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By B. J. Nelson, F. N. Rhines

STUDIES upon the rates of oxidation of copper alloys containing small quantities of the alloying elements1,2 have shown that steady growth of the scales at predictable rates is limited to a small concentration range and to oxidation at temperatures above 600°C., whereas unpredictable and erratic oxidation behavior is found with alloys containing larger additions and at low temperatures. The latter effect appears to be associated with modifications in the geometric disposition of the oxides. At low concentrations of the baser elements in copper, simple oxidation behavior is typified by the formation of two distinguishable zones of oxidation: (I) a subscale composed of discrete particles of the oxide of the alloying element embedded in substantially pure copper and (2) an external scale composed of cuprous oxide (with a very thin layer of cupric oxide on the outside) containing particles of the alloying element distributed throughout, but most profusely near the metal surface (see Fig. 2, top). Where this type of structure obtains, the process of oxidation is believed to be implemented, and its rate controlled, by the diffusion of the reacting elements through a continuous matrix phase; i.e., through the alpha (metallic) phase of the subscale and alloy and through the cuprous oxide of the external scale. Copper is presumed to diffuse outward through the cuprous oxide layer to the external surface, where it reacts to form more cuprous oxide.3 Oxygen is delivered at the oxide-metal interface in the form of cuprous oxide, which may either react with the alloying element to deposit its oxide at the inner limit of the external scale or dissolve in the pure copper that remains at the surface of the metal after it has become depleted in its oxidizable alloying elements. Both oxygen and the alloying element are pictured as diffusing through the metal, the oxygen inward and the alloying element outward. Where the two diffusion streams meet in sufficient concentration the oxide of the subscale is precipitated. If the oxygen pressure in the surrounding atmosphere is just below the pressure necessary to maintain cuprous oxide undecomposed, no cuprous oxide can be formed; some of the oxide of the alloying element may form upon the external surface, if its decomposition pressure is below that of cuprous oxide, and a normal subscale appears. This condition is achieved experimentally by enclosing the alloy with cuprous oxide together with an excess of copper. At temperatures from 600°C. downward, the precipitated oxides tend to accumulate at the grain boundaries of the alpha phase where a relatively small volume establishes a partial barrier to the diffusion of the reactants. Similarly, large volumes of precipitated oxides tend to deposit in various patterns that may be expected to hinder the diffusion of the reactants in the

Jan 1, 1943

By Lloyd B. Underwood

Dr. Gardener, in Chapter 2, has presented a comprehensive state-of-the- art review of site investigations For tunneling. Nearly all of the techniques he discussed will also be required for future site investigations. Therefore, this chapter will be devoted to a few rather new exploration techniques plus ideas for improving some of the present-day methods. In March 1962, the first symposium on "Remote Sensing of Environment" was held at the University of Michigan.l Since that time, four additional symposiums have been held at the same University. Also, the technical Literature has recently included a number of articles on remote sensing techniques. A recent one appeared in the February 1968 issue of Materials Research and Standards.Vt was entitled "Developments in Remote Sensing Applicable to Airborne Engineering Surveys of Soils and Rocks," and was written by Dana C. Parker. Mr. Parker predicts that aerial reconnaissance will someday supplant soil augers, rock drills, surface reconnaissance, and geophysical surveys as the engineer's primary means of obtaining information about soils and rocks. He states, "The engineer wishing to survey a route or a site or to locate rock and soils suitable for construction projects will be able to push some buttons in an airplane and record all the data required for determining the relevant conditions. In a short time after he returns to earth with his rolls of film and charts, he will be able to reduce and analyze the data by partially computerized techniques and to compile a concise and comprehensive engineering report that gives all the relevant information about rocks, soil, water, and vegetation in the area he surveyed. Most important he will feel as confident with his recommendations, derived primarily from image characteristics and spectral power distributions, as his predecessors did with recommendations based on more tangible evidence obtained from drill cores and surface reconnaissance." The airborne sensors for engineering surveys of soils and rocks are those that sample some electromagnetic property of the materials that com- prise the terrain and cover its surface. In addition to cameras, these include

Jan 1, 1970

By T. F. Witherbee

AS the forms of blown-out furnaces are of much interest to ironmasters and metallurgists, the manner of taking the accompanying sections of the Cedar Point stack is here given. The diagrams show the original and also the final shape of the furnace after a two years and twelve days' blast,, during which the following solid materials passed through it, viz.: Coal, 41,000 tons; ore, 57,000 tons; limestone, 30,000; total, 125,000 gross tons. Product, 411/4 tons per day Bessemer pig iron. The apparatus used in taking the sections was a modification of that proposed by Mr. Frank Firmstone,* and consisted of a sliding rule, to follow around the circumference of the stack, which rule was connected by a string to a segment of a circle of 24 inches radius. The segment was carried by an arm which connected it to a huh as a centre, 2 inches in diameter. A second string was wound around the hub, and communicated motion to a pencil-carrier, the pencil of which marked out on paper the exact outline, and reduced it to a scale of & inch to the foot. The whole machine was made in about three hours, with the facilities of a carpenter's shop, and gave in operation every irregularity of the lining. The sections were taken at salient points, by lowering a hanging staging on which the apparatus was placed. Tracings from the paper of the machine were made, and, as in this case several copies were required, the tracings were glued on to thin sheets of basswood, and patterns carefully sawed out with a bracket saw.

Jan 1, 1879

By J. Wes Blakely

In the mid-1950s the importation of foreign oil began to encroach on traditional coal markets such as railroad steam engine fuel, home heating, electrical generating plants, and others. Many of the smaller coal companies with substantial coal reserves subsequently found that they could no longer continue to mine economically and merged in various ways with larger established coal mining concerns. As the seats of top management and authority were removed from the mines to large metro centers such as New York, Pittsburgh, and Chicago, the more personal relationship between mine workers and management that had existed prior to these mergers began to be eroded and replaced by "remote control" mine management. The disappearance of this face-to-face contact of upper management with mine employees tended to create barriers blocking simple effective communications between coal mine management and labor. In examining the human relations aspects of the coal mining industry, many elements, some concerned with work and others not, have depicted the industry as almost devoid of good applied human relations and communications practices, and, in truth, little has been done to alleviate this situation. In past years many coal producing companies, with the exception of one of the largest, failed to adequately define the term "communications ' as it applied to their companies, whether internally or externally. Internally many still place heavy reliance on written communications such as company-wide newspapers to do the job of communicating with their employees which they feel ought to be done. One company puts an inordinate belief in its company "newspaper" as the primary instrument to stimulate its work force into increasing productivity. Primarily aimed at the workers, who greatly outnumber the salaried administrative people, this publication mainly documents the fortunes of individual mine workers who are felt to have achieved something with their lives, e.g., a mine worker who had managed to put four children through universities, the

Jan 1, 1981

By J. Wes Blakely

In the mid-1950s the importation of foreign oil began to encroach on traditional coal markets such as railroad steam engine fuel, home heating, electrical generating plants, and others. Many of the smaller coal companies with substantial coal reserves subsequently found that they could no longer continue to mine economically and merged in various ways with larger established coal mining concerns. As the seats of top management and authority were removed from the mines to large metro centers such as New York, Pittsburgh, and Chicago, the more personal relationship between mine workers and management that had existed prior to these mergers began to be eroded and replaced by 'remote control mine management. The disappearance of this face-to-face contact of upper management with mine employees tended to create barriers blocking simple effective communications between coal mine management and labor. In examining the human relations aspects of the coal mining industry, many elements, some concerned with work and others not, have depicted the industry as almost devoid of good applied human relations and communications practices, and, in truth, little has been done to alleviate this situation . In past years many coal producing companies, with the exception of one of the largest, failed to adequately define the term “communications” as it applied to their companies, whether internally or externally. Internally many still place heavy reliance on written communications such as company-wide newspapers to do the job of communicating with their employees which they feel ought to be done. One company puts an inordinate belief in its company "newspaper" as the primary instrument to stimulate its work force into increasing productivity. Primarily aimed at the workers, who greatly outnumber the salaried administrative people, this publication mainly documents the fortunes of individual mine workers who are felt to have achieved something with their lives, e.g., a mine worker who had managed to put four children through universities, the

Jan 1, 1981

By G. R. St. Pierre, S. W. Gilby

The equilibrium vapors established over Fe-Cr-Ni alloys containing up to 50 pct Cr at 1600°C were determined by collecting the effusate from thoria Knud-sen cells. From these data, the activities of iron and nickel in the ternary alloys have been calculated. In a separate set of measurements, a mass spectrometer was used to determine the activities of the three components in a series of Fe-Cr-Ni alloys. In binary Ni-Cr melts, the activity coefficient of chromium referred to pure solid chromium as standard state is less than one at low chromium contents but is greater than one for melts containing more than 30 at. pct Cr. For Ni-Cr melts containing less than 10 at. pct Cr, In ?Cr = 0.15-0.92 N2. Ternary activity diagrams for Fe-Cr-Ni alloys are presented. In iron-rich alloys, the interactions between the three components are negligible; however, in nickel-rich alloys, the three principal interactions have significant positive values. THE activities of components in binary Fe-Ni alloys have been measured both in the solid solution1-3 and liquid solution4-6 temperature ranges. The determination for Fe-Ni melts have been made by three different methods: transpiration,4 Knudsen-cell effusion with analysis of an accumulated condensate,' and Knudsen-cell effusion with direct measurements of relative component intensities by mass spectrometric methods.6 The results obtained by the three different methods in three different laboratories are in excellent agreement and considerable confidence is placed in the activity coefficients for Fe-Ni melts. At 1600°C, the activity coefficients in dilute solution are ?°Ni = 0.66 and ?oFe = 0.40 for the pure liquid components as standard states. Measurements made on solid solution Fe-Cr alloys7-10 indicate that the component activities are slightly greater than ideal. The measured activities in iron-rich Fe-Cr liquid alloy11-16 indicate almost ideal behavior for this system. The recommended activity coefficient of chromium in dilute solution in liquid iron at 1600o C, ?oCr, is 1.18 when referred to pure solid chromium as standard state and 1.04 when referred to pure undercooled liquid chromium as standard state." The conversion factor of 1.14 is based on a melting point of 1857°C and an enthalpy of melting of 4047 cal per g at. for chromium.21,37 The activity coefficient of iron in dilute solution in liquid chromium has not been measured. Activity measurements on solid Ni-Cr alloys have been made by several investigators.17-20 During the review of this manuscript, Fruehan12 published the results of a study on liquid Ni-Cr alloys at 1600°C. He used galvanic cells22 with ZrO2(CaO) as the electrolyte and Cr/Cr2O3 for the reference electrode. His results indicate that ?oCr in nickel at 1600°C is about 1.01 when referred to pure solid chromium and about 0.89 when referred to pure undercooled liquid chromium as standard state. The activity coefficient of nickel in liquid chromium is unknown. The compositions of vapors freely evaporating from some molten Fe-Cr-Ni alloys have been measured by Lyubimov, Granovskaya, and Berenstein.23 Their results, combined with known vapor pressures, indicate strong positive deviation for chromium in iron-rich alloys and strong negative deviation for chromium in nickel-rich alloys. EXPERIMENTAL PROCEDURES This research was undertaken to determine the activities of components in ternary Fe-Cr-Ni melts containing up to 50 at. pct Cr. At the initiation of the research, we decided to use a Knudsen-cell method wherein a portion of the effusing vapor is condensed on a cold plate.' The composition of the equilibrium vapor for each alloy composition is determined in this method by holding the system under constant conditions for a period of time sufficient to collect enough condensate on the cold plate for chemical analysis. The activities of components in ternary alloys can be calculated from such vapor composition determinations by Eq. [1].24

Jan 1, 1970

By R. E. Boehler, N. C. Ludwig

At Buffington Station, Gary, Ind., Universal Atlas Cement operates fourteen 8 x 101/2 x 155-ft cement kilns in mill 6 and two 11 x 360-ft kilns in the Harbor plant. The No. 11 and 12 kilns in mill 6 are equipped with Manitowac recuperator sections. This report describes studies in measuring exterior shell temperatures on several of these kilns and the development of a traveling radiation pyrometer with certain novel features. Preliminary Work: At first various temperature-sensing devices were placed on the steel shell: 1) crayons with calibrated melting points, 2) colored paints with temperature-calibrated pigments, 3) aluminum paints with temperature-calibrated binders, and 4) metal-stem dial thermometers. The colored paints and aluminum paints failed to indicate the temperatures correctly. The crayons and thermometers did indicate fairly correct temperatures, but it proved impossible to apply enough of these on the shell to detect all the potential areas where hot spots might develop. Furthermore, considerable labor was required to apply these sensors and read the temperatures. Consequently no further work was done with these devices. Formation of Hot Spots: In the burning or clinker-ing zone of a cement kiln, the thickness of the protective coating and thickness of the brick govern the amount of heat transmitted to the steel kiln shell. Usually the protective coating consists of 4 to 8 in. of fused cement clinker. The formation of a hot spot is usually caused by loss of coating? that is, localized areas of the coating become thin or fall away from the refractory. This is generally caused by excessive temperature in the burning zone over a fairly long period of time. It may also be caused by a sudden thermal change in the burning zone. Variations in raw feed composition and in feed rate require changes in the fuel and air rates, and when these are not appropriately altered, conditions may develop in the kiln that will result in loss of coating. Luminescence on the kiln shell indicates that a hot spot has developed to a point that usually alters the refractory's thermal conductivity properties. When this thermal weakness zone occurs in the burning zone of the kiln, constant vigilance is required to protect it by maintaining proper coating. Even so, it has been the writers' experience that within a period of several days to about four weeks the hot spot usually recurs with greater severity. This necessitates shutting down the kiln and re-bricking the affected area. One of the prerequisites of a good burnerman is the ability to maintain a protective coating despite the many variables in operation. When he knows that it is getting thin or that an area has dropped off, he reduces the firing rate and kiln speed and brings feed into the affected area in an effort to rebuild the coating. But when powdered fuel is burned, the atmosphere of the kiln may prevent the burnerman's observing the condition of the coating closely at all times without taking off the fire. It is not considered good practice to do this frequently, as it imposes a thermal shock on the coating and upsets operation of the kiln. To help the burnerman scan the shell of the kiln along the burning zone, therefore, a radiation pyrometer, connected to a potentiometric recorder, was mounted on a slowly moving steel cable. The theory of operation, construction details, and adaptability of the radiation pyrometer are included in an excellent monograph' and also in a textbook.' Shell temperatures of the Atlas Cement kilns were measured with a Brown Instruments Div. low intermediate range Radiamatic unit, of range 200" to 1200°F, and a circular chart Electronik potentio-metric recorder, of range 500" to 1000°F. In Bulletin 59095M the supplier publishes standard calibration data (millivolts vs degrees Fahrenheit) for this radiation pyrometer, These data, however, apply only to flat surfaces having emissivities of unity. Calibration of Radiation Pyrometer for Use on Curved Surfaces: When applied to surface temperature measurements, the radiation pyrometer reading depends on the nature of the surface, the material of which it is composed, and also to some extent on the temperature of the surroundings. Although the present radiation pyrometer is designed to give a calibrated response under ideal (black body) conditions when used commercially, it must be calibrated empirically. The calibration procedure, given below, follows that described by Dike (Ref. 1, pp. 38-39). Calibration tests on plane and curved surfaces showed that the response of the radiation pyrometer was very

Jan 1, 1961

Discussion of the paper of Frederick W. Apgar, presented at the Butte meeting, August, 1913, and printed in Bulletin No. 7S, June, 1913, pp. 1011 to 1022. L. C. GRATON, Cambridge, Mass.:-I presume I am one of the few who are exceedingly interested in microscopic work, and I am sure we have all enjoyed this paper very much. I will not attempt to express my own feelings in regard to it beyond saying that it seems to me that this sort of investigation and study has been overlooked and slighted, and its possibilities are very great. There are one or two, details which impressed me, because they were novel to me, and one was the development of secondary galena with dull luster. I have never seen any galena which seemed to be secondary, and have never seen any that was secondary or primary that did not have a bright luster. KIRBY THOMAS, New York, N. Y. (communication to the Secretary *) :-The present-day mining engineer is expected to " see into the ground farther than the point of the pick " and he is justified in making free claim to his ability to do so. Mr. Apgar has recorded the development of the application to the work of the engineer of a very useful but tardily recognized instrument-the petrographic microscope, an instrument which is helping to shatter the proverbial "point of' the pick" limitation-and he has shown its use and its possibilities very clearly. Some further field examples of the use of the microscope in engineering problems may add to the appreciation of Mr. Apgar's scholarly paper. In exploration by diamond drills in the Sudbury, Ontario, nickel district it is often of great importance to determine when the drill has passed out of the norite and into the foot-wall formation. Structural calculations may give a clue to the expected point of contact, but the variations are considerable, and, since to stop the drill before reaching the contact is futile, and too continue beyond it is needless, it becomes of theoretic and economic importance to determine positively the lithological nature of the corer at critical stages in the work. In some places the foot-wall is an earlier norite, only distinguishable from the nickel norite (Sudbury-: ite), by means of an examination of the rock slides with a petrographic; microscope. Again, certain diabase dikes which cut the norite and. the foot-wall formations cannot be easily or with certainty distin-

Jan 11, 1913

By Colin Baker, G. C. Smith

Investigation of the initiation and propagation of ductile failure in OFHC copper was undertaken to determine the role of nonmetallic inclusions. The effect of inclusion initiated voids on the formation of the internal cavity and the final shear separation was studied by metallographic eranzination of strained test pieces. A strain anneal technique was used to enlarge the voids under uniaxial stress conditions to elinzinate triaxial stress effects. Measurements of void size us stress and strain were made to show the point at which void im'tiation begins and becomes an important factor in the deformation process. The work of separation of copper-cuprous oxide was determined to attempt to correlate the breakdown of the matrix inclusion interface with void initiation and propagation. The zloid shape and position relative to the tensile axis suggested an interface breakdown mechanisnz of initiation. Evidence is presented that shows a basic similarity between the central cavity propagation and the 45-deg shear portions of the failure. DUCTILE fracture has been studied by a number of workers1-lo and attention drawn to the importance of hard second phase particles in the initiation of the failure. Holes formed at the matrix-particle interface can elongate by plastic deformation and then subsequently expand sideways to link up and produce a major crack. This is usually observed first in the center of the macroscopically necked region of a test-piece where the hydrostatic stresses are at a maximum. As the crack spreads sideways towards the free surface of the specimen, well defined shear zones develop from the crack tip and the final separation is along a direction at approximately 45 deg to the stress axis. This shear failure may also be associated with voids formed adjacent to second phase particles. In this way a cup and cone type fracture is produced. The stage at which separation takes place between particles and the surrounding matrix has not been clearly identified. In addition, although researchers have dealt with anisotropy of tensile behavior" as a result of material fabrication variables, not much is known about the microstructural features of aniso-tropic behavior. In the present work evidence on these points is presented in relation to the behavior of copper containing second phase particles of cuprous oxide. I. MATERIALS AND PROCEDURES EMPLOYED The material used was +-in. diam or 2-in. sq cold-drawn OFHC copper bar which contained 0.6 pct by volume of cuprous oxide inclusions. These ranged in COLIN BAKER, Junior Member AIME, formerly at -mnF of Metallurgy, University of Cambridge, Cambridge, England, is presently Research Scientist Reynolds Metals Co., Richrnand, Va. G. C. SMITH, Member AIME, is Senior Lecturer, Department of Metallurgy, University of Cambridge. Manuscript submitted June 20, 1967. IMD size from approximately 1 to 6 p in length and 1 to 4 p in width. The shape was generally slightly ovoid. Tensile tests were made on specimens having a gage length of 2.5 cm and diameter of 0.643 cm. Metallographic examination was carried out by sectioning deformed and fractured specimens; in addition fracture surfaces were examined optically and with a scanning electron microscope. Some measurements of the work of separation between copper and cuprous oxide were made, using a sessile drop technique which was a modification of that used by Kingery and umenick." The best metallographic results were obtained by using a vibratory polisher, which minimized smearing of the surface. 11. RESULTS A) Initial Experiments. Specimens from the +-in. diam rod were annealed for 2 hr at 650°C in uacuo, at which temperature complete recrystallization occurred without any change in the form of the inclusion. They were then fractured at temperatures from -190" to 600°C. Cup and cone fractures were obtained at all temperatures from -196" to 400°C. With increase in temperature there was, however, a continuous increase in the extent of the central transverse area and a corresponding decrease in the shear portion of the fracture. Above 400°C, the fractures became intergranular. Sections of specimens tested below 400°C revealed extensive small voids which were always associated with inclusions. However, the voids only reached dimensions greater than the inclusion size in the region of the macroscopic neck, where they were many times longer. Lateral expansion was found only near the fracture surface of the test pieces. As observed by Puttick, the voids were either (a) triangular holes initiated in the direction of the tensile axis and elon-

Jan 1, 1969

By J. F. Smith, J. E. Davison

The heat capacity of CaMg2 was measured over the temperature interval, 4.8° to 287°K, by the technique of low-temperature adiabatic calorimetry. Heat content measurements were performed with a drop calorimeter over the temperature interval, 273" to 673°K. From these data the thermodynamic functions, (FT - H0)/T, ST - So, and & - Ho, were evaluated. A third-Law calculation of the standard entropy of formation of CaMg2 yields a value of -0.25 * 0.06 cal per (°K g-atom) , and the free-energy function derived from this study when combined with existing equilibria data yields a value for the standard enthalpy of formation which is in agreement with direct calorimetric enthalpy measurements. The accompanying paper' shows that the enthalpy of formation of CaMg2 has been determined with good precision by three different calorimetric techniques.'-= TWO independent determinations of the Gibbs free energy of formation of CaMg2 have also been made; both determinations were based on vapor pressure measurements, being in one case hydrogen vapor pressures over ternary Ca-Mg-H alloys4 and in the other case magnesium vapor pressures over binary Ca-Mg alloys.5 The present determination of heat capacity of CaMg2 below room temperature and of the heat content of CaMg2 above room temperature was undertaken to provide supplementary data. These data are useful in their own right but can in addition be used to evaluate an entropy of formation for CaMg2 which, because of the interrelation of free energy, enthalpy, and entropy, can be used as a check of the self-consistency of the composite of the presently available information. LOW-TEMPERATURE HEAT CAPACITY The heat capacity of CaMg2 was measured over the temperature interval 4.87° to 286.64°K in an adiabatic calorimeter. The physical details of the calorimeter and the experimental procedure for measuring the heat capacity of a specimen have been adequately described by Gerstein et a1.6 The source and purity of the calcium and magnesium are described together with the methods of sample preparation and chemical analyses in the accompanying paper.' Results of chemical analyses of the material which was used in the present investigation are shown in Table I. These analyses show that, on the basis of the published phase diagram,7 the heat capacity sample contained a slight excess of a calcium while the heat content sample contained a slight excess of magnesium. However, in both cases the excess was small, and X-ray diffraction patterns showed reflections which were without exception attributable to CaMg2. The sample which was used for heat capacity measurements weighed 69 g while the sample container and addenda weighed 132 g. The sample was in the form of annealed powder, 50 to 60 mesh, and was sealed into the sample container under 0.1 atm of helium. Copper fins inside the sample container facilitated thermal equilibrium of the powdered Sample. Time intervals of the order of 10 min were required for thermal equilibration, and such times are normal for this calorimeter regardless of the form of the sample. The observed heat capacities were corrected for the small excess of a calcium through use of the heat capacity values tabulated by Hultgren et a1.8 The corrected heat capacities are tabulated as a function of temperature in Table II. The free-energy function and the absolute entropy of CaMg2, which were calculated from the experimental heat capacity data, are listed in Table 111. A smooth curve was fitted to a plot of the experimental values of the heat capacity and in only two instances above 30°K did the plotted points deviate from the curve by more than 0.2 pct. Below 10°K the deviation of several of the points was as much as 50 pct. These large percentage deviations were attributed to the small value of the heat capacity and to the low sensitivity of the platinum resistance thermometer in this temperature range. The deviations in the region of 10°to 30°K were less than 5 pct. Although the percentage deviations of some of the low-temperature measurements are large, the actual value of these deviations is small since the magnitude of the heat capacity in that temperature range is small. The error in the value of the third-law entropy at 298.15°K was estimated to be less than 0.01 cal per (°K g-atom). A value of -0.25 ±0.06 cal per (°K g-atom) was obtained for the standard entropy of formation at 298.15°K from the relation:

Jan 1, 1969

By A. H. Larson, R. J. McClincy

Laboratory-scale decopperizing experiments with multiple sulfur addifions were conducted at 330°C on ternary Pb-Cu alloys containing, as the third elenlent, Sn, Ag, As, Sb, Bi, Zn, and Au, common impurities in lead blast-furnace bullion. For silver and tin, an increased rate and extent of 'cofifier removal was obsert3ed. The elements As, Sb, Zn, Au, and Bi had no effect or less effect as compared to sulfur additions with no i)npurily additions. THE production of primary lead in the blast furnace yields an impure lead frequently containing such impurities as copper. antimony. arsenic. tin, gold, silver iron, oxygen. and sulfur. By cooling this lead to a temperature near its melting point. most of the iron, sulfur, and oxygen and part of the other impurities are removed in the form of a dross. With incipient solidification of the lead, the copper concentration wil have been reduced to 0.02 to 0.05 pct. depending upon the concentration of the other impurities. according to Davey.' Since copper interferes with the treatment of silver after the desilverizing process, it is desirable to decrease the copper content of the lead still fur-ther before the lead is desilvered. The decopperizing of the lead is accomplished by stirring a small quantity. approximately 0.1 pct. of elemental sulfur into the lead at a temperature near its melting point, 330" to 360°C. The copper is removed as a copper sulfide which constitutes a small fraction of a voluminous dross consisting mostly of lead sulfide and entrained metallic lead. The residual copper concentration following the decopperizing operation is frequently as low as 0.001 to 0.005 pct. Thi fact has aroused considerable interest because the equilibrium copper concentration of lead in contact with solid PbS and solid Cu2S is at least an order of magnitude greater, 0.05 pct Cu at 330C. 1, 2 Most investigators have suggested that various impurities in the lead bullion are responsible for the very low copper concentrations frequently encountered in practice. There is little agreement, however? as to which of the impurities are helpful and which are not.3"11 Also. few investigators have sought to explain the mechanisms responsible for the removal of copper to very low concentrations. Willis and Blanks9 have proposed that a nonstoichiometric copper-deficient cuprous sulfide forms in place of the supposed Cu2S. Being copper-deficient, this sulfide phase would possess a low copper activity, and the diffusion of copper dissolved in the liquid lead into this phase would be greatly facilitated. Pin and wagner2 have investigated the removal of copper from liquid lead by studying the effect of impurity-doped lead sulfide on the decopperizing of pure Pb-Cu alloys. Samples of the doped PbS were held in contact with copper-saturated lead for 1 week at 33'7°C. They reported a beneficial effect on decopperizing with bismuth and antimony and no effect with tin or silver. which is directly opposite to the results observed in practice and those reported by Davey 3 and this studv. The purpose of this paper is to describe the effects of certain additive elements on the extent to which copper can be removed fro111 liquid lead by successive additions of sulfur. The impurity elements were added individually to prepared Pb-Cu alloys. The resulting ternary alloys as well as a binary Pb-Cu alloy were then decopperized with repeated additions of sulfur. EXPERIMENTAL Materials. Granulated test lead with a purity of 99.999 pct and the additive elements Cu. Ag. Sb. Bi. Zn. Sn. and Au with purities of 99.99 pct were American Smelting and Refining Co. research-grade materials. The major impurities in the lead were 1 ppm each of iron and copper. all others being less than 1 ppm. The arsenic used was a technical-grade arsenic of 98+ pct purity. Reagent-grade flowers of sulfur were melted under argon to provide small pieces free of fines. Apparatus. The decopperizing experiments were carried out in a 25-mm-OD by 375-mm-long Pyrex tube sealed at one end. The tube was mounted vertically in a resistance-heated. hinge-type tube furnace controlled to within ±lcC. Temperature measurement was accomplished by means of a standardized chromel-alumel thermocouple sealed into the base of a silica. paddle-type stirring rod. All decopperizing experiments were carried out under an argon atmosphere. Procedure. A Pb-Cu starting alloy containing 0.05 pet Cu was prepared under carbon and poured into cold tap water to produce shot. The ternary alloys were prepared by melting together 100 g of the starting alloy and a sufficient amount of the impurity element to yield the desired concentration. The resulting alloy was then homogenized in a Pyrex tube at 450C with continuous stirring. The furnace temperature was then lowered to the operating temperature of 330°C. When thermal equilibrium had been obtained at the operating temperature, individual additions of 0.2 pct (0.2 g) of solid sulfur were added to the melt and stirred in. Stirring was continued for a period of 3 min. discontinued for 5 min. and resumed for the remaining 2 min of a 10-min cycle. This cycle was repeated for as many sulfur additions as desired. When the decopperizing experiment had been completed the lead bullion was quenched and samples of the bullion and dross phases were taken for analysis. Results. The results obtained in the decopperizing

Jan 1, 1970

By A. H. Geisler, F. Keller

Some of the important changes that take lace in the structure of aluminum alloys are largely submicroscopic in character. This is especially true of the changes that accompany age-hardening and recrys-tallization. Although improved metal-lographic practices have been helpful in indicating some of these changes indirectly, results are limited by the resolving power of optical microscope lenses. The electron microscope, however, provides a new and important means for investigating the fine structure of metals in a range not possible heretofore. It is anticipated that this microscope will yield new and useful information to metallurgists when suitable techniques are developed to utilize its very high resolving power. Several unique methods have been devised to permit the examination of the structure of opaque samples by the electron microscope. These are all based 011 the principle of producing a very thin film that represents the prepared surface of the opaque metal sample, which can be examined in the transmission microscope; however, the available methods fall into three categories, depending on the manner in which the film is obtained. With the oxide-film method developed by Mah13-l7 a very thin surface layer of the metallographic sample is converted into oxide by a thermal, chcmical or anodic treatment. .After removal from the metal sample by one of the special techniques described by Evans,l9 this oxide film is examined in the electron microscope, and is found to portray the structure of the original metal surface. Films formed on aluminum,8,l7 nicke1,7 iron3,8,9 and a nickel-beryllium alloyl1 by heating; films formed on iron8,9 by chemical action; and films formed on aluminum3-'" by anodic oxidation, have been examined. The other two are more recent methods developed principally in this country; they consist in making the thin film in the form of a mold or replica of the surface contour of an etched sample. With the negative replica method the thin film is made directly on the sample; with the positive replica method it is made on a negative reproduction of the sample. With both methods, variations in the contour of the metal sample, caused mainly by etching, produce variations in the thickness of the surface replica. Because of the direct dependence of the amount of scattering of the illuminating electrons upon the thickness of the film penetrated, only the variations in thickness of the replica are responsible for tones in the electron image. Negative replicas are made by forming a thin film of some suitable material directly on the polished and etched metal sample, and derive their name from the fact that after removal from the sample they have the high and low points in the sample reversed, as shown in Fig. I. Nega-

Jan 1, 1944

By F. Keller, A. H. Geisler

Some of the important changes that take lace in the structure of aluminum alloys are largely submicroscopic in character. This is especially true of the changes that accompany age-hardening and recrys-tallization. Although improved metal-lographic practices have been helpful in indicating some of these changes indirectly, results are limited by the resolving power of optical microscope lenses. The electron microscope, however, provides a new and important means for investigating the fine structure of metals in a range not possible heretofore. It is anticipated that this microscope will yield new and useful information to metallurgists when suitable techniques are developed to utilize its very high resolving power. Several unique methods have been devised to permit the examination of the structure of opaque samples by the electron microscope. These are all based 011 the principle of producing a very thin film that represents the prepared surface of the opaque metal sample, which can be examined in the transmission microscope; however, the available methods fall into three categories, depending on the manner in which the film is obtained. With the oxide-film method developed by Mah13-l7 a very thin surface layer of the metallographic sample is converted into oxide by a thermal, chcmical or anodic treatment. .After removal from the metal sample by one of the special techniques described by Evans,l9 this oxide film is examined in the electron microscope, and is found to portray the structure of the original metal surface. Films formed on aluminum,8,l7 nicke1,7 iron3,8,9 and a nickel-beryllium alloyl1 by heating; films formed on iron8,9 by chemical action; and films formed on aluminum3-'" by anodic oxidation, have been examined. The other two are more recent methods developed principally in this country; they consist in making the thin film in the form of a mold or replica of the surface contour of an etched sample. With the negative replica method the thin film is made directly on the sample; with the positive replica method it is made on a negative reproduction of the sample. With both methods, variations in the contour of the metal sample, caused mainly by etching, produce variations in the thickness of the surface replica. Because of the direct dependence of the amount of scattering of the illuminating electrons upon the thickness of the film penetrated, only the variations in thickness of the replica are responsible for tones in the electron image. Negative replicas are made by forming a thin film of some suitable material directly on the polished and etched metal sample, and derive their name from the fact that after removal from the sample they have the high and low points in the sample reversed, as shown in Fig. I. Nega-

Jan 1, 1944

By Charles M. Brown, Russell Franks, W. O. Binder

Occasionally in the application of the austenitic chromium-nickel steels to corrosive conditions, failures have occurred by cracking without serious general over-all attack of the metal. As pointed out by Foyt and Scheil(1),2 and by Scheil, et al.(2) as well as by Hodge and Miller(3), the stress-corrosion failures that have occurred have been limited in number, and have taken place only when the steels were exposed to certain corrodents. These investigators have stated that while stress- corrosion cracking can be intergranular in nature and originate at the grain boundaries of the austenitic chromium-nickel steels, it can also take place in trans- granular fashion. They have shown that the cracking may be either initiated at the grain boundaries and may propagate along grain boundaries for some distance and then suddenly extend across grains, or it may begin in a transgranular fashion and suddenly proceed along grain boundaries until the cracking stops. Their data further show that when austenitic stainless steel is subject to intergranular attack, stress will concentrate and cause cracking in service. These investigators have studied the effect of the metals titanium and columbium which are added to the steels to impart immunity to intergranular attack, and molybdenum which is added to improve resistance to general corrosion.

Jan 1, 1945

By Robert Livermore

IT has been a noteworthy feature of the Cobalt camp, that many of the valuable ore deposits have been covered, wholly or in part, by small but usually deep lakes, such as Cobalt, Cart, and Peterson lakes, and with the subject of this article, Kerr lake. In the early days of the camp many water-covered areas, which have since been found to be valuable, were ignored, or neglected by owners, or simply perfunctorily staked for water rights. Kerr lake is probably the evidence of a fault or sharp fold, having a general east and west strike, and containing a series of ore-bearing fissures, parallel generally to the strike, although having some notable exceptions to the general rule. On the north side of Kerr lake the formation is of diabase, while on the south side it is of Huronian slates and conglomerates. These Huronian measures extend out under the lake, dipping gently to the north to a lateral distance not yet definitely determined, owing to the lack of development under the deepest parts of the lake. Probably the contact between the diabase and Huronian or else between the former and the .underlying Keewatin formation occurs somewhere near the center of the lake. Kerr lake originally covered 45 acres. Of this the Kerr Lake Mining Co. owned 12, the Drummond Mine, 7, and the Crown Reserve Mining Co. the remainder of 26 acres. Since the latter's property was originally entirely under water, it was necessary for the owners to make land for buildings and shaft room. Accordingly, in 1908, a trench was blasted out which deepened the outlet, and lowered the lake 8 ft. As many of the rich veins of the Crown Reserve and Kerr Lake companies were under water, mining was pursued under some disadvantages. Fortunately the rock is tight and solid, and mining has been done sufficiently far from the surface to avoid unnecessary risk. Nevertheless, there was always danger of encountering open seams, through which too large a flow of water for comfortable working might come. Careful soundings were made over the veins, y means of steel-shod pipe, through mud and water to bedrock, but there was sometimes an element of uncertainty as to whether actual bedrock had been reached. Furthermore, the necessity of leaving safe backs between workings and lake tied up large quantities -of-ore, -and- made development- in certain

Jan 7, 1914

By Robert Livermore

It has been a noteworthy feature of the Cobalt camp, that many of the valuable ore deposits have been covered, wholly or in part, by small but usually deep lakes, such as Cobalt, Cart, and Peterson lakes, and with the subject of this article, Kerr lake. In the early days of the camp many water-covered areas, which have since been found to be valuable, were ignored or neglected by owners, or simply perfunctorily staked for water rights. Kerr lake is probably the evidence of a fault or sharp fold, having a general east and west strike, and containing a series of ore-bearing fissures, parallel generally to the strike, although having some notable exceptions to the general rule. On the north side of Kerr lake the formation is of diabase, while on the south side it is of Huronian slates and conglomerates. These Huronian measures extend out under the lake, dipping gently to the north to a lateral distance not yet definitely determined, owing to the lack of development under the deepest parts of the lake. Probably the contact between the diabase and Huronian or else between the former and the underlying Keewatin formation occurs somewhere near the center of the lake. Kerr lake originally covered 45 acres. Of this the Kerr Lake Mining CO. owned 12, the Drummond Mine, 7, and the Crown Reserve Mining CO. the remainder of 26 acres. Since the latter's property was originally entirely under water, it was necessary for the owners to make land for buildings and shaft room. Accordingly, in 1908, a trench was blasted out which deepened the outlet, and lowered the lake 8 ft. As many of the rich veins of the Crown Reserve and Kerr Lake companies were under water, mining was pursued under some disadvantages. Fortunately the rock is tight and solid, and mining has been done sufficiently fay from the surface to avoid unnecessary risk. Nevertheless, there was always danger of encountering open seams, through which too large a flow of water for comfortable working might come. Careful soundings were made over the veins, by means of steel-shod pipe, through mud and water to bedrock, but there was sometimes an element of uncertainty as to whether actual bedrock had been reached. Furthermore, the necessity of leaving safe backs between workings and lake tied up large quantities of ore, and made development in certain

Jan 1, 1915

By Frederick Forscher

Frederick Forscher (Nuclear Materials and Equipment Gorp.)—It is gratifying to see another series of experimental results that essentially reconfirms our reported observations of "Strain-Induced Hydrogen Embrittlement in Zirconium" (F. Forscher: AIME Trans., 1956, vol. 206, p. 536, noted as Ref. 3 of paper). However, several important considerations may have been overlooked, or—at least—have not been specifically pointed out. It is the purpose of this discussion to present some of these considerations. The statement is made that "the equilibrium concentration of hydrogen in solution at 20°C in zirconium is approximately 10 ppm; i.e., no zirconium hydride precipitates are formed at or below this hydrogen content." This is perhaps the case in the unstressed condition. In the presence of triaxial (plastic) strain however, even as little as 1.4 ppm H2 (Forscher's Figs. 6 and 11) will cause porosity near fracture in 20°C tests. The necked-down region that develops during a tensile test provides the triaxiality necessary for these pores to open. Both Beevers' and Forscher's micrographs show that porosity is concentrated in the necked region. So-called "pure zirconium" containing about 10 ppm H2 also shows pronounced porosity near fracture (Beevers' Fig. 3). Since it is generally agreed that such porosity is

Jan 1, 1965

By W. H. Hough, P. B. Leavenworth

Development in the Upper Texas Gulf Coast during 1943 resulted in the discovery of 11 new fields as compared with 12 discovered in the same area during I942. Of the 11 new fields, eight are classed as oil and/or condensate and three as gas fields. In addition to the new discoveries, several more or less important new horizons and extensions were encountered in some of the older fields, as noted in the text under the heading "New Pays and Extensions.'' Drilling During the year, 418 wells were drilled, as compared with 356 drilled during 1942. Of these, 323 were field wells, of which 188 produced oil, 21 were gas wells and 114 were dry holes. The remaining 95 viere wildcats, 12 of which produced oil, 4 produced gas and 79 dry holes. Distribution of themwildcats with respect to the various trends may be summarized as follows: over the 91,340,492 bbl. produced in the same area during 1942. The production statistics in the text and the accompanying tables include condensate or distillate as oil production, because many Gulf Coast fields produce oils with a wide variation of specific gravities, all of which are commingled in pipe lines. Table 3 shows by counties all of the drilling and production" data applicable to this particular area. Outstanding Fields of 1943 The Upper Texas Gulf Coast covered in this report has 178 more or less active oil and gas fields, including the 1943 discoveries. Of these Table 4 lists those that were most important from the standpoint of production. Each of these fields pro duced in excess of one million barrels of oil during 1943. Some of the interesting facts to be noted from this list of some 26 oil fields are: (I) four of the fields— namely, Conroe, Hastings, Friendswood and Thompson—each produced more than 10 million barrels during 1943, whcrcas Conroe and Hastings were the only fields that produced 10 million barrels during 1942; (2) some of the older fields (discovered prior to 1920), such as Barbers Hill, West Columbia, and Hull, are still producing in excess of one million barrels annually; (3) some of the fields more than doubled their 1942 production—e.g., Anahuac and Friendswood. The large increase in production in practically all instances is the result of increased allowables from wells drilled prior to 1943 and

Jan 1, 1944

By W. H. Hough, P. B. Leavenworth

Development in the Upper Texas Gulf Coast during 1943 resulted in the discovery of 11 new fields as compared with 12 discovered in the same area during I942. Of the 11 new fields, eight are classed as oil and/or condensate and three as gas fields. In addition to the new discoveries, several more or less important new horizons and extensions were encountered in some of the older fields, as noted in the text under the heading "New Pays and Extensions.'' Drilling During the year, 418 wells were drilled, as compared with 356 drilled during 1942. Of these, 323 were field wells, of which 188 produced oil, 21 were gas wells and 114 were dry holes. The remaining 95 viere wildcats, 12 of which produced oil, 4 produced gas and 79 dry holes. Distribution of themwildcats with respect to the various trends may be summarized as follows: over the 91,340,492 bbl. produced in the same area during 1942. The production statistics in the text and the accompanying tables include condensate or distillate as oil production, because many Gulf Coast fields produce oils with a wide variation of specific gravities, all of which are commingled in pipe lines. Table 3 shows by counties all of the drilling and production" data applicable to this particular area. Outstanding Fields of 1943 The Upper Texas Gulf Coast covered in this report has 178 more or less active oil and gas fields, including the 1943 discoveries. Of these Table 4 lists those that were most important from the standpoint of production. Each of these fields pro duced in excess of one million barrels of oil during 1943. Some of the interesting facts to be noted from this list of some 26 oil fields are: (I) four of the fields— namely, Conroe, Hastings, Friendswood and Thompson—each produced more than 10 million barrels during 1943, whcrcas Conroe and Hastings were the only fields that produced 10 million barrels during 1942; (2) some of the older fields (discovered prior to 1920), such as Barbers Hill, West Columbia, and Hull, are still producing in excess of one million barrels annually; (3) some of the fields more than doubled their 1942 production—e.g., Anahuac and Friendswood. The large increase in production in practically all instances is the result of increased allowables from wells drilled prior to 1943 and

Jan 1, 1944

By Samuel Taylor

IT is customary for the president of an engineering society, in his annual address, to describe either some engineering problem with which he has beer connected or to review the work of the society during his administration. My first thought, this being the sesquicentennial year of our nation, was to review the advance in coal mining for the past fifty years, during which period I have been more or less intimately con-nected with the bituminous coal industry, and have personally witnessed most of the great changes which have occurred in methods and machinery used in the production of coal, but preparation of the requisite address would take more time than could be spared to prepare it, and its presentation would consume so much time that it .would not be suitable. The new arrangement providing for giving the presi-dent's address at the business meeting makes it more .appropriate to review the work of the Institute during the past year, together with some suggestions which appeal to me as being of advantage to the future wel-fare of the Institute, which I will try to do briefly. The work of the business office has been reviewed in the Secretary's report and it will not be necessary for me to dwell on it. Suffice it to say, it seems to be going along very well. Additional work could be done which would be to the advantage of the Institute, if we had the money with which to defray the necessary ex-pense incident to it, but I will refer to this again later. I would be derelict if I did not refer to the splendid work of the Secretary and the Assistant Secretary. Keeping in touch with all the sections, which number now about 26, and affiliated student societies which number 40, besides special committees, and represent-ing the Institute on various boards, provides work enough to occupy the Secretary's time almost exclu-sively. In addition to this the Secretary and the As-sistant Secretary have the work of editing and publishing the TRANSACTIONS of the Institute; the issuing of the magazine, MINING AND METALLURGY, in the splendid manner in which it goes out to the mem-bership is no light task and I think they should receive the commendation of the membership for this work.

Jan 3, 1927