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By John F. Myers

Since the art of comminution has lain practically dormant for many years, it is very interesting that R. T. Hukki approaches the subject with a new concept. One is reminded of the research carried on by A. W. Fahrenwald of Moscow, Idaho, a few years ago. Fahrenwald mounted a steel bowl on a vertical shaft. The balls and ore placed in the bowl were rotated at fast speeds, thus simulating the supercritical speeds used by Hukki. The rolling action of the balls against the smooth shell liner has pretty much the same effect. The action is horizontal in one case and vertical in the other. Both researchers report good grinding activity.

Jan 8, 1958

By T. M. Morris

G. L. Simard and D. J. Salley—The authors and ourselves" independently came to similar conclusions both as to the value of tracer methods for the study of flotation and the general nature of collector-mineral interaction. The dodecylamine-quartz system appears to be simpler than the dithiophosphate-galena one, and the results therefore appear clearer. It is evident from a comparison of the two papers, however, that care must be used in extending the results to other more complicated systems. In the case of dodecylamine-quartz, the possible influence of micelle formation is of interest. There is no a priori reason why complete monolayer formation should necessarily occur at the concentration for micelle formation, since sorption depends on the nature of the substrate as well as on the properties of the solute in solution which alone determine micelle formation. Indeed, the fact that the onset of increased adsorption, point B in fig. 2, occurs at a concentration one tenth the critical value for micelles might imply that micelle formation does not have an influence. Interestingly enough, the data may be handled by the methods used for multilayer adsorption of gases on surfaces. Thus, if the amount adsorbed is plotted versus concentration, a sigmoid type curve is obtained, similar in form to a so-called Type I1 isotherm13 generally attributed to multimolecular adsorption. A monolayer value of about 0.12 mg per g may be estimated from the knee of this isotherm. On the other hand, if a plot is made according to the multilayer gas equation for adsorption to an unrestricted number of layers, eq 38,13 assuming the critical micelle concentration as the saturation concentration, the data above 120 mg per liter fall on a straight line from which a monolayer adsorption of 0.3 mg per g results. These considerations suggest that the monolayer may occupy an area somewhat less than the geometric value of 0.4 mg per g, and that micelle formation may indeed be a factor in the adsorption. the angle between the solid-liquid and liquid-gas interfaces, measured through the liquid. The value of the equilibrium contact-angle is uniquely determined by the value of the interfacial energies of the three intersecting interfaces and is independent of other forces in the system. When the liquid-gas interface intersects the solid at an edge—as was the case for all the experiments reported in this paper—the orientation of the solid-liquid interface is indeterminate or varies through 90" for a right-angle edge. Mr. Morris has called the angle between the horizontal and the liquid-gas interface for this edge condition a "static contact-angle." I feel that this term is unnecessarily misleading. In the first place, "static contact-angle" sounds too much like "equilibrium contact-angle." In the second place, the magnitude of the "static contact-angle," which I would prefer to call the "supporting angle," is determined by the forces in the system other than those derived from the interfacial energies, hence "contact angle" is misleading. If Mr. Morris had said that the "supporting-angle" is variable and depends on the weight of the particle and size of the bubble and that it has a maximum possible value equal to the equilibrium contact-angle, his discussion would have been more accurate. T. M. Morris (author's reply)—Mr. Kellogg puts forth a reasonable criticism of some of the terminology used in the paper. I agree that the term "static contact angle" may be misleading. Substitution of the term "supporting angle" or "vector angle" may be more suitable. F. X. Tartaron—In this paper the author presents a very interesting mathematical development of the forces present when a mineral particle adheres to an air bubble. Excellent concordance is obtained between mathematical formulation and experimental results. It is the writer's understanding that when the mineral surface presented to an air bubble is greater than the area of contact, the maximum contact angle is obtained. However, this contact angle represents distortion of the bubble, the normal shape of which is spherical or in cross-section, circular. This distortion produces a force that acts in opposition to the force of adhesion between the bubble and particle. Hence, at maximum contact angle, the force of adhesion between bubble and particle is at a minimum for static conditions. However, when the size of bubble is increased, the size of particle remaining the same (and all other conditions remaining the same), the contact angle decreases, the distortion of the bubble decreases and the force in opposition to adherence of bubble and particle also decreases. Thus, there is stronger attachment between bubble and particle. When this situation is applied to actual flotation conditions, it is doubtful that it has any significance. The reason is that the bubbles are normally so much larger than the particles, that in substantially all cases, it is probable that negligible distortion of the bubble takes place. In table IV, the author makes computations for bubbles from 0.50 to 2 mm diam. This is from 0.02 in. to 0.08 in. Certainly the bubbles generated in a flotation machine are far larger than this. The surfaces of the author's bubbles range from 0.79 to 12.6 sq mm. The area of contact of the glass rod (0.15 mm diam) is 0.017 sq mm. Thus, ratio of bubble surface to mineral area of contact ranges from 47 to 741 in round numbers. If we take a %-in. diam bubble and a 65-mesh (0.208 mm) particle of cubical shape, the ratio of bubble surface to mineral area of contact is 2931. Mineral particles do not readily become attached to air bubbles. Taggart has shown that in pneumatic flotation machines collector-coated particles are only temporarily attached to bubbles. They keep falling off and down in the froth but at a delayed rate as compared with gangue. Spedden and Hannan's motion pictures confirm the difficulty of attaching particles to air bubbles. In the agitation froth process, according to Taggart, air is precipitated from the water selectively on to the collector-coated particles and these

Jan 1, 1951

By T. M. Morris

G. L. Simard and D. J. Salley—The authors and ourselves" independently came to similar conclusions both as to the value of tracer methods for the study of flotation and the general nature of collector-mineral interaction. The dodecylamine-quartz system appears to be simpler than the dithiophosphate-galena one, and the results therefore appear clearer. It is evident from a comparison of the two papers, however, that care must be used in extending the results to other more complicated systems. In the case of dodecylamine-quartz, the possible influence of micelle formation is of interest. There is no a priori reason why complete monolayer formation should necessarily occur at the concentration for micelle formation, since sorption depends on the nature of the substrate as well as on the properties of the solute in solution which alone determine micelle formation. Indeed, the fact that the onset of increased adsorption, point B in fig. 2, occurs at a concentration one tenth the critical value for micelles might imply that micelle formation does not have an influence. Interestingly enough, the data may be handled by the methods used for multilayer adsorption of gases on surfaces. Thus, if the amount adsorbed is plotted versus concentration, a sigmoid type curve is obtained, similar in form to a so-called Type I1 isotherm13 generally attributed to multimolecular adsorption. A monolayer value of about 0.12 mg per g may be estimated from the knee of this isotherm. On the other hand, if a plot is made according to the multilayer gas equation for adsorption to an unrestricted number of layers, eq 38,13 assuming the critical micelle concentration as the saturation concentration, the data above 120 mg per liter fall on a straight line from which a monolayer adsorption of 0.3 mg per g results. These considerations suggest that the monolayer may occupy an area somewhat less than the geometric value of 0.4 mg per g, and that micelle formation may indeed be a factor in the adsorption. the angle between the solid-liquid and liquid-gas interfaces, measured through the liquid. The value of the equilibrium contact-angle is uniquely determined by the value of the interfacial energies of the three intersecting interfaces and is independent of other forces in the system. When the liquid-gas interface intersects the solid at an edge—as was the case for all the experiments reported in this paper—the orientation of the solid-liquid interface is indeterminate or varies through 90" for a right-angle edge. Mr. Morris has called the angle between the horizontal and the liquid-gas interface for this edge condition a "static contact-angle." I feel that this term is unnecessarily misleading. In the first place, "static contact-angle" sounds too much like "equilibrium contact-angle." In the second place, the magnitude of the "static contact-angle," which I would prefer to call the "supporting angle," is determined by the forces in the system other than those derived from the interfacial energies, hence "contact angle" is misleading. If Mr. Morris had said that the "supporting-angle" is variable and depends on the weight of the particle and size of the bubble and that it has a maximum possible value equal to the equilibrium contact-angle, his discussion would have been more accurate. T. M. Morris (author's reply)—Mr. Kellogg puts forth a reasonable criticism of some of the terminology used in the paper. I agree that the term "static contact angle" may be misleading. Substitution of the term "supporting angle" or "vector angle" may be more suitable. F. X. Tartaron—In this paper the author presents a very interesting mathematical development of the forces present when a mineral particle adheres to an air bubble. Excellent concordance is obtained between mathematical formulation and experimental results. It is the writer's understanding that when the mineral surface presented to an air bubble is greater than the area of contact, the maximum contact angle is obtained. However, this contact angle represents distortion of the bubble, the normal shape of which is spherical or in cross-section, circular. This distortion produces a force that acts in opposition to the force of adhesion between the bubble and particle. Hence, at maximum contact angle, the force of adhesion between bubble and particle is at a minimum for static conditions. However, when the size of bubble is increased, the size of particle remaining the same (and all other conditions remaining the same), the contact angle decreases, the distortion of the bubble decreases and the force in opposition to adherence of bubble and particle also decreases. Thus, there is stronger attachment between bubble and particle. When this situation is applied to actual flotation conditions, it is doubtful that it has any significance. The reason is that the bubbles are normally so much larger than the particles, that in substantially all cases, it is probable that negligible distortion of the bubble takes place. In table IV, the author makes computations for bubbles from 0.50 to 2 mm diam. This is from 0.02 in. to 0.08 in. Certainly the bubbles generated in a flotation machine are far larger than this. The surfaces of the author's bubbles range from 0.79 to 12.6 sq mm. The area of contact of the glass rod (0.15 mm diam) is 0.017 sq mm. Thus, ratio of bubble surface to mineral area of contact ranges from 47 to 741 in round numbers. If we take a %-in. diam bubble and a 65-mesh (0.208 mm) particle of cubical shape, the ratio of bubble surface to mineral area of contact is 2931. Mineral particles do not readily become attached to air bubbles. Taggart has shown that in pneumatic flotation machines collector-coated particles are only temporarily attached to bubbles. They keep falling off and down in the froth but at a delayed rate as compared with gangue. Spedden and Hannan's motion pictures confirm the difficulty of attaching particles to air bubbles. In the agitation froth process, according to Taggart, air is precipitated from the water selectively on to the collector-coated particles and these

Jan 1, 1951

US 4,185,193-Method of assaying the vicinity of a borehole for uranium ore or thorium ore. A pulsed neutron source IS operated to irradiate the earth formations with fast neutrons. A detector responds to the delayed fission neutrons emitted by the ore as a measure of ore concentration and to the delayed neutrons from oxygen-17 as a measure of the neutron output of the source. The measurement of ore concentration is corrected In accordance with the measured changes in the neutron output of the source. R L. Caldwell, assigned to Mobil Oil Corp. Jan. 22, 1980 4 pp (250-269). Filed: 5-18-78 (906,907).

Jan 1, 1982

By J. A. Rowland, C. W. Funk

THIS investigation is a part of the United States Bureau of Mines work in conserving the Nation's resources. The isothermal sections presented were developed as a guide to a comprehensive investigation of the properties and fabricating characteristics of copper-base alloys containing manganese and tin. These alloys are being investigated as possible replacements for the commercial bronzes containing substantial quantities of tin. Development of the isothermal sections has, therefore, been limited to the area between 0 to 20 pct Mn and 0 to 25 pct Sn. Since Heusler1 reported the ferromagnetic properties of the Cu-Mn-Sn alloys in 1903, the system has been the subject of several investigations. These studies were largely concerned with correlation of magnetic properties and crystal structure.2-6 Vero,' however, established the solidus surface of the system, between 20 pct Mn and 40 pct Sn, by thermal and microscopic methods. The a, ß, and y solid solutions were also observed by Vero and reported to extend into the interior of the ternary system. For the present study, the annotated diagram of the Cu-Sn system prepared by Raynor' and the Cu-Mn diagram by Dean and coworkers9 were used as the binary borders of the ternary system. Procedure The metals used in this investigation were electrolytic manganese, washed cathode copper, and three-star tin. The manganese, produced at the Boulder City pilot plant of the Bureau of Mines, had a purity of 99.9 pct; the copper contained less than 0.004 pct Bi and 0.001 pct S; the tin contained 0.070 pct Pb, 0.070 pct Sb, 0.050 pct Fe, and 0.065 pct Si. Heats of 1 lb were melted in alundum crucibles with a 3-kw induction furnace. The heats were chill-cast in iron or copper molds to form 6-in. ingots 3/4 in. in diameter. Molds were washed with graphite or zirconia, depending on the manganese content, and preheated to 150°C. The maximum impurity content of any alloy was 0.03 pct Fe, 0.02 pct Si, and 0.02 pct Al; in most cases, they contained less than half this quantity of any of these impurities. Composition of the alloys and their treatment prior to homogenizing are shown in Fig. 1. Designations adjacent to each composition refer to the heat numbers. With a few exceptions, ingots containing 20 pct Sn or less were hot-swaged. These ingots were swaged, after a 24-hr preheat at 650°C, to obtain a total reduction of 70 pct in cross section. Intermittent reheating was necessary, and reductions were limited to either 0.025 or 0.050 in. in diameter per pass. Selection of a 200-hr homogenizing treatment was based on extensive experiments which indicated that virtual equilibrium was reached after 150 hr. Structures were retained by quenching in water. Grain sizes in the specimens homogenized at 350" and 450°C were generally small. These homogenizing treatments were preceded by a 50-hr anneal at 650°C to facilitate phase identification by increasing the grain size in these specimens. The specimens were furnace-cooled from this temperature to the homogenizing temperature, and the heat treatment was continued for the standard 200-hr period. The homogenized samples were bisected to provide an internal section for metallographic examination. Optimum definition of the microstructure was obtained by successive polishing and etching. Quarter-strength ASTM copper reagent No. 13 gave the most satisfactory results.10 Filings from interior sections of the samples were used for diffraction studies. These filings were annealed in evacuated glass tubes at homogenizing temperatures for periods exceeding 50 hr and quenched in water. During this treatment the manganese content was reduced by significant amounts, probably by vaporization. This change in composition was considered in applying the diffraction data, which were used only as a means of identifying phases where the data were consistent with the metallographic evidence. Phase Identification The a solid solution is readily distinguished by the copper-colored, twinned, polyhedral grains, as shown in Fig. 2, and a face-centered cubic X-ray pattern. Tukon indentations, using a 25-g load, indicate a Knoop hardness of 155 for a quenched from 650°C. Using white light developed by a Wratten 78 A filter, the ß grains in etched specimens have a dark brown tint in contrast to the lighter copper-colored grains of the a phase. Knoop hardness values of 284 were obtained for the ß structure in specimens quenched from 650°C. The ß structure was also distinguished from the a phase by its body-centered cubic lattice. The acicular structure appearing in Fig. 3 was evident in several alloys of higher tin content after quenching from either 750' or 650°C. Since a trans-

Jan 1, 1954

By E. A. Slover

THE usual reverberatory system of smelting cop--1- per concentrate or calcine has for its component parts a furnace and one or two waste heat boilers. These parts are operated on a basis of compromise, since the furnace can send gas to the boilers at too high a temperature and the boilers by plugging, due to dust or slag, can place a definite limit on the amount of fuel the furnace can burn. Over the years the copper concentrate smelting furnace has had few advances in design. The simple rules of design such as the flame should wipe the bath and the speed of the gases should be reasonably low for dust carrying purposes seem to cover the main features. In the construction of the individual furnaces some innovations are always being introduced. Among these are charging so that the work of smelting is a complete bath process, the use of suspended brick arches in place of sprung arches, the use of basic brick, not only in the crucible, but also in roof and sidewalls, the use of various means to feed the charge, the use of magnetite or other heavy material to construct the hearth, water cooling of bridgewall and slag skimming bay, the smelting of raw charge instead of calcine, the use of preheated air, and possibly the use of oxygen-enriched air for combustion. But the general outlines of the furnaces have not changed much except as to size. Furnaces at Hurley As shown on Fig. 1, the furnace at Hurley is 126 ft long between the longitudinal buckstays and 32 ft wide at the skewback plates. The foundation is a concrete retaining wall with piers at intervals that go deeper into the earth. Purposely the wall at the burner end of the furnace is not backed-up as tightly as the other parts of the foundation so that movement due to expansion may take place here rather than into the boiler foundations. Within these foundation retaining walls of concrete, the earth has been removed to allow the placement of the crucible brick base inside of which a silica hearth is laid 4 ft 6 in. in depth. No expansion is left in the brick base and crucible where they are in contact with the hearth. The hearth itself is of quartzite crushed to 1 in. size with fines left in the product. An 8 in. layer is laid and tamped with paving tampers to about 6 in. in thickness. Then a layer of silica flour is spread and vibrated into the hearth. This operation is repeated until a depth of 4 ft 6 in. is occupied by the silica mass onion-skinned in layers of approximately 6 in. Before firing the entire hearth is covered with broken slag to a depth of 4 in. so that a seal may be formed on the hearth. The crucible is completely faced with magnesite chemically bonded brick while the outside, against the foundation, is made of silica brick. The side-walls are carried up with silica brick in which expansion joints are left at intervals. Above the crucible the sidewall is corbelled to form a shelf on which the charge may build up along the side-walls, see Fig. 2. The arch of the furnace is sprung 20 in. silica brick, with the longitudinal centerline horizontal the length of the furnace, and some 9 ft in the center above the bath. Both straight and wedge brick are used in the construction and a thin silica mortar is troweled for joints. After the arch under heat has assumed its permanent shape, a silica slurry is spread over the arch to fill any cracks that have formed, thus giving bearing surface to the brick and preventing dust from entering the body of the arch to act as a future fluxing agent. The uptake of the furnace slopes up to the boiler entrance where a brick pilaster divides the gas stream for the two boilers. Over this flared uptake is a suspended flat arch of firebrick. The pilaster and sidewalls are constructed of firebrick but the bottom of the uptake is lined with silica brick and fettled through holes in the roof with siliceous fettling. Close to the entrance of each boiler is a brick covered slot through which water-cooled dampers may be lowered in event of boiler trouble. These water-cooled dampers are hung permanently in position ready to be lowered when needed. Flexible hoses to follow the dampers as they are lowered are connected at all times and individual chain blocks are used to lower the dampers. A pump supplying water is started before the dampers enter the heat. Charging of the furnace along the sidewalls for some 80 ft from the bridgewall is accomplished by electric vibrating conveyors fed by belt from charge storage bins above the furnace. These conveyors

Jan 1, 1954

By Herbert H. Kellogg

C. M. Decroly (University of Brussels, Belgium) — The importance of the fluorides in the process metallurgy of special metals has already been accepted and it will probably increase in the future. Free energy diagrams as such established by Professor Kellogg are therefore very useful. It is interesting to note that the absolute value of the standard free energy of formation of HF increases with temperature, whereas for almost all the other fluorides it decreases; consequently it should be theoretically possible to reduce all the fluorides of the metals which, at low temperature, have a greater affinity for fluorine than hydrogen by this last element, provided a sufficiently high temperature is used in order to have a good efficiency. However, with regard to the reduction of UFe by hydrogen, I doubt that it will be possible to obtain directly the metal at comparatively low temperatures. There are other uranium fluorides which are more stable than UF6 and it is very likely that such fluorides will be obtained first. For example, in considering the reaction: UF6gas + H2gas + UF1so1id + 2 HFgas it is found, using the thermodynamic data of Brewer et al, that ?H298 = —66 kcal and ?G°298, = —65.2 kcal. As a result, the reduction of UF6 to UF4solld should proceed spontaneously even at ordinary temperature. On the other hand, the standard free energy of formation of UF4solid at 298°K is AG°298 = -209 kcal per mol of F2. The reduction of UF4 by hydrogen will be practically difficult and, as it is known, the only practical way of reducing this compound is to use alkaline-earth metals such as calcium or magnesium. I should like to point out, further, that the fluorination of many metal oxides can be carried out very easily by using the ammonium difluoride method of preparation, which renders the use of fluoride gas unnecessary. The first compound formed is generally a double fluoride of the metal and ammonium. This compound can be decomposed by heating either in a vacuum or in an inert atmosphere, ammonium fluoride being volatilized leaving the metal fluoride in a very pure state. H. H. Kellogg (author's reply)—Professor Decroly is quite right in pointing out that the formation of lower halides of uranium may complicate the reduction of UF6 by H2. I was unable to find his reference to the free energy of formation of UF4 in the compilation of Brewer.13 however. The value of AG°298, = —209 kcal for formation of ½ UFa seems rather high, and I hope the source of this value may be made clear.

Jan 1, 1952

By K. A. ACKLEY

The petroleum industry experienced a year of satisfactory accomplishment in Oklahoma during 1945. Crude oil production was increased, a new record for recent years was established in well completions, and refinery operations were maintained at a maximum level. Daily average crude oil production increased to 382,000 bbl., reflecting a 13.5 per cent gain compared with production during the previous pear. Total wells drilled during 1945 amounted to 2556, a gain of 28.7 per cent over 1944 Refinery throughout averaged 187,500 bbl. daily, an increase of approximately 4 percent over the preceding year.

Jan 1, 1946

By L. BENEDICT

COMMENTING on the report of the latest Royal Commission for India, the September, 1926, issue of the National City Bank's monthly letter states, among other things, that "The decision of the Royal Commission is against the proposal for a gold coinage, but in favor of placing the silver coins and paper currency now redeemable in silver on a gold basis." Also, it quotes the following from the Royal Commission's report: The essence of the proposal * * * * * is that the ordinary medium of circulation in India should remain as at present the currency note and the silver rupee, and that the stability of the currency in terms of gold should be secured by making the currency directly convertible into gold for all purposes, but the gold should not circulate as money. It must not circulate at first, and it need not circulate ever. In this connection it may be stated that during the last one hundred and fifty years or so unsuccessful attempts have been made by the governments of different nations of the world to devise a plan or plans by which gold and silver could be used concurrently for money purposes and, particularly, as standard money; such, for example, as bimetallism, which, of course, is impracticable. But, since none of such plans has been adopted generally it is logical to conclude that their proponents did not shape them so as to conform to the basic principle of standard money, or else political issues were deemed to be dominant, or, perhaps, it was partly due to each.

Jan 1, 1926

By W. D. Robertson, D. A. Koss, A. J. Goldman

THE significance of the hcp (E) structure, which appears when Fe-Cr-Ni alloys (stainless steels) are transformed martensitically, has been the subject of considerable study and speculation.'-7 It has been proposed that the hcp structure is an intermediate phase in the transformation: fcc (austenite) — hcp (E) -bcc (0, martensite). However, recent studies by transmission electron microscopy6,7 have indicated that the hcp structure may be a consequence of the large shear strain (10 deg) associated with the fcc to bcc transformation. That is, the transformation to a bcc structure is accompanied by extensive dissociation of dislocations in the parent austenite, which has a low stacking-fault energy.'-'' X-ray diffraction analysis of the transformed alloy reveals a pattern of lines corresponding to an hcp structure, together with the parent austenite and the bcc product. The fact that the hcp structure is observed only in association with the bcc product in these alloys1'4'6'7 lends support to the conclusion that the hcp structure is a secondary product of the transformation. But, the evidence is circumstantial and more definite resolution of the two possibilities mains to be obtained. If the hcp structure is an intermediate product of the transformation, as in 1) above, then two distinct Ms temperatures should be observed, Ms and To evaluate this possibility, three different techniques that are particularly sensitive to the structural changes accompanying such transformations have been used in an attempt to detect two transformation temperatures in an Fe-15.1 Cr-11.7 Ni alloy: 1) high-sensitivity differential thermal analysis, 2) the temperature dependence of resonant frequency (elastic moduli), and 3) internal friction of cylindrical specimens vibrating in either longitudinal or torsional modes. To obtain the necessary sensitivity, a differential thermal analysis technique was developed for the purpose, Fig. 1. The differential temperature between a nickel standard and the specimen was amplified to produce a sensitivity of 0.02OC (0.7 v) in temperature difference. The specimen and the standard were surrounded by a copper block and the entire assembly was immersed in a solution of methyl and ethyl alcohol, freezing point, - 140OC, which provided the necessary thermal stability to reduce temperature fluctuations to negligible proportions. A cooling rate of about 1.5OC per min was obtained by bubbling liquid nitrogen through the liquid bath. In order to calibrate the experiment with respect to the evolution of heat in the transformation from fcc to hcp structures, differential cooling curves were obtained for an Fe-19.8 Mn alloy, which transforms martensitically to E.'"-' a Ms(e) temperature of 145°C was clearly defined by a temperature

Jan 1, 1964

By Tell Ertl

THE Piceance Creek Basin in northwestern Colorado is believed to contain the richest large deposit of oil shale in North America. The major portion, about 1650 sq miles, is bounded by the White River on the north, the Grand Hogback, which runs from Meeker to Rifle, on the east, the Colorado River to the south, and the drainage basin of Salt and Douglas Creeks on the west. The Basin is a plateau 7000 to 9000 ft high, composed of 3000 ft of the Green River series of Eocene age and surrounded by a steep escarpment of 1000 to 3000 ft. From the escarpment the beds dip gently toward the center. Although oil shale is found in all members of the Green River series, the rich thick beds are found chiefly in the Parachute Creek member. This is normally capped by 100 to 200 ft of the Evacuation Creek, the youngest member of the Green River series. Actually the Piceance Creek Basin oil shale is not a shale, nor does it contain oil. It is magnesium marlstone holding solid organic matter capable of being broken down by heat into gases, some of which can be condensed into oil. The marlstone is resilient nonporous rock, difficult to sample by pick or hammer and moil. Many companies and individuals prospected the Colorado oil shale shortly after the first World War,' see Fig. 1, but because of the discovery of large quantities of petroleum in the late 1920's in Cali- fornia, Oklahoma, and East Texas, interest in oil shale development waned and did not revive until World War 11. In 1944 the writer, employed by the Bureau of Mines, prospected the high grade oil shale in numerous places along the southern outcrop of the Piceance Creek Basin. Several channel samples about 100 ft in length were cut, see Fig. 2. An eight-man crew needed a week to cut a satisfactory channel 80 ft long in the cliff face. The Phillips Petroleum Co., the Union Oil Co. of California and others also prospected the oil shale outcrop. In 1945 the Bureau of Mines initiated a core drilling program for the purpose of obtaining accurate samples from the Piceance Creek Basin. The U. S. Geological Survey set up a program for the geological study of the Basin that is still going on." Until the end of 1951 a total of 31 holes was drilled for core with diamond drills, and, in addition, cuttings through the oil shale have been obtained from 4 gas wells drilled by standard rotary oil well rigs. The Bureau of Mines drilled 12 of the holes, the Union Oil Company of California 8, the Standard Oil Company of California 6, the Sun Oil Company 3,

Jan 1, 1953

By J. G. Thompson

Determinations of the hydrogen content of irons and steels invariably are subject to two serious difficulties: (I) the determination of amounts of 0.001 per cent or less of any constituent requires an analytical procedure of unusual precision and accuracy, and (2) the hydrogen content of many samples is dccidedly not stable; i.e., there is no assurance that the content at the time the analysis is made is the same as it was when the sample was taken or at some previous time in the history of the piece. In respect to both the precision and speed of the determination, the vacuum-extraction procedure for the determination of hydrogen possesses advantages over the vacuum-fusion procedure, which has been the recognized standard for the detcrmination of other gaseous elements in sted-— oxygen and nitrogen for example. The basic facts upon which the vacuum-extraction procedure is based—i.e., the evolution of gas from solid steel when it is heated in vacuum, and the fact that the evolved gas is rich in hydrogen—were observed by Graham1 many years ago. Subsequent investigations have shown that hydrogen exists in steel chiefly as interstitial solid solution (i.e., in atomic dispersion) and perhaps to some extent as hydridcs that are unstable and decompose to form atomic hydrogen. In either case practically all of the hydrogen in steel at elevated temperatures exists in the atomic condition and consequently is able to diffuse readily through the metal. In contrast to this, other gaseous elements, such as oxygen and nitrogen, normally are present in steel chiefly in the form of relatively stable compounds such as oxides or silicates and nitrates; i.e., the oxygen and nitrogen atoms are fixed in stable combinations and are not free to migrate. The only oxygen or nitrogen that can diffuse in steel is the small amount in solution (atomically dispersed) and the rate of diffusion of these atoms is much less than that of hydrogen because of their greater atomic volume and lower mobility. Consequently, it is possible to extract most or all of the hydrogen from solid steel in a reasonable time at moderately elevated temperatures, but the procedure is not applicable to the determination of oxygen or nitrogen. It is only within the last decade that these observations have been developed into an analytical procedure for the determination of hydrogen. Apparatus and Procedure The apparatus used at the National Bureau of Standards,6 for the determination of hydrogen by the vacuum-extraction procedure, is shown schematically in Fig. I. The specimen, freshly cleaned and dried,* is suspended on a fine wire within the quartz furnace tube that is connected to the reservoir system and analytical train.

Jan 1, 1945

By Tell Ertl

THE Piceance Creek Basin in northwestern Colorado is believed to contain the richest large deposit of oil shale in North America. The major portion, about 1650 sq miles, is bounded by the White River on the north, the Grand Hogback, which runs from Meeker to Rifle, on the east, the Colorado River to the south, and the drainage basin of Salt and Douglas Creeks on the west. The Basin is a plateau 7000 to 9000 ft high, composed of 3000 ft of the Green River series of Eocene age and surrounded by a steep escarpment of 1000 to 3000 ft. From the escarpment the beds dip gently toward the center. Although oil shale is found in all members of the Green River series, the rich thick beds are found chiefly in the Parachute Creek member. This is normally capped by 100 to 200 ft of the Evacuation Creek, the youngest member of the Green River series. Actually the Piceance Creek Basin oil shale is not a shale, nor does it contain oil. It is magnesium marlstone holding solid organic matter capable of being broken down by heat into gases, some of which can be condensed into oil. The marlstone is resilient nonporous rock, difficult to sample by pick or hammer and moil. Many companies and individuals prospected the Colorado oil shale shortly after the first World War,' see Fig. 1, but because of the discovery of large quantities of petroleum in the late 1920's in Cali- fornia, Oklahoma, and East Texas, interest in oil shale development waned and did not revive until World War 11. In 1944 the writer, employed by the Bureau of Mines, prospected the high grade oil shale in numerous places along the southern outcrop of the Piceance Creek Basin. Several channel samples about 100 ft in length were cut, see Fig. 2. An eight-man crew needed a week to cut a satisfactory channel 80 ft long in the cliff face. The Phillips Petroleum Co., the Union Oil Co. of California and others also prospected the oil shale outcrop. In 1945 the Bureau of Mines initiated a core drilling program for the purpose of obtaining accurate samples from the Piceance Creek Basin. The U. S. Geological Survey set up a program for the geological study of the Basin that is still going on." Until the end of 1951 a total of 31 holes was drilled for core with diamond drills, and, in addition, cuttings through the oil shale have been obtained from 4 gas wells drilled by standard rotary oil well rigs. The Bureau of Mines drilled 12 of the holes, the Union Oil Company of California 8, the Standard Oil Company of California 6, the Sun Oil Company 3,

Jan 1, 1953

By John A. Mathews

RESEARCH in the steel industry, as in other lines of manufacturing, has for its principal purpose the increasing of profits. That is what manufacturing companies are for, and all departments of the organization must be so coordinated as to lead to profitable operation. To divide a payroll into productive and non-productive labor is misleading. Productive labor, in fact, is necessary labor, and non- productive labor is the labor we can get along without. One might as well say that the steering wheel is not a part of an automobile as to say that the directing minds of an industry are non-productive. Legitimate manufacturing profits in a steel company or any other company are the reward that the public pays for service rendered or risk taken. The desire for profits is the impelling motive that leads investors .to take risks and build up industries that give employment to others. Every department of a company, be it executive, manufacturing, financial, sales, or research, must contribute to the one end which brings success-profits.

Jan 1, 1921

By Nathaniel Hen

IN the United States, in the 2 1/2 years since the rescinding of the wartime order closing gold mines, conditions have not yet returned to normal. Shortages of man power have prevented some mines from operating at all, and most of those in operation are still at reduced capacity. This fact, combined with shortages of materials, the high cost of supplies and labor, high tax rates, and a fixed price for the product have made the past years rather rough ones for gold producers. In foreign countries conditions are rather similar. In Canada several new mines are coming into production and some others are enlarging. Costs have not increased as much as in the United States and gold production is being encouraged. Recently a bonus of 20 per cent on increased production has been proposed. In South Africa, where gold mining is of major importance in the national economy the industry is also in a favored position with government; new discoveries of major importance there will markedly increase the gold output. Demand for labor is rap-

Jan 1, 1948

By D. T. Peterson, T. Carnahan

The diffusion coejTicients of carbon, nitrogen, and oxyget were determined in $ thorium over the tempernilcre range 1440" io 1715°C. The diffusion coyfiicir?zls are given by: D = 0.022 exp (-27,000/RT) jor carbo)~, D = 0,0032 exp(-l7,00Q/RTj for nitrogen, and D = u.0013 expt(-11,UOU/RT) for oxygen. Cavl~orz was found to increase the hardness of thoriunz nearly linearly with concentration over the range 100 to 1000Ppm carbon. ThORIUM has a fcc structure up to 1365°C and a bcc structure from this temperature to its melting point at 1740°C. Diffusion of carbon, oxygen, and nitrogen in bcc thorium was of interest in connection with the purification of thorium by electrotransport.' In addition, it was possible to measure the diffusion of all three of these interstitial solutes in the same bcc metal. Only in niobium, tantalum, vanadium, and a iron have all three interstitial diffusion coefficients been measured in a given bcc metal. Diffusion coefficients have been measured for carbon and oxygen in a thorium by Peterson2, 3 and for nitrogen by Gerds and Mallett.4 Activation energies for diffusion are reported by the above authors to be 38 kcal per mole for carbon, 22.5 kcal per mole for nitrogen, and 49 kcal per mole for oxygen. Values of the diffusion coefficients of carbon and nitrogen in 3 thorium have been reported by Peterson et al.' However, these were secondary results of their investigation of electrotransport phenomena in thorium and it was hoped that the present study could provide more precise data. EXPERIMENTAL PROCEDURE The specimens used in this study were the well-known pair of semi-infinite bar type. The couple was formed by resistance butt welding two 0.54-cm-diam by 3.0-cm-long bars of thorium together under pure helium, the concentration of the solute being greater in one cylinder than that in the other. The finished couple then contained a concentration step at the weld interface and diffusion proceeded only along the axis of the rod. The thorium used in this study was prepared by the magnesium intermediate alloy method.5 The total impurity content was less than 400 ppm. The major impurities were: carbon, 100 ppm: nitrogen, 50 ppm; and oxygen. 85 ppm. The total metallic impurity content was less than 150 ppm. The high solute concentration portions of the diffusion couples were prepared by adding the solute to the high-purity thorium in a non-consumable electrode arc melting procedure. Carbon and nitrogen were added in the form of spectroscopic graphite and nitrogen gas while a Tho2 layer was dissolved by arc melting to add oxygen. High-purity thorium formed the low concentration portions in the carbon and nitrogen couples. The low oxygen portions were obtained by deoxidizing high-purity thorium with calcium for 3 weeks at 1000°C according to a method reported by Peterson.3 The high C-Th contained 400 ppm C, the high N-Th contained 400 ppm N, the high 0-Th contained 220 ppm 0, and the low 0-Th contained 25 ppm O. The high O-Th was brine-quenched from 1500°C to retain most of the oxygen in solution at room temperature. These concentration levels were all below the solubility limits in 0 thorium at 1400°C. A resistance-heated high-vacuum furnace was used to heat the couples. The samples were mounted horizontally on a tantalum support which had small grooves near each end. Spacer rods of thorium, 0.4 cm in diam, were placed in these grooves to prevent contact between the sample and the tantalum support. This arrangement should have prevented contamination of the sample by contact with the support. In further effort to reduce contamination, the oxygen diffusion couples were sealed inside evacuated outgassed tantalum cylinders lined with thorium foil. Thorium rings around each end of the samples acted as spacers in this case. Pressure during diffusion runs was about 10-6 torr after an initial outgassing stage. Temperature measurements were made by sighting on black body holes in the sample support adjacent to the samples with a Leeds and Northrup disappearing-filament optical pyrometer. Temperatures were constant during a diffusion anneal to ±5C. The observed temperatures were corrected for sight glass absorption after each diffusion run. The pyrometer was checked against a calibrated electronic optical pyrometer and a calibrated tungsten strip lamp with the electronic pyrometer being taken as the standard. All temperature readings agreed to within ±3C over the temperature range 1450" to 1690°C. Time corrections due to diffusion during heating and cooling were necessary because of the short diffusion times. The diffusion times ranged from 6 min for the oxygen sample run at 1690°C to 90 min for the carbon sample run at 1500°C. A series of temperature vs time plots were made for heating and cooling of the samples to the various diffusion temperatures. This data was then used in a method according to shewmon6 to determine the time corrections. The corrections amounted to

Jan 1, 1970

By Tell Ertl

THE Piceance Creek Basin in northwestern Colorado is believed to contain the richest large deposit of oil shale in North America. The major portion, about 1650 sq miles, is bounded by the White River on the north, the Grand Hogback, which runs from Meeker to Rifle, on the east, the Colorado River to the south, and the drainage basin of Salt and Douglas Creeks on the west. The Basin is a plateau 7000 to 9000 ft high, composed of 3000 ft of the Green River series of Eocene age and surrounded by a steep escarpment of 1000 to 3000 ft. From the escarpment the beds dip gently toward the center. Although oil shale is found in all members of the Green River series, the rich thick beds are found chiefly in the Parachute Creek member. This is normally capped by 100 to 200 ft of the Evacuation Creek, the youngest member of the Green River series. Actually the Piceance Creek Basin oil shale is not a shale, nor does it contain oil. It is magnesium marlstone holding solid organic matter capable of being broken down by heat into gases, some of which can be condensed into oil. The marlstone is resilient nonporous rock, difficult to sample by pick or hammer and moil. Many companies and individuals prospected the Colorado oil shale shortly after the first World War,1 see Fig. 1, but because of the discovery of large quantities of petroleum in the late 1920's in California, Oklahoma, and East Texas, interest in oil shale development waned and did not revive until World War II. In 1944 the writer, employed by the Bureau of Mines, prospected the high grade oil shale in numerous places along the southern outcrop of the Piceance Creek Basin. Several channel samples about 100 ft in length were cut, see Fig. 2. An eightman crew needed a week to cut a satisfactory channel 80 ft long in the cliff face. The Phillips Petroleum Co., the Union Oil Co. of California and others also prospected the oil shale outcrop. In 1945 the Bureau of Mines initiated a core drilling program for the purpose of obtaining accurate samples from the Piceance Creek Basin. The U. S. Geological Survey set up a program for the geological study of the Basin that is still going on.2 Until the end of 1951 a total of 31 holes was drilled for core with diamond drills, and, in addition, cuttings through the oil shale have been obtained from 4 gas wells drilled by standard rotary oil well rigs. The Bureau of Mines drilled 12 of the holes, the Union Oil Company of California 8, the Standard Oil Company of California 6, the Sun Oil Company 3,

Jan 1, 1952

By B. E. Parsons

Curtailment of production of crude oil, to the extent of effecting an approximate balance in supply and demand, was a problem confronting the oil industry in California throughout the year 1930. At the beginning of the year, with drilling operations only slightly checked, the California industry faced a steadily increasing potential production, an actual production in excess of market requirements and stocks of crude oil and refined products which had reached staggering proportions. During the year, the intensive development of the Playa Del Rey field and extensions to several oil fields, together with flush production from numerous large wells from both new and old fields, caused a steady increase in the state's potential production to a record peak in November of 1,186,000 bbl. daily. Despite the burden of this steady stream of flush production and the handicap of incomplete cooperation in several fields, curtailment successfully lowered the trend of crude oil production in California, except for the period of an open-flow test to determine actual potential production in several important fields in February. Under the curtailment programs in effect, the state's production of crude oil for the year was reduced 22 per cent. under the production of 1929 and even slightly under the production for the years 1927 and 1928. The total stocks of crude oil and refined products were reduced 2.7 per cent. during 1930, as compared to an increase of 30 per cent. in total stocks of all products during 1929. Drilling operations were reduced 28 per cent. as compared to drilling activities during 1929. Voluntary curtailment of drilling programs by many operators, particularly the major companies, accounts for the greatest portion of the reduction in drilling activity. The decline in drilling activity at Santa Fe Springs and in the east-side fields of the San Joaquin Valley was more than offset by development in new fields and extensions to deeper zones of old fields. There were 755 new wells completed during 1930, as compared to 910 completions in 1929. At the close of the year, 220 wells were drilling in the oil fields of California, 9 of which were being drilled in search of deeper producing horizons.

Jan 1, 1931

By A. Mitchell

An approximate phase diagram has been developed for the CaF2-CaC2 system, indicating a eutectic point at 1240°C, Ncac2 = 0.13, and no detectable solid solution in either phase. The liquidus line is shown to correspond to a simple c22- ion in solution. A thermo-chemical study of&apos; the reaction between carbon-saturated Ni-Ca alloys and CaC2-CaF2 liquids indicates that lhe Raoullian activity coefficient of CaC2 in dilute solution in Cap2 al 1500°C lies between 8 and 10. Some effects of the stabilily of Cap2-CaC2 solutions at high temperatures on electroslag remelting praclice are outlined. THE alkaline earth acetylides. MIIC2, have a reasonably high thermochemical stability at high temperature in the solid state,&apos; with the exception of magnesium, which forms an unstable acetylide at low temperatures (-500°C) and a carbide, Mg2C3, in the range 700&apos; to 1000°C. The acetylides of calcium and barium have been shown to have limited solubility in their respective chlorides,&apos; and further these solutions contain the acetylide as a C: ion.&apos; The equivalent magnesium solutions have not been studied. Although calcium "carbide" is used as a desulfuriz-ing reagent in steelmaking. and is possibly present as an acetylide-oxide phase in very basic electric arc practice slags, the acetylide ion appears to be substantially unstable in a silicate slag.* As a conse- *This instability arises from equilibria in the reaction: CaC2 + CO = (Ca0) + 3C where the low intrinsic solubility of CaC2 in silicate lattice, and the low activity of CaO in a silicate solution where CaO/Si02 < 1, combine to give a very small equilibrium concentration of CaC2 in solution in such silicate slags at temperatures in the region of I 500°c, even under carbon-saturated conditions. Under highly basic conditions, a liquid CaO-CaC2 phase may separate from the silicate system quence of this, the possibility that reactions involving CaC2 in silicate solutions are of importance to general steelmaking practice is remote. However, in operations involving a slag primarily based on a halide, or alkaline earth oxide, we must take into account the possibility that CaC2 will appear in quantities sufficient to significantly affect both the chemical and physical properties of the slag. The work outlined below presents a study of the CaF2-CaC2 system intended to provide sufficient data to allow an estimate of the importance of this system to electroslag remelting and welding practice. However, we should indicate at this point that there will be other processes, e.g., heat treatment, flux cleaning of castings, fused salt electrolysis, and so forth, where alkaline-earth halide fluxes are in contact with carbon, graphite, or carbides, and where halide-acetylide solutions must be taken into account. EXPERIMENTAL 1) Structural Studies. In view of the difficulty ex-perienced in handling CaC2 prepared from calcium turnings and propane gas at 700°C, it was decided to use solutions prepared directly in the equilibration apparatus, Fig. 1. The starting materials were: a) Ni-Ca-C alloy, prepared by adding calcium to liquid nickel held under calcium fluoride in an induction-heated graphite crucible; b) calcium fluoride, prepared by fusing calcium fluoride powder (British Drug House "EXTRA PURE") calcium fluoride in an induction-heated graphite crucible, in air, followed by electrolysis between graphite electrodes at 1 amp cm-2 density, for 10&apos; coulombs per g CaF2. This procedure decomposes the CaO produced by hydrolysis during the fusion step, replacing it by CaC2; Ca2+ + 2e-Ca*(l) Ca*(l) + 2C(gr)-(CaC2)caF2 O2- -2e-O*(g) O*(g) +C(gr)-CO(g) This results in a composition of between 2 and 5 wt pct CaC2 in CaF2. Fifty grams (in lumps) of this material were placed in a graphite crucible, together with Ni-Ca-C alloy (averaging 20 wt pct Ca), and the equilibration apparatus assembled. The alloy reacted with the crucible at high temperature to give CaC2, which dissolved in the calcium fluoride solution to give the desired composition. Cooling curves were plotted manually for these liquids, with rapid stirring and CaF2 seeding to minimize supercooling, and using a Pt/Pt 13 Rh thermocouple calibrated on the freezing points of nickel and copper. This gave a reproducibility of ±0.l°C. and an absolute accuracy of the thermocouple of ±l°C. An example curve is shown in Fig. 2, with the CaF2 end of the binary system in Fig. 3. The CaF2-CaC2 ingots were crushed, under dry nitrogen, and sampled for chemical analysis and X-ray examination. Analytical details are given in the Appendix. Powder diffraction data indicated that the only phases present in all samples examined were calcium fluoride and tetragonal (Types I and 111) calcium acetylide,4 with no evidence of solid solutions or compound formation. 2) Thermochemical Studies. The apparatus used to obtain activity data on CaC2 in these systems is shown in Fig. 4. It consists of an arrangement whereby the graphite crucible and its contents (CaF2-CaC2. Ni-Ca-C) can be rapidly cooled without exposure to air. Trial experiments to determine an equilibration time by ap-

Jan 1, 1969

By W. E. Rice

The ceramic industry has to do with forming or molding articles of clay, and imparting to them their characteristic properties of permanence, strength and color by subjecting them to heat treatment in kilns. This heat treatment is commonly known as "firing" or "burning." The art of firing clay ware antedates the industrial use of coal; hence wood was the fuel first used, and the earliest kilns were built to burn wood. The majority of the clay ware produced today is fired in periodic kilns that are essentially enlarged structures similar to the earliest enclosed kilns; a kiln consists of a large chamber 16 to 32 ft. dia. (or rectangular) in which the ware is charged and fired either in direct contact with flame or hot gases from the fuel, or in saggers which shield the ware from direct contact with the gases. The fuel is burned in a number of small furnaces built in the thick wall that encloses the chamber; these furnaces are from 16 to 36 in. wide and from 3 to 5 ft. long; some of them have horizontal or sloping grates, but many have no grates; the last are called "dead-bottom" furnaces. The temperature necessary to mature the charge in the kiln varies for different clays; for some it is as low as 1800°, and for others as high as 2700" F. Wood was an ideal fuel for the low temperatures that were used in early kilns; it burns freely and produces a long, clean flame, which promotes uniform distribution of the heat in the kiln; it does not coke and so restrict the passage of air through the fuel bed; the ash does not melt in the fuel bed to form clinker; and the ash that is carried into the chamber and deposited on the charge does not contain iron and sulfur to discolor the clay. The extent of the ceramic industry now precludes the general use of wood in kilns, so that today this industry is one of the large users of bituminous coal, burning more than eight million tons annually in kilns. Manufacturing plants usually are at or near the source of clay, with deposits of coal suitable for kilns occurring near the clay. The cost of coal is the largest single item of expense in the manufacture of clay ware, and, because all coals are not equally suitable for the process, the careful selection of coal is important. In this selection the desidera-

Jan 1, 1932