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By R. C. Gifkins, K. U. Snowden

The value of the index n in power ktivs for the stress sensitivity of minimum creep rale at lead is derived front results drawn from lite literature and from previously unpublished nork on commercial (99.99 pel) and high-purity (99.999 pel) lead polycryslalline and hi crystal specimens. In tests al 0.5Tm (22 to 50'C) for slvesses below 250 psi, n fulls to mily for poly-cr,yslullirle specimens, single crystals, and bicrystals, and toy grain boundary sliding in bicrystals. Between 250 and 500 psi there is a tyansilion range and, for the polycrystalline specimens al least, u high-stress regime for 500 to 1500 psi where n is 5 or 6. These results are such that none of the suggested stress taws can he used to extrapolate to very loir stresses. Meclianisms for deformation in Ike grains and toy grain boundary sliding in the low-strcss regime are outlined. In particular, the mechanism for grain boundary sliding involves sliding controlled by diffusion from tensile to compressire Ledges. predictions based on this model give promising numerical agree-nicul with experiment. II is suggested that the mechanism for grain boundary sliding may he important in other circumstances, e.g., in creep of ceramic materials or superplaslicity, because it can operate with lille or no dislocation aclirity. WhEN the stress dependence of secondary creep rate is represented by a power law the values taken by the stress exponent n are found to vary between 1 and 7, see, c.g., Garofalo.' In Eq. 1 11 u is the applied stress and A a constant. The case for accepting values of v = 1 rests principally upon tests at high temperatures (>0.9Tm) and there have only been isolated tests at lower temperatures (rather than plots of creep rate against stress) for which the creep rates are such that some form of Nabarro-Herring creep with n = 1 is applicable. Hanson5 and Greenwood and cole6 plotted creep rate against stress for tests made in the vicinity of 0.5Tw, and found a "creep yield", so that below a certain low stress the creep rate was linearly related to stress: these observations appear to have been subsequently ignored. Various models have been proposed which agree with a large body of experimental results in which n equals -5 at high stresses (e.g., weertman7 and McLean8). Various alternatives to Eq. [1] have been proposed principally as a means of unifying creep data, but sometimes, it seems, in order to obviate the necessity for assuming a series of regimes of deformation associated with the various values of n; further refer- ence to these will be made in the section on stress laws. This paper calls attention to extensive results which show n = 1 for the creep of lead at room temperature (0.5 T,). RESULTS Fig. 1 is a composite diagram based on figures in the literature6,9,10 with additional results obtained by the present authors and their colleagues11,12 in the course of a number of investigations not directly concerned with stress sensitivity. In Fig. 1 In creep rate is plotted against In stress. The curves show results for two kinds of material. Lead I is of commercial purity (99.99 pct Pb) and lead IT a specially refined material, hydrogen-purified to remove oxygen; it contains 99.999 pct Pb. Curve A is for lead I in polycrystalline form (grain diameter 0.02 to 0.05 cm) at room temperature (22' to 26°C). Curve B1 is for lead I, polycrystalline, tested at 50C. Curve B2 is for lead 11, polycrystalline (grain diameter 0.02 cm), tested at room temperature (22 O- Curves C to F relate to tests made of bicrystals of lead 11: all of the same nominal orientation ("Y" in Ref. 12). Curves C and V are for creep within the component crystals of the bi crystals at 22°C (AB and CD in Fig. 2). Curve E is for creep measured in a gage straddling the boundary, approximately 0.15 mm either side (BC in Fig. 2). Curve F shows rates of grain boundary sliding (as distinct from strain rates in the other curves), obtained by averaging the offsets of six marker lines on the bi-crystal boundaries. The principal feature of the results is that the stress sensitivity falls into two distinct regimes, according to whether the stress is below approximately 250 or above 500 psi (there is a transitional range between 250 and 500 psi). The new result is that below -250 psi two of the curves (A and BI) give a value of n 1, and the other curves also drop below n - 2 to -1.5 but do not extend to low enough stresses to show clear evidence of n 1. At very high stresses the curves tend to give values of n - 6, as previously determined in other investigations. Curve R2 for the high-purity lead in polycrystalline form at room tenlperature almost merges with B, and thus gives new significance to the values for stresses of 150 and 200 psi; previously'3 these points had seemed to fall away from the curve of slope -3, but they now can be seen as almost completing a transition to n = 1. It should be noted that there was originally considerable apparent scatter in the results for the high-purity lead. However, this was found to be associated with annealing conditions or variations in residual content of oxygen and curve B2 was constructed using the highest rate (i .e., the rate for the purest lead) determined for each stress during the course of various investigations over the years: altogether, some forty tests were used in constructing curve R2.

Jan 1, 1968

By C. G. Bieber, J. R. Mihalisin, R. T. Grant

A growing demand for longer service life of gas turbines has placed increasingly rigorous requiret~rents upon superalloys employed for that application. Long-titne testing at high temperature has revealed that phase transformations occur in all superalloys. A common one of particular interest is o formation. Presented here are studies made to identify a and to characterize its formation and effect on properties in three cast nickel-base superalloys—IN 100 alloy, alloy 713C, and alloy 713LC. Methods are discussed by which o can be eliminated or inhibited in IN 100 alloy and alloy 713C. Evidence was obtained to indicate that some types of o may be more detrimental than others. Limitations in the electron vacancy approach to o prevention are pointed out, and it is shown how alternative approaches, such as reducing a complex superalloy matrix to the form of a pseudo-ternary system permitting equilibrium diagram treatment, lead to additional insights into the formation of in these alloys. AROUND 1960. Beiber1 developed IN 100 alloy, which still remains one of the strongest commercially available nickel-base superalloys. The principle used in the design of this alloy was to produce large quantities of y' phase in a y matrix through the use of copious amounts of aluminum and titanium. In 1963, ROSS' showed that when certain heats of this alloy were held for a long time at 1650°F they formed an acicular phase, subsequently identified as a.3 a is a hard and brittle phase first discovered in the Fe-Cr system by Bain and Griffiths.4 They termed it the "B" constituent. Subsequently this same phase was found in other systems, primarily those of the transition elements, and acquired the name "a" by which it is now known. The crystal structure of the a phase was first determined in the Fe-Cr system in 1950.5 It was shown to be tetragonal with a c/a ratio of about 0.52. as is the case with a found in other systems. This characteristic crystal structure is now the means by which a is identified. In superalloys, such as IN 100 alloy. large amounts of o impair the high-temperature creep strength and drastically reduce room-temperature tensile ductility. Discovery of o phase in some heats of IN 100 alloy quickly led to investigations of other superalloys for similar transformations. It was found that many of the stronger, more highly alloyed. super-alloys were indeed susceptible to o formation. This investigation has been concentrated on three commercial alloys: IN 100 alloy, alloy 713C, and alloy 713LC. J.R.MIHALISIN,MemberAIME, and C.G.BIEBER are with The International Nickel Co., Inc., Paul D. Merica Research Laboratory, Sterling Forest, Suffern, N. Y. R. T. GRANT, Member AIME, is with The International Nickel Co., Inc., Pittsburgh, Pa. Manuscript submitted May 22. 1968. IMD A detailed study has been made of the phase transformations and their relation to a formation along with a consideration of electron vacancy approaches for predicting a-forming propensity in these alloys. EXPERIMENTAL PROCEDURE Phase transformations were studied by light and electron microscopy, electron diffraction, microprobe investigations, and X-ray diffraction. Specimens for light micrographic examination were prepared by conventional grinding and polishing followed by etching with glyceregia (2:l HC1/HNO3 + 3 glycerine by volume). Photomicrographs of stress-rupture specimens were taken adjacent to the fracture unless otherwise noted in the text. Negative replicas for electron microscopy were taken from surfaces electropolished with a solution of 15 pct H2SO4 in methanol. For carbon extraction replication, a solution of 10 pct HC1 in methanol was used. A Siemens Elmiskop I was used for all electron microscopy. Selected-area diffraction studies were made at 80 kv using evaporated aluminum for standardizing the patterns. A nondispersive electron microprobe attachment was used to analyze the extracted precipitates chemically. The fluorescent X-rays were recorded using a flow counter containing P10 gas (90 pct Ar-10 pct methane) with a beryllium window and a single-channel pulse-height analyzer. The pulses from the analyzer were passed to a scaler-ratemeter and differential curves of counting rate vs pulse amplitude were obtained. The base line of the analyzer was driven with a synchronous motor at 0.5 v per min and a channel width of 0.5 v. The time for 105 counts was printed out for each 0.5-v increment. The microscope was operated at 80 kv with beam currents of 1 to 20 pa. This equipment detects elements from atomic number 13 to 40. X-ray diffraction studies were usually made on residues electrolytically extracted in 10 pct HC1 in H2O, although in one case a pattern was obtained from an etched surface of a metallographic specimen. A Siemens Crystalloflex IV was used with iron-filtered CoKa radiation. X-ray patterns were recorded using a goniometer speed of : deg per min. The scintillation counter and pulse-height analyzer operated at a channel height of 10 v and a channel width of 12 v. The equipment was calibrated with a powdered gold standard. The residues usually contained a number of phases. several of which could not be found in the ASTM card file. In addition, as is shown for the case of a phase in IN 100 alloy, other phases had a somewhat different lattice parameter from that reported in the ASTM card file, making it difficult to separate and identify constituents by comparison with ASTM d spacings. For these reasons, phases were identified on the basis of the lattice parameter obtained by indexing the ob-

Jan 1, 1969

By Hansheinz Portisch, Harold Margolin

A surface expansion was found to occur sometime after etching in Ti-A1 alloys containing 9.5 to 12.5 wt pct Al. The structure formed, grew, and disappeared with tzrrze. The surface expansion was followed by microscope observations and interferometric and lattice parameter measurements. Activation energy measurements for the growth of the "expansion structure" and chemical analysis indicated that the phenomenon occurred as a result of hydrogen pzckup during etching. It is proposed that hydrogen initially enters octahedral sites of Ti3Al coherent with a Ti and later shifts to the tetrahedral sites. It is postulated that expansion occurs when hydrogen enters the tetrahedral sites. The expansion structure disappeared, it is proposed, because of diffusion of hydrogen from the surface into the body of the alloy and because of loss of coherency of Ti3Al. In examining Ti-A1 alloys, Ence and arolinl observed markings on the surface of specimens. These markings did not appear after electropolishing only, but rather appeared only after etching. The markings appeared to grow as a function of time after etching and later seemed to disappear. Although the markings had some similarity to precipitates, showing, frequently, a Widmanstatten type of arrangement, the observation that other microstructural markings continue to be seen within the new structure suggested that it was actually not a precipitate. The source of this structure was unknown and an attempt was made in the present investigation to develop some understanding of its nature. It has been labeled expansion structure. 1) EXPERIMENTAL PROCEDURE A) Alloys. Alloys in the range 6.5 to 14.5 wt. pct A1 were studied. Bars, 4 in. sq, forged from Bureau of Mines (73 Bhn) titanium consumably arc-melted 4-lb ingots,' as well as 50-g arc-melted buttons of desired aluminum contents were used. The 50-g buttons also used Bureau of Mines titanium (73 Bhn) and aluminum of 99.99 pct purity. Buttons containing up to 8.5 wt pct A1 were hot-rolled from a furnace at 900' . Those with higher aluminum contents were hand-forged on a titanium anvil, and heated with an oxygen-hydrogen torch in the region of 1200" to 1300°c. Frequent reheating kept the samples at the desired temperature range. After a reduction of about 30 pct, the samples were water-quenched. To eliminate any contamination picked up either during hot rolling or forging, at least 1 mil of the surface of the sample was taken off. B) Heat Treatment. Prior to heat treatment all alloys were vacuum-annealed to remove hydrogen. Samples were annealed at 900' until a vacuum of 10'5 mm Hg was established. After this treatment, the samples were wrapped in molybdenum sheet and heat-treated in argon-filled quartz capsules, which were broken under water or iced brine at the conclusion of the heat treatment. All heat treatments under dynamic vacuum were performed in a rapid-quench furnace. This consisted of a molybdenum-lined quartz tube attached to a vacuum system and through a stopcock to a beaker of water. At the completion of the heat treatment the vacuum stopcock was closed, the furnace shut off, and dropped below the quartz tube. Then immediately the inlet stopcock was opened and water admitted until the tube was filled. The steam formed was allowed to escape through the inlet stopcock. This method was used in heat treatments up to llOO°C. C) Metallography. Specimens for metallographic examination were ground, then electropolished using a Disa Electropol machine with a perchloric acid electr01te. Specimens were etched with R-etch.3 A standard etching time of 3 min was used, with the specimen being agitated during immersion. D) Sample Preparation for X-ray Analysis. Samples 0.2 to 0.5 mm in diam were produced from heat-treated rods which were turned to 2 mm diam on a lathe and then rotation-etched. An etchant consisting of 1 pt HF, 7 pt HN03, and 12 pt HzO was satisfactory. With the rod rotating in a vertical position at 50 to 100 rpm, a needle with uniform dimensions could be obtained. Care had to be taken to insure that the rod was at the center of rotation, otherwise cavitation developed. If a small unevenness developed, it was possible to grind it off with a fine emery paper. E) X-ray Diffraction. All X-ray work was done on a North American Phillips X-ray diffraction apparatus and a Jarrell Ash microfocus X-ray unit. The Phillips unit was used with a copper target and nickel filter. The Jarrell Ash unit was fitted with a cobalt target and iron filter. For the Phillips unit 35 kva and 20 ma were used, whereas for the microfocus unit with the 100-p fixed-focus gun 40 kv and 1.5 ma were used. It was found that alignment of cameras on the Jarre11 Ash unit was very critical. The X-ray beam contains an intense area which is not the beam center. The cameras were aligned with the intense region by monitoring the beam coming out of the camera with a Geiger counter. Adjustments were made until a maximum intensity was obtained. A Phillips diffractometer with a Brown chart recorder furnished some of the lattice parameter data. The divergence slit up to 80 deg 28 was I deg; above 80 deg, a 4-deg opening was used, while the scatter slit was1 deg and the receiving slit had a 0.003-in. opening. The general scanning rate was 1 deg per min, while peaks of special interest were rescanned at -j deg per min. For elevated-temperature X-ray diffraction a Uni-cam High Temperature Camera with a film diameter

Jan 1, 1969

By R. M. Goldhoff, H. J. Beattie

The high-temperature properties of a 1 Cr-Mo-V forging steel are described. A series of controlled heat treatments was designed to delineate the effects of austenitizing and tempering treatments, temile strength, and grain size on such properties. Studies indicate that the mechanical properties and their varlations under creep can be described by the initial metallurgical structures and their changes droPirzg exposure, particulavly the carbide reactions. Such structures are described and correlated with the mechanical properties. FOR many years the large steam turbine industry has relied on the 1 Cr-Mo-V type forging steel for critical applications. Because of its adequate heat resistance and relative economy, it is currently in use in the temperature range up to about 1050" to 1075°F. Attempts to understand the large property variations attainable in this steel involve the structural modifications due to the wide latitude in its heat treatment. The heat treatment essentially involves a two-step process which includes solution-ing of carbides in the austenite range followed by a suitable tempering treatment below the critical to adjust the level of properties. The latter step is referred to as "secondary hardening" and is basically an ordinary aging reaction involving carbides. In the commercial heat treatment of large components of such steel, homogenizing and stress-relief anneals may be included and have some importance in determining subsequent properties. Several studies of the engineering properties of this steel as a function of transformation micro-structure have been reported.1 3 However, in this steel the carbide reactions, which are a function of composition and heat treatment, appear to be the property-controlling factor rather than the micro-structure defined as a transformation product. Thus, the tempering resistance of this type of alloy steel is mainly a function of the size and distribution of alloy carbides.4 However, it is also necessary to consider the stability of the microstructure and the effect of dynamic carbide reactions on subsequent properties. It is the purpose of this paper to show the interdependence of properties and corresponding structures, particularly carbide reactions, developed for a limited set of controlled heat-treatment conditions applied to 1 Cr-Mo-V steel. MATERIALS AND PROCEDURE The material for this work came from a large production forging whose chemical composition is shown in Table I. The property data accumulated on this steel as a function of heat treatment were room-temperature tensile and smooth- and notch-bar creep rupture at 1050°F (notch geometry: shank diameter = 0.357 in., depth = 50 pct, radius = 0.005 in.). To achieve controlled structural variations the temperature and time of both austenitizing and tempering were varied in a manner to produce a series of eight steels each at one of two grain sizes and one of two hardness levels in proper combination for valid comparisons. This will be clear upon examination of Table I. Structural studies involved the use of optical and electron microscopy as well as X-ray and selected-area electron diffraction. To reveal the nature of carbide precipitations, electrolytic extraction techniques were used with subsequent analysis of the residue by X-ray diffraction. Weight losses of the steel specimens during electrolysis were measured and successive chemical fractionations of the residues were applied and checked by X-ray examination. The details of fine structural distributions, morphologies, and crystallography of the precipitates as well as dislocation distributions were investigated by examining in the electron microscope three common types of preparation. a) Relief Replicas. Mechanically polished sections were etched in 2 pct nital, replicated with a nitrocellulose film, which was shadowed by chromium vapor deposited at a glancing angle of 20 deg. b) Extraction Replicas. A thin film of carbon was vapor-deposited on the polished and etched surface. The carbon films were then etched off and gathered on electron-microscope supporting grids. The carbides left imbedded in the carbon replica in their original distribution were then examined crystallo-graphically by selected-area electron diffraction. c) Thin Films. Specimens were mechanically ground and polished down to a thickness of 0.001 to 0.003 in. Final thinning was done electrolytically in a "chrome-acetic" electrolyte. When holes began to appear in the foil, the voltage was interrupted and applied in several 1-sec bursts. Sections of the foil between holes were thin enough to pass a 100-kv electron beam that carries an image.

Jan 1, 1965

By R. C. Gould, A. M. Skov, L. F. Elkins

Comparison of long term decline in oil production during cyclic waterflooding or pressure pulsing of part of the Driver Unit with steady injection-imbibition flooding in the Tex Harvey area led to large expansion of flood in the Driver Unit on the steady injection basis. While the flood has been successful, the major problem has been attainment of satisfactory oil production rates in most of the wells. Large volume fracture treatments of low capacity wells were unsuccessful in achieving sustained increases in production. A two-section area in the Driver Unit has already recovered 620 bbl of oil per acre by waterflood but other areas have not performed so well. Sun Andres water containing 300 to 500 ppm H,S is sweetened to 0.5 to 1 ppm H,S by extraction with oxygen-free flue gas. This prevents contamination of gas produced in the area and apparently it has reduced corrosion in minimum investment, thin-wall, cement-lined water dktribution systems. Cement-lined tubing in injection wells has mitigated corrosion as effectively as thick polyvinyl chloride films have, and at less cost. Introduction As reported in the literature the Spraberry field of West Texas has presented unusual problems for both primary production and waterflood ing. Earlier information from the Spraberry Driver Unit included conception and evaluation of cyclic waterflooding or pressure pulsing in a nine-section pilot test as an aid to extraction of oil from the tight matrix rock and as a boost to normal capillary imbibition forces An additional 5 years' operation in that area, and performance of expanded steady injection water-flood, now covering a total of 68 sq miles, are reported herein. In addition, since the Driver Unit is one of the largest waterfloods in areal extent in the U. S., many operating experiences are presented for the benefit of engineers concerned with operation of other Spraberry floods or with other waterfloods where this reservoir technology and/or water handling technology may be adaptable in part. These include: (1) attempts to improve producing well capacity through large volume fracture treatments, (2) long-term performance of water treating plants utilizing oxygen-free flue gas to extract H,S from sour San Andres water, (3) performance of thin-wall cement-lined pipe in water distribution systems including comparison between those sections carrying raw San Andres water and those carrying treated water, and (4) comparison of performance of various lining materials and subsurface equipment in water supply and water injection wells. These experiences are reported without regard to whether results are good, bad or indifferent. Since the operations reported are limited to the techniques, materials, and equipment actually used in the Driver Unit, no comparison is possible with results of other approaches used in other Spraberry floods or in waterfloods generally under different conditions. However, an attempt is made to quantify these experiences as much as possible in the space available to permit other engineers to select those parts applicable to eheir problems. Background The Spraberry, discovered in Feb., 1949, is a 1,000-ft section of sandstones, shales and limestones with two main oil productive members—a 10- to 15-ft sand near the top and a 10- to 15-ft sand near the base, having permeabilities of 1 md or less and porosities of 8 to 15 percent. Extensive interconnected vertical fractures permitted recovery of oil on 160-acre spacing from this fractional-millidarcy sandstone, but they made capillary end effects dominant. Primary recovery by solution gas drive is less than 10 percent of oil in place, with most wells declining to oil production of a few barrels per day when reservoir pressures are still in the range of 400 to 1,000 psi. Partial closing of the fractures with declining reservoir pressure is believed to be the cause of such low production rates at these relatively high reservoir pressures. In 1952 Brownscombe and Dyes proposed that displacement of oil by capillary imbibition of water from the fractures into the matrix rock might significantly increase oil recovery from the Spraberry, overcoming otherwise serious channelling of water through the fractures." A pilot test conducted by the Atlantic Refining Co. during 1952 through 1955 indicated technical feasibility of the process; but low oil production rates averaging I5 to 20 bbl/well/D failed to create significant interest in large-scale waterflooding at that time." Humble Oil & Refining Co. conducted a highly successful 80-acre pilot test during 1955 through 1958 with

Jan 1, 1969

By W. S. Gillam

A need for new supplies of fresh water exists today and in many specific areas that need is urgent. One solution lies in saline water conversion, a problem complicated by cost factors. The principles involved in saline water conversion, the status of development, and the estimated costs (present and future) of several processes are presented. Among the methods discussed are distillation, electrodialysis, and freezing. In general, the costs presented are based on a standardized procedure for estimating conversion costs, permitting a valid comparison among the various processes. The need for new supplies of fresh water and the potential benefits to be derived from an abundant supply of converted water are recognized by practically everyone concerned with water problems. The water supply problem exists today; it is urgent in many specific areas in this country and also in the world, and it will become more acute in the future. One answer to the growing problem of adequate water supplies is the development of new sources. Very significant quantities of brackish underground and surface waters exist in certain areas and an inexhaustible supply of ocean water is available. Thus in many areas water resources can be extended through saline water conversion. Congress recognized the need for new sources of fresh water in 1952 and passed the Saline Water Act, Public Law 448, amended it in 1955, and in September 1958, enacted Public Law 85-883, calling for the construction of at least five demonstration plants. The program is administered by the Dept. of Interior through the Office of Saline Water, and its primary objective is to reduce the cost of converted water produced, whether it be by development of new processes or improvement of known processes. This is a most difficult problem and one that will require several years of prodigious effort. It is difficult—not because of any intricate or new chemistry, engineering, or physics involved—but because of the difficulty in converting water at low cost. Whatever the sources of the saline water, the salts which are held tenaciously in solution must be removed before the water becomes suitable for industrial or domestic uses. Saline water is a relatively simple system of salts dissolved in water. It has certain chemical and physical properties that determine the various methods by which the salts may be separated from the water. The system, although not complex, in most instances, has had countless years in which to reach equilibrium and is, therefore, comparatively stable. Because of its stability, separation of saline solutions requires relatively large quantities of energy. The unique properties of water depend on the fact that its molecules are chemically active. The chemical and physical properties of water are associated with the type of bonding involved in the water molecule. Chemical changes such as hydrolysis, or rusting of iron, involve the breaking of chemical bonds between the hydrogen and oxygen atoms. Physical changes, such as evaporation in a boiler, the melting of ice, or the viscous resistance to flow in a pipe, involve breaking of the hydrogen bonds. (The hydrogen nucleus is so small that it can attract two negative atoms.) Thus water molecules not only combine with molecules of other compounds but even with one another; e.g., each molecule may be bounded to four other molecules. Water molecules cling to the ions of dissolved salt to form water-encumbered hydrated ions and they cling to one another to form entangling networks through which hydrated ions can be propelled only by tearing the networks apart. That is one reason why considerable energy still needs to be expended in our simplest procedures for purifying water. If water molecules did not have this habit of clinging so tenaciously to other molecules, and to one another, it would be easy to push salt ions past the water molecule and get a separation. But the water would not then dissolve salt, so the problem would not exist.' Water when heated evaporates very slowly, relative to other liquids having simple molecules. Vaporization involves the separation of molecules from the liquid, and this means overcoming the attraction between molecules which is due to the hydrogen bonding. The heat of vaporization for water is high; consequently, the boiling point of water is also high. Water boils at 100" C; hydrogen sulfide (H2S) at -60" C; oxygen (02) at -183" C; nitrogen (N2) at -196" C; and methane (CH4) at-161°C, even though the latter has about the same molecular weight as water. Because of these peculiar properties of water, it exists as a liquid on earth instead of a gas such as hydrogen sulfide or nitrogen and oxygen.

Jan 1, 1961

By J. W. Clark, C. T. Sims

Wrought chromium-base alloys containing yttrium, cubic monocarbides of the Ti(Zr)C type, and similay alloys containing manganese and rhenium have been melted and fabricated. Strength has been studied by hot hardness and elevated-temperature tensile and rupture measurements, low-temperature ductility by tensile testing, and surface stability by oxidation testing. In additiod, studies have been conducted of the carbide stability, and of aging behavior. The carbide dispersion generates effective elevated-temperature strength, which is further enhanced hv strain-induced precipitation. The dispersion exhibits classical dissolution and aging response. The ductile-to-brittle transition temperature of these alloys is above room temperature. The alloys reported show fairly good oxidation resistance, but nitrogen contamination can cause fortnation of a hard Cr2N layer under the oxide scale. Manganese does not appear to be a promising alloying element in chromium. In the years 1945 to 1950, the metal chromium was considered as a possible base for alloy systems due to its considerably higher melting point than superalloys, its low density, its high thermal conductivity, and its apparent capacity for strengthening. However, this interest in chromium was short-lived. It was found difficult to melt and cast, to be exceptionally sensitive to the effect of minor imperfections, to have a lack of ductility at both room and elevated temperatures, and to be subject to a deleterious effect of alloying elements upon the ductile-to-brittle transition temperature.' Since then, chromium, as a practical alloy base, has remained virtually unstudied. Further, purposeful ignoring of chromium has been promoted by statements that its bcc structure would not allow it to be strengthened to useful values, when compared to the "austenitic" alloys.2 Recently, a new look has been taken at chromium-base alloy systems. Study of the literature will show that chromium, providing some of its disadvantages could be eliminated or minimized, actually has a rather attractive potential as an alloy-system base. Analysis of rather scattered data suggests that chromium is quite capable of being strengthened to high levels. Also, significant strengthening of its two sister elements in Group VI-A, molybdenum and tungsten, has been demonstrated in a number of commercial and exploratory alloys. Chromium should be similar. Since chromium does not readily form a volatile oxide like tungsten or molybdenum, it offers a much higher probability of giving birth to alloy systems with useful oxidation resistance. Concerns about possible high elemental vapor pressure have been mitigated by recent data.3 In addition, the physical properties exhibited by chromium are attractive for application as a high-temperature structural material. For instance, its thermal conductivity varies from 49 to 36 Btu-ft/hr-sq ft-°F over its range of usefulness (which is two to four times higher than most superalloys), its density is about 7.2 g per cc (20 pct less than most nickel-base alloys), its coefficient of thermal expansion varies from 4 to 8 x 10-6 per OF, and it has a relatively high modulus of elasticity, approximately 42 x 10' psi.4 Alloying studies on a chromium base in the past have usually encompassed rather sweeping solid-solution alloy additions for strengthening. This is not consistent with contemporary alloying practice in Group VI-A. For instance, molybdenum, also in Group VI-A, is primarily alloyed for strength improvement by use of heat-treatable carbide dispersions.5 Chromium and molybdenum are similar in their chemical activity and other properties. Thus, strengthening of chromium by carbide dispersions was studied. Chromium-base alloys are plagued with room-temperature brittleness, although high-purity unal-loyed chromium can be made ductile.4,8 Use of yttrium as a scavenger has done much to improve ductility and resistance to nitrogen embrittlement in chromium systems,7 so it was utilized in this program. It has also recently been found8 that small rhenium additions (1 to 5 pct) create improvement in the ductility of Type 218 tungsten wire. This is apparently related to the remarkable effect of rhenium additions near its terminal solid solubility in all Group VI-A metals.9'10 Investigation to establish if dilute concentrations of rhenium would also be effective in chromium appeared to be logical for this program. Since rhenium is too expensive to be practical in alloys for application as structural components, ductility improvements through solid-solution alloying were also sought by substitution of manganese for rhenium; manganese, like rhenium, exists in Group VII of the periodic system. The optimum amount of carbide dispersion for chromium-base alloys was obtained by analogy with molybdenum. Strengthening in molybdenum is achieved by use of Ti-Zr carbide dispersions. A

Jan 1, 1964

By S. Kwon, J. W. Wilson

"In salt and potash mines, the time-dependent deformation mechanism should be clearly understood based on in situ measurements to predict the performance of a mining design. In this study, in situ deformation measurements from the Waste Isolation Pilot Plant (WIPP) and other salt and potash mines were used to determine the transition time from the primary to the secondary creep stage and to investigate the influence of adjacent excavations such as a nearby tunnel excavation, panel excavation and/or pillar extraction on rock deformation. IntroductionThe deformational behaviour of underground excavations in salt and potash mines is complex due to the time-dependency of the rocks. When the material properties are determined from laboratory tests, they should be carefully applied to in situ conditions, because in situ conditions are completely different from laboratory conditions. For instance, in situ deformation measurements show that the deformation rate decreases with time similar to those observed in the laboratory during the early stages. However, the rapid decrease of deformation rate does not come from the microscopic strain hardening effect observed in laboratory tests, but mainly from stress relief around the opening after its excavation (Baar, 1977). It is, therefore, recommended to undertake in situ measurements and use them to understand the deformation mechanism.Even though in situ measurements are widely accepted as important information for understanding the deformation mechanism of salt and potash (Barr, 1971; Kovari and Amstad, 1993), not many publications have focused on the fundamentals of data measurement, the application of the measured data, and the development of data analysis techniques. Recently, several new techniques for better understanding the deformation mechanism of rock salt have been developed that are based on in situ measurements. Kwon and Miller (1995) developed a new technique for describing the actual deformational behaviour of an underground excavation in rock salt. The migration of “zero strain boundary,” which represents a no movement boundary around an underground excavation, could be calculated by the technique developed by Kwon and Miller (1996). Kwon and Wilson (1997, 1998) applied neural network techniques to in situ deformation measurements to predict the deformational behaviour of the underground excavations at the Waste Isolation Pilot Plant (WIPP) located in the United States.In this study, in situ deformation measurementsfrom the WIPP site and other salt and potash mines in the United States were extensively analyzed to understand the deformation mechanism of the underground excavations in the rock mass."

Jan 1, 2002

By Frederick A. Mumpton

Recent findings by medical workers on the association of certain zeolite minerals with the high incidence of pleural mesothelioma in two small Turkish villages have caused considerable excitement both in medical circles and in the synthetic and natural zeolite businesses. The 42 cases diagnosed between 1970 and 1977 in one community of 600 population in a region of altered volcanic tuff represent a virtual epidemic of this rare malignancy which normally strikes only about one person in a million. Cancer workers around the world expect that detailed environmental and epidemiological studies of the disease in these areas will shed considerable light on the cause of this particularly lethal form of lung cancer. Scientists and engineers developing uses for zeolite materials in industry and agriculture, however, are justly concerned that the preliminary results available on this situation will be used by environmental and regulatory organizations to label an entire group of miner- als as carcinogens on the basis of what is little more than circumstantial evidence. Although there is no question as to the large number of cases of mesothelioma in these areas of central Anatolia, the work to date has suffered from a lack of sound geological and mineralogical input. Ataman (1) stated that a "correlation" exists between mesothelioma and zeolites in this region; however, the geological data needed to document a direct relationship between the presence of zeolites in the volcanic tuffs surrounding the villages in question and the rate of malignant lung disease in the inhabitants have g been obtained, nor has evidence that suggests a cause-effect relationship between zeolites and cancer been reported. To provide fundamental information on the distribution of zeolite minerals in areas of central Turkey where high incidences of pleural mesothelioma have been reported and to evaluate from first-hand knowledge the published reports and news releases of medical workers engaged in assessing the problem, the following investigation was made.

Jan 1, 1979

By H. E. Heide

"Before the war, the United States was the world’s leading consumer of tin, the industrial applications of which had become widespread. Domestic production was negligible, and requirements were met almost entirely by imports, principally from British Malaya, United Kingdom and China. Average annual imports for the years 1925-1929 amounted to 78,009 long tons.With the advent of war in Europe and signing of the Japanese-German pact, it was realized that foreign sources of supplies were threatened, and steps were taken by Congress to forestall critical shortages of tin and other minerals. These steps in regard to tin included stock-piling, improving reclamation and conservation, increasing South American production, constructing a smelter in the United States for treatment of tin, ores, and intensifying the search for domestic tin deposits. Annual imports were raised to 140,873 long tons by 1941. On 1945, annual imports had shrunk to 37,675 long tons and consumption had been reduced to 52,100 tons of primary and secondary tin but not tin content of scrap alloy.The Strategic Minerals Act, passed by the Congress in 1939, authorized the investigation of domestic tin deposits.As Alaska had supplied virtually all of the domestic output of tin, an investigation of Alaska deposits was undertaken in 1940 and 1941 by J. B. Mertie, Jr., and Robert R. Coats of the Geological Survey.The Lost River lode tin mine on the Seward Peninsula was examined by H. E. Heide of the Bureau of Mines in 1942. Possibilities for developing a significant amount of tin appeared favorable, and exploration of the ore bodies was started in August 1942."

Jul 1, 1946

By Charles W. Bloomquist

The profitability of miscible flooding in a hypothetical target oilfield is examined. The major costs, including Windfall Prof it Tax, are identified and their re1ative importance are discussed. The sensitivity of profit to important physical and economic variables is evaluated and discussed, including variance in oil recovery, oil price, injectant requirements, injectant cost, and capital requirements. Economic sensitivities to important development and operating decisions such as timing, Spacing, Slug size, and gas recycling are also analyzed. The Windfall Profit Tax (WPT) as it applies to gas miscible EOR projects is reviewed. The effect of WPT on each of the various project cases is analyzed and the effect of reduced WPT on remaining production from existing operations is evaluated. Tax implications are compared for integrated vs. "independent" controlled projects and the alternative of expensing vs. capitalizing tertiary injectants is also evaluated. The impact of the Net Income Limitation in reducing WPT. during early and late project life is determined and discussed.

Jan 1, 1982

By Franklin D. Slagle

Porosity and bulk-and sand-grain-density values were determined for 2,040 core samples of 30 formations from 47 wells in New York, Ohio, Pennsylvania, and West Virginia, and are compiled for petroleum industry use in well-log evaluation and geologic studies.

Jan 1, 1967

By Richard F. Hewlett

Computing average grade and tonnage either for an entire ore deposit or for individual blocks of ore is a continuing problem in mining. As part of a research program, investigating application of statistical techniques to mine sampling, Bureau of Mines engineers at the Denver Mining Research Center have made extensive use of an electronic digital computer for developing mine sampling theory, simulation of ore deposits, and analysis of mine sample and assay data. This report is one of a series describing use of the digital computer for rapid solution of computing problems in the mining industry.3 4 Development of a computer program to compute ore reserves by the commonly used triangular method was necessary so that results could be made available for analysis within hours.

Jan 1, 1963

By John J. Stetler

The Companhia Vale do Rio Doce in Brazil operates one of the most extensive systems in the world for the mining, transportation, processing, pelletizing and shipping of high grade hematite iron ore and pellets. Current shipping of unbeneficiated, sized, high grade ore from its ports at Tubarão and Vitória is now at the rate of 17,500,000 metric tons annually. An increase in this annual rate is now under study. Using the technology and facilities of Lurgi (1) and Arthur G. McKee company CVRD undertook a program to process and pelletize two types of fines - "Blue Dust" and ?Itabira Fines?. Blue Dust is a high grade fine ore which was bypassed while mining the direct shipping ores and which, also, exists as a very large ore body called the Conceição Mine. Itabira Fines is a lower grade of fine ore which is comprised of in-situ fines and, also fines which are generated in sizing the direct shipping ores for a rigid specification market.

Jan 1, 1970

By W. W. Adams

This bulletin covers all mines in the United States that were operated in 1936 to produce metallic ores and all mines that were operated to produce nonmetallic minerals other than coal, stone, sand, gravel, or their products. Reports from mine operators revealed a better safety record for fatal accidents in 1936 than in any other year except 1934 during the 26 years for which annual surveys of accidents in the mineral industries of the United States have been conducted by the Bureau of Mines. On the other hand, the record for nonfatal injuries, although better in 1936 than in any year prior to 1930, was not as good as it was from 1930 to 1935, inclusive.

Jan 1, 1939

By L. J. Buchanan

The relationship between hydrothermal ore deposits and hot spring systems has received intensive study in recent years, particularly as a consequence of interest in the energy potential of geothermal systems. Base and precious metal deposition in surface pools and at shallow depths in modern geothermal systems has been recorded in numerous publications (1, 2, 3) Theoretical studies of hydrothermal fluid flow at depth, connected to surficial hot springs systems, have been presented by White and others (1), Cathles (2) , Henley and McNabb (3). As a result of these and additional studies, numerous hydrothermal ore deposits are thought to have originated as genetic parts of larger geothermal systems. In particular, it appears that metal precipitation is greatly enhanced in zones of boiling where volatiles and steam are escaping (4). High grade, near surface concentrations of base and precious metals, deposited as a result of partial vaporization of rising fluids, are such a common aspect of modern not spring systems that ore deposition models are becoming based on what may be called a geothermal model. In its most general terms, this model requires an anomalously high thermal gradient which acts as the driving force behind a convecting hydrothermal system. The water may be entirely meteoric or may be In part at least of other origins. The water migrates towards the higher temperature area, becomes heated, and picks up alkalies and metals by dissolving minerals along the fluid path. As water exits to the surface above the heat source, a mass balance requires the incoming hot water to rise to replace the lost water. As the water rises past the elevation where the hydrostatic pressure is insufficient to prevent boiling, then boiling will occur. Depending on the salinity and the temperature of the water, boiling can occur anywhere from great depths to near surface. Boiling results in a loss of volatiles, a pH rise in the fluid phase, cooling of the remaining fluid, a rise in oxygen fugacity, a concentration of salts in the remaining liquid, and precipitation of ore and gangue minerals.

Jan 1, 1980

By Robert L. Lappi

Volume I of this report described the demonstration of cross-ridge mountaintop coal mining. This document, Volume II, is intended for use as a supporting document to Volume I. This report describes the MATHMINE Mine Simulation System, a modularized software system used to support the demonstration of cross-ridge Mountaintop coal mining. The MATHMINE Mine Simulation System was used to generate mine plans for coal extraction at lowest cost. The functional details, data requirements and output of the software system are detailed here. The computer program was written in FORTRAN. One module which generates resource location data required the use of SAS?.

Jan 1, 1984

By Robert Lee, Jeff Corace, Rob Cyr

Blasting in the heart of the historic Byward Market District of Canada’s capital, Ottawa, presents a unique set of challenges. The obvious difficulties arising on projects requiring blasting within 3 m (10 ft) of 125 year old buildings in various states of disrepair have been encountered and successfully dealt with countless times before. The complexities increase exponentially when tenuous property boundaries, unknown structural details, litigious histories and the need for encroachment agreements lead to individuals with competing interests all able to impact the same operation. Blasting on three projects in the Market was started in early 2005 after months of negotiation. Ultimately, the potential for the projects to proceed hinged on the ability to successfully disseminate blast data to the various stakeholders. As part of the agreements drawn up, property owners demanded immediate notification of the measured vibration levels with contract provisions including clauses such that any exceedance of the USBM criteria immediately triggered project shut down and complete blasting program redesign, and approval by all parties. With stakeholders located in various cities and, in some instances, on various continents, a conventional attended monitoring strategy would not satisfy the requirements. In response to the critical reporting need, Explotech Engineering Ltd. installed unattended monitoring stations around the sites, all incorporating wireless telemetry. After each blast, data was automatically transferred from the monitoring stations to a web-linked server via the wireless network, where it was immediately available to project stakeholders through a password protected website. The solution required a unique blend of data acquisition, telemetry, database, and security technologies, all married to produce a reliable system that was easy to maintain and use. While these types of systems were originally developed for use as permanent monitoring networks in operating mines and quarries, monitoring professionals are increasingly benefiting from the technology on temporary building projects that have typically been the realm of attended monitoring strategies. Globally, this has emerged as a solution to provide more timely access to data for stakeholders, and to minimize the legal exposure from multiple violations of vibration limits. As this trend is likely to continue, the regulated vibration control industry is likely to see a continued shift in technology development to leverage wireless networks and the Internet to continue to improve data transfer, archiving and distribution.

Jan 1, 2006

By S. K. Kawatra, S. J. Ripke, T. C. Eisele

"An estimated 600,000 tons of bentonite clay are used annually in the U. S. as binder for production of iron ore concentrate pellets. Since this is a significant cost item for the plants, and the addition of bentonite to the pellets contributes undesirable silica into the finished pellets, there is considerable incentive for finding methods to reduce bentonite use. One way to reduce bentonite levels is to selectively use those bentonites that are most effective in this application, so that a lower dosage will still produce a sufficiently strong pellet. Unfortunately, there are no satisfactory methods available for accurately predicting which bentonites are actually most effective, short of using them to actually make pellets. One of the popular methods for attempting to evaluate bentonites is the “Plate Water Absorption” (PWA) test. While some plant operators accept the PWA results as indicating the relative quality of bentonites, others disagree and claim that, over a fairly broad range of values, PWA does not correlate with bentonite performance.Since both Ca+2 and Mg+2 ions are known to reduce the swelling and water absorption capacity of bentonite, it was believed that the presence of these ions in plant recycle water could be changing the bentonite performance. Since the standard PWA test uses only distilled water for its measurements, it could not detect these effects. Experiments were therefore carried out on a number of different bentonites using a modified PWA tests, with plant recycle water replacing the distilled water. These experiments showed little effect of the plant water on the PWA value, and chemical analysis of the water showed that the levels of dissolved salts were quite low.Water and accompanying salts were then extracted from a magnetite concentrate filter cake by rinsing with distilled water. Analysis of this water showed an extremely high level of dissolved salts, particularly salts of calcium and magnesium. When concentrations were compared with the recycle water from the plant filters, it was determined that levels of Ca+2 and Mg+2 retained in the filter cake were over 500 times higher than levels in the recycle water. This extreme elevation of soluble salts in the filter cake is believed to be due to adsorption of these ions into the electrical double layer of the magnetite particles."

Jan 1, 2003

By William Gleason

"It is safe to say that the coal industry, in the United States and globally, is currently suffering through one of the hardest times in its history.A perfect storm of competition, changing energy demands, politics and public perceptions have collided, inflicting significant harm to the industry that many say is irreparable. This, in turn, has led to massive job losses in some regions, heavy cuts in production and even bankruptcy filings from two of the largest coal mining companies in the nation.Cheaper natural gas can certainly take a large share of the blame for the struggle of coal, as utility companies switch from coal to natural gas for power generation. According to the U.S. Energy Information Administration (EIA) the amount of coal used for electricity generation in the United States is at a 45-year low.November 2015 marked the fifth consecutive month that natural gas was the leading source of power generation in the United States. EIA said generators produced 101,866 thousand megawatt hours (MWh) of electricity with gas in November versus just 87,789 thousand MWh with coal, the lowest monthly level since May 1980 when monthly coal use was 84,884 thousand MWh.According to Robert Godby, director of the Center for Energy Economics and Public Policy at the University of Wyoming, there are a number of factors playing a role in the decline of coal, but he points to the advances in fracking as the tipping point.“A lot of people will argue that regulation is the cause of the decline, and it has played a part, for sure, but the story of the recent past is more about what competition has done to the energy market,” Godby told Mining Engineering. “The war on coal was originally declared by natural gas in 2008.”The price of natural gas, which was at $13 per million Btu before the gas fracking boom, has fallen to as low as $1.68 in December 2015. Likewise, Godby said the cost of wind generation is now lower than the cost of generation from coal and the cost of solar generation is coming down as well. In addition to that, the demand for energy has changed in the past five years with more efficiencies in everything from building design to lightbulbs."

Jan 1, 2015