Search Documents

By Helmut Thielsch

MeTallographic specimens whose surfaces are to be investigated are too thick to allow either light or electrons to pass through them for microexamination by transmission. This difficulty is overcome with optical microscopes by illuminating the surface through the objective lens. For electron microscopes best results are obtained by preparing thin replicas of the surface of the specimen, placing them in the microscope and passing the electron beam through them. Since electron microscopes represent a rather recent invention, they have found little application as compared with optical microscopes. This is true because, aside from the cost of new equipment and development of new techniques, some of the older replica methods necessitated the destruction of the surface from which a thin transparent replica was obtained. In other processes in which the surface is preserved, either too tedious a procedure is required, unsuited to "mass-production" requirements of industrial laboratories, or replicas of insufficient contrast and sharpness are produced. In general, investigations with the electron microscope involve five steps: (I) polishing the surface of the metal specimen, (2) proper etching of the surface, (3) preparing the suitable replica from the surface, (4) examination and phorography in electron microscope and (5) interpretation. Preparation of Metal Surfaces Usual metallographic polishing is generclly satisfactory. It is important though that the final polish be applied very carefully, since otherwise evidence of a small amount of deformation might show up even on relatively deeply etched surfaces. A high-power microscope should be used to determine the suitability of the polish and etch. This, of course, is not different from optical examinations, but in these, if a deep etch is used, the problem is less serious. It is frequently difficult to detect with optical microscopes poor polishing aside fiom superficial scratches before etching. Figs. I and 2 show micrographs of "well" and "poorly" polished nickel etched by immersing the sample for 20 min. in a solution containing 8 grams cupric sulphate in 40 C.C. of concentrated HCl and 40 C.C. of Hz0 (Marble's reagent). The sample shown in Fig. I was polished in its final stages for 5 min. on a carborundum wheel followed by ro min. on a rouge wheel, whereas the sample shown in Fig. 2 was polished only I min. on the rouge wheel. Generally, this procedure does not guarantee that the surface of the specimen will be either undistorted or deformed. It was applied here merely to show the effects Of good and poor polishing. To the experienced investigator, plastic deformation is

Jan 1, 1946

By R. H. Richman, F. Borik

A 0.3 pct C-12 pct Cr-6 pct Ni steel was rolled to 93 pct reduclion in area as austenite at 510°C, and then partially transformed as desired to ~rlartensite by qnenching to - 196°C. Pole figures for the austenitic matrix and for the martensitic product were separately determined by an X-ray transmission method. The deforitration texture of' the warm-worked austenite is characlerized by (110)(225) components, and is thus closely similar to those produced in a brasses. The pole jigure of the martensite in partially transformed material agrees well with that which can be constructed by transfortnation of the {110)(225) orientations according to either the Kuvdjuniov- Sacks or the Nishi-yatuu relatiotship. Howeuer, an important result of this construction is that me-third of the predicted orientations are missing. A graphical analysis can then be used to show that in deformed austenite certain crystallographic variants of martensite (related to the most probable austenite slip systems) are suppressed, resulting in this preferred transformation. The evidence for preferred transformation is corroborated by the measured elastic anisotropy of warm-rolled and fully transformed H-11 steel. EXTENSIVE plastic deformation of a polycrystal-line aggregate in a manner that causes flow predominantly in one direction results in a preferred orientation of the constituent crystallites. The particular orientations that are produced depend upon the crystal structure and composition of the material, as well as upon the temperature, mode, and degree of deformation; in any case, the preferred crystallo-graphic orientations, or textures, are reflected in directionality of mechanical properties. Although such anisotropy may be exploited in certain specialized applications, it is more commonly diminished or eliminated by heat treatment lest it interfere undesirably in subsequent forming operations or in structural design. In the recently developed thermomechanical treatments that significantly enhance the strength of some steels,1,2 considerable deformation of the metastable austenite prior to the martensite transformation is essential to the strengthening process. If the austenite is textured by the deformation, and if the transformation to martensite proceeds according to one of the relationships established for transformation in annealed austenite, then it must be expected that the martensite will also possess a preferred orientation even though the multiplicity of martensite orientations possible in a given austen- ite crystal will tend to restore some degree of randomness. The existence of a residual anisotropy, both mechanical 3-6 and crystallographic,' has been substantiated. In the latter crystallographic investigation, preferred orientations were determined for the martensitic structure of an SAE 4340 steel rolled 72 pct as austenite at 833°C and then quenched. However, the choice of a composition that transformed almost completely to martensite during the quench to room temperature did not permit direct measurement of the prior austenitic texture. In fact, when the "ideal orientations'' associated with well-known fcc rolling textures were converted, alone or in combination, to martensite according to the Kur-djumov-Sachs (K-s)' or Nishiyama8 relations, the agreement obtained with the observed martensite texture was only fair at best. Recently a pertinent aspect of the austenite to martensite transformation was reported by Bokros and parker,10 who found that certain habit-plane variants of martensite were suppressed by tensile deformation of Fe-31.7 Ni single crystals prior to the necessary subzero cooling. It might be anticipated that the consequences of such preferred transformation are sustained during the formation of martensite in warm-worked austenite that has a well-developed deformation texture. The present investigation was undertaken first to establish more firmly the relation between preferred orientations in plastically deformed austenite and in the resulting martensite, and second to examine the textures for evidence of deformation-induced preferred transformation. EXPERIMENTAL PROCEDURES An alloy containing 0.3 pct C, 12 pct Cr, 6 pct Ni, and the balance iron, was selected because the mar-tensite-start temperature (M,) of about -100°C allowed convenient experimental manipulation of either austenite or martensite at room temperature. Furthermore, this composition can be readily deformed as metastable austenite at moderately elevated temperatures without intervention of appreciable isothermal or athermal decomposition products. The alloy was austenitized at 1150°C, aircooled to 510°C, rolled unidirectionally at this temperature to 93 pct reduction of cross-sectional area, and finally oil-quenched to room temperature. Partial transformation to martensite was accomplished by quenching to -196°C as needed. The rolled stock was reduced in thickness from 0.067 to 0.010 in. by etching in a solution of 5 pct HC1, 45 pct HNO3, and 50 pct water, and further thinned by careful mechanical polishing to maintain the two sides of the sheet parallel within 0.0003 in. After mechanical polishing to 0.005 in., electropolishing in 1:9 perchloric-acetic acid solution produced a final thickness of 0.002 in. The preferred orientations were determined from

Jan 1, 1968

By D. H. Desy, L. C. Fincher

The magnesium-rich end of the Mg-Ti phase diagram was investigated. The liquidus, solidus, and solvus boundaries to 1 pct Ti were established. All alloys were prepared by saturating molten magnesium with titanium in a consumable titanium crucible under inert gas maintained at 230 psig. The liquidus of the Mg- Ti system was determined by analysis of dip samples taken from 700° to 1300°C under equilibrium conditions in a pressurized inert atmosphere furnace and by analysis of small ingots rapidly poured and quenched from 1400° to 1500°C. The solubility of titanium in magnesium ranged from 0.018 wt pet Ti at 700°C (0.012 wt pet at 650°C by extrapolation) to 1.035 wt pet Ti at 1500°C. The solidus for compositions ranging from 0.03 to 1.00 wt pet Ti was determined to be 650° ± 1°C by thermal analysis. The titanium solid solubility values ranged from 0.08 wt pet at 350°C to 0.19 wt pet by extrapolation to 650°C. The freezing reaction is peritectic. No intermetallic compounds were found in the system; the phase in equilibrium with molten magnesium saturated with titanium was found to be titanium with magnesium in solid solution. Solid titanium will dissolve at least 1.32 wt pct Mg. PREVIOUS investigations of the Mg-Ti system have shown considerable disagreement on the solubility of titanium in liquid magnesium. Furthermore, the solid solubility of titanium in magnesium has not been well established. Liquidus curves for previous work and for the present investigation are shown in Fig. 1. Aust and Pidgeon1 used a dip-sampling method on molten magnesium held in equilibrium with solid titanium under a protective atmosphere to determine the solubility and found that it ranged from 0.0025 wt pet Ti at 651°C to 0.015 wt pet Ti at 850°C. Eisenreich2 introduced titanium into molten magnesium by means of TiCL4 adsorbed on BaCl2. Ingots were then cast at various temperatures. Making the assumption that only the titanium dissolved in magnesium at the time of casting was soluble in H2SO4, Eisenreich determined the solubility of titanium in molten magnesium to range from 0.003 wt pet at 655°C to 0.115 wt pet at 800°C. Eisenreich also determined the solid solubility of titanium in magnesium to be 0.015 wt pet at room temperature and 0.045 wt pet at 500°C. Since the solid solubility just below the freezing temperature for the bulk of the alloy was much larger than the liquid solubility just above the freezing temperature, Eisenreich concluded that the freezing reaction was peritectic. Obinata et al.3 equilibrated molten magnesium with titanium in hermetically sealed titanium containers which were then furnace-cooled. The titanium content of the magnesium was then determined and found to range from 0.170 wt pet at 700°C to 0.85 wt pet at 1200°C. No intermetallic compound was found in the system. The Armour Research Foundation4 determined two points on the solvus by electrical resistivity methods: 0.00057 wt pet at 200°C and 0.0008 wt pet at 300°C. At higher temperatures, data were meaningless with no trends observable. The authors of this report believed that the lack of significant data at the higher temperatures was due to variations in specimen geometry, although there was no positive evidence to verify this supposition. The present investigation was undertaken to clarify the uncertainty in both the liquidus and solvus of the magnesium-rich end of the Mg-Ti system. EQUIPMENT AND MATERIALS The equipment used in this investigation, with some modifications, was essentially that used by Crosby and Fowler5 in their determination of part of the Mg-Zr phase diagram. The equipment, as modified for this work, is shown in Fig. 2. It consists of a sealed furnace chamber which can be pressurized with inert gas so that melts can be made above the boiling point of magnesium at atmospheric pressure. Melts are made by induction heating in a titanium crucible which, after diffusion of sufficient magnesium into the walls of the crucible to saturate the titanium at the sampling temperature, comprises the solid phase in equilibrium with the molten magnesium. Dip samples may be taken with the sampling tube, or the entire furnace may be tilted so that ingots may be poured into a mold in the side chamber. The principal difference from the earlier apparatus is in the thermocouple, which in the present equipment is enclosed in a protection tube and immersed directly in the melt. The tips of both the thermocouple protection tube and the sampling tube, which dip into the melt, are made of high-purity titanium. The 4 1/2-in.-long titanium tip of the sampling tube is threaded into a steel tube, O in Fig. 2, which extends through the top of the furnace. To determine whether the temperature at the tip of

Jan 1, 1969

By L. C. Graton

Although marked by numerous well-known attributes of its own, gold does not possess a kind and range of physical, chemical and geological characteristics wholly different and apart from those of other metals. Instead, it is merely one of the family of metals, with its individual and distinctive traits subordinate to the underlying family relationships and resemblances. The geologist concerned with pure science will pursue, therefore, the same general course and will examine the same broad kinds of facts and interrelations when studying the occurrence of gold as when studying that of copper or cadmium, or any other metal. But when we come to consider the use and economics of the metals, we discover that gold differs strikingly from all the others. Gold, in short, is unique, not by virtue of its inherent characteristics, but because of a peculiar and concerted psychological regard in which it is held. It will be evident, therefore, that the geologist who would deal with gold supply must give far greater weight to economic considerations than is required in his contacts with any other metal. If the geologist be called the scientist of occurrence, and the economist the scientist of use, the economic geologist stands as the necessary link between them. Perhaps it is in part because the economic geologist has made himself more familiar with the science of occurrence than with the science of use and has thus in some degree failed to bridge effectively the gap between the two fields, especially with regard to gold, that the usen1 of gold now appear to be in a state of general concern and even of alarm for the security and adequacy of future supplies. In the case of no other mineral commodity do the users, as a rule, trouble themselves greatly about the adequacy of supply except in so far as that may affect the price which they shall have to pay for the commodity. Oversupply, with resulting low price, they regard as a gift of good fortune. As to long-term undersupply, they are generally content to go ahead on faith, leaving the producer to discover as best he may the means for meeting their requirements or the inventor to find a substitute. But history has shown that for gold a different situation exists. While

Jan 1, 1931

By N. J. Grant, K. M. Zwilsky

A series of copper-alumina dispersion strengthened alloys were prepared using three different copper and two different alumina powder sizes. Improvements in strength of up to ten times that of pure copper were found in room-temperature as well as elevated-temperature stress-rupture tests. Conductivity values remained from 70 to 90 pct that of pure copper. The best alloys were based on the finest metal powder (1 p) and contained from 7.5 to 10-0 vol pet of 0.018 or 0,033 p alumina. DISPERSION strengthening of metals consists of strengthening a metal matrix by the addition of oxides or other refractory constituents, followed by strain hardening, in order to reinforce the base material and extend its temperature range of application. Since the discovery of SAP by lrmannl and Von zeerleder2 in 1949, many investigators have reported data obtained on a variety of metal-inert oxide alloys.3-7 The present work deals with the mechanical mixing of copper and alumina powders. While several techniques of introducing the second phase have been investigated to date, mechanical mixing so far has been recognized as the simplest, least expensive, and most universally applicable technique that can be used to obtain an ultrafine dispersion of inert particles. In the present case, the effects of changing the metal particle size, the oxide particle size and the volume percent of oxide were investigated. This work is an extension of a previous study.6 EXPERIMENTAL PROCEDURE The starting materials were three different grades of copper powder and two different alumina powders. The three metallic powders were -74 µ(- 200 mesh) electrolytic copper powder consisting of irregular equiaxed particles having a normal screen distribution and analyzing 99.5 pct Cu, and two powders having a 5-µ and 1-µ particle size, average, respectively. The latter powders were produced by the hydrogen reduction of purified sulfate solutions at elevated temperature and pressure and were furnished by the Sherritt Gordon Mines, Ltd. The alumina used was obtained from Godfrey L. Cabot Co., under the trade name of Alon C, one batch of powder having a particle size of 0.018 µ, the other a particle size of 0.033 µ. The crystal structure of these alumina powders was found to be cubic gamma. Each batch of powder was mixed in a Waring Blendor for a total of 15 min, followed by a low-temperature reduction in hydrogen and vacuum compacting in cylinders which were hydrostatically pressed at 35,000 psi to give a compact that could be handled conveniently. Six of the compacts were hydrogen sintered at 900°C while the remaining four were sintered at 1000°C. Subsequently, all compacts were hot extruded at 760°C with a reduction of area ratio of approximately 20 to 1. Evaluation of alloys included density and resistivity measurements, room-temperature tensile tests, stress-rupture tests at 450°C plus one other temperature per alloy, hardness tests, microstruc-tural examination, X-ray analysis of the dispersed phase after dissolving the metal phase, and oxidation studies on two of the alloys. A vacuum-melted, wrought copper rod was tested together with these alloys for comparison purposes. RESULTS Table I is a summary of the compositions, sintering temperatures, densities and conductivity values of the ten alloys prepared. All alumina additions are given in volume percent, and will be referred to as

Jan 1, 1962

By L. E. Porter, H. P. Hassel

The state of California produced 310,-996,696 bbl. of oil and about 415,832,000 M cu. ft. of gas in 1944. Such oil production represented 18.5 per cent of the nation's production, as compared with 19 per cent in 1943 ,The tremendous demand placed upon the California fields is indicated by the monthly production in 1944, as follows: Month Barrels per Day Jan................... 809,262 Feb.................. 820,712 Mar.................. 824,592 .4pr ................. 829,973 May.................. 832,068 June.................. 846,038 July.................. 849,231 Aug.................. 858,932 Sept.................. 885,823 Oct................... 877,667 Nov.................. 876,613 Dec.................. 883,847 In all, 2100 wells in proved areas and 269 wildcats were drilled in California during the year 1944. At the end of the year, approximately 270 wells were drilling in the state, as compared with 156 wells at the same time in the preceding year. Nine new fields or new zone discoveries were made during the year, which, according to best estimates, will contribute some 77,000,000 bbl. of new reserves; in addition, the extensions of old fields will increase the new reserves about 165,000,000 bbl., or a combined total, through dis- coveries of new fields, zones, and extensions, of 242,000,000 bbl., offsetting to the extent of about 78 per cent the total oil produced during the year. Geographically, the reserves from these new field and zone discoveries and extensions are distributed as follows: Per Cent San Joaquin Valley........ 72 Coast Area............... 24 Los Angeles Basin Fields. . . 4 100 The state's reserves of crude oil at the end of the year have been estimated to be distributed as follows: The outstanding development project for the year was that of the United States Navy in the Naval Petroleum Reserve No. I, Elk Hills field. During the year, 115 wells were completed in this field, and at the close of the year an average of 19 strings of tools were drilling. This program is being jointly conducted by the Standard Oil Co. of California with the Navy and is designed to increase the production of Naval Petroleum Reserves from approxi-

Jan 1, 1945

By E. C. Potter

It is not the purpose of this paper to enter into the minutiae of a subject so vast, upon which volumes have already been written and volumes more might still be written, but simply to pass in review the characteristic features of that practice, which, dating from the blowing-in of the Edgar Thomson "A" furnace in 1879 and continuing down to the present day, has given to American blast-furnace operations a new significance. The blowing-in of " A" furnace marked the beginning of a new era in the science of iron-smelting if, indeed, it was not the very birth of science as applied to this industry in the United States. American blast-furnace practice in its generic sense and world-wide significance dates from that day, and really all that is valuable, all that is remarkable or worthy of discussion, is embraced in the experiences and achievements of the past fifteen years. Back of that we find only the dead level of mediocrity, or worse, a dispoition to " let well enough alone;" a general, almost universal, employment of " rule of thumb " methods. The application of scientific principles and methods was rare and, indeed, previous to the introduction of the Bessemer process in the early seventies, science had no place in controlling the operations of the American blast-furnace. The old practice consisted mainly in dumping raw materials in at the top of the furnace and tapping out iron and slag at the bottom, for the successful consummation of which the furnace-manager directed his best energies toward keeping the furnace as free as possible from "gobbing" with, alas ! but indifferent success. The burdening of the furnace was based largely on Mark Twain's receipt for " Johnny-cake," altered to suit the circumstances, viz.: a lot of ore, a lot of fuel and about a quarter of a lot of flux. The possible capacities of furnace-plants were not nearly realized. Enormous wastes were permitted, unheeded because not understood. In the use of fuel quantum suff. was always the rule. Increase of product was not thought of because it was not deemed wise or safe to attempt

Jan 1, 1894

By Donald A. Corrigan, John Chipman

It is shown that the heat of solution of nitrogen in liquid-iron alloys is Proportional to the interaction coefficient. This proportionality forms the basis for a method of predicting nilrogen solubility at any temperature when the interaction coefficient is knoun at 1600°C ov when the solubility is known at some one temperature. A method for predicting the solubility of nitrogen in liquid steels, including alloy steels, was proposed some years ago by Langenberg.' Since the data available at that time were restricted to temperatures of about 1600°C, his predictions were similarly restricted. More recently, Nelssonz devised an approximate method for estimating nitrogen solubilities at higher temperatures. It is the purpose of the present paper to present a method by which the solubility of nitrogen at any temperature within the steelmaking range may be predicted from the known interaction coefficients at 1600°C. Nitrogen in iron and in all of the alloys to be considered here is known to obey Sieverts' Law; hence the activity of nitrogen in an alloy of fixed composition is proportional to its concentration, here expressed in weight percent. The activity of nitrogen is defined as equal to its weight percent in the binary Fe-N solution at any temperature. Its activity coefficient in any alloy is the comparison being made at equal values of T and PN2. In all alloys the activity coefficient changes with composition, log fN being a linear function of the percent of alloying element at low concentrations. In the following calculations the alloy compositions are restricted to those in which this linear relation is exhibited. For most systems this is a fairly wide range, for example up to 5 pct V and to 10 pct Cr or Ni. For this composition range. complex alloy is the same as that in the Fe-N-j ternary solution. Langenberg's method of prediction was based on Eq. [3], the values of log fN for various additions being taken from a graph. Instead of using the simple addition indicated in Eq. [3], he used a more complex method suggested for Fe-S-j alloys by Morris and Buehl.3 For the composition ranges in which Eq. [2] is valid the two methods are equivalent. Nelson extended the prediction to other temperatures on the assumption that logfN is inversely proportional to absolute temperature. It may be shown that inverse proportionality would result if the partial molal entropy of nitrogen were unaffected by addition of the alloy element, an assumption which Nelson designated as a "regular" solution. It has been shown recently by the authors4 that this assumption is not a good approximation. The heat of solution of nitrogen (N2) in an alloy may be obtained if the solubility is known as a function of temperature. Measurements of this nature have been reported recently by Beer5 for Fe-Mn alloys, by Nelsson2 for Fe-C, by El Tayeb and parlee6 for Fe-V, and by Pehlke and Elliott7 for many alloys embracing a wide range of compositions. In connection with the work of the last named authors it is noted that their Fig. 22 gives the heat effect per half mole rather than per mole of N2. In using their data we have shifted some of their values slightly by using the best straight line in preference to their curve. Their data, supplemented by others from the literature, are summarized in Table I. In Fig. 1 the heat of solution of nitrogen is shown as a function of composition for the several alloy systems. The difference between the heat effect in the alloy. AH; and that in pure

Jan 1, 1965

By T. H. Oxnam

The predominating value of the ores now being treated by the Palmarejo and Mexican Gold Fields, Ltd., is silver, although some gold also is carried. The present method of treatment consists of wet-crushing and concentrating, followed by the cyanidation of the un-roasted sands and slimes. The sands are treated by leaching, and the so-called " accumulated slimes " by a system of agitation and decantation. It is only within very recent years that the cyanidation of unroasted silver-ores has been commercially successful. In fact, at the time operations were begun at the cyanide-plant at Chinipas, February, 1902, I knew of no other leaching-plant treating similar ores successfully. The cyanide treatment of the Palmarejo ores differs but little from the ordinary practice in cyaniding gold-ores; and perhaps but little, if any, new information concerning the metallurgy of silver is to be gleaned from it. Palmarejo Mines. The Palmarejo mines are located in the southwestern part of the State of Chihuahua, Mexico, on the foothills of the Sierra Madre mountains, at an elevation of 3,200 feet. The mills, 12 miles distant, are situated on the Chinipas river, near the town of Chinipas, which is about 150 miles northeast of Agiabampo, on the Gulf of California. Supplies are shipped via this port as this route is the best and most direct to the property. The ore-bodies in the Palmarejo mines have been deposited along a series of rock-fractures, caused by an intrusion of eruptive rock. The most important of these fractures or fissures, both in width and value, are the Prieta and Blanca veins, which

Jan 1, 1906

By M. S. Burton, J. E. Ritter

The sessile-drop technique was employed to study the effect of atmosphere and alloy additions of titanium and chromium on the surface tension and contact angle of nickel on sapphire substrates at 1500oC. Shear tests were conducted on the solidified sessile drops. The liquid-gas surface tension of pure nickel on sapphire was found to be 1747 ergs per sq cm, with a contact angle of 109.6 deg. The surface tension and contact angle were not affected significantly by the four atmospheres, vacuum, impure argon, pure argon, and pure hydrogen. Small additions of titanium and chromium decreased the contact angle and for the same alloy content, contact angles were lower in pure argon than in pure hydrogen. On the basis of shear-test results , the most probable cause for adhesion in the Ni-Al2O system is the formation of NiO:Al2O3 spinel at the interface; in the titanium alloy-Al2O3 system adhesion is thought to be due to a mechanical interlocking effect; in the chromium alloy-Al2O3 system adhesion is believed to be the result of solid-solution formation involving Cr2O3 and Al2O3 at the interface. In the last few years there has been considerable interest in reinforcing metals with ceramic whiskers. It has been postulated that, by reinforcing nickel with sapphire whiskers, high-temperature strengths su- perior to those of the best current nickel alloys can be achieved.' To fabricate a whisker-metal composite having optimum density and strength, understanding of wettability and adherence in the system is of prime importance. Although there has been some previous research in this a a need for further studies has been cited4-8 to understand better the effects of impurities, alloys additions, and atmosphere on the wetting and bonding of metals to metal oxides. The purpose of this research was to investigate the factors involved in the wetting and adherence of nickel/nickel alloys to sapphire (single-crystal a Al2O3). Sessile-drop experiments were conducted in vacuum, impure argon, pure argon, and pure hydrogen, to determine the effect of atmosphere on the contact angle of the metals on sapphire, and the liquid-gas surface tension of pure nickel. The solidified sessile drops were sheared from the sapphire substrate to measure the bond strength between the metal and ceramic. The alloy additions chosen were titanium and chromium since both enhance the wetting of nickel on sapphire.2, 3c Also, titanium is commonly used when brazing metal-to-ceramic seals to improve adherence. Since chromium forms an oxide that is completely soluble in sapphire, it was thought that the oxide could serve as a transition phase to promote bonding between the Ni-Cr alloy and sapphire. I) EXPERIMENTAL APPARATUS AND PROCEDURE The sessile-drop apparatus was a horizontal furnace, with an induction-heated, cylindrical molybdenum susceptor in a water-cooled Pyrex chamber. This apparatus was patterned after that of Williams and Nielsen.7 A flat Pyrex window at each end of the furnace allowed temperature measurements to be made at one

Jan 1, 1968

INTRODUCTION The regional characteristics of porphyry copper deposits in South America southward from Pantanos and Pegadorcito, Columbia, will be summarized. The age of formation of deposits spans the period from the Permian to the present. Where possible, the general characteristics and the individual structural features of the deposits are integrated into the plate tectonic model. Individual deposits cited in this chapter, located in Fig. 1, are the best known and most fully described, and form the Andean copper belt (Peterson, 1958). Smaller porphyry copper deposits fall both east and west of the line of large, high grade deposits (e.g., Chuquicamata and Toquepala) that make up the spine of this belt. Most of those smaller deposits (e.g., Mi Vida [Koukharsky and Mirre, 19761) are omitted from Fig. 1 and Tables 1 and 2, however. Neither the Andean orogen nor the individual deposits within it are as well de- scribed in the literature as are their counter- parts in the Cordilleran orogen of North America. Therefore, generalizations relying on regional geologic mapping, geophysics, and isotopic geochemistry lack details pertinent to this type of deposit in the Cordilleran orogen. The South American porphyry copper province has been described by Hollister ( 1974) to include most of the Andean orogen excepting the tin province of Bolivia. Porphyry copper deposits have not been commonly found within the tin belt, although copper-tin (e.g., San Rafael, Peru) and copper-tungsten (e.g., Llamuco, Chile) de- posits are known. James (1971) shows the depth to the Moho to be appreciably greater where the tin belt exists, but disclaims any genetic significance from the coincident appearance of the tin-tungsten province and the inhibition of porphyry copper development where the sialic crust thickens. Dates on tin mineralization in this belt (Clark and Farrar, 1973) are similar to some dates for porphyry copper mineralization known else- where in the Andean orogen. It seems that some mechanism is needed to explain the geographic separation of porphyry copper- molybdenum and simultaneous tin-tungsten- molybdenum metallization within the same tectonic system and appearing at similar distances from the trench. The thickened crust of the tin belt is one of the few known differences. Tables 1 and 2 list some of the most important porphyry copper deposits explored to date, but do not include Antaminas, Peru. or a number of other large skarn deposits

Jan 1, 1978

By A. A. Jr. Smith, J. S. Smart

Numerous investigations of the effects of the various impurities common to commercial coppers have been published, and the data have found wide use in industry. Naturally, emphasis has been placed on the oxygen-bearing coppers of the tough-pitch variety, but need is now evident for data covering the oxygen-free condition as well. Furthermore, relatively few of the important reactions between oxygen and the various impurities are well understood, and often the data at hand are not applicable to the low concentrations encountered in commercial coppers. This paper presents the changes in conductivity and softening temperature derived from individual additions of the group VIII triad, iron, cobalt and nickel, to high-purity copper, and constitutes a portion of the copper-research program being conducted at the Central Research Laboratory of the American Smelting and Refining Co. The method of preparation of high-purity copper and its alloys in either the oxygen-free or oxygen-bearing form has been described previous1y.l The purity of this material, and the methods developed to produce it, provide the means for direct investigation of the very low concentration range in which the various impurities generally exist in commercial coppers. The usual necessity for extrapolation to this range using the results obtained from higher concentrations, and the interfering effects of extraneous impurities, are thus simultaneously circumvented. Since previously published data have adequately presented the effects of higher concentrations of iron, cobalt and nickel, the present investigation has been confined to the composition range o to 0.05 per cent. All alloys were initially prepared in the form of oxygen-free continuous cast rod, the weighed alloying additions in suitable form being charged with the pure copper to the continuous casting crucible. The best of the available high-purity alloying materials were used, and spectrographic analyses confirmed the absence of interfering elements from the alloys formed. Each series was compounded in the direction of increasing concentration, starting with pure copper in a new crucible and finishing with the 0.05 per cent alloy. Composition was closely controlled by adding the alloying element in the form of a carefully compounded and analyzed master alloy rendered uniform by continuous casting. The accuracy of this method of synihesis was proved by chemical analysis of the more concentrated alloys, and, accordingly, there is every reason to credit the stated composition of the very dilute alloys in the range where chemical analysis becomes highly uncertain. Oxygen-free samples for measurements of conductivity and softening temperature Were obtained by drawing the continuous cast rod to wire of 0.08I-in. diameter. employing a number of intermediate anneals to refine the grain structure. The

Jan 1, 1942

By A. A. Jr. Smith, J. S. Smart

Numerous investigations of the effects of the various impurities common to commercial coppers have been published, and the data have found wide use in industry. Naturally, emphasis has been placed on the oxygen-bearing coppers of the tough-pitch variety, but need is now evident for data covering the oxygen-free condition as well. Furthermore, relatively few of the important reactions between oxygen and the various impurities are well understood, and often the data at hand are not applicable to the low concentrations encountered in commercial coppers. This paper presents the changes in conductivity and softening temperature derived from individual additions of the group VIII triad, iron, cobalt and nickel, to high-purity copper, and constitutes a portion of the copper-research program being conducted at the Central Research Laboratory of the American Smelting and Refining Co. The method of preparation of high-purity copper and its alloys in either the oxygen-free or oxygen-bearing form has been described previous1y.l The purity of this material, and the methods developed to produce it, provide the means for direct investigation of the very low concentration range in which the various impurities generally exist in commercial coppers. The usual necessity for extrapolation to this range using the results obtained from higher concentrations, and the interfering effects of extraneous impurities, are thus simultaneously circumvented. Since previously published data have adequately presented the effects of higher concentrations of iron, cobalt and nickel, the present investigation has been confined to the composition range o to 0.05 per cent. All alloys were initially prepared in the form of oxygen-free continuous cast rod, the weighed alloying additions in suitable form being charged with the pure copper to the continuous casting crucible. The best of the available high-purity alloying materials were used, and spectrographic analyses confirmed the absence of interfering elements from the alloys formed. Each series was compounded in the direction of increasing concentration, starting with pure copper in a new crucible and finishing with the 0.05 per cent alloy. Composition was closely controlled by adding the alloying element in the form of a carefully compounded and analyzed master alloy rendered uniform by continuous casting. The accuracy of this method of synihesis was proved by chemical analysis of the more concentrated alloys, and, accordingly, there is every reason to credit the stated composition of the very dilute alloys in the range where chemical analysis becomes highly uncertain. Oxygen-free samples for measurements of conductivity and softening temperature Were obtained by drawing the continuous cast rod to wire of 0.08I-in. diameter. employing a number of intermediate anneals to refine the grain structure. The

Jan 1, 1942

By L. G. Sprague

THE fact that this latest and most modern of the Universal Atlas Cement Company's plants at Northampton, Pa., is the fifth to be built on these same properties, and their development has been coincidental with the development of the portland cement industry in the United States, makes it appropriate to sketch briefly the history of the successive steps. In 1889 the original Atlas Portland Cement Co. started its first plant at Coplay, Pa., which is just across the Lehigh River from the present operation. Here the first successful rotary kiln was operated. These kilns were 6 ft. in diameter and 60 ft. long; they used oil for fuel until 1895, when the company developed the first burner for pulverized coal. Shortly thereafter the Atlas company acquired property on the Northampton side of the river and built its plants Nos. 2, 3 and 4 within the following 10 years. During the same period the production of portland cement in the country was increasing rapidly; owing largely to the development of the rotary kiln and improved grinding machinery, which lowered the cost and improved the quality of cement. The general tendency has been to increase the length of the kiln and grind both raw material and finished product finer. In 1930 the Atlas Portland Cement Co. and the Universal Portland Cement Co. united to form the Universal Atlas Cement Co., and the same policy of improving the product has been continued. Because of the large amount of research carried on by manufacturers and consumers, including government agencies, there is a demand for cement of different chemical and physical characteristics for different kinds of structures. Hence many engineers in recent years have been asking for cements of certain definite chemical analyses, which they think are best for their particular jobs. This has compelled the manufacturer to make several different types of cement by variations of chemical composition. These are generally made by adding silica, iron and lime to the standard mixture, which necessarily increases the cost of the product. Therefore the Universal Atlas Cement Co., in planning the modernization of its Northampton plant, gave this particular phase of the problem considerable study. Research and experimentation have developed the practicability of making a wide variety of differently proportioned raw materials for cement by a process of subtraction rather than by addition. With such process, it is possible to discard the undesirable aluminates and silicates from the ample supply of impure limestone available from the company's property rather than by adding high-grade limestone obtained from distant sources. This procedure requires mineral separation by centrifugal sedimentation and froth flotation. Since the chemical and mineral constituents of Lehigh Valley "cement rock," together with the methods of separating them, have been thoroughly described in published

Jan 1, 1943

By R. M. Hardgrove

Pulverized coal was first used for firing cement kilns about 45 years ago, with such success that it has continued in general use. Based on cost, pulverized coal is usually the most economical fuel. In some localities natural gas or oil is cheaper, but 85.5 per cent of all cement kilns at present are fired with pulverized coal. The pulverized-coal flame is well suited to kiln conditions. Its soft, luminous nature gives it a high radiating property and the length of the flame can be readily varied to suit conditions in a kiln of any length. Ash and slag cause most of the dificulties incident to the burning of coal. In a. cement kiln, however, the ash, being similar in composition to the raw mix and being deposited uniformly in the mix and clinker, occasions no difficulty as long as it remains constant in quality and quantity. Until 6 years ago almost all cement kilns using pulverized coal employed the bin system. The coal was dried and pulverizeti in a separate plant and delivered into a bin at the kiln. Thus the bin system requires driers, storage-type pulverizers, conveying systems, individual kiln bins, pulverized-coal feeders and primary air fans. The direct-fired system requires only a pulverizer and a blower. Fig. I shows typical plants. The first installations of direct-fired pulverizers were of the impact type but fineness of pulverization was both inadequate and variable. About 1927 a few direct-fired installations employing tube-type pulverizers were made, which were much more satisfactory. As more efficient pulverizers were developed from 1934 on, equipment for direct firing was installed at a large number of plants, until now 196 of about 900 kilns in use in the United States are direct-fired. Most of these replaced antiquated bin systems. Process of Burning Cement Clinkers The process of burning cement clinkers is fundamentally one of heat transfer. In boilers and other heat-exchange apparatus the area of the surface receiving heat from the gases is the best unit for comparing output, This seems to be equally true for kilns. The inside kiln surface is the heat-receiving surface and its area is used as the unit of kiln size in the following comparisons. Heat input is based on British thermal units in the fuel. E. G. Bailey,' in his work on boiler-furnace heat absorption, has used the unit "B.t.u. available." This is the practical calorific power of the fuel, plus the heat in the air used for combustion. In other words, it is the heat available for useful work in the furnace or kiln. The unit of kiln output is barrels per hour. The composition of the raw mix, the percentage of water in the slurry of wet plants and hardness of burning all affect the output. These conditions, however, are hard to evaluate and probably have less effect on the output than irregularities of raw feed and clinker discharge and inexpert control of combustion. Wet vs. Dry Plants The study presented here covers 88 plantsl of which 41 are wet and 47 dry. Of

Jan 1, 1942

By R. M. Hardgrove

Pulverized coal was first used for firing cement kilns about 45 years ago, with such success that it has continued in general use. Based on cost, pulverized coal is usually the most economical fuel. In some localities natural gas or oil is cheaper, but 85.5 per cent of all cement kilns at present are fired with pulverized coal. The pulverized-coal flame is well suited to kiln conditions. Its soft, luminous nature gives it a high radiating property and the length of the flame can be readily varied to suit conditions in a kiln of any length. Ash and slag cause most of the dificulties incident to the burning of coal. In a. cement kiln, however, the ash, being similar in composition to the raw mix and being deposited uniformly in the mix and clinker, occasions no difficulty as long as it remains constant in quality and quantity. Until 6 years ago almost all cement kilns using pulverized coal employed the bin system. The coal was dried and pulverizeti in a separate plant and delivered into a bin at the kiln. Thus the bin system requires driers, storage-type pulverizers, conveying systems, individual kiln bins, pulverized-coal feeders and primary air fans. The direct-fired system requires only a pulverizer and a blower. Fig. I shows typical plants. The first installations of direct-fired pulverizers were of the impact type but fineness of pulverization was both inadequate and variable. About 1927 a few direct-fired installations employing tube-type pulverizers were made, which were much more satisfactory. As more efficient pulverizers were developed from 1934 on, equipment for direct firing was installed at a large number of plants, until now 196 of about 900 kilns in use in the United States are direct-fired. Most of these replaced antiquated bin systems. Process of Burning Cement Clinkers The process of burning cement clinkers is fundamentally one of heat transfer. In boilers and other heat-exchange apparatus the area of the surface receiving heat from the gases is the best unit for comparing output, This seems to be equally true for kilns. The inside kiln surface is the heat-receiving surface and its area is used as the unit of kiln size in the following comparisons. Heat input is based on British thermal units in the fuel. E. G. Bailey,' in his work on boiler-furnace heat absorption, has used the unit "B.t.u. available." This is the practical calorific power of the fuel, plus the heat in the air used for combustion. In other words, it is the heat available for useful work in the furnace or kiln. The unit of kiln output is barrels per hour. The composition of the raw mix, the percentage of water in the slurry of wet plants and hardness of burning all affect the output. These conditions, however, are hard to evaluate and probably have less effect on the output than irregularities of raw feed and clinker discharge and inexpert control of combustion. Wet vs. Dry Plants The study presented here covers 88 plantsl of which 41 are wet and 47 dry. Of

Jan 1, 1942

By E. A. Reilly, G. R. Gardner, F. P. Lasseter

THE methods that may be applied to the treatment of slurries and water, as these are related to practical coal-preparation problems, are concerned essentially with the movements of solids suspended in water. It is assumed that there are no fundamental differences between the principles involved in the treatment of coal slurries and the phenomena encountered in general mineral-dressing practice, and the latter are presented in some detail. Basic principles ,are correlated with present practice for both the anthracite and the bituminous coal fields, and methods are discussed which are designed to utilize best all the material subjected to treatment and suggest a sound approach to the solution of problems relating to the return of clear water to process or to streams. In order to approach the practical phases of the subject with sufficient understanding of the basic principles, it is necessary to discuss two types of phenomena that are applicable. The first is flocculation and the second is sedimentation. Descriptive matter is given covering the various methods and types of equipment employed to conduct these operations, with emphasis on their application to water and coal-slurry treatment. DEFINITION OF TERMS Definitions of terms are consistent with modern developments, and on form, in general, with their usage in mineral-dressing practice. Because of variations in coal-preparation methods, it is impossible to define a rigid upper limit of particle size for a coal slurry or sludge which will apply generally. Limits vary somewhat with the particular treatment method employed at a given plant. For purposes of definition, this limit is chosen as the particle size for which preparation methods such as Chance cones and jigs are usually dispensed with, and other methods, such as the Hydrotator, tables, and froth flotation, are employed. Generally the limit will be 10 to 6 mesh. In assuming this variable upper limit of particle size in a coal slurry, it is recognized that the size ranges discussed will duplicate sizes dealt with

Jan 1, 1943

By B. H. Caudle, B. M. Hickman, I. H. Silberberg

Secondary recovery projects often are not started in oil reservoirs until dictated by rising GOR's or declining oil production. Such circumstances require a well dispersed injection pattern to prevent the oil bank from bypassing the production wells. Many times this purpose is served by using the five-spot or line-drive patterns, in which half of the wells are made injection wells. A regular injection pattern is proposed that is based on the same well spacing as the five-spot but in which only a third of the wells need be converted to injection wells. Fluid flow model studies on this proposed pattern show that production histories will be as good as those for a five-spot pattern at mobility ratios of three and above. The model data are presented in a form that may be used to predict recoveries from both homogeneous and stratified formations. Introduction The injection of fluid into a petroleum reservoir usually is prompted by an actual, or predicted, loss in the productivity of the reservoir. Often, an oil reservoir is produced by pressure depletion until high GOR's dictate a change in policy. Fluid injection also causes increased ultimate recovery, but this usually is of less importance to the operator than is the maintenance of the production rate. It is a fact that the ultimate recovery in any particular fluid injection project is relatively independent of the number and spacing of the injection wells as long as the reservoir voidage through the production wells is balanced by the total injection rate. However, the response of a production well is directly affected by the distance it lies from an injection well. In places where the well productivities are declining, the injection wells should be spaced as evenly as possible among the producing wells ("dispersed" injection pattern). More particularly, if the production response depends upon the formation (and subsequent production) of an oil bank, each production well should be surrounded by injection wells. Otherwise, the oil productivity will increase very little as the oil bank moves past the well.'.' An evenly spaced injection pattern has the best chance of generating an oil kick in the production wells. If reservoir voidage and injection rates are to be equal, the ratio of injection wells to production wells must be equal to the ratio of the average injectivity to the average productivity (in reservoir volumes). This ratio is in strumental in choosing the injection pattern. Table 1 shows the production well to injection well ratio for the dispersed injection patterns that have been described in the literature.'-' All of these patterns will have comparable recoveries and response times (for the same basic distance between wells). The choice of pattern there fore depends upon the relative injectivity and productivity of the wells and upon the type of drilling pattern employed. Another important factor may be the ability of the proposed production wells to make up the lost productivity from those wells converted to injectors. These factors become more pronounced at the higher oil viscosities (low gravity oils). All other things being equal, the probable ratio of single well injectivity to single well productivity will be equal to the water-oil mobility ratio of the proposed flood. Thus, high mobility ratios (due to low gravity oil) should call for fewer injection wells — as long as these injection wells are "dispersed" to obtain more even pro duction response for the remaining wells. Secondary re covery projects in oil reservoirs seldom, if ever, will have mobility ratios requiring more injection wells than production wells. Thus, only the last five of the patterns listed in Table 1 will be of significant interest in oil recovery. Almost every development drilling program calls for the wells to be drilled along equally spaced rows and

Jan 1, 1969

By S. S. Clarke

Late in 1942, the increasing demand for zinc, coupled with the growing shortage of miners and the knowledge that some abandoned mines would have to be reopened for prospecting and development, led to considerable thought as to the possibilities of further mechanization in order to conserve man power. The ore bodies, locally termed "sheet ground," are an important ore bed in some mines and are in the lower part of Boone formation of the Mississippian Series. Some mines contain interbedded layers of nearly pure galena and sphalerite in horizontal sheets ranging in thickness from a thin seam to several inches and is persistent over large areas. This type of ore body offered the best opportunity for study and experiments. The use of Jumbo drill carriers was advanced but some doubt was expressed as to the adaptability of Jumbos as then in use to mine headings as compared to post and arm mounting (Fig I). Another consideration was the introduction of truck haulage when several mines were trackless. A drill frame, built to carry 2 4-in. drifters, was mounted on a truck chassis. This design proved a failure as it was not rigid and the resiliency of the tires and springs allowed too much play. Long screw jacks were then used to hold the truck firmly in place, but placing the jacks and securing the truck required more effort and time than setting up post drills, so the truck carrier was abandoned. The use of a bull dozer underground had been under consideration for some time to be used in "brunoing" the broken dirt from behind pillars and other inaccessable places so the slusher drags could load without double dragging the dirt. A dozer with hydraulic blade lift was purchased and R. I. Tuthill, Superintendent of Section 30 Mines, suggested that a long drill arm be substituted for the blade, and the drills mounted on the cross member. The hydraulic lift would permit drilling holes at any required spacing. The "cat" was very mobile and answered the problem of a trackless mine. The initial tests showed that the "cat" would make a good carrier, but the hydraulic controls were not positive enough to keep the drills in alignment while drilling. The next step was to build a small hoist. This hoist was attached to the power take-off on the "cat" and by means of sheaves and a double line of 3/8-in. hoist cable, a positive control for raising and lowering the boom was obtained. To avoid serious injuries to the drillers should the cable break, a safety chain was fastened to the drill boom and hooked into a slot in the back of the "cat" frame. A different power unit was obtained for the "cat," as a state law prohibited the use of internal combustion engines in mines. A custom machine shop had just placed on the market a small hoist powered by a Model A Ford engine that had been very ingeniously converted to a slide valve engine using compressed air. To use this unit on a "cat," our master mechanic de-

Jan 1, 1949

By Walter Knox, Charles H. Sawyer

All of the coals commonly used in domestic bituminous stokers form coke, and satisfactory operation depends upon the fact that the coke formed is so weakly bound together that it breaks readily in the normal operation of the stoker and automatically maintains a good fuel bed. Some coals, because of their tendency to form solid, blocky coke, are practically excluded from use in small domestic stokers as now built. Other coals, some among the best stoker coals available, can form this troublesome coke under certain conditions. Many contradictory methods have been offered as cures for coke formation. Generally the procedure has been to try various adjustments until a combination was found that seemed to give better results. Such random methods of treatment have not provided any reliable information as to causes. The present paper covers a comprehensive test program undertaken by the Koppers Company's Stoker Coal Research Laboratory at Kearny, N. J. The program had two main objectives; first, to discover what factors affected coke formation, and second; to define corrective steps that could be applied in stoker service work. Conclusions and Results i. The design of the stoker outweighs in importance all other factors capable of improving coke formation. 2. Insufficient air supply aggravates the formation of large blocky coke, although raising the air above 30 to 40 per cent excess (as determined during steady running) does not further improve the character of the coke formed and only reduces its accumulation at the expense of efficiency, increased fly ash, poorer clinker-ing, and other disadvantages. 3. Increasing the coal feed results in a somewhat more friable coke structure and is recommended for persistently troublesome jobs. 4. Increasing over-fire draft improves the character of the coke formed and reduces troublesome accumulations by accelerating off-period burning, although at some expense in efficiency and some increase in fly-ash accumulation. 5. Coke structure was not substantially improved by blocking some of 'the retort tuyeres, although the blocking of tuyeres at the feed-screw end of a rectangular retort did lead to somewhat improved performance, possibly because of considerably better distribution of coke in the fuel bed. 6. With the equipment tested no difference was shown between installation of the same stoker in a steam boiler and a warm-air furnace, or between a sand-filled and a ventilated type of hearth. 7. The following design features had no noticeable effect on coke formation: a. Presence or absence of coal-tube air as provided by many manufacturers to eliminate smoke-back. B. Presence or absence of a flap damper ill the air duct to minimize off-period burning. c. Continuous or intermittent (ratchet and pawl driven) movement of fuel feed screw.

Jan 1, 1944