to 1500" to 1800°F inside small diameter tubes, the oxide coat transformed to a bright metallic outer layer of nickel or nickel-rich alloy, beneath which appeared a green oxide, followed by intergranularly attacked metal. The obvious explanation is that in the narrow tubes, thermodynamic equilibrium is being established according to the equation NiO + Cr (in alloy) ? Ni + Cr2O3 This reaction is favored due to the fact that the oxygen pressure over nickel oxide is more than 10"' times the oxygen pressure over the green chromium oxide. The initial oxygen in the tubes is depleted very rapidly by oxidation of the wire and of the tube, if it is metallic. A confirmation of the occurrence of the reaction, reduction of NiO by the chromium in the alloy, was obtained by putting oxidized nickel foil into an evacuated quartz tube along with a piece of bright 90 pct Ni-10 pct Cr alloy ribbon, and heating the tube at 1820°F for a number of hours. The nickel oxide on the foil was completely reduced to pure nickel, leaving a bright foil. The 90 pct Ni-10 pct Cr alloy became strongly magnetic and showed the typical green-rot structure. Weights of the samples before and after testing showed the weight loss of the foil to approximately equal the weight gain of the ribbon. Evidently the bottom of long, narrow protection tubes, stoppered or not, may under certain conditions act just as the sealed quartz tubes in respect to being a confined space in which oxygen is not freely replenished. This condition of oxygen depletion can be prevented by introducing a small amount of air into the bottom of the tube. Many conditions becloud the green-rot phenomenon, such as carburization, sulphidization, and the presence of other corrosive agents. However, these experiments have shown that the basic reaction is a case of internal oxidation which can occur simply by adjusting the oxygen pressure to a low enough level so that the atmosphere will leave the nickel intact and oxidize the chromium. The action of the other agents in commercial atmospheres can then be taken up as individual cases. From these and numerous other tests completed to date or still in progress, it is believed that a more critical evaluation of electrical resistance alloys for their resistance to green-rot corrosion can be made. A much better understanding of the mechanism for this type of corrosion should also result. A more complete report on these experiments will be published later. In the May 1953 issue: TP 35213 Discussion: Solubility of Carbon and Oxygen in Molybdenum by W. E. Few and G. K. Manning, discussion by N. A. Gokcen: p. 747, first column, the fifth, sixth, and seventh lines should be the first, second, and third lines, followed by the present first, second, third, fourth, eighth, ninth, and tenth lines.

Jan 1, 1954

By Paul C. Merritt

The story now unfolding on the Mesabi Range is more than just another chapter in the continuing history of iron mining. It is an epic of foresight, research and pioneering instinct just now culminating in the rapid growth of a new industry hardly more than ten years old. And that growth has been impressive. In the decade that has passed since Reserve Mining Co. blazed a trail as the first successful large- scale commercial taconite operation, the number of plants now existing or soon to be operating has grown to six. From Reserve's initial capacity of 3 million tons of pellets per year, total production capacity on the Range has surged to 31.5 million tons while capital investment has leaped from $300 million in 1955 to almost $1 billion today. During the past year alone, more than $500 million has been committed to these projects, an amount probably greater than that going into any other single mining area in the world. There is more yet to come.

Jan 10, 1965

By J. M. Oblak, W. A. Owczarski

A cellular appearing recrystallization product formed by annealing a cold-worked nickel-base super-alloy at 1800°F has been studied by electron nzicroscopy. Prior to deformation, an equilibrium micro-structure of fcc matrix y and cuboidal ,,', Ni (Al, Ti), precipitates of CuzAu structure had been established by an age at 1825°F. The strain-free recrystallization cells consist of very large rodular y' particles in a y matrix. They precipitate is oriented and coherent both before and after recrystallization. The results showed that y' coarsening accompanies recrystallization at 1800°F. However, it does so as a secondary effect and does not necessarily take place at lower temperatures. The structural similarity of this reaction to cellular precipitation in other systems indicates that lattice strain may also play a significant role during some cellular precipitation reactions. THERE have been numerous microstructural investigations of recrystallization in single-phase materials but two-phase systems have received much less attention. The second phase can either remain inert or be altered along with the matrix during recrystallization. If the second phase is an oxidelm3 or a relatively inert pre~ipitate,~, recrystallization is retarded when the interparticle spacing is less than 1 p. Prior to the onset of recrystallization, these materials show a well-polygonized substructure with the subgrain size limited by the interparticle spacing. Since recrystallization by the motion of preexisting grain boundaries6 is not observed, retardation has been related to particle pinning of the subboundaries. This pinning prevents coalescence' or growth8 of subgrains to a critical size (formation of a high-angle boundary) necessary to initiate recrystallization. In a material such as a nickel-base superalloy both y matrix and y' precipitate are altered by the recrystallization reaction. Haessner et al.' studied the recrystallization of a cold-rolled Ni-Cr-A1 alloy by electron microscopy. The material was initially cold-rolled in the supersaturated condition. upon annealing at 750°C, immediate precipitation of 7'occurred. Presence of this 7' greatly retarded the onset of recrystallization which eventually took place by the development of randomly oriented, strain-free grains. The original •/ was dissolved at the recrystallization interface and reprecipitated as oriented, coherent par-tiles in the new grain. Recrystallization caused a refinement of .)' particle size. Recently ~hillips'' investigated recrystallization of Ni-12.7 at. pct Al. Reduction by cold rolling presumably elongated the p' precipitate into lamellae that remained coherent with the matrix. After recrystallization at 600" to 750°C, there was no unusual change in y' particle size al- though there was a tendency toward clustering along the prior rolling direction at 750°C. Above 750°C, the recrystallized grains were generally free of precipitate. Studies in the somewhat analogous Cu-3.23 wt pct CO" and Cu-2 wt pct'2 systems demonstrated that the coherent cobalt-rich fcc precipitate in these alloys obstructed softening, initiation, and completion of recrystallization. The precipitates were deformed into lam~llae during rolling and those of diameter less than 250A remained coherent. Recrystallization took place by the growth of new grains into the recovered or poly-gonized material. In the first study," both matrix and precipitate reoriented in the same manner upon passage of the recrystallization interface. There was no change in particle size or morphology. Tanner and ~ervi,~ on the other hand, observed that motion of the recrystallization fronts was strongly hindered by the pinning action of coherent precipitates in the deformed material. Particles in contact with a pinned boundary coarsened and coalesced leaving a denuded zone in the unrecrystallized region. When the number of pinning points was sufficiently reduced by coalescence, the boundary swept past these particles and through the denuded zone. The authors1' considered this as a variation of discontinuous precipitation with both chemical driving force and deformation strain energy contributing to recrystallization. Preliminary observations by the present authors had revealed that recrystallization in Udimet 700, a nickel-base superalloy, occurred in an entirely different manner. Optical metallography showed that the recrystallized product formed as cellular colonies containing coarse y' particles elongated in the direction of cell growth. In this investigation the structural features of this reaction were investigated by transmission electron microscopy. EXPERIMENTAL PROCEDURE As-received I$-in. rounds of Udimet 700* were (wtpct) 18.4 15.2 4.95 4.42 3.43 0.06 0.031 0.14 Bal. solution-annealed for 4 hr at 2150" and then fast air-cooled. An initial y-~' structure was established by a 4-hr age at 1825°F followed by a fast air,cool. Essentially the equilibrium volume fraction of ?' at 1825°F is precipitated within 4 hr. Microstructural examination showed no measurable increase in the amount of precipitate after longer aging times. Deformation consisted of swaging to 52 pct RA with 6 pct reduction per pass at room temperature. To reduce the precipitation potential to a negligible amount, recrystallization anneals were conducted at 1800"~ (982"~). Microstructures were investigated by optical and transmission electron microscopy. To prepare foils for electron microscopy, the material was first sliced into 30-mil slabs parallel to the swaging direction. Discs were dimpled and electrolytically cut from

Jan 1, 1969

By F. F. Craig

Many full-scale waterflooding operations are preceded by pilot floods, one purpose of which is to provide an estimate of recoverable oil. A laboratory model study was made to determine the influence of the producing wells' effective productivity on the oil recovery efficiency of single five-spot pilots, as well as single injection well pilot floods. The effective productivity is indicated by the value of Condition Ratio, defined as the actual well productivity to that of on undamaged and non-stimulated, normal-sized well in the same formation. The effects of initial gas satrcration and mubility ratio on recovery eficiency were also investigated in this model study. Model test results skowed that at favorable mobiliry ratios, a five-spot pilot flood can provide a direct quantitative estimate of the recoverable oil in the pilot area. If the pilot producer's Candition Ratio is 2.2 or more, upwards of 90 per cent of the recoverable oil in the pilot area is recovered from the inside producer, regqrdless of the mobility ratio or initial gas saturation. This Condition Ratio can be achieved with preyent fracturing techniques. Model studies also showed that over the range of imposed injection pressure differences and regional pressure gradients normally encountered in field operations, there was no effect on the recovery efficiency of a five-spot pilot waterflood. Model studies of single injection well pilot waterfloods showed that with no initial gas saturation, the total oil recovery at the offset producing wells can indicate the oil recovery possible by full-scale waterflooding. It is essential that the Condition Ratios of the offset wells be above 1.4. If an initial gas saturation exists prior to water injection, the recoverable oil cannot be directly evaluated by a single injection well pilot flood. However, the production per formance of such a flood can be used to provide information on volumetric sweep efficiency. INTRODUCTION Oil reservoirs are conlplex structures and cannot always be fully studied in the laboratory. Therefore, many operators consider it prudent to evaluate a waterflood prospect by means of a pilot flood. Pilot waterfloods generally involve one of two well arrangements: a single five-spot pilot waterflood, involving four injectors and an internal pilot producing well; and a single injection well pilot flood (sometimes called an inverted five-spot pilot) having one injector and four sur- rounding pilot producers. Some pilot floods are composed of multiple five-spot pilot patterns. To yield information applicable to field-wide performance, the pilot must be located in a representative portion of the reservoir. Pilot floods generally are conducted for one or more of the following reasons: (1) to determine whether water could be injected at desirably high rates, (2) to determine whether an oil bank or zone of increased oil saturation is formed by water injection, and (3) to estimate the oil recovery by waterflooding. Many of the early pilot water-floods were conducted for only the first two reasons. As soon as a buzz in oil production was obtained in the pilot, water injection was initiated throughout the entire lease or field. A number ot laboratory studies have been directed toward determining conditions under which a pilot flood could yield a quantitative estimate of the oil recovery possible by full-scale pattern flooding. One of the early studies of single five-spot pilot flooding' showed that well damage to the inside pilot producer could reduce the total amount of oil recovered. In a study of the single injection well pilot flood pattern,' the results indicated that if the model boundaries were no closer than a half-well spacing beyond the pilot pattern, the pilot performance in the laboratory is unaffected by these boundaries. In another study,? he effect of initial gas saturation and mobility ratio on the ratio of production to injection rate for various groupings of five-spot patterns was defined by mathematical and analog methods. In a study4 involving both potentiometric and flow model experiments at a mobiliry ratio of unity, four different pilot patterns were studied. These included a single five-spot, a single injection well pilot, a cluster of four single injection well pilots and six inverted five-spots. In this study the ratio of well diameter to the distance between injection and producing wells was held constant at 1:1000. The effect of the 7 ratio-—the ratio of the pressure drawdown at the producing wells to the pressure build-up at the injection wells on the pilot performance-was studied. The values of 7 ratio ranged from 0 to 0.34. Results showed that both the total oil recovery and the total fluid production from the pilot relative to the cumulative injection increased with increasing values of the 7 ratio. The effect of both the ratio of injection to producing rates and mobility ratio on the oil recovery performance of a liquid-saturated single five-spot pilot flood was studied in a series of flow model tests.5 Rate ratios ranged from one to four, and mobility rates ranged from 0.1 to 10. Resulls of these tests showed that at low rate ratios, the pilot producers may recover up to four times the recover-

Jan 1, 1966

By D. F. Toner

THE decomposition of the ß phase in the copper-aluminum system has recently been subjected to considerable investigation1-4 As a result of this work, principally by Haynes, much additional interest has been aroused concerning the various transitional or metastable phases in the Cu-A1 system. No attempt has been made to resolve the question of whether the PI and ß" phases of Klier and Grymko5 are the same as the rosette-shaped phase first observed by Smith and Lindlief6 in 1933 during an isothermal transformation study of an eutectoid alloy. It is the purpose of this study, however, to obtain

Jan 1, 1960

By W. H. Durrell

DISCOVERY of large iron ore deposits in New Quebec and Labrador is, undoubtedly, one of the outstanding mining events of the twentieth century. To give an idea of size, the present concession is almost equivalent to a strip a mile wide around the earth at the equator. Importance of this iron ore area can best be appreciated by comparison to the famous Mesabi Range. On Mesabi, the area of favorable rock is 110 miles long and from 1 to 5 miles wide, with a, productive zone about 70 miles long. On the con- cessions the area of favorable rock in the Labrador Trough is 225 miles long and from 10 to 60 miles wide. In Quebec-Labrador, exploration already discloses that the productive zone is 90 miles long, with good chances of being extended at both ends. The Mesabi is covered generally by thick over- burden, and the iron ore deposits were found by T- test-pitting and systematic test-drilling. In Labrador and Quebec, most ore has been developed from a few surface deposits, and when it is considered that at least 95 pct of the area is covered by over- burden, and that there remains thousands of square miles of favorable territory still to be explored, it can be seen that the possibilities for developing additional ore are tremendous.

Jan 4, 1954

By R. S. Busk

Niels Engel (University of Alabama, University, Ala.)— In this paper it was pointed out that the electron-gas and energy-band theory accounts for the fact that the lattice parameters exhibit a sudden change when the electron concentration (number of bonding electrons per atom) exceeds a certain number around two. This statement is said to support and prove the electron-gas theory. But this theory is not able to account for a series of experimental data. Also several expectations, deduced from this theory, are not found to exist. In Figs. 6 and 7 the energy bands of the second and third periods are given as they must be assumed in order to account for the electrical properties of the elements in these periods. In Figs. 6 and 7 the electron-gas and energy-band theory is compared with the electron-oscillator hypothesis in accounting for the properties of the elements in the second and third periods. Fig. 6 shows the second period, The energy-bands are overlapping and separated to be in agreement with the electrical conductivity of the elements. The oscillator hypothesis explains conductivity due to electron vacancies. In graphite there is a closed s-shell in every other atom and two vacancies in the others. Conductivity is therefore only maintained by migration of s-electrons in graphite. In boron there are no s-electrons. The diatomic molecules of nitrogen and oxygen and the paramagnetism of oxygen can be accounted for by a similar behavior as the s-electrons of the bonding electrons. But this explanation will deviate too much for the purpose of this discussion. Fig. 7 shows the third period. In the energy-band picture about two s-electrons are assumed in magnesium and aluminum, but only one s-electron is assumed in silicon. The diamond lattice is assumed to be controlled by a sp3 hybrid. However the electron distribution develops ideally according to the oscillator hypothesis. Only sodium, magnesium, and aluminum exhibit electron vacancies and conductivity. To account for the insulator properties in Si, P, and S in the third period it must be assumed that the four last added p-electrons must be taken up in bands containing only one electron per band.' (Compare the electron band picture in Hume-Rothery.' Hume-Rothery does not consider the insulator properties of the nonmetals.) In the second period already the first p-electron must have entered a single electron band. Based on the energy-band picture in Figs. 6 and 7, the following questions must be asked: 1—Is it consistent with the energy-band idea that electrons of the same kind (p-electrons) can be divided into separated bands? 2—Is it consistent with the energy band idea that single electron bands can exist? 3—Why are the first two p-electrons (in boron and diamond) separated into two single electron bands in the second period, but overlapping in the third period (aluminum)? 4—Why are s-electrons and d-electrons taken up in continuous overlapping bands, while p-electrons are divided into single electron bands? 5—Why do the peaks and valleys (y and w and further x and z) of the energy band below four electrons per atom not show up in the electrical conductivity of alloys? For example consider the Li-Mg system or the alloys between Mg and three electron metals where the mentioned discontinuity in the lattice parameter is found. 6—Why does the beginning of the p-electron band (x) not show up in the lattice constants similar to the filling up of the s-electron band (z) ? In magnesium alloys the electron-gas theory postulates the first Brillouin zone to be filled at about two electrons per atom. This is claimed to explain the sudden change in lattice spacing and c/a values of several magnesium alloys when the electron concentration exceeds a few percentage points over two electrans per atom. This was emphasized in the paper by Busk. If the electron-gas energy-band theory is correct a sudden change in electrical conductivity and possibly other properties .should be expected when the same electron-concentration or temperature is exceeded. A sudden change in lattice spacing or other properties should also be expected when the filling degree is such that p-electrons are introduced into the p-band, for example at x in Figs. 6 and 7. Such phenomena are at found by experiment. and If the number of electrons should vary with the energy level depending on the average number of bonding electrons per atom, the electrical conductivity should be expected to vary in accordance with the energy band layout (Figs. 6 and 7) caused by different numbers of conducting electrons at different filling up degrees. Nothing indicating such a behavior is observed. In addition to these discrepancies between the electron-gas and energy-band theory and measured data, the theory violates the principles developed along with the Bohr theory of atomic structure. According to these principles a filled shell is saturated and therefore unable to form bonds. Therefore two S-electrons per atom should form a closed or saturated shell, which has been pointed out as accounting for the inability of helium to form bonds. Beryllium, magnesium, or calcium atoms with two s-electrons should be expected to form inert atoms with properties almost like the helium atoms. Several other inconsistencies and disagreements with measured data of the energy-band theory can be mentioned. Some of these are discussed with reference to other papers. 8 Because the electron-gas and energy-band theory seems to fail on several points, I have developed another theory which can account for all the phenomena the electron-gas theory is able to account for. This new theory is further able to account for things which are impossible to explain by the electron-gas theory at the present state.

Jan 1, 1953

By J. D. Shaw, E. B. Gebert, D. O. Noel

It is, of course, expected that manufacture of the various metal powders should involve numerous methods adapted to the specific characteristics of the metals themselves. Several methods for powdering a particular metal may be available, but the physical characteristics of the powder as produced by the several methods may be quite different. In the final analysis, the application of the metal powder dictates the physical properties that the metal powder must possess, and this, to a very large extent, will determine which of several possible methods of manufacture is adopted. Sometimes powder of the same metal is produced by more than one method, each powder having specific characteristics that make it particularly suitable for its application. For purposes of classification, the various methods of powdering metals can be grouped as follows: 1. Machining. 2. Milling (by ball mills, stamps, attrition mills, etc.). 3. Shotting (pouring molten metal into water, air, etc.). 4. Granulation (by stirring molten metal while solidifying). 5. Atomizing (disintegrating by steam, compressed air, etc.). 6. Condensation of metal vapor. 7. Reduction of oxide powders. 8. Chemical precipitation. 9. Electrolytic deposition. 10. Sintering (for producing alloy powders). 11. Formation of an alloy followed by dissolving or otherwise removing one of the alloying constituents. Machining Turnings, cuttings, filings, etc., are, of course, produced as by-products in machine work of various kinds, and find certain applications as metal powders. For example, iron powder so produced is used extensively as a reducing or precipitating agent and as a constituent in certain hard-finish cements.

Jan 1, 1938

By D. O. Noel, E. B. Gebert, J. D. Shaw

It is, of course, expected that manufacture of the various metal powders should involve numerous methods adapted to the specific characteristics of the metals themselves. Several methods for powdering a particular metal may be available, but the physical characteristics of the powder as produced by the several methods may be quite different. In the final analysis, the application of the metal powder dictates the physical properties that the metal powder must possess, and this, to a very large extent, will determine which of several possible methods of manufacture is adopted. Sometimes powder of the same metal is produced by more than one method, each powder having specific characteristics that make it particularly suitable for its application. For purposes of classification, the various methods of powdering metals can be grouped as follows: 1. Machining. 2. Milling (by ball mills, stamps, attrition mills, etc.). 3. Shotting (pouring molten metal into water, air, etc.). 4. Granulation (by stirring molten metal while solidifying). 5. Atomizing (disintegrating by steam, compressed air, etc.). 6. Condensation of metal vapor. 7. Reduction of oxide powders. 8. Chemical precipitation. 9. Electrolytic deposition. 10. Sintering (for producing alloy powders). 11. Formation of an alloy followed by dissolving or otherwise removing one of the alloying constituents. Machining Turnings, cuttings, filings, etc., are, of course, produced as by-products in machine work of various kinds, and find certain applications as metal powders. For example, iron powder so produced is used extensively as a reducing or precipitating agent and as a constituent in certain hard-finish cements.

Jan 1, 1938

By H. Rush Spedden, A. M. Gaudin

IN the belief that a critical study of its operating problems might be a sound investment, the Cuban American Manganese Corporation initiated an ore-treatment research in cooperation with the Massachusetts Institute of Technology. One of the early objectives of this research naturally became the relationship of the microscopy of the Cuban ores of the Corporation to their flotation treatment. The operations in Cuba have already been described by F. S. Norcross, Jr.7 and the laboratory study of manganese oxide flotation goes back a number of years .4 Broadly speaking, the difficulties encountered in the flotation of manganese ores are that the consumption of reagents is extremely high, the concentrate contains more silica than is desirable and the tailing losses are relatively high. An appreciable betterment on any of these scores would achieve a definite betterment in costs, quantity of minable ores, and quality of product. The microscope study discussed in this paper was made on samples from the Quinto mine, from the Ponupo mine, and from mill products at various stages of passage of the ore through the mill. The writers have had access to Company records and in particular to the petro¬graphic studies made on thin sections of ore by the late Professors R. J. Colony and Philip Krieger, of Columbia University. They acknowledge their debt to both of these men for the help derived from the reports. Manganese oxides are black, friable, smudging. It is, therefore, very difficult to judge operations by inspection. The mineralogy of manganese compounds seems to be confused, and the authors believe that many more minerals have been described than actually exist. Much of this difficulty is due to the prevalence of the structural conditions that will be discussed further in this paper; namely, the porosity and the friability of the ores, and the extremely intimate association of minute manganiferous mineral crystals with impurities of various sorts. By all odds the most important manganese mineral in Cuba is the one that in this paper is called "psilomelane." The name "psilomelane" has been used in so many different ways that the choice of it for this ore may not be approved by all. However, it seems to be the best under the circumstances. This mineral accounts for about 97 per cent of the manganese in the ores of the Quinto and Ponupo mines and in the mill feed. The remaining odd 3 per cent consists mostly of pyrolusite together with minor amounts of other manganese oxide minerals. DESCRIPTION OF PSILOMELANE Aggregate Structure In grains or lumps, psilomelane has a characteristic fibrous appearance and seems

Jan 1, 1942

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 E. S. Bumps, M. Baeyert, W. F. Craig

SOME time ago during a study of impact properties of tempered martensite,1 it was postulated that the consistently good ductility of tempered martensite might be caused by its relatively small and peculiarly shaped ferrite grains. The fer-rite grains of tempered martensite have approximately the same size and shape as the martensite "needles." Thus they form an interlocking mass of needle-shaped grains quite different from equiaxed or lamellar ferrite grain structures. When the common mechanical test methods are applied to steel, variations are often observed in the ductility of specimens that have closely similar hardness and tensile strength values. The ductility so measured appears to be structure dependent. When steel from the same heat has been heat treated to produce different structures with the same hardness, the elongation and reduction of area values from the tensile test and the transition temperature determined by the notched-bar impact test vary according to whether pearlite, tempered martensite, or other structural constituents were produced by the heat treatment. It has been widely recognized that tempered martensite gives a consistently good performance, when tempered to the same hardness as many other structures with which it has been compared. In recent years the isothermal transformation of austenite to specific structural products and the quantitative evaluation of the character of these products with respect to their nature and response to deformation has received considerable attention. The objective of the present study was to pursue somewhat further the dependence of ductility upon structure; specifically, it was desired to ascertain whether ferrite grain structure, including both shape and size of the grains, can account for the consistently good performance of tempered martensite in the notched-bar impact test. It was thought that a simple experiment would indicate whether the ferrite grain structure plays any part in the good ductility exhibited by tempered martensite in contrast to other steel structures with different types of ferrite grains. By determining the impact transition temperature, it was proposed to compare spheroidites having similar carbide particle size and spacing but obtained in such a manner that their ferrite grain structures would be very different. Spheroidite obtained by tempering martensite, with its small, needle-shaped grains, was to be compared with spheroidite from pearlite. If the latter is produced by sub-critical annealing, the ferrite grains correspond to the pearlite colonies. Thus, if the pearlite was not too coarse, the ferrite grains of spheroidite from pearlite are equiaxed in contrast to the needle-shaped grains of spheroidite from martensite. It was thought that the ferrite grain structure of spheroidite from martensite might depend to some extent upon the grain size of the prior austenite. The austenite grain boundaries limit the maximum attainable size of the martensite needles and thus of the ferrite grains in the derived spheroidite. In order to evaluate any possible influence of prior austehite grain size, spheroidites were to be prepared from martensites that had been formed from fine-grain austenite and also from coarsened austenite. As the carbide particle size and distribution were to be essentially alike in the various spheroidites, the difference would be in the ferrite grain size and shape. Thus any marked difference in transition temperature could be attributable to the character of the ferrite grain structure. There are certain considerations in assuming that these spheroidites would be equivalent in all respects except ferrite grain structure, and an attempt was made to take them into account. One of the considerations was the choice of the carbon content of the steel. An approximately eutectoid steel was selected for two reasons. First, the pearlitic structure would contain no proeutectoid ferrite which might complicate the picture by producing a non-uniform ferrite grain structure in the resulting spheroidite. Then, too, the high-carbon content would inhibit ferrite grain growth during the sub-critical treatment. Another factor to be taken into account was the choice of an alloying element to assure a martensitic structure throughout on quenching the impact specimens. Nickel was chosen, because it is a common alloying element and resides in the ferrite both upon its formation from austenite and throughout tempering. The formation of alloy carbides, or even a large solubility of the alloying element in cementite, would have complicated the interpretation by changing the composition of the ferrite .during spheroid-ization. The possibility of temper brittleness was minimized insofar as possible by using a tempering temperature as high as consistent with the 1 pct of nickel in the steel, namely, 1150°F. While it certainly is not claimed that no difference other than ferrite grain structure could exist between the spheroidites, nevertheless, reasonable precaution has been exercised within the limits of steel metallurgy. It is believed that any large difference in transition temperatures would reflect the difference in ferrite grain structure and that relatively good ductility in the spheroidites from mar-

Jan 1, 1951

By H. W. Reinhardt, J. W. Dally

A dynamic photoelastic analysis of stress waves interacting with a free surface is described. The free surface is that of a bench with a fixed bottom so common in quarry applications. The stress waves are generated by line charges of lead azide (Pb N,). Four models of identical geometry are investigated with the direction of detonation of the line charge varied between the four models. Dynamic photoelastic patterns are recorded and analyzed to indicate which method of detonating the line charge produced the largest magnitude of tension at the free surface. The mechanics of rock breakage by means of explosives has received considerable treatment by many investigators including Duvall, Obert, Broberg, Rinehart, and Langefors1-11 over the past two decades. Indeed in more recent years several texts12-15 have been written on the topic, treating a wide variety of subjects which are logically related to the modern technique of rock blasting. In rock blasting the chemical energy of a concentrated explosive contained in a relatively small diameter borehole is utilized to fragment the rock. The explosive is transformed into a gas with enormous pressures which exceed 10-5 bars18 This high pressure shatters the rock in the area adjacent to the borehole and produces dilatational and distortional stress waves which propagate radially away from the borehole. The state of stress associated with these outgoing waves produces a system of cracks which extend for a few feet from the borehole. The breakage produced in this manner is limited as the dynamic stress in the pulse attenuates markedly with distance. In the absence of a free surface, the stress wave propagates away from the source without further fracture. With a free face of rock near the drill hole, another mode of breakage occurs which is due to scabbing failure of the layer of rock adjacent to the free face. These scabbing failures are produced by the reflection of the incident waves and the conversion of compressive stresses into tensile stresses sufficiently large to fracture the rock. The detailed nature of the interaction of the stress waves with the free surface is complex and difficult to treat analytically. However, dynamic photoelasticity offers an experimental approach which gives a fullfield visual display of propagating stress waves and the reflection process. Applications of static photoelasticity to solution of problems related to mining technology have become relatively common (see, for instance, Refs. 17 and 18) with a plastic model loaded to produce a state of stress representative of that occurring in the workings of a mine. The application of dynamic photoelasticity is ex tremely limited. Tandanand and Hartman19 have used a multiple spark camera to study fracture in glass and plastic plates impacted by a chisel-shaped tool. This paper describes a dynamic photoelastic analysis of stress waves interacting with a free surface. The free surface is that of a bench with a fixed bottom so common in quarry applications. The stress waves are generated by line charges of lead azide (Pb-N6). Four models of identical geometry are investigated with the direction of detonation of the line charge varied between the four models. Dynamic photoelastic patterns are recorded and analyzed to indicate which method of detonating the line charge produced the largest magnitude of tension at the free surface. Experimental Procedure The model illustrated in [Fig. 1] was fabricated from a sheet of Columbia Resin CR-39 to represent a bench with a fixed bottom. Properties of the CR-39 pertaining to these dynamic experiments are listed in [Table 1]. Scribe lines on 1-in. centers are used to identify locations along the bench face. The bench height was 8 in., the burden was 3 in., and the overall dimensions of the sheet, 16 and 18 in., were large enough to eliminate reflections from nonessential boundaries during the period of observation of the dynamic event. To simulate a charge in a borehole, a groove 0.062 in. wide and 0.080 in. deep groove was cut into the sheet from one side. The lower end of the groove was 1 in. or 1/3 the burden distance below the bottom of the bench. The upper end of the groove was 3 in. or one times the burden distance below the upper level of the bench. The groove was packed with 60 mg of Pb No per in. of length, and ignited with a bridge wire detonator. Four different ignition procedures were used to examine the effects of detonation direction on the stress wave interaction with the free face of the bench. In Test 1 the line charge was ignited at the top and the line charge detonated downward. In Test 2 the line charge was ignited at the bottom and the charge burned upward. In Test 3 the charge was ignited in the center with the top half burning upward and the bottom half burning downward. Finally in Test 4 the line charge was ignited at both ends simultaneously. Sixteen high-speed photographs of the photoelastic fringe patterns representing the stress wave propagation were recorded for each of the tests. A Cranz-Schardin multiple spark gap camera 20,21 was operated at framing rates which were systematically varied from 110,000 to 250,000 frames per sec during each test.

Jan 1, 1972

By A. S. Emanuel

A correlation has been developed for calculating the phase behavior of, gas-condensate systems at reservoir conditions. The correlation is based on the principle of corresponding states and has been coded for an IBM 7094. Experimental K-values were determined for several gas-condensate systems at reservoir conditions to evaluate various semi-empirical parameters of the correlation. The approximate range of application of the correlation is 150 to 300F and 1,500 to 6,000 psi. INTRODUCTION The rapid development of digital computers during the past several years has made feasible the calculation of hydrocarbon phase behavior by methods based on rigorous thermodynamic principles. Good correlationsl have been developed for low to moderate pressures, but these techniques have not yet been extended successfully to reservoir fluids at high pressures. Consequently, the determination of phase behavior of oil and gas systems at reservoir conditions is still based almost entirely on generalized data correlations or on experimental studies of the fluid in question. While these methods have been used successfully many times, they do have inherent limitations that restrict their applicability. Generalized correlations, such as the NGShlA K-charts, are limited to the range of pressure, temperature and components for which the data were determined. The accuracy of these correlations is often questionable because the effect of total system composition is not well defined. Experimental studies offer a reliable method for determining phase behavior, but usually the studies are costly and time consuming. Recently, Leland and co-workers presented a new approach to calculating phase behavior from the principles of corresponding states.6-8 Corresponding states methods determine the thermodynamics properties of a given system by comparison with a reference substance whose properties are known. The accuracy of this approach depends on close chemical and structural similarity between the reference substance and the system in question and between components within the system itself. For high accuracy, it is usually necessary to correct for chemical and structural dissimilarities. In principle, however, the corresponding states method should be no less accurate at high pressures than at low pressures, provided reference substance properties are known. This paper describes an empirical modification of the basic correlation proposed by Leland, et al.6 for the specific purpose of calculating the phase behavior of gas-condensate fluids at reservoir conditions. The modified correlation, which has been programmed for an IBM 7094, may be used for either approximate or precise determination of fluid behavior depending on the amount of analytical and, experimental data available for the system. BASIC THEORY The basic theory of the corresponding states phase equilibria correlation was first published by Leland, Chappelear and Gamson.6 Subsequently, Leland, Chappelear and Leach published methods for improving the accuracy of the original theory.7-9 The aim of the correlation is to calculate the K-value of each component of a given system as a function of pressure, temperature, and over-all composition, where Once the K-values are known, the phase behavior may be determined directly by an appropriate flash calculation. The basic equation for calculating component K-values was taken from the work of Joffe. 4 For any component i of a mixture, the K-value is given by

Jan 1, 1969

By C. H. Hitchcock

Report C6 of the Second Geological Survey of Pennsylvania, by Charles E. Hall, describes the rocks of the Philadelphia belt, and sets forth conclusions widely different from those derived by others from the study of similar strata along the same stratigraphical line. Mr. Hall classifies these rocks into three groups: First, the Philadelphia schists and gneisses, well shown within the city limits and

Jan 1, 1884

By S. A. Falconer

This paper deals with the practical application of the Dutch State Mines cyclone separator for fine-coal cleaning. The more important operating variables are discussed, and results of a number of continuous- scale tests on various fine coals with a 6-in. cyclone separator are given. Descriptions of the Cyanamid Pilot Plant and the 50 tph Cyclone Separator Plant at the Emma Washery in Holland are included.

Jan 7, 1950

By John T. Eash

During the course of the war the supply of tin in this country has steadily decreased and a continued effort has been made since the beginning of the emergency to use alloys that are either tin free or contain appreciably lower quantities of it. Even with the use of emergency materials, the tin supply has become particularly acute, and it is estimated that after recovery of the far eastern mines probably one to two years will be required before our normal annual supply is attained. One of the major tin-consuming fields is the bronze industry. Recommendations were made several years ago by the War Production Board toward the use of bronzes of lower tin content and manganese bronze and yellow brass for the customarily used tin-bronze alloys. The substitution of 88-5-5-2 copper-nickel-tin-zinc for composition G received considerable attention before the war, and consequently this alloy and modifications of it have been adopted for some current structural and pressure castings requiring high mechanical properties. Another of the commonly used bronzes is the 10 per cent tin 10 per cent lead copper alloy for heavy-duty bearings. It has been known for some time that about 2.5 per cent nickel could be substituted for an equal amount of tin with retention of equivalent casting and tensile properties; however, it was desirable that a still greater conservation of tin be made. Consequently the present paper deals with the development of an alloy of low tin content that could be used for bearings. Selection or Composition While the final criterion of the suitability of an alloy for a bearing must of course be determined by practical applications where all the ramifications of service conditions are encountered, certain short cuts in the initial selection of compositions are necessary to avoid an extensive and time-consuming investigation. The present program has been to match certain metallurgical properties of the 80-10-10 bronze that have been shown by previous investigations to be related to good bearing qualities. Such properties as microstruc-ture, hardness, compressive yield strength, ductility, and castability have been considered, and certain simple wear tests have been made. Of the readily assessed characteristics desired in a good bearing alloy, one can be certain that a uniform distribution of lead is required in a leaded bronze. It has generally been found that segregation of lead is one of the chief difficulties with this type of material. Tin has a powerful effect on lead distribution, and with 10 per cent present produces a random distribution of chunky particles, such as are shown in Fig' 1. I' In the tin bronze contains the hard alpha + delta

Jan 1, 1946

By John T. Eash

During the course of the war the supply of tin in this country has steadily decreased and a continued effort has been made since the beginning of the emergency to use alloys that are either tin free or contain appreciably lower quantities of it. Even with the use of emergency materials, the tin supply has become particularly acute, and it is estimated that after recovery of the far eastern mines probably one to two years will be required before our normal annual supply is attained. One of the major tin-consuming fields is the bronze industry. Recommendations were made several years ago by the War Production Board toward the use of bronzes of lower tin content and manganese bronze and yellow brass for the customarily used tin-bronze alloys. The substitution of 88-5-5-2 copper-nickel-tin-zinc for composition G received considerable attention before the war, and consequently this alloy and modifications of it have been adopted for some current structural and pressure castings requiring high mechanical properties. Another of the commonly used bronzes is the 10 per cent tin 10 per cent lead copper alloy for heavy-duty bearings. It has been known for some time that about 2.5 per cent nickel could be substituted for an equal amount of tin with retention of equivalent casting and tensile properties; however, it was desirable that a still greater conservation of tin be made. Consequently the present paper deals with the development of an alloy of low tin content that could be used for bearings. Selection or Composition While the final criterion of the suitability of an alloy for a bearing must of course be determined by practical applications where all the ramifications of service conditions are encountered, certain short cuts in the initial selection of compositions are necessary to avoid an extensive and time-consuming investigation. The present program has been to match certain metallurgical properties of the 80-10-10 bronze that have been shown by previous investigations to be related to good bearing qualities. Such properties as microstruc-ture, hardness, compressive yield strength, ductility, and castability have been considered, and certain simple wear tests have been made. Of the readily assessed characteristics desired in a good bearing alloy, one can be certain that a uniform distribution of lead is required in a leaded bronze. It has generally been found that segregation of lead is one of the chief difficulties with this type of material. Tin has a powerful effect on lead distribution, and with 10 per cent present produces a random distribution of chunky particles, such as are shown in Fig' 1. I' In the tin bronze contains the hard alpha + delta

Jan 1, 1946

By David W. Kennedy, Stephen P. Harrison

In the past few years, a new system has been developed for ventilating longwall panels in some gassy coal mines in the Northern West Virginia area. This system utilizes a five or six foot diameter air shaft to ventilate a group of three or more longwall panels dependent on conditions. This shaft exhausts all the air needed to, ventilate the active longwall and adjacent gob areas. By law, this bleeder fan can handle double the maximum methane concentration allowed in a normal return air course. As a result, the methane that must be diluted by the primary ventilation circuits is reduced. This new ventilation system was first conceived by mine management as a means of coping with a sudden shift in production mode that occurred a few years ago. Formerly, production often consisted of room and pillar mining with continuous miners. The high methane liberation rate was handled by driving entries around a large block of coal prior to mining. This isolated the future mining area from the adjacent coal seam and allowed a major portion of the trapped in situ methane to bleed off. Also, these bleeders served to exhaust return air from the mining area. Once the bleeders were established, productive mining could start. When the decision was made to shift production mode from continuous miners to longwall mining, some of the bleeders did not encompass large enough unmined areas under the old ventilation system to initiate longwall production. Also, many other established continuous miner section bleeders were either improperly positioned or too restricted for longwall ventilation. Unfortunately, standard bleeder development can take up to two years' time. In order to eliminate the old style bleeder system and maintain or increase the margin of safety for ventilation, the bleeder shaft system was conceived. With this system, the only entries developed are those necessary for the longwall, significantly reducing the production delay. In this area, the Pittsburgh #8 coal seam dips to the northwest. As a result of this dip, the bleeder shaft is constructed in the northernmost set of tailgate entries. In this manner, groundwater accumulations can be pumped to the surface and bleeder entries kept dry. During the initial longwall entry development, the bleeder fan can be used to ventilate entries adjacent to virgin coal where significant methane liberation often occurs. Once longwall production starts, the bleeder shaft exhausts the entire air quantity necessary to safely ventilate the longwall. As the bleeder entries deteriorate, the air quantity and pressure characteristics must be increased. The extreme flexibility of the centrifugal fan used at the surface allows the air quantity and pressure to be adjusted without stopping the fan. This improves safety by decreasing the possibility of a methane buildup resulting from the fan being out of service. The bleeder shaft system of ventilation, developed by mine management in Northern West Virginia, can provide a safe means for effectively ventilating longwall panels in excessively gassy mines. This system should be considered where mining conditions are comparable.

Jan 1, 1982