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By R. P. Rothwell

About thirty miles north of the city of Belleville (which is situated on a branch of Lake Ontario), and in the township of Marmora, Ontario, there is found a belt of gold-bearing quartz veins, which present geological mineralogical, and economic features of great interest to the profession. The district in which these veins are found is characterized as a rolling country, with low rounded hills of syenitic granite, overlain on the flanks of the hills by Silurian limestones, which lie in nearly horizontal beds, and in some places are so fine in texture as to afford lithographic stone of a fair quality. The gold-bearing veins run north and south through this belt of syenitic granite, and are quartz-filled true fissures, with micaceous or talcoid slates forming the walfs of and horses in the veins. This

Jan 1, 1881

By S. P. Rothwell

ABOUT thirty miles north of, the city of Belleville (which is situated on a branch of Lake Ontario), and in the township of Marmora, Ontario,: there is found a. belt of gold-bearing quartz veins, which present geological, mineralogical, and economic features of great interest to the profession. The district in which these veins are found is characterized as a rolling country, with low rounded bills of syenitic granite, overlain on the flanks of the hills by Silurian limestones, which lie in nearly horizontal beds, and in some places are so fine in texture as to afford lithographic stone of a fair quality. The gold-bearing veins run north and south through this belt of syenitic granite, and are quartz-filled true fissures, with micaccous or talcoid slates forming the walls of and horses in the veins. This

Jan 1, 1881

By Frank G. Breyer

C ONDITIONS have not been favorable for new developments in any line. It has been a period, how- ever in which recent developments have been subjected to the severest tests. Those which have been able to hold their own in the severe competition of 1932 must be considered fully proved commercial processes. The continuous vertical-muffle retort plant at Palmer- ton is reported to have been in operation at practically full capacity throughout the year. The high quality of metal produced and the low operating costs are factors which have kept this plant running when many of the older furnaces were shut down. The plant at Meadow- brook, W. Va., is also reported to have been in steady operation throughout the year. Average retort life is said to be better than two years with about three-quarters of the original retorts still in operation after 2 ½ years.

Jan 1, 1933

By Richmond Bennett

Airborne geochemistry became a reality with the advent of a high-sensitivity air¬borne gamma ray spectrometer with large volume NAI(Tl) crystal detectors. The high-sensitivity spectrometer measures small variations in the concentration of potassium (as Ks°), thorium (as Tl308) and uranium (as Bi.214) along the flight lines in the area surveyed. Hydrothermal dispersion patterns are indicated by anomalous measured values of the concentrations of potassium, thorium, uranium, or their ratios. In two recent Australian survey areas, copper mineralization was located along favorable structures within hydrothermal dispersion patterns delineated by airborne geochemical surveys. In metamorphic terrane where there had been po¬tassium metasomatism, the hydrothermal dispersion patterns were indicated by high potassium/uranium ratios (K40/Bi). In a sedimentary environment that had been intruded by a stock, the path of hydrothermal fluids was indicated by uranium (Bi214), thorium (TV'), and uranium/ thorium (Bi214/Tl208) ratios.

Jan 1, 1972

[Officers and Committees of the Society of Petroleum Engineers 1 Officers and Staff of the AIME 2 Officers of AIME Sections Predominantly Petroleum in Membership 3 Society of Petroleum Engineers By-Laws 5 Alphabetical List of Members 9 Geographical List of Members 110 List of Members by Companies 127 Advertisers' Index 137]

Jan 1, 1961

By M. E. Wadsworth, T. L. MacKay

Sintered UO, samples were leached in sulfuric acid solutions of various concentrations. A pressurized system was used so that it was possible to investigate the kinetics of the reaction to 270°C with oxygen overpressures as high as 900 psi. The rate was observed to be a function of the concentration of hydrogen ions and directly proportional to the partial pressure of oxygen. Evidences are presented which indicate that a UO2 surface site reacts with a molecule of water to form a hydroxyl complex which in turn can dissociate with the characteristics of a weak acid. A rate determining step has been proposed which involves the reaction between an oxygen molecule and the hydroxyl complex on the surface of UO,. ThE 2 principal methods for uranium dissolution are carbonate and acid leaching. The sulfuric acid leach is the more popular and is used for the treatment of the majority of the ores of Africa, Canada, and the United States. Low recoveries in basic leach circuits led investigators at the University of British columbia1 to study leaching of uranium ores in pressurized vessels. Early in the study of dissolution of uranium it was found that only uranium in the hexava-lent state could be leached in acid or basic circuits. Therefore, the use of oxygen over-pressure in an autoclave offered an interesting approach to solving the low recovery problems of carbonate leaching. UO, was used in this study because it could be obtained in high purity and also because it is representative of the most refractory of the primary uranium minerals. A pressurized system was used to provide a means whereby important temperature and pressure parameters could be varied for the evaluation of the kinetic processes. The mechanism for the dissolution of UO2 should be similar for any of the uraninite type minerals. At the present all of the kinetic studies that have been conducted have been in carbonate media. Peters and Halpern2 carried out a kinetic study of the leaching of pitchblende. Their specimens were pitchblende ores selected on the basis of high grade and homogeneity. Pearson and wadsworth3 conducted a kinetic study of the dissolution of UO2 in carbonate solutions with results very similar to those obtained by Peters and Halpern. EXPERIMENTAL The UO2 as received* was found by spectroscopic *Mallinckrodt reagent, supplied by the Atomic Energy Commission. analysis to have a purity of 99.94 pct 0.03. It was ground in a mechanical agate mortar and screened through a 400-mesh sieve. Thin flat disks of UO2 were prepared by pressing the sized powder in a specially constructed die at a total pressure of approximately 25 tons per sq in. The pressed disks were approximately 0.25 cm thick, 1.6 cm diam, and 3.5 g in weight. As pressed, the samples were approximately 65 pct of theoretical density. It was essential that a binder such as poly-vinyl alcohol be added before pressing to prevent formation of cracks when fired. It was found by trial and error that pressed disks sintered close to 1870°C in a hydrogen atmosphere, reach densities between 91 and 91.5 pct of the theoretical density. At this density the samples had no measurable porosity based upon a 2-hr emersion in boiling water. An X-ray examination of these sintered UO2 disks showed them to be identical with the original UO2 received. Reaction of UO2 with the alundum furnace core was prevented by placing molybdenum between the samples and the core according to the method of Corwin and Eyerly.4 Leaching studies were carried out in a specially designed autoclave, the details of which have been presented e1sewhere.6 The main features of the equipment as applied to a kinetic study are: 1) solution samples may be removed during the course of a single run; and 2) temperature and agitation are carefully controlled. Two-ml samples removed from the autoclave during the course of a run were analyzed for U3O8 content with a Beckman model DK-2 spectrophotometer by the method of

Jan 1, 1959

By W. R. Ingalls

THE paramount subject of interest and concern at the present time is the readjustment in economic conditions following the cataclysmic disturbance produced by the war and the misconceptions leading to an orgy of extravagance that prevailed during two years following the armistice he, time is too short for me to undertake to review the nature and extent of the upheavals occurring between August, 1914, and October, 1920. Bulky volumes will be written about them. . But I shall have to refer to some of the results in order to outline a prognosis. It is the future, not the past;' that is of most interest to us. Let me be so bold as to say, without further preface, that I am not optimistic as to the near future. .We shall, indeed, have revivals in trade, but they will be delusive if their nature be not 'understood. We shall build hopes and expectations upon political maneuvers and events, only to find in the end that they were folly. In the meanwhile fundamental economic influences will continue to exert their steady and irresistible pressure. The new administratiow at Washington has no magic wand with which to kindle the fires in our idle steel furnaces, or create a million new houses for the people; nor can the premiers of Europe put into motion the spindles of the cotton and woolen mills, or by any incantations compel the people of the Orient to buy goods. The people of the Orient, and of, Europe, and of the two Americas are in the grip of the same economic forces. The readjustment has proceeded further in some parts of the world than in others. In the United States I do not think we, have gone more than over the threshold. I shall tell you why 1 think thus, but in telling you I shall be limited, in view of the immensity of the subject, to a series of bald statements, without much elucidation.

Jan 1, 1921

By P. G. Shewmon, H. E. Collins

We have studied the effect of adsorbed sulfur on the surface self-diffusion of copper using eight diflerent surface orientations and the grain boundary grooving method. The eight orientations studied were the four lying near the low-index surfaces—(loo), (Ill), and two directions in the (110)-plus four higher-index surfaces. Surface-diffusion measurements were made over a range of HZS concentrations (in Hz) from 3 to 1500 ppm between 830°and 1050°C. The results can be divided into two groups—Group 1 contains the two (110) surfaces while Group 2 contains the remaining six surfaces. In Group 1, increasing the temperature increases the effect of Hz S on DS for the Hz S range 5700 ppvn. Qs and Do increase with increasing H2S concentration in this Hz S range. Beyond this range, increasing the temperature decreases this effect on D,; also Q, and Do decrease. In Group 2, increasing the telnperature decreases the effect of H2 S on D, for the H2S range studied, and Qs and Do decrease with increasing Hz S concentration. In any study of surface phenomena, there invariably arises the question of the possible presence of and effect of adsorbed impurities. Such questions are well-founded since the presence of adsorbed atoms can sometimes produce marked changes in the kinetics of surface-energy-driven processes. In the last few years, values of the surface self-diffusion coefficient, D,, have been determined on a variety of metals by studying the decay of scratches or the growth of grain boundary grooves.L~3-L0~L3 Yet there has been relatively little work done in which the concentration of an adsorbed impurity was systematically varied and the effects observed. Work of this sort would provide some basis in fact for the assertions often made about the ro1.e of adsorbed impurities in the differences between the results of different workers in different atmospheres and on different metals. It also is relevant to those cases in which surface monolayers produce profound effects in commercially important processes. The most marked example of such effects is the ability of nickel or palladium to increase the sintering rate of tungsten by many orders of magnitude.' The aim of this work was to study the effect of sulfur partial pressures on the surface self-diffusion of copper. It was felt that this in conjunction with a study of the degree of adsorption and type of active sites involvedL8 would provide a wide range of data for one system and hopefully lead to some insight into the mechanism by which sulfur adsorption influences copper diffusion. The main reasons for choosing the Cu-S system were, first, faceting was reported not to accompany the adsorption of sulfur. This is required if our experimental technique is to work. Second, Oudar has determined a high temperature adsorption isotherm for this system, an event which puts the Cu-S system almost in a class by itself.I4 EXPERIMENTAL PROCEDURE Initially, we considered studying the effect of an adsorbed impurity on surface self-diffusion of copper using isolated (or single) scratch smoothing as the technique and oxygen as the impurity. Copper was chosen as the material because the effects of orientation and anisotropy of the surface self-diffusion coefficient, D,, of copper in a dry hydrogen atmosphere had been studied extensively by Gjostein' and by Shewmon and ~hoi.~,~ The isolated scratch technique was chosen because both the effects of surface orientation and anisotropy of D, in a given surface could be easily studied with this method.~ Oxygen was tried as the impurity because Robertson and Shewmon""~ had studied its adsorption on copper at 1000°C over the range of oxygen partial pressures of 10"22 to 10-l3 atm. After several preliminary runs, it became evident that neither the scratch technique nor the impurity oxygen would be satisfactory for this work. Scratching deforms an annealed surface so that the region near the scratches recrystallizes, thereby disrupting the scratch profiles. One can avoid this by deforming the specimen sufficiently before scratching to give complete recrystallization on subsequent heating.4 However, as a result of Gjostein's success in scratching and annealing undeformed gold single crystals without local recrystallization,13 we attempted something similar with copper single crystals using a 0.7-mil diamond phonograph needle mounted in a Tukon hardness tester. All specimens recrystallized upon being annealed. Also, some copper specimens were sent to Gjostein to be scratched using his technique. The results were the same. As a result, the scratch technique was dropped in favor of the grooving of symmetric grain boundaries. Preliminary work using oxygen showed that faceting began to occur before oxygen adsorption had any measurable effect on D, at 938°C (at Pbo/P, = 0.12). Since heavy faceting would interfere with the measurement, we decided to use a sulfur-containing atmosphere (H2S/H2). Work by Oudar and Benard' and Robertson" showed that sulfur absorbed on copper and that faceting was not observed.

Jan 1, 1967

By Waldemar Lindgren

CONTENTS. [ ] I.-CHARACTER OF THE DEPOSITS. 1. Principal Features. IN many schemes of classification and description the term contact-deposit has been somewhat loosely applied to all accumulations of useful minerals (other than those of unquestioned sedimentary origin) which are enclosed between two different rocks. As thus used, the term may include deposits of widely differing origin, and, unless qualified, is not in place in a genetic classification. The present paper deals with a special class of contact-deposits. In many geological provinces, granular igneous rocks, such as granite, diorite and syenite, have broken through and invaded sedimentary rocks. The molten magma may in part have reached the surface and there solidified with relative rapidity as a lava. The largest masses of it, however, did not reach the surface, but cooled very slowly at considerable depth under great pressure, and eventually consolidated into a rock of granitic texture. Uplifts and extensive erosion may have followed; and at the present day, in many places, thousands of feet of material have been removed, bringing to the surface the intrusive granular rocks and their once deep-seated contacts with the sedimentaries which they shattered at the time of in-

Jan 1, 1902

By Mitchell, Edmund I.

VARIOUS suggestions as to proper fees for engineering services have been put forth by individual practitioners and by the American Institute of Consulting Engineers, the Connecticut Society of Civil Engineers, the Iowa Engineering Society and the Mahoning Valley (Ohio) Engineers, for the guidance of both the engineer and his client. The American Institute of Architects also has a schedule of minimum charges (revised 1908). So far as can be determined, however, the four national societies representing civil, mining, mechanical and electrical engineering have never given consideration to this question. An examination of technical periodicals published during the past decade shows that these schedules make provision for three methods of charging; i.e., (A) a percentage of the cost of the completed project; (B) a per diem rate; and (C) a fixed sum. Suggested minimum charges are as follows:

Jan 1, 1921

By H. W. Mead, C. E. Birchenall

SELF-DIFFUSION of iron in austenite is a process which may play a significant role in some of the practically important reactions which occur in solid irons and steels. It also provides a system in which the interaction of vacancies on substitutional sites and atoms in interstitial positions may be investigated. For both purposes, accurate values of the diffusivities are required. Two sets of previous measurements exist, each containing features which require checking. In the course of an investigation to determine the rate of diffusion of iron in certain steels, Garwick and Rosenqvist' measured the self-diffusion coefficient of iron in a 0.10 pct* C steel and obtained a dicated that while at lower temperatures D increased with increasing carbon content, at the higher temperatures it first increased and then decreased. At the same time the activation energy decreased linearly from a value of 69,000 cal per g-atom for pure iron to 33,000 cal per g-atom at 1.06 pct C. This rapid decrease in activation energy implies that iron at higher temperatures within the austenite range would diffuse more slowly in high carbon steels than in steels of lower carbon content. Experimental Procedure The radioactive iron used in this work was obtained from Oak Ridge National Laboratory. The unit consisted of about 1 microcurie each of Fe7 and Fe It was allowed to decay for two years. At the end of this time most of the Fe with a half-life of 46.3 days, had decayed, while most of the original Fe(half-life 2.91 years) still remained. The iron as chloride was extracted into an ether layer, using the method of Ashley and M~rray. After evaporation of the ether the iron chloride was dissolved in 250 ml of aqueous solution containing 2.4 gpl Fe. The compositions of the steels used are listed in Table I. Disks of ¾ in. diam and about ¼ in. thick were machined from these steels for use in diffusion couples. The disks were surface ground on both sides to ensure parallel opposite faces. One face of each disk was polished through 000 emery paper. Half of the prepared disks were plated with radioactive iron. For this, 1 ml of the radioactive iron

Jan 1, 1957

By R. W. Bartlett

The rates of oxidation of tungsten have been determined at temperatures between 1320" and 3170°C and oxygen pressures to 1 amn using a surface -recession measurement technique. Above approximately 2000°C and 10-6 atm the rate is independent of temperature and can be calculated from gas collision theory assuming a constant reaction probability, e, of 0.06. Oxygen molecules react at surface sites where oxygen atoms have previously chemisorbed. This provides a direct pressure dependence at low pressures but at high pressures tungsten oxide molecule s form an adjacent gas boundary layer which lowers the PO2 at the tungsten surface. A correction for this effect using free-convection theory fits the rate data over the entire oxygen-pressure range from 10-8 to 1 atrn as well as data using O2-A mixtures. Below 10-6 atrn and above 2000°C, e decreases with increasing temperature because of desorption of oxygen atoms. Below 2000°C the rate decreases with decreasing temperature at all oxygen pressures following an apparent activation energy of 42 kcal per mole and depending on (Po2)n with n varying between 0.55 and 0.80. MOST of the previous tungsten oxidation studies have employed gravimetric methods and have been limited to temperatures below 1000°C where the weight loss associated with evaporation of tungsten oxides is negligible compared with the weight gain from oxidation.' At higher temperatures, oxygen-consumption rates have been determined from pressure measurements, usually at constant flow rates, by Langmuir,2 Eisinger,3 Becker, Becker, and Brandes,4 and Anderson.5 The sensitivity of this method decreases with increasing pressure and, with the exception of Langmuir's work, these investigations were confined to pressures below 10-6 atm. Above approximately 1300°C, depending on the oxygen pressure, the rate of oxide evaporation is greater than the oxide-formation rate and the recession of the tungsten surface can be measured optically without interference from an oxide layer. This was first done by Perkins and crooks6 who heated tungsten rods in air pressures from 1 to 40 torr at temperatures between 1300" and 3000°C. The present investigation of the oxidation kinetics of tungsten at high temperatures emphasizes oxygen pressures from 10-6 to 1 atm. This is the range of interest for earth atmosphere re-entry applications of tungsten for which little data were previously available. APPARATUS The apparatus is a modification of the type used by Perkins and crooks.' Ground tungsten seal rods, 6 in. long by 0.125 in. diam, were mounted vertically between two water-cooled electrodes, one fixed and the other having free vertical travel. The movable counter-weighted electrode is prevented from undergoing horizontal displacement by three sets of runners mounted at 120-deg intervals. Electrical contact is made by means of a water-cooled mercury pool. A 24-in. vacuum bell jar having a volume of approximately 267 liters was used as the reaction chamber with the sample holder mounted in the middle of the chamber. Power was supplied from an 800-amp dc variable power supply. Temperature readings were made by means of a Latronics automatic two-color recording pyrometer. With this instrument, corrections for emissivity are not necessary provided the spectral emissivi-ties at two closely spaced wavelengths are equal. Supporting measurements were made with a micro-optical pyrometer corrected for emissivity of bare tungsten and window absorptivity. The micro-optical pyrometer was calibrated against a National Bureau of Standards calibrated tungsten lamp and both pyrometers were periodically checked against the melting points of tungsten and molybdenum using the oxidation apparatus. Above 10-6 atm, pressures were measured with an Alphatron gage calibrated against a McCleod gage. At 10-6 atm, a hot-filament ionization gage was employed. A magnified image of the self-illuminated tungsten rod was formed using a 360-mm objective lens mounted outside the bell jar. When the experiment exceeded 1 hr, the image was focused on a ground-glass plate about 10 ft from the tungsten rod at about X8 and the recession of the thickness of this image was monitored with a Gaertner cathe-tometer. When faster rates were encountered, a 35-mm time-lapse cinecamera with a telephoto lens and bellows extension was substituted for the ground-glass plate and cathetometer. Diameter recession rates were determined from the photograph image projected on the screen of an analytical film reader. EXPERIMENTAL PROCEDURE After installing the rod in the apparatus and cleaning it with acetone, the system was evacuated to 5 1 x 10-5 torr. Before oxygen was introduced,

Jan 1, 1964

By J. W. R. Rayner

THE conventional method of making water gas involves individual plants for the separate carbonization of coal to coke and the subsequent gasification of coke with steam. The process demands lump coke, preferably made from the best quality of coking coals. The ash in the coke should have a high melting point and the gasification process suffers a loss of efficiency when cokes with law ash-melting points are used. In Britain, these coals are generally the most expensive and they are readily available only in certain localities. The coals not suitable for making lump coke, or yielding only poor quality coke, are much more widely available and are generally cheaper. DEVELOPMENT OF ALTERNATIVE PROCESSES In Germany, processes have been developed and operated commercially for the production of water gas from very low-rank coals such as brown coal and lignites, but much less effort has been spent on processes to use coals of intermediate rank, which are widely available in Britain. The brown-coal processes use coal in the form of either dust or briquettes. The most successful of the dust-gasification methods is the Winkler process, which made a substantial contribution to German oil production during the war. It uses coal in the site range 0 to 8 mm and the fuel bed is blown with a mixture of oxygen and steam at a rate high enough to give it a characteristic boiling motion or, in present-day phraseology, at a rate more than sufficient to fluidize it (Fig. 1). Air cannot be used to provide the heat required for gasification, for various reasons. In the first place, to make the process continuous by mixing air and steam would involve the production of a lean gas-containing much nitrogen. If a separate blow were used, a large amount of potential heat would be lost because the blow gas in such a process would contain a very high percentage of carbon monoxide. Oxygen is necessary therefore and oxygen remains relatively expensive for use in gasification. In the Winkler generator, formation of clinker caused by local overheating does not occur, because of the mobility and high heat transfer of a fluidized bed. These properties of fluidized dusts have been used most successfully

Jan 1, 1953

By Philip D. Wilson

AS thin most important and vital component of an airplane aluminum hay rapidly become the heart and tome- of the war program. Its production ham increased amt will continue to increase, in comparison with its pre-war position further than that of any of lie other important critical metals except magnesium. Compared with the 1939 production of tons of primary ingot coming from four plants, all owned by the Aluminum Company of America the 1942 figures are more than three timer as large. Including, recoverable scrap and contracted ingot from Canada the 191,, supply of aluminum for the United States will be over siren times dial of 1939- A substantial part of this increase has been achieved during the past year as total production in 1941 was only some 307,500 tons. During 1942 six great new ingot plants sponsored and owned by the Government have come into production and three others are nearing completion.

Jan 1, 1943

By L. H. E. Weyher

As a result of past developments, mainly at universities, the coal industry has had access for a decade or more to a number of computer programs for coal mine planning. Using some of these programs Bethlehem Steel's Research Department in 1969 launched jointly with Bethlehem Mines Corporation an extensive research and development program aimed at: (1) testing the capabilities of these programs through trial applications as the need and opportunity existed, (2) defining what additional capabilities were required to make mine planning computer systems fully useful in the hands of Bethlehem's mine-planning engineers in the field, and (3) developing and implementing in the field the mine-planning systems agreed on. This program is now nearing completion, and several of Bethlehem's operations routinely use the planning tools that were developed. The progress of this research program is discussed in terms of our initial trial applications of computer methods to mine planning and the incorporation of several innovative features into our new set of computer programs, in particular, the use of time sharing, data base management systems, and general-purpose simulation languages.

Jan 1, 1977

By ZJ. H. Brophy, A. L. Prill, H. W. Hayden

The effect of Group VIII transition-element additions on the sintering of tungsten powders is shown to be dependent on the phase relationships of the particular tungsten-Group VIII metal alloy system. The acceleration of sintering with nickel additions is diminished by alloying nickel with copper which is known to diminish both the tungsten solubility in nickel and the solid-vapor surface energy. In work previously published on the effects of additions of Ni, Pd, Pt, Rh, Ru, and Ir, which form solid solutions or intermediate phases of wide composition width with tungsten, sintering behavior is independent of element concentration beyond that concentration necessary to form a continuous layer on the surface of the tungsten powders employed. The sintering behavior of tungsten with additions of iron or cobalt, which form intermetallic compounds with tungsten, is highly dependent on addition-element concentration. Additions in excess of amounts necessary to form continuous layers lead to successively decreased sintering rates. The effects of certain Group VIII transition metals on the sintering rates of tungsten at temperatures below those at which a liquid phase would be predicted have recently been investigated by the present authors1-4 It was found that small additions of palladium, nickel, rhodium, platinum, and ruthenium accelerate the rate of tungsten sintering. Additions of iridium decelerated the rate of densification compared to that of pure tungsten in the same temperature range. In all cases the rate of densification changed with increasing amounts of these additions, up to those compositions at which a continuous layer was formed on the surfaces of the tungsten-powder particles. The rate of densification was then independent of further increases of the compositions of any of these addition elements. These observations were consistent with a sintering model in which the addition element formed an interface with tungsten in which tungsten dif-fusivity was either greater or less than its grain boundary self-diffusivity. Kinetic analysis of this model indicated that linear shrinkage should vary according to the relation:

Jan 1, 1964

By D. E. Thomas

Oxidation rate constants were determined for Cu-Pd and Cu-Pt alloys as a function of alloy composition and temperature. Reaction products were identified. Relationship between oxidation rate constants and diffusion constants in the reaction zones is discussed. THE mechanism of oxidation of alloys is consider--'¦ ably more complex and not so well understood as that of pure metals. The oxidation of a one-phase binary alloy of which one component is a noble metal should logically be the simplest case of alloy oxidation, for in this case one is concerned presumably only with the oxidation of the base metal and the diffusion process by which it reaches the reaction site. This had led a number of investigators to study such systems. Probably the earliest work was that of Tammann and Rienacker' on the tarnishing of Cu-Au alloys at temperatures up to 300°C. These alloys oxidize according to the logarithmic law, that is, the film thickness is proportional to the logarithm of the time. The rate of film formation was found to decrease with increasing gold content. Raub and Engel² investigated the oxidation of Au-Cu, Cu-Pd, Au-Ag-Cu, Au-Pd-Cu, and Ag-Pd-Cu alloys at 750°C in air. These alloy systems form a continuous series of solid solutions at the temperature of oxidation with the exception of those containing silver. Au-Cu alloys oxidize parabolically, the rate constant decreasing slowly with increasing gold content up to about 15 atomic pct* Au, and more rapidly thereafter. An alloy with 14 pct Cu forms only a very thin layer of CuO on the surface and probably also a subscale.† Alloys containing more than 14 pct Cu have scales consisting of CuO and subscales of Cu,O embedded in nearly pure gold. The Cu-Pd alloys obey the parabolic law except for slight deviations for alloys containing 53 and 84 pct Cu. The overall oxidation rate decreases rather smoothly with increasing palladium content. A scale consisting of a thin layer of CuO and a thick layer of Cu²O and a subscale of Cu²O embedded in nearly pure palladium was observed for alloys containing 84, 53, and 30 pct Cu. An alloy with 19 pct Cu formed only a subscale of CuO embedded in nearly pure palladium, and an 8 pct Cu alloy formed only a thin film which was presumed to be PdO. The ternary alloys considered by Raub and Engel oxidized in much the same way as did the binaries. Wagner and Grunewald³ found that Ni-Au alloys, oxidized at 900°C in oxygen, formed a scale of NiO and a subscale containing NiO and gold. The overall oxidation rate increases with increasing gold content, passes through a maximum and then decreases to zero for pure gold. The fact that gold increases the oxidation rate was attributed to "pores" in the scale. Kubaschewski' investigated the air oxidation of alloys of platinum or gold with up to 10 pct Cu or Ni at temperatures in the range 300" to 1550°C. Parabolic behavior was noted for all alloys except Au-Ni, with rates decreasing in the order Au-Cu, Au-Ni, Pt-Ni, Pt-Cu. The diffusion coefficients for the latter three systems are known, and they decrease in the same order. However, activation energies for the oxidation of these alloys do not agree with the activation energies for diffusion in the respective alloy systems. Kubaschewski and Goldbeck7 nvestigated the oxidation of Ni-Pt alloys in air at temperatures of 600"

Jan 1, 1952

By D. Cox, M. J. Duggin, L. Zwell

The carbides of approximate composition and Mn have been studied using X-ray diffraction techniques. Those carbides of the type (Fe,Aln)zC ave isostructural with cementite. The cell pararmeters a and c have minimum values at approximately 10 at. pd substitution of manganese for iron; no satisfactory explanation has yet been found for this phenomenon. The carbide fFeMn4)C has a monoclinic unit cell whose dimensions are close to those of ,11,15Cz A neu-troip-dij~ractiot~ study of (F'eAlrz4)C~ reveals that, like MnsCZ, it is isostructural with Pd5Bz. The iron and manganese atoms occupy the palladium atom sites, while the carbon atoms were found to have the same atomic coordinates as the hovon atoms. A neutrorr-diffraction study of indicates that the carbon-atom positions are very close to those occupied in (Fez.,ll/lr~,.3)C. In both carbides studied, tlre iron and manganese atomzs were found to be essentially randomly distributed, although, in the case of (Fe,.811fn1.2)C, it is possible that there may be a slight preference of manganese atoms for- the general (d) positions and a corresponding slight preference of iron atoms for the special (c) positions. It has been found that a complete range of solid solution exists between Fe3C and Mn3C at 1050°C,I although Mn3C becomes unstable when the temperature is reduced to 95O0C,' and can only be retained by rapid quenching. It is also known that a complete range of solid solution exists from Fe5Cz to M~SC~,~ although the stability range of carbides of the type (Fe,Mn)sCz as a function of the relative proportions of iron and manganese is not known. X-ray examinations of Oh-man's carbide3 and Spiegeleisenkristall,~ which have the approximate compositions (Fe3.67Mnl.33)C2 and (Fe3-,Mn,)C, where x lies between 0.4 and 1, respectively, have been made. The following carbides have also been studied: ] The lattice parameters determined during these investigations are listed in Table I. It is seen that carbides of the type (Fe,Mn)sCz have a monoclinic unit cell while carbides of the type (Fe,Mn)3C have an orthorhombic unit cell. It is evident that the variation of lattice parameters with manganese content is not linear for carbides of the type (Fe,Mn)3C. The coordinates of the atoms in (Fe2.7Mno.3)C have recently been determined by single-crystal analysis., The fractional atomic coordinates have been shown by Fasiska and jeffrey to be in good agreement withj those deduced from an earlier analysis of Fe3C by Lipson and etch.' However, it was impossible to determine whether iron and manganese atoms occupied ordered positions because of the small difference between the atomic scattering factors of iron and manganese. The atomic positions in Mn5Cz (Refs. 8 and 9) and Fe5C2 (Refs. 7 and 8) have been obtained only by comparisons made with the isostructural compounds P~SB~.' Since X-ray diffraction techniques were used in these investigations, accurate positioning of the carbon atoms, which have a low atomic scattering factor, was difficult. No attempt has been made to determine the atomic positions in the other carbides previously studied. It was felt that an investigation of the lattice parameters of a number of intermediate carbides of the types (Fe,Mn)sCZ and (Fe,Mn)& would be of interest. It seemed likely that a neutron-diffract ion study of such carbides would indicate whether ordering occurred between the iron and manganese atoms because of the large difference between the neutron-scattering cross sections of iron and manganese. It also seemed probable that such an investigation would provide a determination of the atomic coordinates of the carbon atoms. I) EXPERIMENTAL DETAILS Specimens, each weighing approximately 20 g, were carefully prepared according to the following proportions: The components were 500-mesh powders of 99.995 pct purity iron and spectroscopically pure carbon and a 200-mesh powder of 99.995 pct purity manganese. The component powders were intimately mixed by prolonged shaking, then each specimen was inserted into a spot-welded cylindrical container of tantalum foil, whose end was closed but not sealed. Each specimen in its envelope was then sintered at 1050° C for 24 hr in a thin-walled evacuated quartz capsule, such a time having been previously found sufficient for equilibrium to be attained.' Each specimen was then quenched in order to attempt to retain the high-temperature phase, as the literature indicates that transformations may occur on cooling. Debye-Scherrer X-ray photographs were taken of each specimen using a 114.6-mm-diam camera, Fig. 1, patterns 2 to 6. The exposure time was 6 hr using filtered iron radiation at a tube voltage of 40 kv and a tube current of 12 ma.

Jan 1, 1967

By R. H. Oliver

The purposes, types, preparation, and testing of flocculants are discussed. A flocculation compendium is included, indicating choice of flocculant for a given set of conditions. An economic evaluation of the process is presented. Solid-liquid separation is a major expense in most mineral processing flowsheets today. Proper use of flocculation can often lower the overall cost of a solid-liquid separation by reducing the size of sedimentation or filtration equipment. PURPOSE OF FLOCCULATION When is use of a flocculant justified in terms of overall process economy? 1) when it results in process improvement, such as producing a clear liquor for electrolysis, precipitation, ion exchange, or solvent extraction; 2) when it results in satisfying requirements of pollution abatement ordinances; 3) when it results in increased recovery of values that would otherwise be lost; or 4) when it results in considerable savings in capital expenditure due to use of smaller equipment. When can the use of a flocculant adversely effect overall process economy? 1) when it results in increased filter cake moisture, 2) when it results in decreased filtration rates, 3) when it results in considerable bulking of sedimentation underflow, 4) when it contaminates either the supernatant or sludge, or 5) when the cost of using the flocculant is greater than the savings due to its use. First step in consideration of flocculants for a given application is establishment of desired goals in terms of increased clarity of effluent, increased recovery of solids, or decreased size of equipment. The most economical solution to a solid-liquid separation problem is that combination of equipment and flocculant costs which meets the established goals at the lowest total annual expenditure. This economic decision can be made only after technical data has been obtained as outlined in next four sections. TYPES OF FLOCCULATION Flocculation is a process wherein individual particles are united into more or less tightly bound agglomerates or flocs, thereby increasing effective particle size of solids suspended in a liquid. Degree of flocculation of a suspension of finely divided solids in a liquid is controlled by a combination of probability of collision between particles and probability of adhesion after the collision has occurred.' Probability of collision can be increased commercially through use of a paddle-type flocculator, combination flocculator, and clarifier or flocculating-type feedwell. Probability of adhesion usually can be increased by addition of a reagent known as a flocculant. Reagents act as flocculants through one or a combination of three possible mechanisms. The first is electrolytic neutralization of inter molecular repulsive force due to Zeta potential. This neutralization enables Van der Waal's cohesive force to hold the particles together after they collide.' The second is the precipitation, within a definite pH range, of voluminous metallic hydroxide flocs which entrap fine particles. This process is known as coagulation.14 Third is the bridging of two or more particles by either natural or synthetic long-chain, high-molecular-weight organic polymers. This bridging is accomplished by adsorption of two particles at different sites on the same molecule or by bonding of two molecules, each adsorbed to a different particle. Considerable effort has been expended in explaining the action of these polyelec-trolytes and detailed accounts are available in the literature. CHOICE OF FLOCCULANTS It is impossible, at the present time, to specify the optimum type or amount of flocculant for a given application from a knowledge of the material to be treated. The standard procedure is to choose reagents or combination of reagents most likely to be effective on the slurry; then test them.' The accompanying Flocculation Compendium (Table I) contains details of all currently available reagents sold as flocculants and it should be used when selecting the group of reagents for tests. This selection can be based on information listed in columns 4 and 5. Column 4 presents industries in which each floc-

Jan 1, 1961

By A. W. WALKER

All branches of production engineering showed steady and definite progress during 1941. Most of it has been of the slower and more conservative type rather than the sensational. To a large degree the changes have been influenced by the expanding war economy, and this tendency will probably be even more marked during the coming year. The stress of the times is placing more emphasis on the principles of engineering and conservation, with the object of obtaining the greatest possible recovery with a minimum waste or expenditure of equipment. Also available material supplies are often being turned to new uses.

Jan 1, 1942