Search Documents

By D. Turnbull, R. E. Cech

FISHER, Hollomon, and Turnbull have developed a theory for the nucleation of martensite. They first tested the theory on Fe-C alloys and low alloy steels. The major factor influencing nucleation of martensite was considered to be statistical composition fluctuations occurring in small regions at high temperature and frozen-in on quenching. These local regions of varying size and composition serve as nucleation centers. They become supercritical, one by one, as temperature is progressively lowered, resulting in temperature-dependent or athermal transformation. Fisher next applied nucleation theory to substi-tutional solid solution alloys. Detailed predictions were made for Fe-Ni alloys because of the availability of free energy data on this system. It was shown that composition fluctuations that were significant energy-wise did not occur, and nucleation frequencies could be calculated from average properties of the system. Nucleation was predicted to occur as time-dependent and having the functional relationship to give a C curve of nucleation frequency vs temperature. The analysis further predicted that the nucleation frequency was extremely sensitive to composition. Experimentally, it would be found that the transformation in some compositions is so slow that measurable amounts will not form in a reasonable length of time. With other compositions, only slightly different, the nucleation frequency becomes so great that the material becomes transformed while still distant in temperature from the maximum nucleation frequency. On quenching an alloy of such composition, the observed transformation kinetics would be similar to those found in Fe-C alloys. Cech and Hollomon repeated experiments of Kurdjumov n which the kinetics of transformation were similar to those predicted by Fisher for Fe-Ni alloys. The alloy studied in this investigation contained 73.3 pct Fe, 23.0 pct Ni, and 3.7 pct Mn. Fisher,' using an idealized model for the extent of transformation as a function of the number of martensite crystals per grain of parent phase, derived nucleation frequencies from the transformation curves of Cech and Hollomon. Complicating influences such as coupling effects between grains in the polycrystalline specimens were neglected. Nevertheless, excellent agreement was found between the theoretically and experimentally derived nucleation frequencies. These experiments, however, could not provide a critical test of the theory. Experimental nucleation frequencies could vary widely from those calculated, depending upon the extent of deviation from ideal partitioning and the extent of coupling effects. Further, since the compositions of material theoretically analyzed and experimentally determined were different, the free energy changes involved in the experimental work could only be estimated. Also, the effect of heterogeneities on the transformation kinetics was not considered. For these reasons, it was decided that experiments designed to test the validity of the Fisher analysis must be conducted on binary Fe-Ni alloys, which were the ones considered theoretically by Fisher. The martensite transformation in Fe-Ni alloys has been the subject of considerable study. Machlin and Cohen have shown that transformation proceeds in a manner quite unlike that in any other ferrous alloy system. They found that single crystals would transform to a large extent in a single burst. In large grain polycrystalline specimens, frequently more than one grain and sometimes the whole specimen would transform at the same instant in this manner. Results on filings indicated that different particles would undergo the burst transformation at widely different temperatures. These results support the conclusion that the transformation behavior could not be described by a single nucleation frequency as would be the case if the nucleation were homogeneous. It appeared that further work was necessary to define the factors responsible for burst-type transformation, so that the conditions could be altered to favor homogeneous nucleation of martensite if such could be accomplished. This report summarizes the results of some experiments conducted with powdered Fe-Ni alloys for this purpose and the re-

Jan 1, 1957

Map

Jan 1, 1957

By C. H. Bushell, M. Malnarich

REAGENT control in flotation is more an art than a science. Operators vary the amount of reagents used according to the metallurgy obtained. The amount of collector may be increased, for example, if tailings losses are high and decreased if concentrate grades are low. Often control decisions are based on only one assay, such as the tailings analysis by microscopic or quick assaying techniques. This method of control has given reasonably satisfactory results but is clearly far from perfect. No adjustment in reagent addition can be made until information is received that metallurgy has deteriorated, that is, until the optimum time for adjustment has already passed. The first adjustment probably will be an overcorrection or an undercor-rection, and time will be required to establish the best new addition rates. The seriousness of the problem depends on variability of the ore. In ore of continually shifting composition and complexity, mill results will shift back and forth from excessively high concentrate grades and high tailings losses to excessively low concentrate grades and low tailings losses. Economic incentive for improved control also increases with increasing size of mill. Even a small improvement in percentage recovery in a large mill pays for expensive control equipment. The Sullivan concentrator of The Consolidated Mining & Smelting Co. of Canada Ltd. at Kimberley, B. C., treats 11,000 tpd of complex lead-zinc ore, a scale of operations which justifies an extensive research program on automatic control. Work has followed two separate lines: 1) development of faster analytical methods for pulps, and 2) study of metallurgical control by measurement and control of reagent concentrations in flotation solutions. Although work is incomplete in both phases, a progress report can be given on the development of reagent control. The primary requirement in flotation is selective attachment of particles of one mineral to air bubbles while the other minerals remain detached. Hydrophobicity of mineral surfaces is established by the collector, which coats the minerals by adsorption. The requirement of selective affinity for air bubbles is therefore equivalent to requiring selective adsorption of a collector. Adsorption theory, supported by abundant experimental evidence, shows that the amount of a reagent adsorbed at a surface must be a function of its residual concentration in solution. As the concentration in solution rises, the amount adsorbed increases, usually following some type of logarithmic curve. Selective adsorption must depend on a natural difference in the minerals, but ordinarily the differences in affinity are not great enough to obtain complete coverage of one mineral while the others are completely uncoated. An optimum concentration will exist, below which coverage will not be great enough to float enough of the valuable mineral, and above which too much unwanted mineral will float. All other reagents, except some frothers, affect the amount of collector adsorbing at constant residual collector concentration in solution, either by adsorbing competitively with the collector, or by a

Jan 1, 1957

By R. T. Johansen

A gradual decrease in injection rates commonly occurs as a water-flooding project becomes older. This decrease can be attributed to changes in reservoir conditions, such as swelling of clay minerals, fillup, or gradual plugging of the sand face. However, a rapid decrease in the rate of injection indicates abnormal behavior and is cause for alarm. Extreme plugging conditions can completely stop injections into a formation. Such behavior in wells was the main concern of the tests described in this report. An accepted method of alleviating this condition is by backflowing input wells - closing the supply lines to the wells and allowing the reservoir pressure to force water back into the wellbore and to the surface. If backflowing is not successful, a string of smaller diameter pipe sometimes is run inside the casing, and the sand face is flushed with a waterspray. More drastic treatment is to inject acid into the wellbore to dissolve extraneous matter, or even part of the reservoir material, in an attempt to restore the permeability of the sand immediately around the wellbore. Any of these procedures can he coordinated with bailing and swabbing of the well for cleanout purposes.

Jan 1, 1957

By R. W. Guard, W. R. Hibbard

As part of a program to determine the deformation characteristics of pure metals, the tensile creep properties of high purity aluminum (99.994 pct Al) have been determined using a constant stress loading. The effects of prior annealing temperature, stress, and temperature were studied. These data have been examined on the basis of present-day theories. None of the methods was found to give an accurate representation of the data over all conditions studied. The structures of several specimens after creep were examined by optical and X-ray metallography. Marked changes in the grain size were found and it was substantiated that the magnitude of these changes was greatly influenced by the applied stress (or creep strain). The changes in fiber texture which occur on creep deformation are shown to be consistent with those observed on deformation at lower temperatures. UNDERSTANDING the properties of new mate-*-J rials under different experimental conditions must be based on considerable knowledge of the mechanisms involved in plastic flow and how to control them. Tension and creep tests have been carried out on a number of pure metals in order to document their deformation characteristics. It is hoped that a comparison of these data with theory will indicate those areas where work on mechanisms and their relation to metallurgical variables may be most fruitful. Since aluminum has often been used for studying the qualitative aspects of creep behavior, it was chosen for detailed study. The effects of annealing temperature, stress, and test temperature on the constant stress creep behavior were studied. Although most of the tests were made above one half the absolute melting temperature, a few tests were made at lower temperatures to give qualitative comparisons. Some specimens were examined metallo-graphically and by X-ray diffraction techniques after creep. Since only a limited number of specimens could be made from the available material, no effort was made to study detailed changes in sub-grain structure or other metallographic features. Servi and Grant3 nd Dushman et al.' have previously published studies of high temperature creep of high purity aluminum. In both cases, a great deal of emphasis was placed on the minimum creep rate.

Jan 1, 1957

By W. A. Haley

The purpose of this investigation was to develop and improve mining methods for mining thin coal beds, to increase productivity, and to increase the recovery of coal. German coal planers and a modified longwall system of mining were introduced into American mines and are bringing about increased productivity and better recovery as compared with the conventional methods displaced. Since the first installation, 4 additional planers have been purchased by coal companies and over 1-1/2 mil¬lion tons of coal has been mined by them, using the modified longwall mining method. INTRODUCTION Except from 1932 to 1934, the growth of mechanical loading in underground bituminous-coal and lignite mines in the United States has increased steadily. The amount of coal loaded mechanically in underground mines has increased from 0.3 percent in 1923 to 79.6 percent of the total underground production in 1953.3/ The use of new and improved mining machines and auxiliary equipment, together with new techniques in mining methods, usually has resulted in increased productivity.

Jan 1, 1957

By J. R. Low

The brittle fracture of a Tic-lnconel cermet at room temperature is shown to occur primarily as a result of the cracking of the larger carbide particles (at a tensile strain of approximately 0.3 pct), followed by cracking of adjacent, smaller carbides and, finally, by the rupture of the lnconel matrix between cracked carbides (at a strain of-1.2 pct). No evidence was found for separation at the interface between carbide and matrix at any point in the fracture process. MATERIAL used in this study was a Tic-Inconel cermet prepared by infiltration (50 pct Tic, 50 pct Inconel: designated as TC66-I). A thin section of this material was brazed to a piece of low carbon steel and then mounted in lucite for metal-lographic preparation." After grinding, polishing, Deformation and fracture of the specimen was accomplished by bending the specimen as a simply supported, centrally loaded beam, in a bending fixture which could be placed in the stage of a microscope, with the tension side of the bend specimen under the microscope objective.? This method of deformation and observation has the advantage that the surface under examination is the most severely deformed portion of the specimen. The procedure followed was to deform the specimen a small amount, scan the surface at Xl OOO for any evidence of deformation or cracking, deform another small increment, scan the surface again, and so on until a

Jan 1, 1957

By S. A. Braley

DRAINAGE of acid mine water into surface streams of coal mining areas is one of the most serious problems of stream pollution, since there is no known method that completely prevents its forming and no economically feasible treatment after it has formed. The mine acid problem differs from other pollution hazards because acid production does not end with cessation of mining but actually becomes more evident when pumping is stopped. The acid problem in the Pennsylvania, Ohio, West Virginia, and Kentucky bituminous coal areas of the U. S. began with the first operation in 1761, and the volume of acid discharge today is largely the cumulative result of years of mining. Provided they lie above the drainage area, the oldest mines, now long abandoned, are almost without exception producing acid in the same manner as those now operating or recently abandoned. It is well to consider some of the many procedures that have been used to determine the composition

Jan 1, 1957

By John J. Gilman

F many years it has been suspected that a correlation existed between pits produced by etching and the density of dislocations in crystals. In 1953, the interest in this correlation was greatly stimulated when Vogel et al' demonstrated a 1:l correlation between etch pits and dislocations in low angle grain boundaries of germanium. About two years ago, the author began attempts to produce etch pits at dislocation sites in zinc mono-crystals. These attempts met with success a year or so ago,' and since that time a survey has been made of the etch pit patterns that are associated with various modes of deformation in zinc monocrystals. Unfortunately, the etching technique that will be described is too delicate for use as an accurate quantitative tool. Nevertheless, it has been of considerable assistance in clarifying the structure of plastically deformed crystals. Technique Many attempts were made to produce etch pits in high purity zinc crystals. It was found that several techniques would produce surface grooves at grain boundaries that had misorientation angles greater than about l°, but no technique was successful for boundaries with smaller angles. Among the things that were tried were: electrolytic CrO, (both etching and polishing concentrations), HNO, in various water and alcohol solutions, dilute HC1, many 0-0,-Na,SO, solutions, Cr0,-HC1 solutions, picral, electrolytic Na,S,O,, and electrolytic NaOH and KOH. A few attempts to use cathodic sputtering and thermal etching were also made.

Jan 1, 1957

By Irving Fatt, Robert J. S. Brown

INTRODUCTION The wettability of reservoir rocks is recognized as one of the major factors that determines their multiphase flow properties. Multiphase flow properties in turn govern reservoir performance. For this reason, the reservoir engineer is vitally interested in the wettability of reservoir rock. The production research scientist is interested in wettability because the solution of the problem of improving waterflood recovery by use of surface-active additives may hinge on a detailed understanding of the wettability of reservoir rock. Early workers believed that all reservoir rocks were preferentially water wet. Continued study soon uncovered certain rocks which had flow properties that indicated that they were preferentially oil wet. Recent studies show that there is a spectrum of wettability. Some reservoir rocks have multiphase flow properties which indicate that they have an intermediate wettability. The differences in recovery observed among different reservoirs may, in part be the result of small differences in wettability. Differences in wettability amcng reservoir rocks may be the result of differences in the fraction of the total surface area that is preferentially oil wet and preferentially water wet. Nuclear magnetic relaxation measurements may provide a method for determining the fraction of preferentially oil wet and preferentially water wet area in porous media. Measurements to be reported here were made on water-saturated unconsolidated sand packs which were mixtures of preferentially oil wet and preferentially water wet sands. The resulting data show definitely that the fraction of each wettability in these sand packs can be determined by this nondestructive method of measurement. THEORY OF NUCLEAR MAGNETIC RELAXATION The details of the theory of nuclear magnetic relaxation have been presented previously1. In this paper, only a very brief review of the theory will be given to show its application to the measurement of fractional wettability. Nuclear magnetic relaxation is a process of adjustment undergone by certain atomic nuclei when their magnetic environment is changed. They adjust, or relax, to be in equilibrium with a new magnetic field. The reason that some atomic nuclei are affected by a magnetic field is that they themselves behave in some respects like tiny magnets. In particular the proton, the nucleus of the hydrogen atom, behaves as a magnet. The proton spins, somewhat as the earth spins on its axis. The spinning charge produces a magnetic field just as current traveling in a loop of wire produces a magnetic field. No net charge is required, however; for instance, the neutron has spin and magnetic moment. When the spinning proton is subjected to an externally applied magnetic field, its axis tends to line up with the magnetic field, somewhat as a compass needle tends to line up, but the spinning proton cannot do this as easily as the needle can. The proton also has mass, and its spinning mass makes the proton behave somewhat like a gyroscope. As is well known, a force which tends to change the axial direction of a gyroscope merely causes the gyroscope to precess: lhat is, the axis begins to trace out a conical surface. The gyroscope cannot actually assume the position suggested

Jan 1, 1957

By D. R. Shreve, L. W. Welch

An analysis for predicting the behavior of reservoirs exploited by a combined gas drive and gravity draintrge mechanism is presented. The method allows the prediction of gas-oil ratio, oil production rate, and cumlulative oil recovery for high relief pools in which pressure is maintained either by gas injection in the crest of the structure or by a combined gas and water injection program. The reservoir is represented by a model of communicating vertical prisms, with production or injection at the upper or lower boundaries of each prism. The theory of macroscopic gravitational segregation of two fluids within a reservoir is discussed in detail for all ranges of saturation. A description of an application of the analysis to a typical field problem is also presented. INTRODUCTION The importance of gravity drainage as a producing mechanism has become more evident during recent years. However, many of the reservoir engineering methods which have been used in the past for predicting the behavior of reservoirs producing by this mechanism have required such drastic, simplifying assumptions that the calculated performance in some cases does not resemble the actual pool behavior. The mechanism of fluid displacement in porous media has been described by Buckley and Leverett,1 and a simplified "one zone" method based on this development has been used by engineers to evaluate the performance of gravity drainage pools. Welge2 has modi- fied this approach so that the calculation time has been markedly decreased. In addition, many other authors3-9 have analyzed various phases of the gravity drainage producing mechanism during the past several years. In a high relief reservoir in which gravity may affect the recovery mechanism, there are two main types of exploitation programs which can be employed: 1. Reservoir pressure is maintained by injecting gas into the upper portions of the reservoir. In this case gas is not released from solution and, if dynamic pressure drops are small compared to the total pressure of the system, the gas and oil may be considered to be immiscible and to have constant fluid characteristics. 2. Reservoir pressure is not maintained and a "natural depletion" mechanism prevails. The term "natural depletion" can be used to describe the production history of a reservoir in which a gradual decline of average pressure and the associated release of solution gas continue throughout the producing life. In this mechanism gas is released throughout the reservoir and there is a continuous change in the characteristics of both the gas and the oil phases. It is the purpose of this paper to present the results of mathematical developments by which a method has been devised for evaluating the performance of reservoirs which are depleted by the first type of exploitation program discussed above. It should be mentioned that, although throughout the analysis gas and oil represent the two fluids existing in the reservoir, the method is equally applicable to gravity drainage in water-oil systems. STATEMENT OF PROBLEM In reservoirs of pronounced structural relief, where the closure of the oil section is great or the angle of

Jan 1, 1957

By R. V. Smith, M. H. Cullender

Rigorous equations for calculating subsurface pres.tures in flowing and static gas wells, and pressures along horizontal pipelines are presented in this paper. These general equations, based on the mechanical encrgy balance, contain no assumptions regarding temperature and can be used with either straight-line or curved temperature gradients. The friction factors recommended in this report are based on an absolute roughness of 0.0006 in. Flow is always considered to he turbulent. Although these general flow equations are solved by numerical means, the methods are as convenient as many of those used today to calculate pressures in gas wells and pipelines. These numerical methods are illustrated for flowing and static columns of gas in wells and for flow in pipelines. The authors believe that the use of these methods will result in more accurately calculated pressures in gas wells and pipelines and that [he methods are more flexible than any in use at the present time. Also, the methods are easily adaptable to automatic computers. INTRODUCTION The problem of calculating subsurface pressures in gas wells and along flowing pipelines has been studied by many investigators with the results that two widely-used methods have been presented in technical literature. One approximates conditions in a gas well or pipeline by assuming that temperature and compressi- bility are constants tor the entire gas column. The other method assumes that temperature is constant at some average value but permits compressibility to vary with pressure at the constant temperature. While these approximations may be justified for relatively shallow and low-pressure wells, they become more and more unrealistic as the calculations are applied to the deeper high-pressure wells. In wells or pipelines where there is an appreciable change in temperature between the inlet and outlet ends of the flow string, it is equally as important to consider the change in compressibility with temperature as it is to consider the change with pressure. Consequently, the methods presented in this paper were developed to provide a workable procedure for calculating pressures in gas wells and pipelines which makes no assumptions regarding either temperature or compressibility. The friction factors recommended for use with the equations were the result of study of published literature and extensive experimental work with gas wells. The F,. values in Appendix IV which contain the friction factor are equivalent to an absolute roughness of 0.0006 in. as calculated by the Nikuradse equation. The absolute roughness of 0.0006 in. was previously published by Cullender and Binckley2 for gas wells; it is in agreement with 0.00065 in. of Smith, Dewees, and Williams1 for gas wells and 0.00065 in. of Baker and Swerdloff4 for pipelines; it is in reasonable agreement with 0.0007 in. reported by the Bureau of Mines and the American Gas Assn.5 for large transmission lines. However, any type of friction factors may be used in the equations by a change in the F, values in Appendix [V].

Jan 1, 1957

By R. I. Jaffee, C. M. Craighead, G. A. Lenning

The effects of increasing hydrogen content, introducing a notch, and changing the strain rate on properties of titanium and one of its alloys were investigated over a range of testing temperatures from —196° to 200°C. Both high purity and commercial purity A-55 titanium were used as representative a materials, while a commercial Ti-8 pct Mn alloy was used for an a-P alloy. It was found possible to analyze the data, using the ductile-to-brittle transition temperature concept. Increasing hydrogen, the presence of a notch, and increasing the testing speed raised the transition temperature for the a materials. The presence of hydrogen and notches raised the transition temperature of the a-B alloy also. However, increasing the testing speed generally decreased the transition temperature of the a-p alloy. IN previous papers, the authors have shown that hydrogen is most detrimental to the notch-bend impact toughness of a-titanium' and to the tensile ductility of a-B titanium alloys.' These general effects have been confirmed by Kessler and co-workers," and by Kotfila and Erbin." Kessler showed that the slower strain rate in notch-rupture tests was a more sensitive measure of hydrogen embrittle-ment of a-B alloys than the tensile test. In the present paper the authors cover, with tensile and notch-bend tests, the effect of testing speed, notches, and testing temperature on hydrogen em-brittlement. High purity and commercial purity titanium, examples of u materials, and a commercial a-,f3 Ti-8 pct Mn alloy were investigated. The purpose of the investigation was to correlate the factors producing embrittlement. Materials The high purity titanium for this investigation was obtained by arc-melting crystal bar from Foote Mineral Co. into 1 Ib ingots. As-cast hardnesses for these ingots ranged from 60 to 90 Brinell. The arc-melted ingots were forged to % in. diam rods at 1470°F. These rods were swaged to & in. diam at room temperature prior to machining of the specimens for hydrogenation and testing. The commercial A-55 titanium and the Ti-8 pct Mn alloy were obtained from Rem-Cru Titanium Inc., as % in. diam rod. The A-55 titanium was hot swaged to 1/4 in. diam at 1300°F prior to machining of the specimens for hydrogenation and testing. The a-p C-11OM alloy was hydrogenated prior to hot swaging to 1/4 in. roc1 at 1300°F. Hydrogenation prior to fabrication permitted testing of the a-P alloy in the equilibrated and stabilized condition. The equilibration and stabilization treatment used was an air anneal for 1 hr at 1300°F, followed by furnace cooling to 1100°F and then air cooling. Hydrogenation was done in a Sieverts apparatus described previously.' The hydrogenation treatment consisted of heating for 1/4 to 1/2 hr at 820 °C in purified hydrogen, slow cooling to 680"C, holding 1 hr for homogenization, and rapid cooling to room temperature. Intended hydrogen levels for the a-tita-nium materials were 0.05, 0.5, 1.0, 1.5, and 2.0 atomic pct—about 15 to 430 ppm. For the Ti-8 pct Mn alloy, the intended hydrogen levels were 0.05, 0.5, 1.0, 2.5, and 5.0 atomic pct—about 15 to 1100 ppm. The material for the 0.5 atomic pct level of hydrogen was vacuum annealed prior to hydrogenation to increase the accuracy of the addition. Vacuum annealing to remove hydrogen consisted of heating for 6 hr at 820°C, and resulted in a hydrogen content of about 10 to 15 ppm. When hydrogen contents were above 0.5 atomic pct—100 ppm—the hydrogen was added without prior vacuum annealing.

Jan 1, 1957

The negative charges on diaphragms of quartz, tungstic oxides, stannic acid, acid dyestuffs, soaps, and glass have for a number of years been explained on the basis of chemical equilibria—a hydrogen ion or light metal ion passes into solution leaving the solid complex ion negatively charged. While there are a number of observations which indicate a proportionality between the ( potential and the streaming potential it should be recognized that all the experimental evidence thus far presented shows that if hydrogen ion concentration is kept at a constant value, electrokinetic phenomena are influenced by salts. The multivalent ions exert the greatest effect on the reduction of osmotic flow. In the interpretation of all electrokinetic data the assumption is made that the potential of the solid remains constant. That this is not true is evidenced by the values of [ potential for quartz in contact with conductivity water as reported by the several investigators and by the authors of this paper. It is apparent that the nonreproducibility of surfaces will always prevent the obtaining of exactly comparable data. At best the experimental technique described depends on a theory which is capable only of showing a trend—another quartz surface should exhibit similar but not identical potential curves. It seems entirely reasonable to assume that the negatively charged laurate ions should have little or no attraction for a negatively charged quartz surface. The weight of previous experience in selection of flotation activators points unerringly to the usefulness of the multivalent metallic ions. The primary reason why the divalent barium ion is not available to two negative charges on the quartz surface might easily be that of distance between such adjacent negative charges. Otherwise activation could not occur, and the quartz could not assume the remaining unit positive charge of the barium ion. For this case no electrical double layer theory seems necessary. Clearly this is, at the negatively charged quartz surface, a case of partial chemisorption of the cationically divalent barium ion followed by the anionic neutralization of the remaining cationic charge by the freely moving laurate ion. It is hoped that the authors will continue with this interesting technique and that their results will continue to indicate trendwise what is known about the

Jan 1, 1957

By R. R. Wells

This report summarizes the results of laboratory testing of copper-bearing magnetite ore from the Poorman, Bush & Brown, and Copper Center deposits, Kasaan Peninsula, Prince of Wales Island, southeastern Alaska. The ores contain minor amounts of chalcopyrite and pyrite. Intimate association of these sulfides with magnetite necessitates fine grinding for adequate liberation and rejection of copper and sulfur and for the production of high-grade iron concentrate low in objectionable impurities. Laboratory tests indicated that the optimum results can be obtained by flotation of ore ground to minus-100-mesh, with subsequent wet magnetic separation treatment of the flotation tailing. A summary of results obtained by this treatment of the three samples tested is shown in table 1.

Jan 1, 1957

IN NOVEMBER 1933 I had the pleasure of receiving an autographed copy of a small brochure entitled "Birth of the Porphyry Coppers." The author, James Colquhoun, a distinguished British mining engineer, had been the dominant figure in the Arizona Copper Company, Limited, which, until its acquisition by the Phelps Dodge Corporation in 1921, had been the principal producer of copper in the Morenci district. In addition to the highly productive Humboldt and Longfellow mines it owned the Clay property, which, of course, has now become Arizona's No. 1 copper mine. Except for Utah Copper it is the premier Porphyry copper enterprise in the United States. Mr. Colquhoun's little volume was inspired by THE PORPHYRY COPPERS which had appeared early that year. In a most courteous and friendly way he adduces data to show that "we (Arizona Copper Company Limited) were successfully treating low-grade porphyry ores in quantity for at least four years (1901 to 19W) before the Utah Copper Company did anything at all." This last remark is based on the figures in THE PORPHYRY COPPERS showing that Utah's first production came from the Copperton pilot plant in 1905. Mr. Colquhoun traces the story of Morenci beginning in 1883 when he first arrived there. He tells how the rich self-fluxing ores (containing lime- stone, silica, and iron in proportion to permit direct smelting to produce black copper) were gradually exhausted. High-grade siliceous ore could be mixed in limited quantity with the self-fluxing ores; and oxidized ores were leached to contribute substantially to the production of the district. But

Jan 1, 1957

By John C. Machisak

Statistical data on injuries in the metal and nonmetal industry of the United States first became available to the Bureau of Mines by collecting reports from the operators for the calendar year 1911. Since then reports have been collected annually. The present bulletin, covering the calendar year 1954, is the 31st publication (1933-34 was published as Bulletin 398) containing statistical data on injuries at metal and nonmetal mines and related plants, and it 1s the first such bulletin to be published since 1942. The last publication was Bulletin 461, Metal and Nonmetal-Mine Accidents in the United States, 1942. The unpublished statistics for 1943-53 may be found in the Appendix of this bulletin. The Bureau of Mines is authorized to collect data on injuries and related employment at metal and nonmetal mines, but there is no Federal law that compels operators to submit such information. Therefore, all materials submitted are voluntary responses to the Bureau's requests for information. The figures presented herein may not be complete for the entire industry, nevertheless, every effort has been made to make them so, and the data given are believed to be representative of the hazards to which metal and nonmetal workers are exposed. Moreover, the figures are comparable as between States-which is significant in view of the lack of uniformity among the States as regards classes of plants covered by State laws, classes of injuries covered by State reports, and other factors that tend to make it impracticable or impossible to compare the injury experience of one State with that of another or comprehend the relative importance of the various causes of injuries in the industry as a whole.

Jan 1, 1957

Jan 1, 1957

By John Chipman, Peter J. Koros

The distribution of copper between liquid silver and liquid iron, Fe-C, and Fe-C-Si alloys was studied at 1600°C. From the data and the activity of copper in silver obtained from the phase diagrams, the activity coefficients of copper in iron up to 3 atomic pct are log y, = 0.90 — 2.4 N, and y": = 8.0. The effect of carbon up to saturation is expressed as log y = 1.8 Ni. The effect of silicon up to 11 atomic pct is insignificant. SLOWLY rising copper content of steel being produced is focusing attention on the lack of information on the behavior of copper in liquid steel. Chou' measured the activity coefficient of copper in liquid iron through its distribution between liquid silver and iron. He obtained a value of 9.12 at infinite dilution. Chipman' calculated the activity coefficient of copper in liquid iron at 1600°C from the phase diagram and obtained a value of 12. Ameiln and Pfeiffer- investigated the possibility of removing copper from liquid steel through the use of lead, silver, and bismuth as solvents. They also calculated that the activity coefficient of copper in liquid iron would be increased five or sixfold by addition of 4 pct C. Langenberg and Lindsay' are investigating the effectiveness of lead and sodium sulfide in removing copper from liquid iron. The experimental method was similar to that used by Chou' and Chipman and Floridis." Silver, copper, and iron were melted together, the copper distributing itself between the two layers so that at equilibrium a,.,, (in Ag) - a,.,, (inFe) and N,.,, (in Ag) yc,, (inFe) (in Ag). [21 N,.,, (inFe) Thus, from the concentration of copper in each layer and the activity coefficient of copper in liquid silver, the activity coefficient of copper in liquid iron can be calculated. The effect of an alloying element such as carbon on the activity coefficient of copper can also be determined from its effect on the distribution, provided the new element is essentially insoluble in silver. The one serious limitation of this method is the increasing mutual solubility of silver and iron in the presence of a third component. The mutual solubilities of pure iron and silver are negligible, but increase with increasing copper concentration beyond the range investigated. Ag-Cu System—The activity coefficient of copper in silver at 1600°C had to be estimated, since direct experimental data are not available. Kawakami" measured the heat of mixing of Ag-Cu alloys at 1200°C by a calorimetric technique. Scheil' calculated the heat of mixing in this system by use of the phase diagram, assuming that the solution is random and that the heat of mixing is independent of temperature. The terminal solid solution may be assumed to obey Raoult's law within the requirements

Jan 1, 1957

By Herbert H. Kellogg

The chemistry of sulfide roasting is analyzed to show those aspects of performance which Thecan be predicted from considerations of thermodynamic equilibrium. It is concluded that equilibrium calculations can serve as a yardstick for prediction of roaster-gas composition and sulfate formation in the calcine for fluid-bed roasting practice. A method of calculation which combines the equilibrium and stoichiometric factors is outlined, and illustrated by an example from the roasting of Cu-Fe sulfides. ON first examination the roasting of sulfides would not seem to be a process to which equilibrium calculations could be applied to yield results of practical value. The burning of sulfides is an ex-tremely spontaneous reaction, excess air is always used to obtain rapid reaction, and in most traditional roaster designs (hearth roasting) the temperature and gas composition vary widely from point to point in the roaster. These are all conditions which promote a non-equilibrium state in the roasting process. However, the introduction of the fluid-bed roaster1 has brought to roasting practice new conditions of operation, so that equilibrium calculations can be used to predict certain limited aspects of practical operation. The fluid bed is characterized by uniformity of temperature, gas composition, and calcine composition from point to point throughout the bed. These relatively uniform properties of the bed make the meaningful calculation of the equilibrium state of certain reactions in roasting possible. It is the purpose of this paper to analyze roasting from an equilibrium viewpoint, to show where the method may be expected to yield valuable information, where it fails, and to outline methods of calculation. Main Roasting Reaction The reaction MS (s) + 3/2 0, = MO (s) + SO, [I] might well be called the main roasting reaction. It adequately accounts for the well known facts that metal sulfide and air are the main reactants, and metal oxide and SO, the main products. Deviations from this simple stoichiometry will be discussed under side reactions. For all metal sulfides, Reaction 1 is strongly exothermic and the equilibrium position is far to the right. Since the reaction is exothermic, the equilibrium shifts in the right-to-left direction as the temperature is raised. However, at all practical roaster temperatures (between 500" and 1200°C), the amount of this shift is small, and the equilibrium position remains far to the right. The main roasting reaction is essentially irreversible, and the application of equilibrium considerations to this reaction will not be! a fruitful field of investigation. A knowledge of the rate of this reaction. although not the proper subject of this paper, is of great importance to the roasting process. Analysis of the factors which influence this rate shows that: 1) The rate will increase rapidly with increased temperature. 2) The rate will be proportional to the partial pressure of oxygen at the surface of the reacting particle. Because of diffusion effects, the partial pressure of oxygen at the particle surface may be considerably less than in the bulk of the roaster gas. For this reason, intimate contact between gas and solid and high relative velocity between gas and solid, such as can be obtained in a fluid bed or flash roaster, will markedly increase the rate of reaction. 3) The rate will be proportional to the surface area of metal sulfide. Therefore, smaller particle size will permit a more rapid rate per unit of weight. To achieve practical rates of roasting the partial pressure of oxygen in the roaster gases must be maintained at a finite level at all times. Even where the gas-solid contact is very good, as in the fluid-bed roaster, the oxygen content of the gas must not be allowed to drop below some limiting value (perhaps 1 pct), or the rate of the main roasting reaction will become too small for practical operation. Side Reactions in the Gas Phase The gas phase during roasting of metallic sulfides contains the elements oxygen, sulfur, nitrogen, by-

Jan 1, 1957