Search Documents

By H. F. Bishop, F. A. Brandt, W. S. Pellini

The solidification mechanism of experimental steel ingots (7x7x20 in.) was studied by thermal analysis. It was determined that solidification proceeds in wave-like fashion at rates which are determined by the carbon level, superheat, and mold thickness. The thermal cycles of the mold walls were related to the course of solidification. ESPITE marked advances in the field of solid state transformation, metallurgical research has contributed comparatively little exact quantitative data on the mechanism of solidification of metals. There is, therefore, a great need for such data in the various metallurgical industries. The mechanics of solidification of ingots have been investigated in the past primarily by studies of the rate of skin formation as indicated by bleeding or "pour out" tests. The "pour out" method, however, is a tool which gives only approximate information. In the case of alloys with wide solidification ranges, such as irons and certain nonferrous alloys, the method will not work at all; in the case of alloys of intermediate solidification ranges, such as commercial steels, the information may be misleading. Thus, the general adoption of this method has resulted in divergent conclusions regarding the solidification process. Chipman and Fondersmith1 by means of bleeding tests have shown that the linear growth of a solidifying ingot wall follows a parabola of the general form, D = K C, with the start of solidification delayed until superheat is exhausted, as indicated by the constant C. These tests were carried only to a wall thickness of about 5 in. using an ingot of approximately 17x39 in. in cross-section; hence the latter stages of solidification were not studied. Matuschka2-3 indicated that linear solidification of ingots is rapid at first, then slow, but toward the end of solidification the rate becomes extremely rapid again. Spretnak's4 bleeding studies indicated that, wall growth is expressed more rigorously by two parabolas, and that their point of intersection corresponds to a change of solidification mode from columnar to equiaxed. Spretnak also showed that the K values of the first parabola are always the same regardless of superheat. Nelson bled ingots of square cross-section and found that linear wall growth is initially rapid but decreases continually until the end of solidification. He also concluded that rate of solidification in ingots of square cross-section increases 2.15 pct for every 10 pct increase in cross-sectional area of the mold. The mold ratios considered (ratio of cross-sectional area of the mold to cross-sectional area of the ingot) were all less than 2 to 1. The subject of solidification has also been treated mathematically in many cases, but because of the lack of accurate thermal constants and the simplifying assumptions required, as their authors generally acknowledge, they represent only approaches to the actual conditions of ingot solidification. A third method of studying solidification is the electrical analogue method promulgated by Pasch-kis6-7 and by Jackson and coworkers.8 This method treats solidification as a heat transfer problem with the solidification cycle synthesized on an electrical circuit. Paschkis in his treatment of solidification considered the fact, which was generally ignored, that solidification of steel is not simply the growth of a plane solid wall but a more complex process occurring over a temperature range as indicated by the constitution diagram. Undoubtedly, the anomalous results obtained by bleeding tests arise from the inability to measure quantitatively this mushy condition. The shape of Paschkis' solidification curves are more nearly in accord with those of Matuschka, in that they indicate rapid linear solidification at the beginning and end of solidification with intermediate solidification occurring at a slower rate. Paschkis indicates a definite lengthening of solidification time with increasing superheat. Thermal analysis is a direct method providing exact information for all types of metals regardless of solidification range and was thus adopted in the present program to follow the entire course of solidification from the surface to the centerline of the ingots. The method has the added advantage of being adaptable to following the thermal cycle of the ingot mold during the course of solidification. Test Methods The ingots studied were of square cross-section, 20 in. long, tapered from 71/4 in. at the top to 63/4 in. at the bottom, and fed with a hot top 7 in. in diam and 12 in. high. The molds were uniform in wall

Jan 1, 1953

By W. A. Backofen, G. Y. Chin, W. F. Hosford

The ductile fracturing process was studied in single-crystal and poly cvystalline aluminum deformed in tension over a temperature range from 295° to 4.2°K. At temperatures as low as 77°K, the fracture of "inclusion-free" material, including zone-refined aluminum, was by rupture (-100 pct RA). At 4.2 OK, fracture was brought on by adia-batic shear. Metallographic examination did not disclose any voids or slip-band microcracks, thus negating for inherently ductile metals any mechanism of void nucleation by vacancy condensation or of cracking due to dislocation pile-ups. In Izigh-purity aluminum not treated to be inclusion-free, fracture at temperatures as low as 45°K was of the double-cup type and a result of void formation. The reduction-of-area decreased as temperature was lowered, corresponding to the earlier appearance of voids. Such behavior was rationalized in terms of a larger increase, with decreasing temperature, in the .flow stress relative to the strength of the inclusion-matrix interface. Evidence for low-temperature adiabatic shear was found in discontinuous flow at 4.2"K, in the transition to a localized shear fracture at low temperatures, and in the suppression of shear fracture with an elastically hard pulling device. A simple analysis for the initiation of adiabatic shew permitted a general correlation of the various contributing factors. It has been pointed out that the duration of shear depends upon effective mass and elastic stiffness of the deformation system. IT has long been recognized that fracture* may Throughout this paper, the term "fracture" is taken to mean any process that results in the separation of a material into two (or more) parts. Thus rupture as it may be encountered in a tension test leading to 100 pct reduction-of-area is included in this category. occur in a ductile mode, and that the process can be of great practical as well as general interest. Much information about ductile fracture has also been accumulated over this period, but only recently has an understanding of mechanism begun to appear. Ludwik,' in 1926, first reported fracture in a tensile specimen starting with a central crack in the necked section. Since then, other studies have disclosed that such cracks may form by the coalescence of voids nucleated in this region where hydrostatic tension is highest.2-4 Rogers and Crussard et al.' have emphasized void formation and reori-entation along localized shear bands as a mode of crack propagation. pines6 has considered the tensile rod as a bundle of fibers joined by weak interfaces, which subsequently separate to allow individual fiber contraction. The notion of cavity growth and coalescence by purely plastic processes was discussed by Cottrell: who added that the tensile reduction-of-area ought not to be sensitive to temperature. On the other hand, it has been observed that the reduction-of-area is greatly increased if tests are carried out at high temperaturesa or under high hydrostatic pressure.' Fracturing anisotropy in wrought products lends support to the idea of void formation from preexisting flaws strongly aligned by earlier processing.''-l2 There is evidence that many voids result from the fracturing of inclusions or separation at the inclusion-matrix interface Another possibility is that voids grow out of pore volume produced in the initial solidification and never fully removed in later working. In general, a structure 3f particles, pores, and weak interfaces can be expected, at least in materials of engineering interest. Vacancy condensation has been suggested as an alternative mechanism of void formation for materials considered to be inclusion-free.13 Yet experience has shown that tensile reduction-of-area increases with purity, to the extreme of rupture as so often observed in single crystals. Adiabatic shear has an important bearing on ductile fracture. It occurs when the decrease of flow stress, as a result of local temperature rise from heat generated during straining, becomes larger than the increase due to strain and strain-rate hardening. As demonstrated by experiments on punching of plates,14 a large temperature rise may be brought about by rapid straining. Adiabatic flow as a result of the high strain rate reached in an ordinary tensile specimen just prior to separation may account for the cone formation in cup-and-cone fracture;14 evidence of such local heating has been presented.15 For geometrical reasons, however, pure sliding along the conical surfaces is unlikely, and separation under tensile forces is probably an important accompanying feature of the shear.7 In deformation processing operations, a high shear-strain rate may exist at boundaries between plas-

Jan 1, 1964

By O. F. Kammerer, W. E. Miller, D. H. Gurinsky, J. Sadofsky, J. R. Weeks

Zirconium and titanium inhibit solution mass transfer of steels by liquid bismuth, mercury, and lead. It is shown that in bismuth and mercury, these adsorb on the surface of the steels and subsequently react with nitrogen and possibly carbon from the steels to form inert, adherent surface layers of ZrN, TiN, or TiN + Tic. Data are presented which describe the condition under which thase deposits form. These inhibitors decrease the solution rate of iron into bismuth, and require a higher supersaturation for precipitation of iron from bismuth. USE of the low-melting heavy metals (bismuth, lead, mercury, and their alloys) as coolants has been limited because solution mass transfer of steels occurs in these liquids; i. e., iron dissolves in the hot sections of the heat transfer circuit and deposits in the colder sections. The rate of solution of iron and the temperature coefficient of solubility are sufficiently great to cause complete or partial stoppage by the deposition in the coldest section of a closed circuit in finite time, even though the actual solubilities are extremely low. In the development of the mercury vapor turbine by the General Electric Co., Nerad and his associates1 discovered that the addition of as little as 1 ppm Ti or Zr to magnesium-deoxidized mercury reduced the mass transfer of ferrous alloys by mercury to a negligible amount. Reid2 reported that titanium was detected chemically on the surface of steels contacted with this mercury alloy in amounts varying from 2.0 to 2.6 mg per sq in., the greatest amount being found in the hottest portion of the circuit. Reid stated that the titanium forms the intermetallic compound Fe2Ti by reaction with iron on the surface of the steels. This compound was presumed to be highly insoluble in mercury. More recently, El-gert and Egan3 have reported a greater than 100-fold reduction in the rate of mass transfer of a 5 pet Cr steel by liquid bismuth upon the addition of titanium (in excess of 50 ppm) and magnesium (350 ppm) in the liquid metal, during experiments performed in thermal convection loops* over the temperature differential 700° to 615° C. Also, Shep-ard and his associates' have reported that the addition of titanium to liquid bismuth and Pb-Bi eutec-tic produced a marked decrease in the rates of solution of both iron and chromium from type 410 steel capsules under static conditions. This inhibiting effect increased with repeated reuse of the capsules. Tests performed in this laboratory under carefully controlled conditions have shown that the addition of zirconium and magnesium, or titanium and magnesium, to liquid bismuth or lead greatly reduces the rate of mass transfer of chromium alloy steels and carbon steels in thermal convection loops with a maximum temperature of 550°C.5-9 The present paper will review the data obtained to date at this laboratory on the behavior of iron and steels in contact with liquid bismuth alloys containing titanium or zirconium, and will attempt to explain the role of the above additives in reducing solution mass transfer. Reaction between the Zirconium or Titanium Dissolved In Liquid Bismuth and an Iron or Steel Surface Reaction between Zirconium Dissolved in Bismuth and the Surface of Pure Iron-—A small pure iron crucible (analyzed by the supplier to contain 0.8 ppm N was contacted with bismuth containing approximately 0.1 pet Mg and varying amounts of a radioactive zirconium tracer. The crucible was then inverted at the temperature of contact. The thin residual layer of adherent bismuth was dissolved in cold, concentrated nitric acid. The crucible surface and the solidified bismuth were then analyzed for radioactive zirconium. An analysis of the activity loss on the crucible surface and the weight loss of the crucible during the nitric acid treatment showed that the acid treatment removed the zirconium that had originally been dissolved in the adherent bismuth, but not any zirconium that may have reacted with the crucible surface. The crucible was then pickled in warm aqua regia to remove all surface activity, hydrogen-fired at 600°C, and recontacted with a new liquid alloy. The results of the experiments contacted 1 hr at 450°C show, Fig. 1, a Langmuir-type adsorption with an adsorption free energy of approximately 17 keal per g atom Zr.5 This deposit was estimated to contain 1 atom of zirconium for each 7 to 8 iron atoms on the crucible surface, assuming a surface roughness factor of the pickled crucibles to be five. Increasing the temperature to 520°C caused consi-

Jan 1, 1959

By J. L. LeBlanc, R. L. Lewis

This study presents an analysis of annular backpressure variations associated with controlled gas kicks and their pronounced effect on casing .strings and exposed under lying formations. A mathematical model describing the volumetric behavior of an extraneous gas as it is transported from reservoir to .surface conditions under changing temperatures and pressures has been programmed in a Kingston FORTRAN II language for digital computer analysis. The gases under investigation typify Gulf Coast reservoir gases within a 0.6 to 0.7 .specific gravity range. The program output has been substantiated by actual field cases. of gas kicks encountered in Gulf Coart we1l.s. The development of empirical equations for calculating suitable gamy deviation factors for unique temperatures and pressures was incorporated in the program to provide realistic solution.. An output listing of annular backpressures and corresponding equivalent fluid densities resulting at a predetermined critical depth (casing setting depth) and total depth for selected .stages of circulation is provided in a chronological .sequence. Additional information including reservoir pressure and temperature, kill rnrid density, produced gas or surface volume of the expanded gas intro vion, drill pipe and annular volumes can he obtained from the model. This paper illustrates that a precise knowledge of the volumetric behavior of extraneous gases in annular flow and its effect on equivalent fluid densities at a critical depth is significant and should receive .serious consideration in controlling threatened blowouts and in the design of drilling programs. Surface pressures in excess of formation limitations are a threat to zones of lost circula/ion and are potentially injurious to productive intervals. A knowledge of annular backpressure and equivalent fluid density profiles for probable gas kicks aids in a technological accomplishment of drilling programs and provides a .sale tolerance in the event a threatened blowout is encountered. Introduction Drilling operations are frequently interrupted when the drill bit penetrates permeable gas sands with reservoir CtfuJ manuscript was received in Society of Petroleum Engineers ofice Am. 1 1967. Revised manuscript received JuIy 7. 1968. Paper (SPE 1860) kae presented at SPE 42nd Annual Fall Meeting held in Houston. Tex., Oct 1-4, 1967. @ Copyright 1968 American Institute of Mining, Metallurgical, and Petroleum Engineem, Inc. pressures greater than that exerted by the drilling fluid. The differential pressures resulting permit an extraneous influx of gas into the wellbore. A suspension in drilling progress is necessary to restore fluid equilibrium throughout the system. Whether formation gas kicks originate unintentionally or by design, the prospect of a threatened or actual blowout exists and a method assuring a safe and effective well control procedure must be observed. A significant contribution to well control technology was advanced by Records et a1.l in 1962. Using the concept of transmitting a constant equivalent formation pressure at the point of intrusion, Records et al. introduced a calculation technique providing the annular backpressures encountered in a well control environment as a func tion of the volumetric behavior of a 0.6 specific gravity natural gas. In essence, the procedure outlined an annular backpressure schedule in terms of fluid volume circulated at different stages of a well control operation. A number of other publications2-' proposing various techniques for controlling gas intrusions in a wellbore achieve pressure control essentially through maintenance of a constant bottom-hole pressure by surface choke adjustments. The subsequent pressure effects induced in the annulus unfortunately receive little emphasis. Due to the tedious and repetitive nature of annular backpressure computations, a theoretical solution by digital computer is introduced for predicting annular backpressure and equivalent fluid density profiles associated with controlled gas kicks. We point out the effects of volumetric behavior of extraneous gases in annular flow and related field phenomena on equivalent fluid densities at a critical depth. The investigation indicated that equivalent fluid densities at a critical depth are of significance and should receive consideration in the control of threatened blowouts and in the design of drilling programs. Theoretical Considerations The mechanism of vertical gas flow through an annulus is governed by the PVT properties of the fluid, the pressure distribution within the system, the fluid flow rates and the geometry of flow. Due to the numerous variables involved in this type of problem, certain assumptions were imposed in deriving the mathematical model and in establishing the solutions. Two gases, characterized by specific gravities of 0.6 and 0.7, were selected to typify Gulf Coast reservoir fluids. The gas intrustion entered the wellbore as an immiscible 'References given at end of paper. JOURNAL OF PETROLEUM TECHNOLOGY

Jan 1, 1969

By Å. Sterten, R. Tunold, J. Brun, K. Dalatun

c axis compression behavior of beryllium single crystals at three purity levels under hydrostatic pressures up to 27 kbars was determined. Extensive non-basal slip, observed by two-surface trace analysis and transmission electron microscopy, occurred under a hydrostatic pressure of about 12 kbars (175 ksi) for the high-purity (twelve-zone pass) material and at about 19 kbar (275 ksi) for the lower-purity (zone-leveled) material. Prismatic loops with a (c + a) Burgers vector were observed in association with second-phase parti- A principal factor limiting the use of beryllium is its brittle behavior when tested at the usual strain rates (E = 10-4 sec- 1) at temperatures below about 200°C and under impact conditions at temperatures in excess of 200°C. It has been proposed' that the brittle-ness of beryllium is associated with the lack of a sufficient number of independent slip modes and the absence of a slip mode with a Burgers vector out of the basal plane [presumably (c + a) pyramidal slip mode] and to the ease with which beryllium cleaves on the basal and second-order prism planes. The absence of pyramidal slip has been attributed to a high Peierls-Nabarro stress associated with the motion of dislocations with a (c + a) vector and the ease with which cleavage occurs on the basal and second-order prism planes. The experimental evidence in support of the proposed explanation for the brittleness of beryllium is far from complete; for example, that the ductile-to-brittle transition in polycrystalline beryllium is associated with the operation of profuse (C + a) slip has not been unequivocally established. The occurrence of (c + a) slip ({1122}(1123)) has been experimentally established2-5 under conditions where basal and prism cleavage are restricted in a c axis compression test. In these investigations (C +a) slip was found in high-purity beryllium single crystals tested in c axis compression* at 200°C and in Be-4.4 pct Cu and Be-5.2 pct cles in the lower-purity materials tested. The loops were related to surface "extrusions" observed on many of these same specimens. Nonbasal dislocations operating on (1122) planes with a (c + a) Burgers vector were observed. The presence of c and a dislocations together with (c + a) dislocations suggests that the (c + a) dislocations dissociate presumably on unloading or after failure of the test crystals to c and a dislocations. terial, (c + a) slip has only been observed near the the fracture4 surface in room-temperature c axis compression tests. Fracture in these tests occurs without measurable plastic flow, as determined with a strain sensitivity of 10"6. Since it has been shown for many metals that the application of hydrostatic pressure suppresses fracture,?-' it was felt that studying the behavior of unalloyed beryllium single crystals stressed in c axis compression under a hydrostatic pressure would reveal whether (c + a) can occur if fracture was prevented, and that it might elucidate the role of (c + a) slip in the ductile to brittle transition. Evidence that (C + a) slip is associated with increased ductility in a high-pressure environment has been found in stress-strain tests on poly crystalline beryllium.10 The present paper describes a study on the influence of a hydrostatic pressure environment on the occurrence of (c + a) slip in beryllium single crystals. Material of two purity levels was tested in c axis compression over the pressure range ambient to about 27.5 kbars.* 1) MATERIAL PREPARATION AND CHARACTERIZATION Two lots of low-purity single-crystal beryllium were used. The first lot was "ingot secondary refined grade" and designated lot A. The second lot (lot B) was produced by a two floating zone pass zone-leveling operation in an argon-filled sealed quartz apparatus on a 1-in.-diam by 12-in.-long bar of Pechiney secondary refined-grade vacuum-cast and hot-extruded material. The high-purity material (lot C) was made by traversing twelve floating zone passes through a similar bar of Pechiney secondary refined-grade vacuum-cast and hot-extruded material. In a series of spark cutting and lapping procedures,11 single-. crystal specimens some 0.12 in. sq by 0.30 in. high were made with the sides Parallel to the first- and second-order prism planes and the basal plane within 3' of arc of the top and bottom surfaces of the specimen. Such an accurate orientation is necessary because of the large difference in resolved shear stress

Jan 1, 1970

By Richard H. Bube

Photoelectronic radiation detectors may be conveniently classified as homogeneous intrinsic, homogeneom extrinsic, or junction type. Highly photosensitive homogeneous intrinsic photodetectors may be prepared from a number of different II-VI, III-V, or IV materials. Such materials require the presence of specific imperfections that can act as sensitizing centers to provide long majority carrier lifetime. Homogeneous extrinsic photodetectors are of interest primarity for infrared detection, and consist principully of germaniuim and silicon with suitable inpurities. A vaviety of junction photodetectors exist, with silicon us the most common material for them all. The following extrema in performance are found: 1) highest photoconductivity gain in homogeneous intrinsic photodetectors; 2) smallest response time (highest frequency response) in p-i-n junctions; 3) largest gain-bandwidth product in avalanche diodes. ALTHOUGH the total number of materials exhibiting photoconductivity effects is very large, only a relatively few of these have appropriate properties for a practical photoelectronic radiation detector. In fact if one surveys the commercial detectors currently available, one finds that the field is dominated by some ten or fewer materials. These are summarized in Table 1 in terms of the other important variable in detector fabrication, the structure of the material, i.e., whether the material is used as a single crystal or in polycrystalline form, and whether the material is used as a homogeneous detector or whether the detector depends upon the existence of a junction or barrier in the material. The principal wavelength range for each type of material is also shown, together with an indication of the utilization of intrinsic or extrinsic excitation. For the purposes of the present comparison of various detectors, it will be convenient to discuss two main topics: homogeneous photodetectors and junction photodetectors. The performance of a photoelectronic radiation detector is measured in terms of two parameters: the photoconductivity gain, and the response time of the detector. A convenient figure-of-merit is given by the ratio of gain to response time, often called the gain-bandwidth product. The photoconductivity gain is a device parameter since it varies in many cases with the applied voltage and the detector geometry, and should be distinguished from the actual photosensitivity of the material involved. This photosensitivity can be conveniently given as the product of free carrier lifetime and mobility in the material. The photoconductivity gain is defined as the number of charge carriers which pass between the electrodes per second for each photon absorbed per second, where G is the photoconductivity gain, is the pho-tocurrent in amperes, e is the electronic charge in coulombs, and F is the total number of electron-hole pairs created in the photo conductor per second by the absorption of light. The gain may also be expressed as the ratio of the lifetime of a free carrier to the transit time for that carrier, i.e., the time required for the carrier to move between the electrodes. For a material in which one-carrier conductivity dominates, where T is the lifetime of a free carrier, ttr is the transit time for this carrier, p is the carrier mobil-ity, V is the applied voltage, and L is the electrode spacing. From Eq. [2] it follows that the photoconductivity gain is proportional to the photosensitivity of the material (tP), the proportionality constant being The photosensitivity of a material, and hence the photoconductivity gain of a device utilizing the material, depends on the lifetime of the free carriers as a critical parameter. In a homogeneous material this lifetime is determined by the nature of imperfections in the material, and in an inhomogeneous material the lifetime is determined by the specific junction structure. The speed of response, the other basic photodetec-tor parameter, is determined by factors quite similar to those important for photoconductivity gain. Imperfections are of primary importance in homogeneous materials, and the structure of the junction is a determining factor in junction devices. For infrared detectors it has become common to define another quantity designed to indicate directly how effective the detector is in distinguishing between a small photoconductivity signal and random noise due to the detector and its environment. The detectivity D* is given by

Jan 1, 1968

By Robert J. White

Strong's equation for calculating bottom-hole pressure reduction due to gas cutting of drilling mud is corrected, resulting in a simpler equation which is easier to use. Use of the equation is illustrated by examples. It is shown that reduction of weight of a 10 lb/gal mud by 50 per cent at the surface due to gas cutting produces only n 3 per cent decrease in hydrostatic head at the bottom of a 5,000-ft well. It is also shown that at the surface 5 volumes of air per volume of mud are required to reduce the apparent mud weight from 8.5 to 6.5 lh/gal in a 3,000-ft well. Illustrative graphs are included to show the effect of various degrees of gas cutting on apparent mud weight at depths of 2,000, .5,000 and 10,000 ft and to show variation of apparent mud weight, with depth for a 100 lb/cu ft (13.37 lb/gal) mud gas cut to 90 lb/cu ft (12.03 lb/gal) at the surface. INTRODUCTION In 1938, Strong' published the following equation for calculating reduction in bottom-hole pressure due to gas cutting of drilling mud h = 1/D [p + pn/100 In p + p(1-n/100)/p(1- n-100)] where: h = depth in feet P = pressure in atmospheres at depth h due to mud column only D = hydrostatic pressure in atmospheres of a col-umn of uncut mud 1 ft high p = back pressure at well-head (in atmospheres) n/100 = fraction by volume of gas in mud at well-head at back pres-sure p This equation was recently found to contain an error due to an incor-rect expression for variation of vol-ume fraction of gas with pressure. Values calculated by the original equation are close to the correct values for small percentages of gas for which it was derived but become increasingly erroneous as the gas content increases and are completely unusable at the very high gas con-tents employed in aerated mud. DERIVATION The nomenclature used is the same as in Strong's paper. The pres-sure dP exerted by a lamina of thickness dh at a depth h ft is ex-pressed by Eq. 1 where x = volume fraction of gas at depth h dP = D (l - x)dh . . . (1) When we express x in terms of the wellhead per cent gas n, the well-head pressure p and the pressure P at depth h, the result is Eq. 2. x = (np/p+p)/(100-n) + (np/P + p) When this is substituted in Eq. 1 and rearranged to separate the var-iables the result is dh = 1/D [dp + np/100-n dp/(P + p]. Integration between appropriate lim-its results in or if the wellhead is open so that p = 1 atm and we rearrange Eq. 4, the result is loss in head = hD — P = n/100-n In (P + 1) ...(5) Eq. 5 can be solved easily by successive approximation using hD as a first approximation for P on the right-hand side and calculating a first value for loss in head. This can then be used to get a new value of P using the left-hand side of the equation. Values converge very rap-idly even for quite large values of per cent by volume gas n. EXAMPLES The effect on bottom-hole pressure of 50 per cent gas cutting of the mud in a 5,000-ft well using 10 Ib/ gal mud will be calculated, we have: h = 5,000 ft 10 X 7.48 144 X 14.7 = 0.0353 atm/ft hD = 176.5 atm n = 50 Substituting these values in Eq. 5 and using hD as a first approxima-tion of P on the right, we have, approximate loss in head = 50/50 In (176.5 + 1) = 2.30 log 177.5 = 5.17 atm. We calculate a new value of P as follows:

Jan 1, 1958

By Joseph E. Worthington

The present-day Northumberland gold mine is one of the deposits generally characterized as a Carlin-type occurrence. It lies at the crest of the Toquima Range in Nye County near the center of Nevada. Gold mineralization occurs in two modes, in argillaceous and in silicified limestones, and is generally very fine-grained or micron gold. The Northumberland district has had a history that is typical of many western gold districts: minor production prior to World War II and intermittent exploration thereafter until a combination of geological insight, improved economics, and the advent of heap leach technology created the Northumberland gold mine. Nye County, Nevada, was sparsely populated and little explored in the early years of the settlement of the west; the Northumberland district was not established until 1866. Initial interest was in silver and the district operated as a very small producer for the next seventy years. The disseminated gold occurrences in silicified limestones were recognized and Northumberland Mining Co. was organized to develop the property in the late 1930s. Northumberland Mining Co. actually conducted drilling operations (over 200 drill holes) and mined from small open pits in the silicified limestones. They ultimately produced almost 936 kg (33,000 oz) gold before being shut down by War Production Board Order L-208 in 1942. After World War II gold mining activities were essentially nil for over a decade due to the poor economics of gold production. The property was, however, a known gold producer and attracted recurrent exploration attention. About 45 holes were drilled under the direction of Peter Joralemon for private interests between 1959 and 1963. Next Kerr McGee drilled about 25 holes during 1963 and 1964. Some- what later, in 1968, Homestake drilled 20 holes. The property was then acquired by Idaho Mining Co. which drilled about 30 more holes between 1972 and 1974. By this time the Northumberland mine was becoming somewhat shopworn with over 300 holes drilled. Interest in gold prospects was increasing substantially in Nevada, how- ever, due to rising gold prices in late 1974, and several companies were interested in continuing exploration at Northumberland. In 1975 Cyprus Mines Corp. was successful in obtaining a joint venture arrangement with Idaho Mining Co. for further exploration and development of the property. The overall Cyprus exploration program was under the direction of James G. Hansen, Vice President Exploration. The geologist recommending acquisition of Northumberland was Peter E. Chapman who reported to Joseph E. Worthington, Manager of U.S. Exploration for Cyprus. The basis for selection of the Northumberland mine as an exploration target for Cyprus by Chapman was essentially prior knowledge of regional and 16cal geology and of the mine. Exploration for the next few years was directed by Chapman under the supervision of Worthington. During 1975 and 1976 rotary and check core drilling were conducted that indicated that a substantial Carlin-type or disseminated, low-grade gold deposit occurred in two separate bodies. Drilling was based on geologic mapping and rock chip geochemical sampling. Both ore zones were reflected at the surface as gold and arsenic anomalies in rock chips. Heap leach tests attempted in 1977 were aborted by a flash flood, but were completed in 1978. Engineering studies occupied the next couple of years until the property achieved production in the fall of 1981. It is now producing by open-pit mining with gold recovery by heap leaching and cyanide extraction at a rated capacity of approximately 2722 t/d (3000 stpd) ore. Metal recovery has been projected (probably conservatively) at 5 10 kg/a (18,000 oz per year) gold and 1.6 Mg/a (59,000 oz per year) silver. Reserves are reported to be adequate for ten to fifteen years of production. REFERENCES Anon., 1981, "Gold in Nevada," Span Magazine, Vol. 21, No. 3, Standard Oil Co., pp. 6-9. Koschman, A.H. and Bergendahl, M.H., 1968, "Principal Gold- producing Districts of the United States, Professional Paper 610, US Geological Survey, p. 193. Kral, V.E., 195 1, "Minerals Resources of Nye County, Nevada, Bulletin, Vol. 45, No. 3, Geology and Mining Series 50, Nevada University.

Jan 1, 1985

By C. O. Dale, W. J. Rundle

THE upper Mississippi Valley zinc-lead area was the first major lead-producing section in the United States. The lead ore, found near the surface in crevices, was relatively pure galena that could be smelted directly into lead, at first in log hearth furnaces and later in more efficient blast type furnaces. French Canadian fur traders encouraged the Indians to mine the lead ore and showed them how to smelt it into lead that had a high value for bullets1 Nicholas Perrot found lead ore on the Mississippi River bluffs near the junction of Wisconsin and Illinois and in 1690 established a trading post on the Wisconsin side of the river opposite the present site of Dubuque, Iowa.2 Shortly after 1720 discovery of Mine La Mott in Missouri diverted considerable attention from the Upper Mississippi area. Mining continued on a desultory basis with operations concentrated in the Galena, Illinois-Dubuque, area. In 1740 at least 20 miners were at work in the Fever River area around Galena and are reported to have shipped 2500 70-lb pigs of lead to Kaskaskia in 1741." Julien Dubuque established a mining and smelting operation in 1790 near the city that bears his name and was granted sole right to exploit the mining operations on the lands of the Sauk and the Fox Indians. He is reported to have produced 30,000 70-lb pigs of lead in 1805. Following the death of Dubuque in 1810 the Indians refused to let the white miners enter their lands, and little was done on the Iowa side of the river until the Indians were removed by treaty with the United States government in 1832." Early mining was entirely for lead but as the crevices were followed down, increasing percentages of zinc sulphide and zinc carbonate were encountered and at first discarded. Later a market became available for the zinc ores, and hand jigging devices were made to separate the lead, the zinc, and the rock or waste materials. The first record of zinc production from the area is for 1860. Production of zinc passed that of lead before 1900, reached a peak of 64,000 short tons in 1917, fell off rapidly and continually to about 2000 short tons in 1938, and since 1940 has ranged from 11,000 to 19,000 short tons. Lead has been of considerably less importance since 1900, and at present only about 10 pct as much lead as zinc is produced. Practically all of the zinc ore has come from orebodies that are rather flat and wide with considerable length as compared to width. Most of the early lead came from the crevice type deposit, but present production is from the predominately flat zinc orebodies. The Graham-Snyder orebody, scene of Eagle Picher operations, is practically all zinc with little or no lead being recovered. Marcasite, present in varying amounts, makes production of finished concentrates by gravity separation impractical. Satisfactory lead and zinc concentrates have been produced since flotation was introduced in the area in 1927. An acid recovery plant was operated for about 20 years after World War I, but it has been dismantled, and no recovery of the iron sulphides in the ores of the district is being made at the present time. In June 1950 there were three companies operating mines and mills, Tri-State Zinc Co., Calumet & Hecla Consolidated Copper Co., and Eagle Picher Mining and Smelting Co. The Vinegar Hill Zinc Co. had completed a shaft at a new orebody and had started to develop the mine which will supply the Cuba City mill. The Cuba Mining Co. was holding the Andrews Mine inactive. The Dodgeville Mining Co. was not operating but was exploring for additional reserves. Several small mines were selling ore to the Eagle Picher mill. A general area map is given in Fig. 1. The Eagle Picher Mining and Smelting Co. entered the area in 1946 with an active exploration campaign. Leases on a block basis were secured for the area south from the Wisconsin-Illinois line near

Jan 1, 1953

By Marston G. Fleming

E. C. Peterson (Anaconda Copper Mining CO., Darwin, Calif.)—A study of this quite comprehensible and interesting paper by Dr. Fleming brings to mind several observations in the practical application of alkalinity and related factors to the actual practice of lead mineral flotation. Soda ash has long been a widely used and a very helpful alkaline conditioning agent in the flotation of galena from the usual run of lead-zinc ores. Soda ash is one of the common "standard" conditioning agents tried in any laboratory investigation of lead-zinc ores because it has so often proved helpful to galena flotation. However, the use of soda ash in the actual flotation of oxidized lead ores is certainly not widespread. In the flotation of certain lead-zinc ores from the Park City district of Utah, it was found in the usual cyanide-zinc sulphate-xanthate circuit that soda ash had an effect of producing a very condensed and flat froth regardless of the many frothers tried and that substitution of lime for soda ash to produce the same pH (8.0 to 8.4) improved the froth condition. However, the flotation of coarse particles of galena became so critical that some would pass through into the tailing, but caustic soda as a substitute for either soda ash or lime produced a very desirable froth condition in the same pH range and greatly improved the metallurgical outcome. Milling was carried out in typically "hard water" from watersheds of limestone and other calcareous rocks and the ore also apparently contributed magnesium and calcium salts to the pulp. Certain lead-zinc ores of Mexico have shown their greatest flotation response in circuits conditioned with sodium bicarbonate, and such actual mill use was also believed to be related to the water necessarily used in milling. On other lead-zinc ores the optimum has been obtained in actual milling treatment by use of caustic soda in both circuits of the operation. In flotation of oxidized lead ores in which sulphidi-zation is employed by addition of sodium sulphide, very high pH's exist in the flotation circuit. With the usual oxide lead ores, demanding 5 to 15 lb of sodium sulphide per ton of ore, pH's in the circuit (closed and open water-circuits) may range from 9.5 to 12, and for ores that contain much anglesite or a high percentage of iron oxide minerals, sodium sulphide consumption may reach as much as 30 lb per ton of ore and the resultant pH will be correspondingly higher. Yet in such flotation treatment employing either xanthate or oil (high-sulphur crude oil or diesel oils) as the collector, satisfactory to excellent grades of concentrate and lead recovery are obtained. Although there have been great studies and accomplishments in the investigations of flotation fundamentals and flotation theory, and although an investigation to determine the effect of all factors entering into the actual plant flotation of sulphide and oxide ores must become very complicated, as Mr. Fleming has mentioned in his caution regarding the drawing of general conclusions for other ores, it seems that it would be of greater interest if the techniques and investigations could, with time, approach the conditions of actual practice and lead the way to improved and more efficient flotation plant performance. Marston G. Fleming (author's reply)—The gulf between fundamental flotation research and plant operation is, perhaps, less wide than Mr. Peterson suggests. For example, the work described in my paper developed from an extensive investigation of a complex lead-vanadium ore from southwest Africa. This investigation started as a standard ore-testing problem but, at almost every stage, results were obtained which could not be interpreted in terms of previous experience. A program of fundamental research was therefore undertaken and was closely interlocked with the ore testing. This coordinated investigation resulted in a flotation process which has now been proved by two years of successful plant operation, and although the grade and mineralogical constitution of ore as well as smelter requirements have altered more than could have been anticipated, our knowledge of the fundamental character of the problem has made it possible to meet each change in conditions with much more confidence than would have been the case had we neglected this aspect of the investigation.

Jan 1, 1954

By C. O. Dale, W. J. Rundle

THE upper Mississippi Valley zinc-lead area was the first major lead-producing section in the United States. The lead ore, found near the surface in crevices, was relatively pure galena that could be smelted directly into lead, at first in log hearth furnaces and later in more efficient blast type furnaces. French Canadian fur traders encouraged the Indians to mine the lead ore and showed them how to smelt it into lead that had a high value for bullets1 Nicholas Perrot found lead ore on the Mississippi River bluffs near the junction of Wisconsin and Illinois and in 1690 established a trading post on the Wisconsin side of the river opposite the present site of Dubuque, Iowa.2 Shortly after 1720 discovery of Mine La Mott in Missouri diverted considerable attention from the Upper Mississippi area. Mining continued on a desultory basis with operations concentrated in the Galena, Illinois-Dubuque, area. In 1740 at least 20 miners were at work in the Fever River area around Galena and are reported to have shipped 2500 70-lb pigs of lead to Kaskaskia in 1741." Julien Dubuque established a mining and smelting operation in 1790 near the city that bears his name and was granted sole right to exploit the mining operations on the lands of the Sauk and the Fox Indians. He is reported to have produced 30,000 70-lb pigs of lead in 1805. Following the death of Dubuque in 1810 the Indians refused to let the white miners enter their lands, and little was done on the Iowa side of the river until the Indians were removed by treaty with the United States government in 1832." Early mining was entirely for lead but as the crevices were followed down, increasing percentages of zinc sulphide and zinc carbonate were encountered and at first discarded. Later a market became available for the zinc ores, and hand jigging devices were made to separate the lead, the zinc, and the rock or waste materials. The first record of zinc production from the area is for 1860. Production of zinc passed that of lead before 1900, reached a peak of 64,000 short tons in 1917, fell off rapidly and continually to about 2000 short tons in 1938, and since 1940 has ranged from 11,000 to 19,000 short tons. Lead has been of considerably less importance since 1900, and at present only about 10 pct as much lead as zinc is produced. Practically all of the zinc ore has come from orebodies that are rather flat and wide with considerable length as compared to width. Most of the early lead came from the crevice type deposit, but present production is from the predominately flat zinc orebodies. The Graham-Snyder orebody, scene of Eagle Picher operations, is practically all zinc with little or no lead being recovered. Marcasite, present in varying amounts, makes production of finished concentrates by gravity separation impractical. Satisfactory lead and zinc concentrates have been produced since flotation was introduced in the area in 1927. An acid recovery plant was operated for about 20 years after World War I, but it has been dismantled, and no recovery of the iron sulphides in the ores of the district is being made at the present time. In June 1950 there were three companies operating mines and mills, Tri-State Zinc Co., Calumet & Hecla Consolidated Copper Co., and Eagle Picher Mining and Smelting Co. The Vinegar Hill Zinc Co. had completed a shaft at a new orebody and had started to develop the mine which will supply the Cuba City mill. The Cuba Mining Co. was holding the Andrews Mine inactive. The Dodgeville Mining Co. was not operating but was exploring for additional reserves. Several small mines were selling ore to the Eagle Picher mill. A general area map is given in Fig. 1. The Eagle Picher Mining and Smelting Co. entered the area in 1946 with an active exploration campaign. Leases on a block basis were secured for the area south from the Wisconsin-Illinois line near

Jan 1, 1953

By C. O. Dale, W. J. Rundle

THE upper Mississippi Valley zinc-lead area was the first major lead producing section in the United States. The lead ore, found near the surface in crevices, was relatively pure galena that could be smelted directly into lead, at first in log hearth furnaces and later in more efficient blast type furnaces. French Canadian fur traders encouraged the Indians to mine the lead ore and showed them how to smelt it into lead that had a high value for bullets.1 Nicholas Perrot found lead ore on the Mississippi River bluffs near the junction of Wisconsin and Illinois and in 1690 established a trading post on the Wisconsin side of the river opposite the present site of Dubuque, Iowa.2 Shortly after 1720 discovery of Mine La Mott in Missouri diverted considerable attention from the Upper Mississippi area. Mining continued on a desultory basis with operations concentrated in the Galena, Illinois-Dubuque, area. In 1740 at least 20 miners were at work in the Fever River area around Galena and are reported to have shipped 2500 70-lb pigs of lead to Kaskaskia in 1741.3 Julien Dubuque established a mining and smelting operation in 1790 near the city that bears his name 'and was granted sole right to exploit the mining operations on the lands of the Sauk and the Fox Indians. He is reported to have produced 30,000 70-lb pigs of lead in 1805. Following the death of Dubuque in 1810 the Indians refused to let the white miners enter their lands, and little was done on the Iowa side of the river until the Indians were removed by treaty with the United States government in 1832.4 Early mining was entirely for lead but as the crevices were followed down, increasing percentages of zinc sulphide and zinc carbonate were encountered and at first discarded. Later a market became available for the zinc ores, and hand jigging devices were made to separate the lead," the zinc, and the rock or waste materials. The first record of zinc production from -the area is for 1860. Production of zinc passed that of lead before 1900, reached a peak of 64,000 short tons' in 1917, fell off rapidly and continually to about 2000 short tons in 1938, and since 1940 has ranged from 11,000 to 19,000 short tons. Lead has been of considerably less importance since 1900, and at present only about 10 pct as much lead as zinc is produced. Practically all of the zinc ore has come from orebodies that are rather flat and wide with, considerable length as compared to width. Most of the early lead came from the crevice type deposit, but present production is from the predominately flat zinc orebodies. The Graham-Snyder orebody, scene of Eagle Picher operations, is practically all zinc with little or no lead being recovered. Marcasite, present in varying amounts, makes production of finished concentrates by gravity separation impractical. Satisfactory lead and zinc concentrates have been produced since flotation was introduced in the area in 1927. An acid recovery plant was operated for about 20 years after World War I, but it has been dismantled, and no recovery of the iron sulphides in the ores of the district is being made at the present time. In June 1950 there were three companies operating mines and mills, Tri-State Zinc Co., Calumet & Hecla Consolidated Copper Co., and Eagle Picher Mining and Smelting Co. The Vinegar Hill Zinc Co. had completed a shaft at a new orebody and had started to develop the mine which will supply the Cuba City mill. The Cuba Mining Co. was holding the Andrews Mine inactive. The Dodgeville Mining Co. was not operating but was exploring for additional reserves. Several small mines were selling ore to the Eagle Picher mill. A general area map is given in Fig. 1. The Eagle Picher Mining and Smelting Co. entered the area in 1946 with an active exploration campaign. Leases on a block basis were secured for the area south from the Wisconsin-Illinois line near

Jan 1, 1952

By Ian MacGregor

INTRODUCTION I retired in 1977 and have been enjoying myself ever since doing odd jobs for various people - on occasions, politicians. I commend it to you as post retirement - get involved in situations that nobody else will take on. It produces all sorts of excitement, it is a lot of fun and, courtesy of the media, you provide great raw material for their current Punch and Judy shows. The example of the adventures in the Escondida financing made me think about the history of the minerals industry in the United States. In order to see more clearly what is going to happen in the future, we have to look at the past and what we have learned, and try to extrapolate from that a scenario for the future. This paper is about global material cycles and the financial needs of the extractive industries. Since about 2,000 years B.C. we have been living in the Iron Age. Since about 4,000 B.C. we have been living in the Copper Age. These have been the two foundations of modern industrial society. Understanding the use of metals and materials helps us understand the civilization in which we live today. Let me focus more closely on the United States, particularly in this century. In the first two-thirds of this century the United States was growing and expanding and developing. It was providing for its inhabitants a society which was enjoying the benefits of a rising standard of living, improved opportunities and the ability to support a population growing at quite a dramatic rate. It is still growing. In the Department of Commerce, there is a clock that shows how many people there are in the United States. It turns all the time; the numbers are going up. On January 21,1980, when Ronald Reagan was sworn in as President, the number on that clock was a little over 220 million, and in the last week before he left, it was travelling towards 245 million. During his period in Washington, we have added , the equivalent of one total state such as California. That gives the dimensions of the U.S. appetite for raw material inputs. The inputs are of critical importance. COMPARATIVE ADVANTAGE During the first two-thirds of this century, the minerals sector enjoyed comparative advantages. There was a clear understanding of the importance of minerals enshrined in the tax legislation of the country from the early decades of this century - the depletion allowance. No other country identified as clearly that the supplies of minerals were finite. As they are used up, just as with a wearing-out machine, one must get capital back to replace the resource when the time comes. Within the last decade, that idea has been questioned and criticised. It is now seen as giving money away to a preferred part of the economy, instead of recognizing what depletion is all about. In previous times it insured that the U.S. always was able to regenerate the capital in its minerals industry, so that it could remain competitive. The U.S. had plenty of everything, including energy. We had a growing population. Equally important, we had an agriculture that led the world in productivity, even as far back as the turn of the century. It continues to do so. We still retain that comparative advantage, an ability to produce our foodstuffs in quantity and quality at excellent cost. Look at another ingredient of our comparative advantage, the energy position. We ran through the first two-thirds of the century with ever- decreasing energy costs. In the 1940s and 1950s the coal industry went into a decline. Why? Because the $3.00 - $5.00 a ton cost of mining coal in the U.S. represented relatively expensive energy. A ton of good grade bituminous coal contains 25 million BTU's. $0.20 a million BTU's represents $5.00 a ton at the pithead. That price was undermined by the increasing ability to find petroleum at even lower costs. At the apex of the growth of development of the American dominated

Jan 1, 1990

By G. W. Healy, L. F. Sander

was investigated by reacting thin discs of calcium oxide with gas mixtures of CO2, CO, and Son. Its value was 19,300 * 300 cal independent of temperature in this range. No solid solubility of sulfur in calcium oxide was detected within the limits of the experimental method and it is estimated to be below 0.025 pct by weight. The importance of lime in desulfurization is well-established but complete information on the pure phase equilibrium: CaO + 1/2 s2 = CaS + +02 [11 is not yet available. The goal of this work was to evaluate solid solubility of CaS in CaO and to determine the free-energy change associated with Reaction [I] at temperatures of 1400" to 1650°C. The equilibrium constant for Reaction [1] can be written: It is convenient to rewrite Eq. [2] in the form: where A = {Ps /PqJ1'2 has been referred to' as the "sulfurizing power' of a gas mixture. In this work, thin discs of CaO were suspended in a vertical tube furnace and exposed to CO + CO2 + SOz gas mixtures having known values of A. The samples were then analyzed for sulfur. As expected, X-ray diffraction confirmed that CaS was the only sulfur-bearing phase formed at the relatively low oxygen pressures used. EXPERIMENTAL PROCEDURE Reagent-grade CaCO3 was pressed in a 3/8-in.-diam pill die and prefired in air to produce CaO discs weighing between 0.004 and 0.01 g. Several discs were used to provide a suitable weight for chemical analysis while maintaining a large surface area to react with gas mixtures. These were placed in a platinum mesh basket and suspended in the gas stream in the hot zone of a vertical tube furnace. Desired gas mixtures were prepared from cp grade CO and CO2 and anhydrous grade SO2. The method of soap bubble displacement was used to calibrate capillary flow meters. While this gave excellent results with CO and Con, some problems with bubble insta- bility and soap film "drag" arose with the use of SO2 at low flow rates. Hence, frequent sampling and analysis of gas mixtures was carried out to insure proper control of the ingoing SOZ. The furnace used for gas:solid equilibration was a vertical mullite tube externally wound with 60 pct Pt-40 pct Rh wire having a diameter of 0.028 in. An inner tube of $ in. ID served as the reaction chamber having Pyrex ground joints sealed to the mullite to provide gas-tight connections at top and bottom. A Pt-Pt 10 pct Rh thermocouple was inserted into a protection tube adjacent to the sample basket to measure sample temperature during a run. Constant-temperature control to 2C was observed at any desired set point within the range of this investigation. This was accomplished by a control thermocouple imbedded in the furnace windings which served to actuate an electronic controller wired for high-low operation. The sulfur analyses of the solid samples were carried out using a stoichiometric combustion technique based on the method of Fincham and Richardson. Some analyses were done using a modified evolution method3 but these were used primarily to check the results of the combustion method. The results were in good agreement but the combustion technique of-ferred an advantage in economy of time and material. CALCULATION OF GAS EQUILIBRIA Heating a given mixture of CO + CO + SO2 to high temperatures gives rise to a large number of product species. The details of calculating the partial pressures of these products of interaction and dissociation can be found in several references4,5 and need not be repeated here. The thermodynamic data selected for the major species in the gas mixtures are shown in Table I. Equilibrium constants from these reactions were combined with oxygen, carbon, and sulfur balances and a computer program written to facilitate the calculations. Some early difficulties in reproducing experimental results were finally traced to the effect of atmospheric pressure changes. No reference to consideration of this question had been found in the

Jan 1, 1969

By G. A. Vissac

MoIstuRe in coal must be considered as an impurity, just the same as ash, from the standpoint of utilization of the coal. Being incombustible, it reduces directly the heating value of the coal, and in addition absorbs heat for its evaporation. Its presence means useless expenditures in handling and transportation. In coke plants, extra moisture reduces capacity and may cause damage to brick work and equipment. Accordingly, the removal of extra moisture can be considered just as important as the removal of other impurities, such as ashes, in the modern coal preparation plant. Moisture, which can be removed by heating the coal up to a temperature of 100°C, may be retained in various forms: 1. As a film, on the surface of each coal particle, and in the interstices between particles, retained by capillary forces. 2. Or "occluded" inside the coal particles. This occluded moisture may be either free moisture (as in a sponge), or hygroscopic moisture which varies with atmospheric conditions, (also called "regain"). These latter forms of moisture are particularly common in "young" coals (subbituminous and lignites); bloom coals (seam outcrops); fusain; and carbonized products. In our study of coal drying, we shall consider only the removal of free moisture, exclusive from hygroscopic moisture. Dewatering If we reserve the name of drying to the removal of water by evaporation, we must consider the initial phase of the mechanical removal of free moisture as a distinct operation covered by the term dewatering. In all cases the free water carried over the surface of the coal particles or in their interstices, or in their pores, is retained by capillary forces. Dewater-ing is accomplished by breaking or counteracting these capillary forces; removal of as much water as possible by dewatering methods is usually advisable, as the cost of these operations is generally much less than by evaporation. The most common methods of me-chanical dewatering are: 1. "Pressure piling," which reduces the interstitial spaces, accomplished in dewatering bins or over dewatering screens. 2. Or dynamic methods, such as used in centrifuges or over vibrating screens. We shall only mention the " preferential wetting" method, in which surface water can be displaced by hydrocarbons, as offering possibilities, but which, to our knowledge, has not reached yet a practical development. But we must point out that the capillary forces retaining water on the coal surfaces, decrease considerably with increased temperatures. This is the principle used in all modern dishwashing machines; by using very hot water, dishes are extracted almost dry. In line with this development, we favor the type of dryers including a dewatering section; as the coal enters the dryer and is gradually brought up to higher temperatures, its dewatering ability is increased and advantage can be taken of this conditioning, resulting in increased drying efficiencies and reductions in drying costs. Heat Drying In the final phase, the remaining moisture must be evaporated. Coal and water must be brought up to the chosen temperature of evaporation, and heat must be supplied to fill the requirements of the latent heat of evaporation of the water to be removed. Accordingly, drying becomes largely a problem of heat transfer, and drying methods can be classified accordingly, namely: 1. Radiant transfer. 2. Transfer by surface contact and conduction. 3. Transfer by hot gas contact. The first method is not applicable to coal drying; the second method is used in the old type rotary dryer. The third method, the most commonly used in modern coal dryers, will be the only one considered here; and, of course, we shall deal with continuous types of dryers only. The mechanism of complete drying is really very complex-—several phases are involved: 1. The constant rate period. 2. The uniform falling rate period. 3. The varying falling rate period. As most of our practical coal drying problems deal with wet coals (over 6 pct of moisture), and do not require complete drying (under 1.5 pct), we shall deal with the first condition only, namely the constant rate drying. Dryer Calculations Instead of presenting the algebraic formulas, we believe a concrete example will provide a clearer illustration. Assume a feed of wet coal at the rate

Jan 1, 1950

By J. T. Norton, A. L. Mowry

The monocarbides of the A subgroup elements in the fourth and fifth group of the periodic table in addition to being hard and refractory are of special interest in that they are isomorphous in crystalline structure. They are cubic with a sodium chloride type structure in which the metal atoms are essentially close packed in a face-centered cubic arrangement with the carbon atoms placed in the interstices between. Interstitial structures of this close packed type were first investigated systematically by Egg1 and he gave the rule for their formation, stating that the radius ratio of the nonmetal to the metal atom should not exceed the value of 0.59. The carbides of interest are those of titanium and zirconium of the fourth group and vanadium, columbium and tantalum of the fifth group. Table 1 shows the radius ratio using the Goldschmidt radii for 12 coordination for the metal atoms and the diamond radius for the carbon atom. It will be noted that while there is considerable variation in the size of the metal atom, in all cases the ratio is smaller than the limit of 0.59 placed by Hägg. It has been known for some time that these cubic carbides are soluble in one another, at least to some extent or, in other words, the metal atoms can be replaced, one by another without destroying the stability of the structure. Since the stability of these close packed interstitial substances appears to depend more upon geometry than upon the exact chemical nature of the atoms involved, it is of interest to examine the possibilities of replacement in these carbides in some detail. Hume-Rothery2 has pointed out the importance of the difference in size of solute and solvent atom as a factor in limiting the solubility in simple binary solid solutions. Largely on an empirical basis, he states that if the difference in size between solvent and solute atom is more than 14-15 pct of the solvent atom, the range of solubility is very restricted. The atom size was based on the distance of closest approach in the elements involved. While there is some question as to how one should calculate the size of the metal atom in the carbide structures, reference to Table 1 will show that zirconium is the largest and vanadium the smallest of the group and that the difference is about 15 pct. The Ti-Zr difference is about 9 pct and the others are smaller. Thus one would predict that if the size factor controls the solubility, all of the pairs except VC-ZrC would have wide or complete solubility whereas this latter pair is on the border line and might have restricted solubility. The purpose of the present investi- gation was to examine the solubility of the several pairs of carbides by heating them together until equilibrium was established and then examining the product by X rays. Previous Work Agte3 and his associates prepared various transition metal carbides and determined the melting points of binary mixtures. He concluded from the shapes of the melting point curves that there was extensive solubility in the case of the cubic carbides. Umanskii and his colleagues made an investigation of a number of pairs of the cubic carbides, using X rays and plotted lattice parameter vs. composition curves for the systems TaC-Tic, CbC-Tic, TaC-ZrC and CbC-ZrC. All pairs showed a continuous series of solid solutions. The first two pairs gave a linear relation while the latter two showed a negative deviation from Vegard's law. Kiefer and Nowotny, in a paper which became available after the present work was well advanced, investigated the binary pairs of the five cubic carbides by means of X rays. Relatively few points were obtained and results indicated that in some cases, at least, equilibrium was not reached at the temperatures used. The results indicated that solubility in the VC-ZrC system was not complete. All of the results of previous investigations indicated the desirability of a more detailed study. Materials The raw materials used were mono-carbides of titanium, zirconium, vanadium, columbium and tantalum and were the purest which could readily be obtained commercially. Spectrographic qualitative analysis showed that the CbC and TaC contained less than 1 pct

Jan 1, 1950

By W. A. Hoyer

A pulsed high-energy neturon-induced spectral logging tool has been built and field-tested. The reaction of deuterium on tritium is used to generate pulses of 14-Mev neutrons. By detecting only the prompt gamma rays produced by neutron inelastic reactions in the formation, the presence and relative abundance of carbon, oxygen, calcium, silicon and other important elements may be ascertained from a gamma-ray spectrum. Gamma-ray spectra obtained in a shallow test well and in experimental field use show that it is possible to identify formations and their contained fluids. INTRODUCTION The penetrating gamma rays from naturally occurring radioactive elements in subsurface formations have been used for a number of years in well logging as a means of characterizing and distinguishing strata. Still another nuclear logging method which has been employed for some years consists of the bombardment of strata with neutrons and the measurement of the number of gamma rays produced by neutron capture reactions involving elements in subsurface strata.' Since one of the principal elements entering into capture reactions is hydrogen, the latter procedure essentially results in a hydrogen log, whether the hydrogen be in combined form in either oil or water; thus, the log gives an indirect measure of porosity. These methods, with various refinements, have been developed to such an extent that they have become routine procedures in formation evaluation. Neither gamma-ray logging nor conventional neutron logging, however, yields sufficient information to permit unequivocal identification of the mineralogic composition of formations, and neither method gives information which may be used for the positive identification of hydrocarbons in strata. Accordingly, a number of efforts have been made in recent years to gain additional information from nuclear logs. Brannon and Osoba have shown that it is possible to identify naturally occurring radioactive elements in subsurface formations by spectral analysis of gamma rays emanating from these elements. Such an identification is of value in the characterization of strata. A simplified form of spectral analysis of gamma radiation resulting from neutron capture reactions between elements in earth materials and bombarding neutrons has been used with some suc- cess under favorable conditions to differentiate between petroleum and water. This method relies upon the relatively high energy of gamma radiation from neutron capture by chlorine and, in effect, furnishes a chlorine log. In areas in which interstitial water is of sufficiently high salinity, this log can give valuable information on water saturation and, thus, indirectly on hydrocarbon saturation. Still another approach to obtaining more information by nuclear techniques is "activation logging", in which certain elements yield short-lived radioactive isotopes on neutron activation and, thus, can be detected by gamma-ray spectral analysis. From the standpoint of determining by nuclear logging methods the mineralogic composition of strata and the presence or absence of hydrocarbons, it is essential that information be obtained on the presence and relative amounts of several elements such as carbon, oxygen, hydrogen, calcium, silica and others. Some elements, such as hydrogen, chlorine and sulfur, can be determined by spectral analysis of gamma radiation resulting from neutron capture reactions."" Others — carbon and oxygen, for example — do not enter readily into capture reactions but do yield gamma rays of characteristic energies from inelastic scattering reactions with high-energy neutrons. Accordingly, the latter reactions are of particular interest as a means of identifying hydrocarbons in subsurface strata. Several years ago it was recognized that information requisite to the identification of subsurface strata and of contained fluids could be obtained by pulsed operation of a subsurface neutron generator and associated gamma-ray detector. It was contemplated that pulsed operation would be effective in discriminating in time that gamma radiation which results predominantly from inelastic scattering reactions from that gamma radiation arising from neutron capture reactions. Accordingly, research was continued and construction of such a device was initiated. Although many problems were encountered, they were solved successfully. The following sections describe the tool which has evolved, its performance and the results which have been obtained with it to date. THEORY OF OPERATION OF NEUTRON-INDUCED GAMMA-RAY SPECTRAL LOGGING TOOL THEORY OF INDUCED NUCLEAR REACTIONS Of fundamental importance is the fact that an element, when bombarded with neutrons, emits gamma radiation of energy characteristic of that element. In theory, therefore, an element may be identified by

By C. W. Allen, B. D. Cullity

The proportional limit of iron crystals in torsion is governed by the resolved shear stress in the most highly stressed slip systems, averaged around the specimen circumference, and does not obey a critical resolved shear stress law. Crystals of most orientations exhibit a stage of easy plastic deformation, akin to easy glide in tensile or shear specimens. Transient deformation, similar to that which occurs in single crystals of other materials, is also observed. THE torsional deformation of single crystals of magnesium (hcp) and aluminum (fcc) has been described recently by Choi et al.,&apos; especially with respect to the criterion for the orientation dependence of the onset of plastic flow in these materials. The purpose of this paper is to present results of torsion tests of iron single crystals and thus to extend this yield criterion to a bcc metal. In addition to considering the variation of proportional limit with crystal orientation, this paper also briefly treats work hardening, transient deformation, and the mechanism of plastic flow in iron. The effects of the method of surface polishing and the chemical purity of the iron have been investigated. STRESS DISTRIBUTION It is convenient to express the stress at any point of a cylindrical crystal stressed in torsion in terms of t0, which is the shear stress acting at the surface on a plane normal to the axis of the cylinder and in a direction tangential to the cylinder. This stress is given by To = 2T/pr3 [1] where T is the applied torque and r the specimen radius. The shear stress t, resolved in any chosen slip system is given in terms of 7, by1 Ts/TO = sin 0, cos d sin (0, -) + cos , sin d sin d - ) [2] where 0 and d are the angles between the specimen axis and the slip plane normal and slip direction, respectively; h is the angular circumferential position on the specimen at which t, is being determined, measured from an arbitrary reference plane which includes the axis;o and d are the angular coordinates of the projections of the slip plane normal and slip direction on a transverse section with respect to this same reference plane. Slip in iron occurs in a <1ll> direction on the {ll0}, (1121, and (123) planes, which together comprise 48 slip systems. A complete evaluation of the stress distribution in an iron crystal stressed in torsion would therefore require a calculation of Ts/T0 as a function of for 48 different slip systems. Fortunately Gough,&apos;who studied the behavior of iron crystals in alternating torsion, was able to simplify this problem considerably. He showed that it was sufficient to consider a kind of average slip plane for each slip direction, namely the mathematical plane of maximum resolved shear stress containing the slip direction considered. This simplifying approximation is possible because, for each slip direction, the active slip plane or planes lie very near this mathematical plane of maximum shear stress. Vogel and rick&apos; have critically reviewed the early work of Taylor and Elam,13 Taylor,14 and Fahrenhorst and schmid8 from which the identification of the above crystallographic planes as slip planes in the bcc lattice largely stems. While their criticism is clearly justified, their own results do little to clarify the issue. The role of cross slip (screw dislocations changing glide planes) is evidently so important in this case, as Read3 has suggested, that methods for deducing slip systems from observations of gross slip traces are inadequate, such traces commonly arising from complex dislocation motion. Thus the treatment given here involving the plane of maximum resolved shear stress seems a logical simplification especially in view of Gough&apos;s2 study of a iron. There is, however, an assumption built into the subsequent treatment the comparative validity of which is difficult to assess, namely, that slip in all slip systems in iron may be characterized by a common critical resolved shear stress. The shear stress 7, resolved in a slip direction defined by d andd, and on the plane of maximum shear stress containing this direction, is found by first maximizing 7s/70 with respect to either Oo or 4,. The slip plane coordinates are then eliminated by using the relation between 0, ,o and d, d, namely,

Jan 1, 1963

By H. L. Gilbert, W. W. Stephens

Production of anhydrous zirconium tetrachloride by direct chlor- ination of a zirconium oxide carbon mixture in a silica-brick-lined chlorinator is described. Theory and thermodynamics of reactions are discussed. A pilot-model chlorinator and full-scale production equipment are described and operating data are included. ANHYDROUS zirconium tetrachloride required as a starting material in the Kroll process for production of ductile zirconium has been produced in this country principally by chlorination of the carbide or "carbonitride" made by reduction of zircon sand concentrates with carbon in the arc furnace. This process and the equipment used have been fully described.&apos;.&apos; It is well known that zircon or badde-leyite ores may be chlorinated directly with chlorine in the presence of carbon, and this one-step approach would seem at first glance to be preferable to the two steps involved in the carbide-chloride operation. As previously discussed1 considerations leading to adoption of the longer process were: 1—Chlorination of the carbide proceeds rapidly at temperatures below 500°C, whereas temperatures above 900°C were considered necessary for chlorination of zircon-carbon mixtures. 2—The highly exothermic nature of the carbide-chlorine reaction makes it self-sustaining, while heat must be supplied continuously in direct chlorination of the ore. 3—Silicon was thought to be chlorinated along with zirconium in the direct chlorination of zircon, leading to high chlorine consumption. In production of carbide in the arc furnace, silicon is driven off as silicon monoxide and does not enter the chlorinator. 4—For efficient direct chlorination, the ore must be finely ground and intimately mixed with carbon, and the mixture briquetted. 5—Direct chlorination requires a much larger chlorinator for a given production capacity than chlorination of carbide. Recently it has become necessary to produce large quantities of zirconium metal from a chemically purified zirconium oxide. Since the cost of the latter is high, the relatively high losses encountered in production of carbide in the arc furnace could not be tolerated, and a graphite resistor furnace5 was developed for production of carbide, which was then chlorinated in equipment previously used for chlorinating arc-furnace carbide. This method of operation was quite satisfactory, and losses in the carbid-ing step were minimized. However, operating costs were relatively high, and the process did not lend itself particularly well to large-scale operation because of the multiplicity of small units required and the hand labor needed to load, unload, and maintain the furnaces. To chlorinate the carbide, a vertical-shaft chlorinator was used in which the charge was heated with a central split graphite-rod resistor.&apos; Operation of this chlorinator was somewhat less satisfactory with the resistor furnace carbide than it had been with the arc-furnace carbide due, principally, to the differences in physical properties of the carbide. The arc-furnace carbide is obtained as a fused metallic-appearing mass which can be crushed to -1/4 in. with production of a minimum of fines, whereas the resistor-furnace product is lightly sintered and produces a large proportion of fines in crushing and handling. These fines tend to pack in the chlorinator and promote channeling. which results in poor chlorine efficiency and low capacity. Data based on production of 22,000 lb of chloride from resistor-furnace carbide in this equipment are shown in Table I. Necessity for increasing production of chloride from about 2,000 to 15,000 lb per week led to further investigation of possible methods for direct chlorination of the oxide or oxide-carbon mixtures. Direct chlorination of the pure oxide presents much less difficulty than chlorination of zircon sand or oxide ores. The oxide is easily ground to —200 mesh, and no silica is present to cause excessive consumption of chlorine or contamination of the product. Theoretical Considerations The principal chemical reactions involved in chlorination of mixtures of zirconium oxide and carbon may be written as follows: ½ ZrO2 (c) + C(c) + Cl2(g) = ½ ZrCl,(g) + CO(g) [I] 1/2 ZrO, (c) + CO(g) + Cl2(g) = ½ ZrCl,(g) + CO2(g) 121 ½ ZrO2 (c) + ½ C(C) + Cl2(g) = 1/2 ZrCl4(g) + ½ CO2(g) [3]

Jan 1, 1953

By C. S. Finney, John Mitchell

The introduction of ovens for the production of metallurgical coke is believed to be due to L. L. Norton who operated an iron foundry in the vicinity of Connellsville, Pa. Persuaded by his foreman, an English immigrant named Nickols from Durham, L. L. Norton put up a 12-ft square oven which produced coke in 1833. The coal used was taken from a local mine at Mounts Creek. The oven seems to have been used in conjunction with the customary method of coking in mounds. It was in the Connellsville district also, in 1841, that two carpenters, Provence McCormick and James Campbell, formed a partnership with John Taylor, a stone mason, for the manufacture and sale of oven coke. The task of the mason was to construct the ovens, while the carpenters were to build the arks by which the coke could be taken by water to the market at Cincinnati. The following account of the enterprise was given by McCormick: "James Campbell and myself heard in some way that I do not now recollect that the manufacturing of coke might be made a good business. Mr. John Taylor, a stone mason, who owned the farm on which the Fayette coke works now stand, and who was mining coal in a small way, was spoken to regarding our enterprise, and proposed a partnership-he to build the ovens and make the coke and Mr. Campbell and myself to build a boat and take the coke to Cincinnati, where we heard there was a good demand. This was in 1841. Mr. Taylor built two ovens. I think they were about 10 feet in diameter. My recollection is that the charge was 80 bushels. The ovens were built in the same style as those now used, but had no iron ring at the top to prevent the brick from falling in when filling the oven with coal, nor had we any iron frames at the mouth where the coke was drawn. The top and mouth had to be repaired when they fell in. In the spring of 1842 enough coke had been made to fill two boats 90 feet long-about 800 bushels each-and we took them to Cincinnati down the Youghiogheny, Monongahela, and Ohio, but when we got there we could not sell. Mr. Campbell, who went with the boats, lay at the landing some two or three weeks, retailing out one boatload and part of the other in small lots at about 8 cents a bushel. Miles Greenwood, a foundryman of that city, offered to take the balance if he would take a small patent flour mill at $125.00 hi pay, which Mr. Campbell did. He had it shipped here. We tried it, but it was no good, and we sold it to a man in the mountains for $30.00, and thus ended our coke business." So successful did the coke subsequently prove to be in use that the three partners were asked to deliver more. Evidently they had had enough of the coke business, however, for they refused to have anything more to do with it. Few ovens were built between 1841 and 1855, and it is reported that in the latter year, "there were only 26 coke ovens along the river above Pittsburgh". Successful coke makers of these years included Mordecai Cochran, Richard Brookius, and Colonel A. M. Hill. It was the use of coke in 1859 in the Clinton furnace erected by Graff, Bennett and Co. in a plant on West Carson Street, Pittsburgh, that brought the real beginning of the coke-iron era in America. Here the successful use of Connellsville coke as a blast-furnace fuel was demonstrated beyond all possible doubt, and from the year 1859 the coking industry expanded tremendously. The era of beehive coke ovens During the latter half of the nineteenth century and the early years of the twentieth, the major percentage of metallurgical coke produced in the United States came from beehive ovens. It was not until 1893 that the first battery of by-product ovens came

Jan 1, 1961