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By R. J. P. Lyon

It is usually assumed1,2 that ore deposition is relatively slow, taking place over tens of thousands of years. Yet many syntheses and phase changes can be completed in the laboratory in a matter of hours, under essentially the same pressure and temperature conditions to be expected in nature. Much has been written about geothermometry, and Ingerson's recent summary2 an hardly be surpassed. Rather than review the whole field, this article will deal specifically with diffusion rates in solid solutions* of the sulfide minerals. In the study and application of temperature-indicating phenomena to problems of ore genesis, the time factor has often been neglected. In the particular case of sulfide systems, the speed of unmixing and diffusion of the constituent phases in the solid solutions has seldom been considered when laboratory data are applied to the genesis of natural sulfide ores. Chalcopyrite and Bornite Intergrowths: Chal-copyrite and bornite are copper iron sulfides often found in association. In many ores the individual grains appear to have mutual boundaries, but bladed intergrowths are quite common. Early workers in the field, " deduced that while these patterns could have been formed by replacement, they could be experimentally reproduced from the unmixing of solid solutions of the two previously homogenized at 475°C. Much of the ore from Roan Antelope mine in the Rhodesian Copper Belt exhibits these bornite-chalcopyrite intergrowths, from which it has been deduced that the ores could have been subjected to a minimum temperature of 475°C. In several recent interpretations,' this temperature rise has been considered to result from a regional metamorphism of an original syngenetic copper-bearing sediment. The same temperature rise to 475 °C was suggested from similar intergrowths in the sulfide- • The general subject of solid solution in structurally similar minerels is treated in many texts'. :' ' and will not be further elucidated. bearing ore from the Happy Jack uranium mine8 on tile Colorado Plateau, although this temperature had a different origin. In 1931 SchwartzV etermined that 475°C represented the unmixing temperature of his bornite-chalcopyrite solid solutions but, more important, that the characteristic intergrowths of bornite and chalcopyrite could be preserved only if the solid solution were chilled quickly to room temperature. This significant corollary has been almost completely neglected by both Davis and Miller.7,8 By suitably decreasing the cooling rate, Schwartz found that the original pattern of the intergrowth was reformed (Fig. 1). The cooling rate was critical. In cooling from 475°C to room temperature in

Jan 1, 1960

By S. K. Nicol, A. R. Swanson, J. C. Day

Addition of oil to a suspension of hydrophobic coal particles can influence its dewatering characteristics. An agglomeration process occurs in which coal particles are held together by negative capillary pressure at particle/oil/water contacts. Consequently, the units round which flow can occur are enlarged and this improves dewatering parameters such as drainage rate, solids recovery, and equilibrium moisture content. This paper discusses processes which attempt to use this principle, in terms of metallurgical and economic efficiency. The discussion is augmented by results of recent experiments on the effect of oil addition to centrifuges and vacuum filters.

Jan 1, 1980

By AIME AIME

THE list of deaths reported during the year 1904 comprises the following names (the figures in parentheses indicate the year in which the persons named were elected to membership). Honorary Members.-Sir Lowthian Bell, Dr. Thomas M. Drown. Members and Associates.-Jacob Neff Barr (1884), John Walter Best (1899), A. Poyntz Blandy (1903), A. Cass Canfield (1876), William E. Carroll (1901), William E. C. Coxe (1874), Russell W. Davenport (1877), Isidor Davidov (1893), Louis M. Davis (1884), Edward Doerr (1897), Edward M. Ferguson (1878), C. Le Neve Foster (1893), Geo. Clinton Gardner (1878), Wm. J. Harris (1871), Richard P. Heckscher (1893), H. D. Hoskold (1.894), Wm. S. Hungerford (1882), Edwd. K. Landis, (1882), August Lengemann (1902), Wm. M. Lippitt (1900), Henry McCalley (1888), Robert J. McCartney (1897), Arthur McClellan (1871), Arthur S. Mahony (1888), Philip W. Moen (1888), Henry G. Morse (1881), Charles Parkin (1875), Clarence V. Page (1900), Rubens P. Patterson (1886), Henry Paul (1889), W. H. Pettee (1871), James B. Randol (1879), Irving H. Sevier (1904), Win. J. Sims (1902), John H. Slavens (1901), Chas. B. Squier (1886), Chas. W. Stickney (1891), Homer H. Swaney (1903), Walter B. Wilson (1892), Whittaker Wright, The following paragraphs, constituting the concluding portion of the Annual Report of the Council for 1904, have been withheld from publication until now, in order to make them as accurate and complete as possible. Jacob Neff Barr, a mechanical engineer of note, died on May 5, 1904. Being especially interested in railroad work, he invented the Barr contracting-chill process of casting car-wheels,

Jul 1, 1905

By W. C. Lacy

This article is a progress report of a program designed to quantitatively evaluate geological parameters to predict stable slope angles. The author feels that, although there does not appear to be any one technique or characteristics that will suffice as an index to the determination of stable slope angles, a combination of seismic methods as outlined here, detailed geological mapping and logging of core, and a better understanding of the angle of internal friction in rock types will permit accurate estimation. A mining engineer friend once remarked, "If we don't have pit slope failures, the slopes are too flat." Since economic justification of an open pit project is based upon ultimate pit slopes, we cannot wait until the pit is developed and slopes established by trial and error. Some combination of geological and/or geophysical techniques must be developed to permit accurate prediction of stable slope angles and to suggest modification of pit outlines to result in slopes enabling maximum economic yield. This presentation is a progress report of a program designed to quantitatively evaluate geological parameters to predict stable slope angles. The principle of the weakest link applies to any slope stability evaluation and necessitates detailed geological examination and recording of observations. Physical failure will occur along any surface where shearing stress exceeds shearing resistance. Rock conditions are seldom uniform even within a single cut or pit face, so stability conditions will vary. Consequently, both plan outline and ultimate slope limits must be tailored to the specific situation. Economic advantages to be gained by slight increases in slope angles in deep pits are well recognized and stimulate efforts to obtain maximum permissible slope angles. MECHANICS OF SLOPE FAILURE Excellent reviews on the nature of slope failure have been presented+2,6,8,11 For the purpose of this study, the writer considers failure to take place by one or more of three processes: 1) ravelling, 2) translation or slope failure, and 3) rotation or base failure (Fig. 1). The effects of increased pore water pressure in soils were recognized in 1923 by Terzaghi in his development of the concept of effective stress, and he has applied the same principle to jointed rocks designating water pressure as cleft-water pressure.8 Cleft-water pressure in a rock slope reduces normal pressure on the plane of failure, thus reducing shearing resistance and resulting in slope failure. In the following discussion it is assumed that adequate drainage is supplied to prevent any build-up of water pressure. This is the first step in any program to establish maximum slopes. Ravelling: Ravelling occurs in rocks with low cohesion and entails the free movement of individual fragments ranging from single rock falls to running ground. Removal of lateral support wherever slope angle exceeds the angle of repose of the rock parti-

Jan 1, 1963

By W. T. Roberts, N. G. Turner

A study of the fatigue properties of several grades of commercially pure titanium has established that the strain-aging process is of minor importance in the development of a fatigue limit and a relatively high fatigue strength ratio. Metallographic observations and damping measurements at room temperature indicate that striations are able to spread from grain to grain only at stress levels above the fatigue limit. This suggests that the fatigue limit represents the stress above which large-scale dislocation unlocking takes place. Fatigue tests on annealed material at - 60" and - 196" c showed that under conditions when a thermally activated diffusion process would be suppressed the fatigue limit is not eliminated. Prestraining at room temperature did not have a detrimental effect on fatigue strength at room temperature but a decrease was recorded at — 60°C. This is further evidence that initial dislocation locking is a important strengthening mechanism. TITANIUM and titanium alloys have S-N curves with a definite fatigue limit, and a high ratio of fatigue limit to UTS can be attained. Other materials which show similar fatigue characteristics are mild steel and some Al-Mg alloys. The fatigue limit of these materials has been associated with their strain-aging capacity. It is well-known that commercial-purity titanium contains interstitial impurities which can give rise to a sharp yield point, and a small strain-aging effect following static strain has been demonstrated.7 This type of aging reaction is differentiated from the dynamic aging process when aging occurs during plastic deformation, and which is generally observed at elevated temperatures. In a titanium at room temperature, dislocation locking is associated with the interaction of interstitial oxygen, nitrogen, and carbon atoms with dislocations. Ehr-lich has shown that the distortion produced by introduction of these atoms into the hcp lattice has no shear stress component and hence there is no interaction between the stress field and the screw component of a dislocation. Thus the dislocations as a whole are only weakly locked. It is clear that strain-aging effects in hcp a titanium will be much less pronounced than those observed in bcc iron and steel. In recent years, the attribution of the fatigue limit solely to strain aging has been questioned. It has been pointed out that a definite fatigue limit is observed at temperatures as low as -196°C in some titanium alloys,' and strain aging is not expected to be effective at this temperature. The role of initial locking of dislocations in determining fatigue behavior has been examined in low-carbon steel by Oates and Wilson. They showed that under conditions in which the aging potential is low the factors which control the buildup of local stresses and hence affect dislocation unlocking, e.g., grain size, are important. There are indications that other metals can have a definite fatigue limit with no established strain-aging capacity, an example being magnesium12 which has the same crystal structure as a titanium. The spread of plasticity from grain to grain in hexagonal metals may be more difficult than in cubic metals because of the limited number of slip systems in the former, and this may account in part for their fatigue behavior. The present work was undertaken to elucidate the relative importance of crystal structure, strain aging, and initial dislocation locking in determining the properties of commercially pure titanium when subjected to cyclic stressing. 1) EXPERIMENTAL METHODS Three grades of commercial-purity titanium were used and a material of lower interstitial content was prepared by melting high-purity Japanese sponge titanium (referred to as H.P. Ti). The compositions and typical mechanical properties of the materials are shown in Table I. Fatigue tests were made in push-pull (zero mean stress) using an Amsler Vibraphore machine at a frequency of about 160 cps. Two types of fatigue specimen were used—one with a waisted gage length for determination of S-N curves and the other with a parallel gage length for metallographic studies and damping measurements. After careful machining and mechanical polishing, all specimens were electropolished prior to fatigue testing. The electrolyte consisted of 10 parts methyl alcohol, 6 parts 2-butoxyethanol, and 1 part perchloric acid (SG 1.54) and it was maintained at a temperature of -10" to -20°C during polishing. Tests at room temperature were normally carried out with the specimen immersed in a silicone oil bath which could be heated for elevated-temperature tests.

Jan 1, 1969

By H. F. Porter

MUCH has been written relative to the errors involved in the use of a galvanometer for measuring thermocouple electromotive forces. In general, it may be said that accuracy with a galvanometer is secured only at the sacrifice of durability, unless manual adjustment is made in the operation of the instrument to overcome the errors of resistance. and resistance changes. The pyrovolter and the potentiometer both require manual adjustment for every reading, readings being taken on a "null" method. To the end that some of these balances may be eliminated and only an occasional balance be made as a check reading, the "continuously deflecting pyrovolter" was developed. Essentially, the operation of the continuously deflecting pyrovolter is to determine the resistance of the thermocouple circuit, though its value is not noted or indicated, then throwing in series with the thermocouple sufficient resistance to bring the sum up to some standard value for which the indications of the galvanometer will be correct. This result may, however, be accomplished in a somewhat simpler manner, for which general method patents are now in the course of application. If we devise a galvanometer circuit so that by means of a simple adjustment the resistance of the entire circuit will be rendered equal to some constant predetermined value, we may rely on the galvanometer to give correct e.m.f. indications (assuming that the errors of temperature resistance coefficient and cold junction have been properly allowed for), and will indicate temperature continuously where the e.m.f. measured is developed by a thermocouple.

Jan 9, 1919

By Clarence P. Linville

It is recognized that, in all metallurgical operations, the greatest possible uniformity in all conditions is essential to the best results. It is the constant aim of metallurgists to secure this uniformity, and their success in this respect has been in many cases the cause of great advances in the metallurgical processes themselves. Of all such processes, the production of pig-iron in the modern blast-furnace is perhaps the most complex and the most difficult of control. Notwithstanding the great progress of recent years, there is still great difficulty in obtaining anything like uniform conditions and results in the manufacture of pig-iron. The reason is not far to seek. The ores vary in composition and physical properties, often carrying a varying amount of gangue material, unevenly distributed. The coke may vary in composition, cell-structure, moisture, hardness, and other properties. The blast, the weight of which far exceeds that of any other constituent, varies in its moisture-content and consequently in its chemical composition; and its temperature, by reason of the method of heating, is not uniform, but, besides varying from time to time with atmospheric and other outside conditions, has a maximum and minimum for every changing of stoves. Now, with regard to these variations, the modern demand for uniformity has been greatly aided. Chemical analysis has made it possible to select ores so that the composition of the charge can be kept fairly constant; coal may be obtained from a given field, and coked in the same kind of ovens under conditions which make the fuel practically uniform; the Gayley

Jan 1, 1911

By Roswell H. Johnson, W. E. Bernard

To know the rate of declinc of oil wells is very important, yet ordinarily we are prevented from getting this rate because the oil from several wells is put into one or a few tanks as soon as the wells have been connected to the power. The object of doing this is economy of tanks, pipes, labor, and accounting. But we are making a great sacrifice for this small economy. The advantages of the individual records are that we would know better: 1. When the well has ceased to be profitable. 2. When a well has gotten into bad condition. 3. The real record of the yield per acre and the rate of decline of the wells. The lease total is too mixed as to age of the wells for existing records to have much significance. To obtain such individual well records and more accurate logs are the great desiderata of satisfactory management of oil properties. 4. Which wells show the slowest decline—information which is valuable in locating new wells or purchasing adjoining leases. The truth of this statement is evident, when we reflect upon the large number of purchases of producing property. Intelligent appraisal is of the utmost advantage and it is impossible without individual well-pro-

Jan 1, 1918

By Walter Kauzmann

All viscous or plastic flow of incompressible matter is the result of shear strain; the changing shape of any body that is being plastically deformed can be completely described in terms of the shear strain occurring at each point in the body.† Furthermore, the relative amounts of shear strain occurring in different parts of a body under stress depend upon the relative rates of shear strain at those different points, so that if the dependence of the shear rate of any material on the temperature, shear stress, previous history, etc., were understood, the principles of plastic deformation would be known, and we could calculate how a body made of a given material, having a given shape, and subject to a specified system of forces, would change its shape with time. It may be said, then, that the problem of plasticity resolves itself into, first, the problem of the rates of pure shear processes, and second, the application of what is known about pure shear to actual cases. It is the purpose of this work to investigate the former problem —i.e., the dependence of shear rates on temperature, stress, etc.—from the standpoint of .recent developments in the field of chemical-rate theory and with particular reference to the phenomena occurring in the creep of metals and in the plastic flow of crystalline solids in general. It is left for the mechanical engineer, and perhaps the expert in hydrodynamics, to deal with the problem of app1ications.l Resolution of Macroscopic Shear into Microscopic Movements; Resemblance to Chemical Reactions Just as any large body is made up of many small units, or atoms, so macro-scopically observable shear is the result of many microscopic unit shear processes; just as the understanding of the behavior of large bodies demands the understanding of the atoms of which it is made, so the understanding of macroscopic shear demands the understanding of these fundamental unit processes. The study of shear from this "atomistic" point of view has made considerable progress. There has been fairly complete understanding of shear processes in gases for a long time, at least for non-turbulent flow, as a chapter on gaseous viscosity in any text on the kinetic theory of gases will prove' In recent years Andrade2 and Eyring3 have presented important theories for the flow of liquids and amorphous solids. Becker14 Orowan,5 Taylor,6 Burgers,7 and Kanter8 have considered the plastic flow of crystalline solids from this

Jan 1, 1941

By Walter Kauzmann

All viscous or plastic flow of incompressible matter is the result of shear strain; the changing shape of any body that is being plastically deformed can be completely described in terms of the shear strain occurring at each point in the body.† Furthermore, the relative amounts of shear strain occurring in different parts of a body under stress depend upon the relative rates of shear strain at those different points, so that if the dependence of the shear rate of any material on the temperature, shear stress, previous history, etc., were understood, the principles of plastic deformation would be known, and we could calculate how a body made of a given material, having a given shape, and subject to a specified system of forces, would change its shape with time. It may be said, then, that the problem of plasticity resolves itself into, first, the problem of the rates of pure shear processes, and second, the application of what is known about pure shear to actual cases. It is the purpose of this work to investigate the former problem —i.e., the dependence of shear rates on temperature, stress, etc.—from the standpoint of .recent developments in the field of chemical-rate theory and with particular reference to the phenomena occurring in the creep of metals and in the plastic flow of crystalline solids in general. It is left for the mechanical engineer, and perhaps the expert in hydrodynamics, to deal with the problem of app1ications.l Resolution of Macroscopic Shear into Microscopic Movements; Resemblance to Chemical Reactions Just as any large body is made up of many small units, or atoms, so macro-scopically observable shear is the result of many microscopic unit shear processes; just as the understanding of the behavior of large bodies demands the understanding of the atoms of which it is made, so the understanding of macroscopic shear demands the understanding of these fundamental unit processes. The study of shear from this "atomistic" point of view has made considerable progress. There has been fairly complete understanding of shear processes in gases for a long time, at least for non-turbulent flow, as a chapter on gaseous viscosity in any text on the kinetic theory of gases will prove' In recent years Andrade2 and Eyring3 have presented important theories for the flow of liquids and amorphous solids. Becker14 Orowan,5 Taylor,6 Burgers,7 and Kanter8 have considered the plastic flow of crystalline solids from this

Jan 1, 1941

By Van Der Muelen P. A.

SOME time ago, the writer received from W. 0. Borcherdt, Manager of the, works of the Bertha Mineral Co. at Austinville, Va., several specimens of a dense yellowish slag-like material, containing cavities showing clear needle-like crystals, and representing a product formed by the fumes of zinc oxide and basic lead sulphate from the oxide furnace, attacking the firebrick lining of the flues. The matrix, which is of a greenish-yellow color, is made up chiefly of an amorphous glass, carrying numerous crystals, the latter being well-defined, clear, and transparent, but colored a very light yellow by small amounts of ferric oxide. A number of the crystals were carefully separated from the matrix and tested with the blowpipe. They have a fusibility of about 2, yield a globule of lead and a coating of lead oxide before the blowpipe on charcoal, and contain some zinc. Their hardness is 5 to 6. 1 Fig. 1. Under the microscope the crystals appear to be made up of a prism, with narrow faces, and a fairly large pinacoid, but unfortunately show no terminal faces (Fig. 1). Between crossed nicols they gave parallel extinction in. the three planes containing the crystallographic axes, and are therefore orthorhombic. The index of refraction is high. A number of the best crystals were measured on the reflection goniometer, the angles given below representing the average of measurements made on different individuals. mm = 46° 52' mb = 66° 34' a:b:c = 0.4334:1 :?

Jan 5, 1917

By John A. Ruppert, John E. Conley

Shortages of cinders, largely resulting from industrial plants converting to fuel-oil, together with an enhanced building activity, have seriously affected the cinder block and lightweight concrete manufacturers. In the search for other sources of lightweight aggregate, various clays, shales, slates and natural occurring lightweight rocks such as pumice, scoria, volcanic ash and the like have received special attention. Methods and equipment for producing suitable lightweight aggregates have been considered. In addition to an expanded use of the rotary kiln, the traveling-grate and continuous-sintering machines are being installed in many localities.

Jan 4, 1950

By W. B. Braden

This paper presents a suitable method for predicting gas-free oil viscosities at temperatures up to 500F knowing only the API gravity of the oil at 60F and the viscosity of the oil measured at any relatively low temperature. The API pravity and the one viscosity value are used as parameters to determine the slope of a straight line on the ASTM slanaord viscosity-temperature chart. Then, knowing the slope of the line and one point on the line, the vrscosities at higher temperatures can be determined. The line slope correlations were developed at I00 and 210F since viscosity data are frequently measured at these temperatures. A procedure is given for predicting line slopes from measurements at other tetnperatures. A nomogram is furnished for solving the relationship. The correlation has been evaluated at temperatures up to 5OOF for oils varyzng in gravity from 10 to 33 " API. The correiution is applicable only to Newtonian fluids. Comparison at 500F of true viscosities and those predicted from values at 100F shows an average deviation of 3.0 per cent (maximum deviation of 6.0 per cent). Predictions from the values at 21 0F for the same oils how an average deviation of 1.5 per cent (maximum deviation of 3.4 per cent). INTRODUCTION Correlations have been developed by Beal' and by Chew and Connally' for predicting viscosities of gas-saturated oils at reservoir conditions. Each of these correlations requires a knowledge of the solution gas-oil ratio and the viscosity of the gas-free oil at the reservoir temperature. For temperatures below 350F, measurements of the gas-free oil viscosities can be made easily using commercially available equipment. In thermal recovery processes, however, reservoir temperatures well in excess of 350F are encountered. Viscosity measurements at such conditions are more difficult and time consuming and require modification of existing equipment or the construction of new equipment. Measurements are further complicated by the difficulty of handling highly viscous oils associated with thermal recovery processes. Therefore, it is desirable to have a correlation which allows accurate prediction of viscosities at high temperatures. A commonly used technique for predicting viscosities at high temperatures is to measure the viscosities at two lower temperatures, plot the values on ASTM standard viscosity-temperature charts and extrapolate to the temperatures desired. If either of the values is slightly in error, the extrapolated value can be significantly in error. To justify an extrapolation, three points are actually necessary. This procedure can consume much time, particularly with heavy oils. Considering the cost of viscosity measurements, it would be desirable to eliminate the need for direct measurements by having correlations which would allow viscosity predictions from other physical or chemical properties. Beal1 investigated the possibility of correlating viscosity with oil gravity at temperatures from 100 to 220F. While showing that a general relationship exists, he also found significant deviations. It is possible that correlations will be developed based on oil composition as more information becomes available. While not eliminating the need for viscosity rneasurements, the method presented herein requires that only one viscosity measurement be made. The API gravity must also be known. The theory is based on the fact that the viscosity of paraffins (high gravity) changes less with temperature than does the viscosity of naph-thenes or aromatics (low gravity). The gravity. therefore, is used as a parameter to determine the slope of a straight line on the ASTM standard viscosity-temperature charts. The correlation is applicable only to Newtonian oils, and deviations due to thermal decomposition and nonhomo-geneity cannot be predicted. Oils containing additives have not been evaluated. PROCEDURE Fifteen oils were used in developing the correlation; eight were crudes and seven were processed oils. Oil gravities varied from 9.9" API (naphthene base) to 32.7' API (paraffin base). The temperature range studied was 81 to 516F. Each oil used had a minimum of three viscosity measurements and each plotted essentially as a straight line on the ASTM charts. In all, 91 viscosity measurements were used in the correlation. Saybolt, rolling ball and capillary tube viscometers were used for the measurements. Viscosity data for Samples 1, 2, 4, 7, 10, 11 and 14 were obtained in Texaco, Inc. laboratories. The data for Samples 3, 5, 6, 8, 9, 12 and 15 were from Fortsch and Wilson,3 and data for Sample 13 were from Dean and Lane.' All data points used in the correlation are plotted in Fig. 1. It is seen that some of the viscosity values deviated slightly from the straight-line plots at the higher temperatures. Properties of the oils after exposure to the

Jan 1, 1967

By Charles E. Wait

It is said by some that the occurrence of a deposit of sulphide of antimony in Southwestern Arkansas has been known for fifteen or twenty years. Whether or not such is the case I am not prepared to say, but I am not able to find any record of such a discovery, or any analysis of antimony ore obtained from that section, published at so early a period. The present discoveries, that seem to be attracting some attention, date back to the winter of 1873-74. At that time a vein of ore was found by Mr. Robert Wolf, in honor of whom the vein was named, and still is called, "the Wolf lode." At the time of the discovery the ore was unknown to the prospector, and its composition was not thoroughly understood in that locality until samples were sent to several analytical chemists, who pronounced it sulphide of antimony—stibnite. Since the discovery of this ore there have been three mines opened, and a number of interesting minerals of the antimonial series have been found. I have had an unusually good opportunity to collect specimens from these mines; and it is owing to the constant inquiry concerning the character of these ores that I have collected for publication the results of quite a number of analyses, sufficient I trust to clearly point out their composition. This is one of the few localities in the United States where antimony ore is found in workable quantities ; I say workable quantities, because two different shipments of ore have been made to English reduction works, and in both cases excellent returns were made. The discovery of these deposits will, it is hoped, give rise to a prosperous and remunerative industry at no distant day, and when fully developed they may yield ore in sufficient quantity to supply the regulus for the home demand, thus adding wealth not only to those interested, but also to the State of Arkansas. The three mines are situated in the northern part of Sevier County, and may be reached by the St. Louis, Iron Mountain and Southern Railway to Fulton, thence by wagon-road to Columbus, Nashville, Centre Point, and to the mines. During most seasons of the year the

Jan 1, 1880

By Walter O. Snelling

In the course of some experiments more than five years ago, made for a totally different purpose than the investigation of the oil used, I placed a small quantity of a transparent yellow lubricating oil in a bomb-like vessel and heated it to a relatively high temperature. At the end of the experiment I removed the oil from the vessel and was amazed to find that instead of bearing any resemblance to the oil which I had put in, it now had the appearance of ordinary crude oil. The green color by reflected light and the rich red-brown by transmitted light were so unmistakable as to at once lead to further investigation. I subjected the material to fractional distillation, and the surprise which I experienced at the appearance of the oil, changed to amazement when I found that it yielded, on distillation, 15 per cent. of gasoline and 30 per cent. of burning oil, and that its constitution resembled crude oil quite as much as did its appearance. Furthermore, the gasoline and kerosene distillates which it yielded were of a clear water-white color, entirely without treatment with acid or alkali, and were entirely free from the odor familiar in "cracked" petroleum distillates. The result of this experiment was quite too remarkable to be credited without further confirmation, and I at once filled the vessel with some of the same oil that I had used before, and again heated to about the same temperature that I had previously used, and for the same period of time. Upon opening the vessel and removing the contents I found, not the material resembling crude oil that I had obtained before, but apparently only the same oil that I had put in, somewhat darkened in color, but nevertheless far different in appearance from the material obtained in the previous experiment. Evidently some condition existed in the first experiment that had not existed in the second test, and here began a series of tests in which I sought by the change of one variable after another to arrive at the identical conditions which must have existed in the first experiment. Only the fact that the bottle of heavy oil used in the first test was still in its place,

Jan 1, 1915

By A. U. Seybolt

In part 111' of this series it was shown that during the selective oxidation of a 3 1/4 pct Si-Fe alloy in damp hydrogen, only silica, (observed at room temperature) as low cristobalite or low tridy-mite or both, was formed as an oxidation product. In some in- „ stances where the film was fairly thin (probably well under 100A) there was some suggestion of an amorphous form of SiO2. The present investigation of oxidation rate showed that the selective oxidation of silicon-iron can be rather complicated, and apparently impossible to rationalize in an unequivocal manner. In some temperature regions, notably near 800" and 1000°C, the data seem to obey the familiar parabolic rate law. However, at intermediate temperatures complications were noted, some of which are possibly due to the order-disorder reaction in the silicon-iron solid solution. IN an earlier report' it was shown that during the oxidation of 3 1/4 pct Si-Fe alloys in H2O-H2 atmospheres only silica films were formed in the temperature range from 400° to 1000°C in hydrogen nearly saturated with water at room temperatures, or at dew points as low as -45°C. In the work to be reported here, some observations are made on the rate of oxide film formation. As in the earlier investigation, electron diffraction patterns generally showed either low tridymite or low cristobalite or both, except for some very thin films. These sometimes showed diffuse rings, presumably due to a very small crystallite size, or in a few cases, diffuse bands probably caused by an amorphous film. EXPERIMENTAL PROCEDURE Vacuum-melted silicon iron made of high-purity materials was rolled into strips 0.014 in. thick, and cut into samples 1/2 in. wide by 1 in. long. Chemical analysis showed 3.2 pct Si and 0.002 pct C. All samples were surface abraded with 600-grit paper, were solvent cleaned, and then placed in an paper,apparatus containing a "Gulbransen type"2 micro-balance. Here the gain in weight of the samples of about 5 sq cm area could be followed as a function of time during the oxidation caused by the water in atmospheres of various controlled water-hydrogen ratios. The water-hydrogen ratios can most easily be described as varying from a dew point of 0°C (PH2O-p^2 = 6.2 x 10-3 , to K (P j -40°C (PH2O/PH^= 1.3 X 10-* Most of the experiments were conducted at the 0°C dew-point atmosphere because drier atmospheres caused so little gain in weight that the accuracy of measurement was poor. Because of this, only the data obtained at PH2O,/P,,,= 6.2 x X3 will be reported. The temperature range extended from 800" to 1000°C; and most of the oxidation runs lasted for about 24 hr. The reproducibility of any reading was about ± 1 ?, but the sensitivity of the balance was about 0.2 ?. The atmosphere, flowing at 200 cm per-min, was preheated to the furnace temperature before contacting the specimen. While the gas flow caused a measurable lift on the sample, it was ordinarily sufficiently constant so that it was not an appreciable source of error. X-ray and electron diffraction checks of the samples before and after oxidation showed no evidence of preferred orientation, either on the metal samples or on the silica films formed. EXPERIMENTAL RESULTS The data obtained are summarized in Table I, and some are given in detail in Figs. 1 to 4. In the fourth column of Table I, kp refers to the parabolic rate constant in the expression (?/cm2)2 = kpt + c [1] where ? = micrograms gain in weight kp = parabolic rate constant in units r2 /cm4 t = time in minutes c = constant It will be noted that in many cases no value for kp is given; this is because in these instances the data did not obey the parabolic rate law. The silica film thicknesses given in the last columns are values calculated from the weight gain, an average tridy-mite-crystobalite density, and by assuming a perfectly plane surface. Fig. 1 shows the data plotted in the form of Eq. [I], hence a linear plot indicates parabolic behavior. It has been frequently observed in the literature that

Jan 1, 1960

By S. J. Sindeband

J. WULFF*—It seems to me that the author could improve the quality of his high temperature material by using less nickel as a cementing agent in hot pressing. Furthermore, to avoid the presence of undilfused nickel which would not be oxidation resistant, permit me to suggest that he use a nickel-chromium powder containing a small percentage of boron. This would give him a liquid phase at a lower temperature and accelerate both sintering and homogenization. The commercial alloy known ascolrnonoy contains sufficient chromium to be heat resistant and sufficient boron to be of low melting point. Such an alloy may be applicable as a cementing agent in increasing the quality of Mr. Sindeband's alloys. Finally 1 believe the author unfair to himself in expecting a porous material to have properties equivalent to one of 100 pet density. S. J. SINDEBAND—Dr. Wulff's point is well taken. Early in the program we realized the fact that we were having difficulty with these low-melting alloys, and we had hoped, since the colmonoy alloys of which you speak are at the nickel-rich end of the diagram, that by going to the other end of the diagram (chromium boride-rich) we would not have this difficulty. Thus we tried to use very small percentages of binder; but for reasons which are not exactly apparent we found that when we did this it was necessary to raise the pressing temperature to a point which we were unable to attain. For all compositions which we tried using nickel, or for that matter any nickel iron or cobalt containing material as a binder, we found that we would get low melting boride phases, which as you point out are the commercial "strength" of the hard-facing materials. 1 personally believe these owe a great deal of their behavior and even hardness to the nickel boride which is considerable evidence when an alloy of chromium boride is made with nickel. Nickel boride itself is very hard. We did try pure chromium as a binder and found there was considerable difficulty in handling it, particularly since we could not just hot press under

Jan 1, 1950

By J. B. Clemmer, P. E. Churchward, C. Rampacek

A cyclic method for processing manganese ores using sodium sulphate as the basic reagent is described. Sodium sulphate is electrolyzed in a diaphragm cell to give an anolyte-containing agentisdescribed.Sodiumsulphuric acid and a catholyte-containing iselectrolyzedincaustic soda, a part of which is carbonated in a cyclic manner to form soda ash. The reduced ore is leached with the anolyte to dissolve the manganese and the impurities are precipitated by addition of catholyte. Manganese in the pregnant todissolvethemanganeseandtheimpuritiessolution is precipitated as synthetic rhodochrosite with a carbonated catholyte, and sodium sulphate is regenerated. Calcining the manganese carbonate gives a high grade product and the carbon dioxide is returned to the carbonation step. The results of laboratory tests using cells equipped with synthetic-fiber diaphragms and permselective membranes, which permit transfer of anions or cations during electrolysis, are described. A METHOD which has been considered for pro-cessing manganese ores under emergency conditions to recover a product suitable for smelting to ferromanganese involves reductive roasting of the ore for leaching with dilute sulphuric acid followed by precipitation of the manganese from the purified pregnant solution with sodium carbonate. Although the process is operable and involves no novel or untried steps, it is noncyclic in regard to reagents. Research seemed warranted to determine if a cyclic process could be developed by electrolyzing the sodium sulphate formed during precipitation of the manganese with soda ash to regenerate sulphuric acid and sodium hydroxide. Reduced ore would be leached with acid anolyte to dissolve the manganese. The iron, alumina, and other dissolved impurities would be precipitated with the caustic catholyte, and the manganese in the purified pregnant solution would be precipitated as artificial rhodochrosite with carbonated catholyte to regenerate simultaneously sodium sulphate for electrolysis. Waste boiler gas and CO, from calcining the manganese precipitate would be recycled for carbonation of the caustic catholyte. There is a surprising lack of data in the technical literature on diaphragm electrolysis of sodium sulphate. One of the more comprehensive papers, by Atwell and Fuwa, describes the problem involved in electrolyzing byproduct sodium sulphate from the viscose process with particular regard to the design and operation of asbestos diaphragm cells. Frisk' also investigated electrolysis of sodium sulphate from viscose-spinning baths to recover caustic soda and sulphuric acid. The objective in these investigations was to produce, by electrolysis and evaporation, a concentrated caustic-soda solution and a sulphuric-acid solution low in sodium sulphate. Because of these requirements, the process was not too attractive despite a favorable yield of caustic and acid with a reasonable power consumption. Because strong acid and base are not required for processing manganese ores and nonelectrolyzed sodium sulphate is not objectionable in either reagent, the present problem was somewhat simpler than that of these investigators. The purpose of this report is to summarize briefly the results of laboratory electrolysis of commercial sodium sulphate in diaphragm cells of different types and the application of the acid and caustic for processing manganese ores in a cyclic manner. Electrolysis in Permeable Diaphragm Cells The principal problem in electrolyzing sodium sulphate in a permeable diaphragm cell is to prevent mixing of the acid and base formed in the anode and cathode compartments. It is not enough to separate the anolyte and catholyte by a single diaphragm. A three-compartment cell in which the sodium-sulphate solution is fed to the center compartment and flows through the permeable diaphragms to the anode and cathode compartments is more efficient electrically. Diaphragms should be porous enough to allow flow of solution to outer compartments but tight enough to prevent gross mixing of the anolyte and catholyte. In addition to being resistant to acid and alkali, the diaphragms should offer minimum resistance to the flow of current. It is also important that the electrolyte contain a high concentration of sodium sulphate to furnish an abundance of sodium and sulphate ions and thereby decrease the current carried by hydrogen and hydroxyl ions. A practical limitation of sodium-sulphate concentration is imposed by the decreased solubility of sodium sulphate with decreasing temperature. At 20°C, a concentration of 200 g per liter sodium sulphate can be maintained. Little is gained in conductivity by using a concentration greater than 200 g per liter. The small-scale continuous electrolysis tests were made in a 12x12 in. open-top bakelite cell equipped

Jan 1, 1956

By R. R. Knuckey

HAVING been associated with the operation of the de Vooys process for coal, which has treated 13,000,000 tons per annum, and recognizing the process as of value in ore sorting, Huntington, Heberlein and Co. Ltd. (Great Britain) in 1936 made an examination of all other existing methods. In none of the pioneer applications had recognition been given to the necessity for maintaining certain conditions that are essential for sorting certain ores if a truly efficient separation by gravity alone is to be assured. Consequently, in 1936-1937 Huntington, Heberlein and Co. Ltd., with Pearson, employing certain ideas connected with the de Vooys application, commenced the development of a separator that would allow conformance with optimum conditions in the zone where separation is effected. Later, Holt and Wade added to the value of the original application by Wuensch, Rakowsky and others, whose conceptions are being successfully operated today. Meantime, Trostler had enhanced the value of the original H-H. process by improvements that are now embodied in operating plants, and today the process incorporates an improved apparatus and a stable medium that produce the optimum conditions for separation. These conditions are: 1. Elimination of disturbing currents in the separating zone; 2. Reduction to a minimum of medium-density differences throughout. the separating zone; 3. Stable medium of minimum viscosity to permit the unretarded fall of mineralized particles; 4. Removal of products of separation with minimum disturbance to the separating zone. DESIGN OF SEPARATOR The H-H. sink-and-float separator consists of a pyramidal tank in which the separation actually takes place, connected at the bottom with an inclined bucket elevator. The tank and the elevator are filled with medium to within a few inches of the top of the tank. Medium is fed into the separator at a variety of points, according to the type of ore being treated, and it is withdrawn from the separator at two points: (1) together with the float product, by means of a variable-speed paddle, at the surface of the medium, and (2) by flowing over an adjustable weir cut in the side of the elevator casing. The prepared ore is fed onto the surface of the medium. The intermediate paddles, which revolve at a slow speed of 2 to 5 r.p.m., move the floating ore across the bath from feed end to float-discharge end. The ore, which is heavier than the medium, sinks below the sweep of the paddles and reaches the boot of the bucket elevator, which discharges it without disturbance of the separating zone. These arrangements for withdrawing medium from the separator allow the use of minimum flows, which connote minimum

Jan 1, 1943

By R. R. Knuckey

Having been associated with the operation of the de Vooys process for coal, which has treated 13,000,000 tons per annum, and recognizing the process as of value in ore sorting, Huntington, Heberlein and Co. Ltd. (Great Britain) in 1936 made an examination of all other existing methods. In none of the pioneer applications had recognition been given to the necessity for maintaining certain conditions that are essential for sorting certain ores if a truly efficient separation by gravity alone is to be assured. Consequently, in 1936-1937 Huntington, Heberlein and Co. Ltd., with Pearson, employing certain ideas connected with the de Vooys application, commenced the development of a separator that would allow conformance with optimum conditions in the zone where separation is effected. Later, Holt and Wade added to the value of the original application by Wuensch, Rakowsky and others, whose conceptions are being successfully operated today. Meantime, Trostler had enhanced the value of the original H-H. process by improvements that are now embodied in operating plants, and today the process incorporates an improved apparatus and a stable medium that produce the optimum conditions for separation. These conditions are: 1. Elimination of disturbing currents in the separating zone; 2. Reduction to a minimum of medium-density differences throughout the separating zone; 3. Stable medium of minimum viscosity to permit the unretarded fall of mineralized particles; 4. Removal of products of separation with minimum disturbance to the separating zone. Design of Separator The H-H. sink-and-float separator consists of a pyramidal tank in which the separation actually takes place, connected at the bottom with an inclined bucket elevator. The tank and the elevator are filled with medium to within a few inches of the top of the tank. Medium is fed into the separator at a variety of points, according to the type of ore being treated, and it is withdrawn from the separator at two points: (1) together with the float product, by means of a variable-speed addle, at the surface of the medium, and (2) by flowing over an adjustable weir cut in the side of the elevator casing. The prepared ore is fed onto the surface of the medium. The intermediate paddles, which revolve at a slow speed of 2 to 5 r.p.m., move the floating ore across the bath from feed end to float-discharge end. The ore, which is heavier than the medium, sinks below the sweep of the addles and reaches the boot of the bucket elevator, which discharges it without disturbance of the separating zone. These arrangements for withdrawing medium from the separator allow the use of minimum flows, which connote minimum

Jan 1, 1947