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By F. N. Rhines, A. H. Grobe

At elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible1 and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscaleiormation) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detai1.5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the 1-6 and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 40 alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. Experimental Procedure Silver.—The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942

By A. H. Grobe, F. N. Rhines

At elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing. When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible1 and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver. Norbury2 and Leroux and Raub3 have reported internal oxidation (subscaleiormation) in alloys of silver with 2, 7.5, and 30 per cent of copper. The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver.4 Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation. Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detai1.5,6 The present research confirms this anticipation. The oxidation of a series of 20 dilute alloys of silver has been studied metallographically; some types of subscale not encountered among the copper alloys have been found. Instances of internal oxidation in alloys of most of the metals of the 1-6 and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking. A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation; i.e., they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them. In a study of 40 alloys of these white metals only a few cases of internal oxidation have been found. The probable reasons for this difference in behavior will be discussed presently. Experimental Procedure Silver.—The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99.993 per cent Ag)* and the purest avail-

Jan 1, 1942

By Alwyn Birchmore Cox, Ian William Wark

In defending the chemical theory of flotation, Taggart, del Giudice and Ziehl have criticized1 the views of those who prefer to attribute the effects of certain flotation agents to adsorption. Perhaps with some justification, they describe the latter term as the "haven of refuge of writers lost in a morass of shaky experiment and muddy thinking." We prefer to regard it, however, as a haven of refuge for writers who seek a conventional term to describe the formation of films of flotation reagents on solid surfaces, because in many cases it is not yet possible to specify the forces that hold them there. Originally, as Taggart and his associates state, adsorption connoted a concentration difference and nothing more. In recent years, workers in the field of surface chemistry have tacitly added other meanings, and they now speak of orientated adsorption of unimolecular films on a solid sub-strate, of chemi-adsorption, and of exchange adsorption. Thus the term adsorption may connote simply the Gibbs layer of excess concentration at the surface of a solution, or a unimolecular film at the surface of a solid. Perhaps this has led to the misunderstanding of Taggart, del Giudice and Ziehl concerning the relationship between surface tension and adsorption at solid surfaces. The change in "surface tension" accompanying adsorption at a liquid surface can be used as a measure of the adsorption, and the Gibbs equation as quoted by these authors correlates these two conceptions. But, to correlate two conceptions docs not necessarily imply an attempt to explain either, although sometimes such an "explanation" is carelessly inferred. Use of "surface energy per unit area" instead of the numerically equal but more difficult and less definite conception of "surface tension per unit length " would lessen many of the present difficulties. (Compare with Adam.2) At interfaces involving a solid phase, neither '" surface tension " nor " interfacial tension "can have any meaning, but the conception "interfacial energy per unit area" call be understood by anyone who is familiar with the concept of free energy. While it is true that surface energy cannot be directly measured at a solid surface,

Jan 1, 1939

By Ian William Wark, Alwyn Birchmore Cox

In defending the chemical theory of flotation, Taggart, del Giudice and Ziehl have criticized1 the views of those who prefer to attribute the effects of certain flotation agents to adsorption. Perhaps with some justification, they describe the latter term as the "haven of refuge of writers lost in a morass of shaky experiment and muddy thinking." We prefer to regard it, however, as a haven of refuge for writers who seek a conventional term to describe the formation of films of flotation reagents on solid surfaces, because in many cases it is not yet possible to specify the forces that hold them there. Originally, as Taggart and his associates state, adsorption connoted a concentration difference and nothing more. In recent years, workers in the field of surface chemistry have tacitly added other meanings, and they now speak of orientated adsorption of unimolecular films on a solid sub-strate, of chemi-adsorption, and of exchange adsorption. Thus the term adsorption may connote simply the Gibbs layer of excess concentration at the surface of a solution, or a unimolecular film at the surface of a solid. Perhaps this has led to the misunderstanding of Taggart, del Giudice and Ziehl concerning the relationship between surface tension and adsorption at solid surfaces. The change in "surface tension" accompanying adsorption at a liquid surface can be used as a measure of the adsorption, and the Gibbs equation as quoted by these authors correlates these two conceptions. But, to correlate two conceptions docs not necessarily imply an attempt to explain either, although sometimes such an "explanation" is carelessly inferred. Use of "surface energy per unit area" instead of the numerically equal but more difficult and less definite conception of "surface tension per unit length " would lessen many of the present difficulties. (Compare with Adam.2) At interfaces involving a solid phase, neither '" surface tension " nor " interfacial tension "can have any meaning, but the conception "interfacial energy per unit area" call be understood by anyone who is familiar with the concept of free energy. While it is true that surface energy cannot be directly measured at a solid surface,

Jan 1, 1939

By B. A. Stainton, John D. Gill

OUR combined economic activities have as their goal the maximum of individual well-being and national security. In this age of intense international competition the two objectives are closely related. For many decades, the maximum of well-being and ability to maintain national security have moved generally upward. The best single measure-perhaps the only adequate measure -of the level of the rising goal is the per capita real national income (national income corrected for price changes). For centuries before the industrial revolution the income of the world's population changed little from generation to generation. In our country prior to 1800 the growth of national income was hardly measurable from decade to decade. Since 1850, perhaps since the "industrial revolution," the growth of per capita real income has been increasing geometrically. Of major importance is the accelerative growth of the productive ability of our economy. Inadequate consideration of its implications is partly responsible for periodic delays in solving our princi-

Jan 1, 1946

By C. A. Heiland

Measurements of gravity with gravimeters have come into increased use in this country and abroad in the past five years. Probably 100 to 125 gravimeter parties are working in the United States alone. In oil exploration, gravimeter methods have relegated the gravity pendulum definitely to second place, if not third, and now closely rival and possibly surpass the torsion balance in many applications. Gravimeters have lately been applied in mining, although it is doubtful whether they will ever replace electrical or magnetic methods in this work. Notwithstanding the widespread application of gravimeters, there has been no article covering the entire field in the domestic or foreign literature. The purpose of this paper is to meet the demand for comprehensive engineering information on the subject. The working principles of a number of gravimeters will be illustrated and treated in relation to the action of corresponding seismometers and astatization methods. The mathematical discussion of theory has been confined to the most necessary fundamentals and been given in as elementary form as possible. A description of calibration methods constitutes the last part of the paper. The symbols shown at the top of page 197 will be used in equations throughout the paper. Dynamic and Static Gravity Methods Methods of measuring gravity fall into two groups: dynamic and static methods. The first group involves the measurement of time. Examples are: determinations of the period of oscillation of a pendulum, measurements involving the free fall of a body, and comparisons of gravity with the centrifugal force of a rotating body. Measurements in the second group of gravity methods are concerned with deflections of certain indicators when the force of gravity is in equilibrium with another comparison force.

Jan 1, 1940

By C. A. Heiland

Measurements of gravity with gravimeters have come into increased use in this country and abroad in the past five years. Probably 100 to 125 gravimeter parties are working in the United States alone. In oil exploration, gravimeter methods have relegated the gravity pendulum definitely to second place, if not third, and now closely rival and possibly surpass the torsion balance in many applications. Gravimeters have lately been applied in mining, although it is doubtful whether they will ever replace electrical or magnetic methods in this work. Notwithstanding the widespread application of gravimeters, there has been no article covering the entire field in the domestic or foreign literature. The purpose of this paper is to meet the demand for comprehensive engineering information on the subject. The working principles of a number of gravimeters will be illustrated and treated in relation to the action of corresponding seismometers and astatization methods. The mathematical discussion of theory has been confined to the most necessary fundamentals and been given in as elementary form as possible. A description of calibration methods constitutes the last part of the paper. The symbols shown at the top of page 197 will be used in equations throughout the paper. Dynamic and Static Gravity Methods Methods of measuring gravity fall into two groups: dynamic and static methods. The first group involves the measurement of time. Examples are: determinations of the period of oscillation of a pendulum, measurements involving the free fall of a body, and comparisons of gravity with the centrifugal force of a rotating body. Measurements in the second group of gravity methods are concerned with deflections of certain indicators when the force of gravity is in equilibrium with another comparison force.

Jan 1, 1940

By Donald L. Ball

The equilibrium of boron nitride, gaseous nitrogen, and solute boron was investigated in Fe, Fe-C, and Fe-Si rnelts by the Sieverts technique. The free ellergy of dissociation of boron nitride, involving -the implied standard states, was evaluated in the range 1400" to 1600°C as: ?Fo = 38,000 - 23.5T, cal ber mole The solute-solute interaction coefficients eBB, ecB , and eg were determined as 0.058, 0.22, and 0.078, respectively. BORON is an important ingredient in some types of steel and cast iron. It was employed at a particularly high level, 0.01 wt pet, in the as-cast malleable iron "CentraSteel".1 In this material, the boron concentration was critical in order to assure graphite, and avoid primary cementite, in the as-cast structure. One possible function of the boron in this alloy was the nucleation of graphite through the agency of boron nitride, which, conceivably, precipitated from the melt during cooling. A research program was instituted to assess the validity of this proposed mechanism. The first undertaking, reported here, was a determination of the thermodynamic possibility of boron nitride precipitation. Data available in the literature on the activity coefficient of solute boron in iron-base melts are inadequate for the present purpose. They will be reviewed briefly, however, so that comparison can be made, when

Jan 1, 1968

By R. M. Brick, R. G. Treuting

DESPITE the basic importance of slip in the plastic deformation of metals, and the considerable experimental investigation, thought, and speculation that have been devoted to the fundamental nature of these processes, surprisingly few data have been reported regarding the microscopic appear- [ ] ance and distribution of slip lines,[$] the external manifestation of the slip process. Photographs hitherto reproduced in the literature are in general at low or unspecified magnifications with no correlation to the prior shear. A single-crystal cylindrical tensile specimen of alpha brass about ½ in. in diameter, one of many previously prepared by H. L. Burghoff,1 was available for study. A plane about 3/16 in. wide, parallel to the specimen axis and normal to the plane containing the slip direction and the specimen axis, was ground and metallographically polished along the entire 5-in. gauge length. Heavy etching produced a surface free of both scratches and flow. The specimen was strained in tension until slip markings first became visible on the polished surface (Figs. I and 2). Restressing the crystal caused additional markings to appear at an initially lower [ ] stress than previously was required. Stretching the specimen to produce a dense concentration of slip lines caused such variations in level in the polished surface (normal to the slip direction) that microscopic study at higher magnifications became impossible. After annealing 15 hr. at 850°C., the specimen recrystallized to form two grains with a boundary approximately normal to the specimen axis and about midway along its length. Each was X-rayed, and two planes were again polished along the length of the specimen, in this case each parallel to the slip direction in one of the two crystals. A light longitudinal scratch parallel to the specimen axis was drawn down the center of each plane. A Huggenberger extensometer was attached to the crystal A, whose slip plane would have the higher resolved shear stress of the two, and the specimen was again strained in tension.

Jan 1, 1941

By P. G. Shewmon, W. M. Robertson

The derivative of the surface tension with orientation, ??/??, for copper has been measured over the entire unit triangle. This derivative or torque term was determined from the variation of the dihedral angles at the intersection of twin boundaries and free surfaces. High-temperature anneals in graphite with a hydrogen atmosphere gave torque terms of 0.097 at (111), 0.066 at (100), and 0.0257 at (110). A variation from -36oto +23oC in the dew Point of the H2 had no effect on these values, nor did a change from 99.98 to 99.999 pct Pure copper. The removal of graphite from the system decreased ??/?? slightly. Considering the surface near a low-index plane to be smooth except for occasional steps, the free-energy increment per cm of step is calculated, and it is shown that the observed variation of ??/?? is consistent with a random distribution of steps and an interaction energy between steps. Integration of ??/?? gave the relative values of y at (100), (110), and (111) as comPared to ymax: (Y111/Ymax) =0.974, (Y110/Ymax) =0.996, (y100/Ymax) = 0.983. The ratio of the surface tension of coherent twin boundaries to the surface tension of the free surface was found to be (yT/ys) = 0.027 * 0.011. In a crystalline solid the surface tension y (surface free energy per unit area) depends on the orientation of the surface relative to the crystallographic axes of the crystal. Measurements of this variation of y with surface orientation have been reported for metals only within the last few years. Consider the grain boundary groove shown in Fig. 1. Here the three surfaces are all normal to the plane of the paper, and each has a different surface tension, y1, y2, and y3. If the system is at equilibrium, the total surface free energy must remain unchanged for a slight vertical displacement of the intersection (points A, B, and C are kept fixed). As shown by Herring,' the following equation is obtained:

Jan 1, 1962

By A. C. Watts

FOR several years, a mine in Colorado experienced considerable trouble from small fires caused by the blasting of coal. Although a well-known make of permissible powder was used, it was first thought that the powder ignited gas that might be present and that this, in turn, set fire to line brattices or to the coal. Experiments were, therefore, conducted with another make of powder, but the results convinced the superintendent of the mine, Robt. Williams, Jr., that the fires were not caused by the powder but by the high-voltage electric current used for detonating the shots. The mine "makes" gas very freely, giving off from three-fourths to a million cubic feet of methane per 24 hours. The coal is a good grade bituminous of a very free burning quality. Electric shot-firing from the outside after all men and animals were outside had been practiced for a number of years. The shooting circuit was connected with the main power circuit at the mouth of each entry. Shooting circuit switches were mounted in boxes, which were kept locked with the handle of the switch, in open position, showing through the bottom of the box. The door of the box could not be shut and locked when the shooting switch was closed. At the entrance to each room, or working place, a small switch, called the miner's switch, was placed on the shooting line. It was the duty of the miner, when entering his place at the beginning of the shift, to see that this switch was open and that it was kept open until he left the place at the end of the shift to go out of the mine. Grounded return was used for main power lines. The current was 500 volts, direct current, with 100 to 300 amp. The nearest working face was 9600 ft. from the shot-firers' switch outside the mine and the most remote working face was 2 ½ miles. The various working faces were scattered over a wide area between these two points.

Jan 9, 1925

By J. H. Henderson, H. J. Ledbetter, N. B. Gove, J. D. Griffith

INTRODUCTION The results of a series of laboratory flood tests using liquid Iso-butane to displace refined oils from test cores are pre- ented and interpreted on an empirical bask. The study Revealed the similarity of the miscible liquid displacement to that of the immiscible-fluid displacement mechanism. The efficiency of the iso-butane flood decreased markedly as the oil Viscosity increased. but the effect of injection rate on the effectiveness of the primary production stage was negligible over the range investigated. The presence of free-gas saturation prior. to iso-butane breakthrough increased the volume of iso- Butane required to recover a given percentage of the oil present. Injection of liquid i.e.-butane prior to water follicle sculpted in a marked improvement in oil recovery by the water flood. INTRODUCTION The production of petroleum is often enhanced by the injec-1i1)n of extraneous fluids into the reservoir. It has been suggeited that the injection or cycling of a wet gas or a liquefied petroleum gas would he instrumental in increasing the effic.ienr!; of oil recover! to a greater degree than the commonly injected fluids. dry pas and water. Although instances of injection of light liquid hydrocarbons are not unknown, a systrmatic recording of the result is unavailable and superfi- cially, the practice gives the impression of being economicaIIy unsound. For specific types of displacement, analytic: solutions have been advanced which aid in understanding the physical mechanisms involved. However, there is no generalized theoretical concept which permits adequate prediction of displacement efficiency from a knowledge of readily measured reservoir rock and fluid properties. The Buckley-Leverett approach to oil displacement by an immiscible phase is an admirable analysiy of that type of mechanism. Dykstra and Parsons have introduced a useful concept in their evaluation of the role of the mobility ratio and its merit in rationalizing displacement phenomena. Everett, Gooch and Calhoun3 in their report on the effect of viscosity ratio and miscibility have pointed out the lack of a comprehensive theoretical approach and the desirability of investigating the mechanism of miscible-miscible displacement. In lieu of a well-developed theory concerning miscible-111isci1)le displacement and in view of the scarcity of engineering information on actual LPG injection trials, the limited program of laboratory experimentation described below was undertaken. OBJECTIVES The original broad objectives of the program, to study the oil recovery process using LPG as the displacing phase, defined the direction and scope of the laboratory tests. The specific objective. of the experimentation were to evaluate

Jan 1, 1953

By H. J. Levinstein, H. J. Guggenheim

RbFeF3 is a transparent ferromagnet with a large faraday rotation which permits the direct observation of magnetic domain structures in bulk crystals. If the position of dislocations within the crystal were known a study of domain wall dislocation interactions would be possible. In this paper an etch pitting solution is described which gives a one-one correspondent between the etch pits and the dislocations intersecting the (100) surfaces of RbFeF3 crystals. In addition, RbFeF3 is shown to have sufficient plasticity so that known arrays of dislocaticms can be put into the crystal. It is concluded that RbFeF, is an ideal material for the investigation of domain wall dislocation interactions. THE influence of lattice defects on the motion of domain walls in ferromagnetic materials has been studied extensively both theoretically and experimentally.4 The experimental data obtained has been qualitative in nature due to the lack either of a quantitative knowledge of the magnetic domain array in the material or of the nature of the dislocation configuration in the material. At room temperature RbFeFJ has the cubic perovskite structure. It is ferromagnetic below 86°K.5,6 It is also transparent and has a large faraday rotation in the magnetic state.7 The domain structure of this material is observable in three dimensions in crystals which are millimeters in thickness.' Since RbFeF3 satisfies the requirements of having an easily visible three-dimensional magnetic domain structure, it was of interest to determine if the dislocation structure of the material could be determined and if the material was sufficiently plastic so that dislocations could be introduced into the as grown crystals. This is a report of the results of that investigation. EXPERIMENTAL PROCEDURE The crystals of RbFeFs used in this experiment were grown by a technique described elsewhere.5 In order to obtain flat strain-free surfaces, the samples were first cut to the crystal orientation desired and the surfaces were polished by employing standard metallographic techniques. The samples were then immersed in a solution of 1 to 3 g of KOH in 100 ml of water. This solution removes the damaged surface layers uniformly leaving a film on the surface of the sample. Etch pits are obtained by immersing the sample in an approximately 50-50 solution of 30 pct peroxide and concentrated acetic acid. The film formed during the KOH treatment turns deep red in color in the etching solution and flakes off the sample. The etching time required depends upon the pit size desired and

Jan 1, 1970

By A. H. Grobe, F. N. Rhines

AT elevated temperatures the oxide of silver is unstable in the air at atmospheric pressure, consequently no external oxide scale forms upon pure silver under conditions of high-temperature annealing When small quantities of certain alloying elements are present in the silver, the formation of a thin external scale is possible' and in addition there may form a subscale composed of the oxide of the solute element precipitated within the body of the silver Norbury2 and Leroux and Raub3 have reported internal oxidation (subscale formation) in alloys of silver with 2, 7 5, and 30 per cent of copper The presence of the subscale is believed to be responsible, at least in part, for the objectionable "fire mark" in Sterling silver' Several other alloys of silver, after oxidizing heat-treatments, are known to exhibit undesirable polishing characteristics that may be the result of internal oxidation Except for the absence of an external scale of silver oxide, it is to be anticipated that silver alloys will prove to be very similar in their oxidation behavior to the alloys of copper, the oxidation characteristics of which have been studied in some detail 5,6 The present research confirms this anticipation The oxidation of a series of 20 dilute alloys of silver has been studied metallographically, some types of subscale not encountered among the copper alloys have been found Instances of internal oxidation in alloys of most of the metals of the I-b and VIII groups of the periodic system are on record, but evidence of this type of oxidation in alloys of the metals of the intermediate groups is lacking A number of the metals of the intermediate group, among them cadmium, lead, tin, and zinc, appear to provide the conditions essential to subscale formation, i e , they form oxides with a relatively low negative free energy of formation, they dissolve other metals that form more stable oxides, and, presumably, oxygen will diffuse through them In a study of 4o alloys of these white metals only a few cases of internal oxidation have been found The probable reasons for this difference in behavior will be discussed presently EXPERIMENTAL PROCEDURE Silver -The silver alloys employed in the oxidation studies were prepared in heats of 30 grams each from high-purity silver (99 993 per cent Ag)* and the purest avail-

Jan 1, 1942

By C. R. Ramachandra, C. C. Patel

Flotation of chalcopyrite from a low grade ore was studied by using different xanthates and dixanthogens as collectors and by conditioning the flotation pulp with oxidizing gaseous systems. The improvement in the recovery of chalcopyrite with the oxidizing systems was mainly due to the auto-activation of chalcopyrite, leading to the enhanced adsorption of xanthates and dixanthogens even when the latter were formed by oxidation of the xanthates. With air or oxygen as oxidizing system, the amount of ethyl xanthate required at pH 8.5 was much less than normally employed in the industry, the recovery being 97-99% of chalcopyrite with a concentrate of 24% copper. With isopropyl and isoamyl xanthates, the recovery was improved but the grade was lowered. By conditioning the pulp with air-CO2 or oxygen-CO2 mixture, the recovery was lowered with ethyl xanthate only, mainly due to the depressant action of bicarbonate formed. Flotation with dixanthogens gave cleaner concentrates of chalcopyrite. because iron pyrite did not float with these collectors. Of the dixanthogens tried, diisopropyl dixanthogen gave the highest recovery, 99% chalcopyrite with a concentrate containing 28.5 to 30% copper, when the pulp at pH 8.5 was condi-tioned with air. Isopropyl dixanthogen was found to be the best collector of all the xanthates and dixanthogens studied. It was found that the adsorbed ethyl, isopropyl and isoamyl xanthates at chalcopyrite surface, activated by cupric sulfate, and at iron pyrite surface were oxidized to the corresponding dixanthogens to different degrees in presence of air, oxygen, air-carbon dioxide mixture and oxygen-carbon dioxide mixture.' The dixanthogen formed at chalcopyrite surface was, however, firmly adsorbed while that at iron pyrite surface was easily desorbed. Since dixanthogens formed have greater hydrophobicity than the corresponding xanthates, as revealed by contact angles,1,2 the former were expected to improve the flotation results. It was, therefore, thought desirable to find out the effect of air, oxygen, air-carbon dioxide mixture and oxygen-carbon dioxide mixture on the selective flotation of chalcopyrite when individual xanthates were used as collectors. The effect of direct use of dixanthogens as collectors on the selective flotation of chalcopyrite was also investigated. For these studies, low grade chalcopyrite ore, received from the Indian Copper Corp., Ltd. (I.C.C.), Ghatsila, Bihar, was employed. At the milling plant of the I.C.C., chalcopyrite is floated at a pH of 8.5, employing ethyl xanthate as collector. EXPERIMENTAL Materials Employed: XANTHATES - Ethyl, isopropyl and isoamyl xanthates of potassium were prepared in a pure state by the methods described earlier.4 A 0.03% aqueous solution of a xanthate was freshly prepared in air-free distilled water for flotation studies. DIXANTHOGENS - Diethyl, diisopropyl and diisoamyl dixanthogens were prepared by the oxidation of xanthates by iodine and purified by extraction with petroleum ether. A 0.03% alcoholic solution of dixanthogen was used as a collector. FROTHER - A 0.2% solution of pine oil in ethyl alcohol was employed. SODIUM CARBONATE - A 0.4 N solution was used. ORE - The composition of the -100 +200-mesh size (Tyler standard) powdered ore, as determined by standard methods of analysis, was: copper 1.57%, iron 10.29%, sulfur 3.15% and acid insolubles 66.10%. Iron present as chalcopyrite (CuFeS2) was 1.38%, while that present as iron pyrite (FeS,) was 1.37%. Both chalcopyrite and iron pyrite were found to be liberated from the gangue minerals and from each other, as observed under a microscope. Flotation of Chalcopyrite with Xanthates in Presence of Different Gaseous Systems: Fifteen grams of -100 + 200-mesh size ore were shaken well with 100 ml of distilled water. The pH of the pulp was adjusted to 8.5 by the addition of sodium carbonate solution. Then 0.1 ml of xanthate solution (0.005 lb xanthate per ton of the ore) was mixed with the pulp, and the latter together with washings transferred to a

Jan 1, 1963

By D. J. McAdam

In 1917 Haighl presented evidence that under simultaneous corrosion and cyclic stress metals may fail at lower stresses than if the corrosion is prior to the cyclic stress. In 1926 the author, while investigating the cooling effect of water on the fatigue resistance of metals, found that under these conditions steel specimens fail at stresses far below the endurance limit.2 (By "endurance limit" is here meant the fatigue limit obtained with specimens as free as possible from stress concentration and corrosive influences.) This led to an investigation (at the Naval Engineering Experiment Station, Annapolis, Md.) of the influence of cyclic stress on corrosion. This investigation may be divided into three parts. The first part was a general survey of the conditions necessary to cause complete failure under corrosion and cyclic stress of relatively high frequency. The entire process by which metals fail under these conditions was called LLcorrosion-fatigue." Corrosion-fatigue limits" for a large number of metals were determined and the relationships of these limits to chemical composition, heat treatment and physical properties were established. The conclusion was reached that corrosion-fatigue is due to the accelerating influence of cyclic stress on corrosion. Results of this part of the investigation were presented in five papers.*-= The second part of the investigation was a preliminary study of the influence of cyclic stress on corrosion. Each experiment was conducted in two stages. The first was a corrosion stage in which the specimen was corroded under cyclic stress; the second was a fatigue stage, in which the previously corroded specimen was tested (without further corrosion) to determine its fatigue limit. The difference between this fatigue limit and the endurance limit was used as a criterion of the "damage" due to

Jan 1, 1932

Jan 1, 1879

By AIME AIME

BEGINNING Thursday, July 16, the National Broadcasting Co. is broadcasting from 6:30 to 6:45 p.m., over its nationwide network and possibly also by short wave a series of eleven radio programs dealing with the contributions of engineers to the prosecution of the war. The series is being arranged and sponsored by a committee of representatives of the national engineering societies, R. L. Sackett, chairman. The committee began its deliberations before Pearl Harbor and had scripts under way on blackouts, bombs, and damage to structures. The declaration of war emphasized the importance of the proposed radio program. The National Broadcasting Co. and the Office of Civilian Defense enthusiastically endorsed the committee's proposal and have been generous in their help and approval of scripts so far submitted. Controversial matters are included in the broadcasts and changes will be made when requested by O.C.D. up to the minute that a program goes on the air. In this way the latest and authoritative information will be given.

Jan 1, 1942

By R. B. Snow

THIS paper describes a technique of polishing and etching specimens of open-hearth furnace slags or hearth aggregates for identification of the crystalline constituents-lime (CaO), tricalcium silicate (3CaO•SiO2), dicalcium silicate (2CaO-SiO2), monticellite (CaO•MgO-SiO2), or forsterite (2MgO•SiO2), with especial emphasis on the mineral merwinite (3CaO-MgO.2SiO2). With proper standardization, this identification does not require the use of the petrographic microscope. The composition of basic open-hearth slags and furnace bottoms falls, almost without exception, within systems containing CaO, MgO, "FeO," MnO and SiO2, in which the number of basic molecules so greatly exceeds the orthosilicate ratio (two molecules of base to one of silica) that free basic oxides, and combinations between them such as aluminates or ferrites, are present in cooled specimens. Orthosilicates of (CaO + MgO) are the most common in such specimens, since in nearly all cases, except premelt slags, the molecular ratio of (CaO + MgO) to SiO2 is more than 2 to r. When sufficient lime is available it combines with the silica to form dicalcium silicate (2CaO•SiO2), which contains little, if any, MgO, FeO or MnO in solid solution whereas the latter oxides combine to form the oxide solid solution known as periclase. If the lime present is insufficient to form dicalcium silicate (2CaO•SiO2) it combines with MgO to form either merwinite (3CaO•MgO.2SiO2) or monticellite (CaO-MgO•SiO2); these minerals take little if any FeO or MnO into solid solution and the remaining MgO, FeO and MnO combine as periclase. This generalization seems to be valid for basic slags and furnace bottoms, since minerals such as CaO-MnO•SiO2 and CaO-FeO-SiO2 are found only in slags in which the lime-silica ratio is less than 2 and are not observed in specimens from furnace bottoms. The identification of crystalline constituents in such materials, especially of fine crystals in the groundmass, is difficult under the petrographic microscope. They are often masked by their neighbors because of their small size in relation to the thickness of the thin section and because of the presence of opaque or colored constituents. The indices of retraction and the optical sign of the mineral are sometimes difficult to determine because of the small size or because of twinning or of inclusions within the crystal. Moreover, the positive identification of merwinite (3CaO•MgO.2SiO2) from its optical properties is usually difficult in the presence of dicalcium silicate (2CaO•SiO2). CaO, MgO, 3CaO•SiO2 and 2CaO•SiO2 in open-hearth slags have been identified for a number of years in the U.S. Steel Corporation Laboratory by the usual

Jan 1, 1947

By D. J. Jr. McAdam

RESULTS of investigation of corrosion-fatigue of metals at the U. S. Naval Engineering Experiment Station have been presented by the author in four papers. 1,2,3,4 In those papers references were given to the work of Haigh in 1917.5 The investigation at Annapolis included a variety of ferrous and non-ferrous alloys. The experiments showed that even slight corrosion simultaneous with fatigue may cause failure at stresses far below the ordinary endurance limit. The experiments also showed that, for most metals, severe stressless corrosion prior to fatigue is much less damaging than even slight corrosion simultaneous with fatigue. The term "corrosion-fatigue" was restricted to mean the simultaneous action of corrosion and fatigue. The combined effect of corrosion followed by fatigue was called "prior-corrosion fatigue." A stress-cycle graph representing corrosion-fatigue is a curve approaching a horizontal asymptote, the ordinate of which may be called a "corrosion-fatigue limit." To avoid confusion in later discussion, the term "endurance limit" will be restricted to mean the fatigue limit obtained by tests in air with specimens as free as possible from stress concentration and from corrosion. The endurance limit as thus obtained presumably represents an inherent property of the metal.

Jan 1, 1929