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By Werner Goldsmith, Akihiko Kumano

An experimental investigation was conducted to study the response of soft, porous rock, green shale, under dry and liquid-filled conditions to normal impact of hemispherically-tipped cylindrical steel projectiles with diameter and mass of 6.35 mm and 31 g, respectively. Disk-shaped green shale specimens with nominal thickness and diameter of 32 mm and 127 mm, respectively, were tested in the initial projectile velocity range of 18 to 42 m/s. For the liquid-filled tests, the green shale specimens were saturated with kerosene. A total of eight impact tests were conducted. Information on the extent and pattern of the damage in the rock and velocity histories of the projectiles were collected. It was found that while the penetration depth was quadratically related to the initial projectile kinetic energy for the dry case, the penetration depth for the liquid-filled case was directly proportional to the initial projectile kinetic energy. The results of the impact tests under dry and liquid-filled conditions conformed well to a linearly viscous model and a Coulomb frictional model, respectively. The major deformation processes in the dry specimens were found to be compaction and equivolumnial distortion of the material. In the liquid-filled case, however, formation of cracks and equivolumnial distortion with less material compaction were observed. Furthermore, craters were formed as a result of the crack formation in the liquid-filled specimens.

Jan 1, 1982

V. H. GOTTSCHALK, Rolla, Mo. (written discussion*).-In connection with Mr. Waring's quotation of Urbain's work, attention may be drawn to a remark found in the report of the session of the Société de Chimie Physique,1 held in December, 1909, that, while all blendes contain gallium in larger or smaller quantities, those blendes carrying indium are generally free from germanium, and vice versa. Urbain, furthermore, . expresses his conviction that this behavior, being related to the condi-tions of deposition of the ore, should be an important factor in determining the origin and mode of formation of zinc blende deposits., In. searching the literature for the naturally expected sequel to these remarks, there is found a report on the extraction of germanium from blende, after many months' work, on a commercial scale;2 then a paper3 on some Spanish blendes, all containing cadmium, examined by Urbain's 'method (this paper contains, also, very important work on the com-position and color of blendes, as well as on the occurrence of organic .matter and of inclusions in such blendes), and a second paper on Spanish blendes in general, in which this original point of Urbain's concerning the relative quantities of the three rare elements is taken up.4 Angel del Campo finds that of 68 specimens examined, four only were entirely free of germanium, gallium, and indium;. 38 had small proportions, while 19 were notably, and seven relatively rich in the three rare metals. He found the relative frequency to be: gallium in 60, germanium in, 50, and indium in 38; all three occurred in 29 cases; germanium and gallium together in 18; gallium and indium together in four; germanium and indium together without gallium, in none; four had gallium only, three had germanium only, and one had indium only; in 23 it appeared feasible to extract these elements. Finally, it may be worth mentioning that the discovery of gallium in commercial aluminum5 brought forth two

Jan 1, 1918

By Herbert Hoover

This paper is in the nature of a rough preliminary report on the progress that has been made in the application of the mass spectrometer to various problems arising in the petroleum industry. A few years ago the authors considered a number of the problems that were arising in the qualitative and quantitative measurement of small amounts of hydrocarbons. The methods available of making analyses by chemical techniques appeared to leave much room for improvement. Without going into the reasons at this point, attention was turned to the possibility of employing physical instead of chemical methods of accomplish-ing the desired results. A preliminary investigation disclosed that the mass spectrometer presented a possibility of solving many problems which could not easily be accomplished by other methods. Work was begun in developing the necessary apparatus and technique. A great deal of encouragement and many valuable suggestions were received from Dr. Robert A. Millikan, Dr. W. R. Smythe, and Dr. W. N. Lacey, of the California Institute of Technology, and from Dr. E. 0. Lawrence, who recently received the Nobel Prize, of the University of California. The authors particularly wish to acknowl-edge the very great willingness of these out-standing scientists to be helpful in solving many of the problems that were involved. So far as the authors are aware, this was the first application of the mass spectrometer to commercial work. The results were considerably better than had at first been anticipated. Briefly, it is pos-sible to run a qualitative and quantitative analysis of an unknown mixture of hydro-carbon gases, with an accuracy of better than plus or minus 5 per cent of each of the various constituents. An exceedingly high degree of sensitivity has been obtained, and a relatively short time is required to com-plete an analysis. Furthermore, it is un-necessary to separate a mixture of gases into its various components in order to complete the analysis.

Jan 1, 1940

By W. A. Selvig

BY plotting fixed carbon against British thermal units of coals free from mineral matter, and ranging in rank from anthracite to lignite, it is found that the coals of higher rank, from anthracite to the higher rank of the high-volatile bituminous coals, inclusive, can be separated into groups according to their degree of metamorphism by reference to their fixed carbon. Such charts show also that the coals lower in rank can be best separated into groups with respect to B.t.u., especially when plotted on the moist basis, that is, coal containing its natural bed moisture. A tentative scheme for coal classification was presented at the October, 1932, meeting of the Technical Committee on Scientific Classification, of the American Standards Association Sectional Com-mittee on Coal Classification. This scheme was sponsored by Sub-committee IV on Tentative Classification of Coals, under the chairmanship of W. T. Thom, Jr. It proposed the grouping of coals according to rank by reference to fixed carbon and B.t.u., on the basis of coal containing its natural bed moisture but free from mineral matter. This scheme proposed classifying coals into four broad classes: (1) anthracitic, (2) bituminous, (3) subbituminous, (4) lignitic.. The anthracitic class was divided into three groups designated as meta-anthracite, normal anthracite, and semianthracite. The bituminous class also was divided into three groups, low volatile, medium volatile, and high volatile. The high-volatile group was further subdivided into four subgroups according to moisture content, as follows: (1) less than 5 per cent, (2) 5 to 10 per cent, (3) 10 to 15 per cent, and (4) 15 per cent and more. The subbituminous class was divided into two groups, group, 1 including subbituminous coals having calorific values of 10,500 B.t.u. or more, and group 2 including those with less than 10,500 B.t.u. , The lignitic class of coal was divided into two groups both below 8,000.B.t.u., the one group consisting of consolidated and the other of unconsolidated

Jan 1, 1934

By Julian Avery

IN its dual role of pig-iron smelter and gas producer, the blast furnace is a remarkably satisfactory and efficient apparatus. Many metallurgists and engineers have pointed out, however, that since the primary function of the blast furnace is to produce pig iron at the lowest possible cost, its function as a gas producer should be subordinated to this primary pur-pose. During the past 10 years or more, improvements in blast-furnace technique and economy have, in fact, been directed primarily to increasing efficiency in the use of the reducing power of the gases produced by com-bustion of coke at the tuyeres, to reduce iron ore within the furnace. The net over-all result is a decrease in the fuel value of the top gas per unit of volume, and per ton of pig iron, which is evidently more than offset in value by the corollary saving in coke and the possibility of increased furnace capacity, for otherwise there would be no point in making such improvements. The purpose of the present paper is to suggest that, while progress has been made in this direction, there is another approach to the problem of increasing the chemical and thermal efficiency of the blast furnace in its primary role as a pig-iron smelter, which appears to offer possibilities of improvement in over-all economy of a different order of magnitude than results thus far obtained by the use of other expedients. The present argument is based in large part upon the hypothesis that the effi-ciency and economics of pig-iron smelting are seriously and adversely affected by the phenomenon known as "solution loss," and that the problem of solution loss can be successfully attacked by increasing the over-all pressure; i.e., the "top pressure" under which the furnace is operated. It is indicated that pressure operation may also be expected to result in concomitant benefits, which may be summed up as generally improved operating conditions, together with a substantial saving in fuel and/or a substantial increase in furnace capacity.

Jan 1, 1938

The co-operation of the members of the Institute is earnestly sought by the Committee on Nominations, recently appointed by the Board of . Directors, in its work of formulating a ticket for officers and places falling vacant in the Board of Directors in February, 1916. The Committee must present the official ticket of nominations to the Board of Directors at its October meeting. Members are, therefore, urged to send promptly their nominations for officers and Directors in order that the Committee may have an opportunity to give them full consideration. The officers to be elected at the annual meeting in February, 1916, are: One officer, known as Director and President. Two officers, known as Director and Vice-President. Five officers, known as Director; The attention of members is called to Articles V and VII of the Constitution, and to By-Law XIII, which reads as follows: "The geographical districts to be considered by the Committee on Nominations shall he as follows, until otherwise ordered by the Board. District No. 1. New England, New York, and New Jersey, excepting New York City and district., which is provided for in the Constitution. (N. B.-New York City and district is designated District 0.) District No. 2. Pennsylvania. District No. 3. Ohio, Indiana, Illinois, Iowa, and Missouri. District No. 4. Minnesota, Wisconsin, and Michigan. District No. 5. Montana, North and South Dakota, Wyoming, Nebraska, Kansas, Washington, Oregon, Idaho, and Alaska. District No. 6. California and Nevada. District No. 7. Utah, Colorado, Arizona, and New Mexico. District No. 8. Louisiana and Texas. District No. 9. Other Southern States and District of Columbia. District No. 10. Mexico. District No. 11. Canada."

Jan 7, 1915

By Michel T. Halbouty

The area for which oil and gas developments in South Texas are reported for 1940 in this paper covers the same counties that were included in the reports for 1938 and 1939, with the addition of LaSalle County. LaSalle County is includcd in the Laredo district of South Texas, which totals seven counties for that district. The Corpus Christi district remains the same, with nine counties. The two districts together comprise what is known as the South Texas area for this report. Continued exploration along established trends and beyond proven field limits during 1940 provided South Texas with new fields and new producing levels at a rate of discovery fairly comparable with the high records set during recent years. The wells drilled in the counties within this district (including LaSalle) numbered 1656, approximately 8 per cent below the 1801 figure of last year. However, rank wildcats totaIed 336, an increase of 17.5 per cent compared to the 286 drilled in 1939. Therefore, since new field discoveries numbered 25 in 1940 against 29 in 1939, the rate of new field discoveries in 1940, based upon rank wildcats drilled, was I/I3.4 while that of 1939 was I/9.86, which shows a decrease of about 25 per cent in the rate of new fields. The rank wildcat tests in 1940 gave the following results: 18 produced oil, 4 produced distillate with gas, 3 produced. only gas, and 3r1 were dry holes (Table 5). Of the 1320 tests drilled in already proven fields or as extensions to pro+en areas (representing a decline of 12.8 per cent from last year's total of 1515 tests), 1048 produced oil or distillate, 60 produced gas and 212 were dry holes (Table 4). Of the producers, 50 found new sands or crude-in-distillate-sands in existing fields. Among the several fields subjected to extensive development were: Colorado, Jim Hogg County; East White Point, San Patricio and Nueces County; Rincon and Sun, Starr County; Glen, Webb and Zapata Counties; Wade City and Orange Grove, Jim Wells County; Stratton and South Clara Driscoll, Nueces County, and Aransas Pass, San Patricio and Aransas Counties. The development of important crude reserves on structures formerly considered primarily distillate fields has probably been the most important phase of the year's operations in South Texas. The Rincon, Stratton, Agua Dulce, Wade City, Odem and Robston fields provided the new crude sand discoveries. At some places crude production was opened by exploratory wells that found new sand horizons; in others by flank wells that found already discovered distillate sands sufficiently low to provide crude production. Rincon, Starr County, with its multiple sands, is now believed to be one of South Texas' largest crude-oil reserves. Offshore drilling showed important results during the year, including the discovery of two new submerged fields and the extension of the East White Point field into offshore Nueces County. The new marine fields are: East Flour Bluff) 76

Jan 1, 1941

By Michel T. Halbouty

The area for which oil and gas developments in South Texas are reported for 1940 in this paper covers the same counties that were included in the reports for 1938 and 1939, with the addition of LaSalle County. LaSalle County is includcd in the Laredo district of South Texas, which totals seven counties for that district. The Corpus Christi district remains the same, with nine counties. The two districts together comprise what is known as the South Texas area for this report. Continued exploration along established trends and beyond proven field limits during 1940 provided South Texas with new fields and new producing levels at a rate of discovery fairly comparable with the high records set during recent years. The wells drilled in the counties within this district (including LaSalle) numbered 1656, approximately 8 per cent below the 1801 figure of last year. However, rank wildcats totaIed 336, an increase of 17.5 per cent compared to the 286 drilled in 1939. Therefore, since new field discoveries numbered 25 in 1940 against 29 in 1939, the rate of new field discoveries in 1940, based upon rank wildcats drilled, was I/I3.4 while that of 1939 was I/9.86, which shows a decrease of about 25 per cent in the rate of new fields. The rank wildcat tests in 1940 gave the following results: 18 produced oil, 4 produced distillate with gas, 3 produced. only gas, and 3r1 were dry holes (Table 5). Of the 1320 tests drilled in already proven fields or as extensions to pro+en areas (representing a decline of 12.8 per cent from last year's total of 1515 tests), 1048 produced oil or distillate, 60 produced gas and 212 were dry holes (Table 4). Of the producers, 50 found new sands or crude-in-distillate-sands in existing fields. Among the several fields subjected to extensive development were: Colorado, Jim Hogg County; East White Point, San Patricio and Nueces County; Rincon and Sun, Starr County; Glen, Webb and Zapata Counties; Wade City and Orange Grove, Jim Wells County; Stratton and South Clara Driscoll, Nueces County, and Aransas Pass, San Patricio and Aransas Counties. The development of important crude reserves on structures formerly considered primarily distillate fields has probably been the most important phase of the year's operations in South Texas. The Rincon, Stratton, Agua Dulce, Wade City, Odem and Robston fields provided the new crude sand discoveries. At some places crude production was opened by exploratory wells that found new sand horizons; in others by flank wells that found already discovered distillate sands sufficiently low to provide crude production. Rincon, Starr County, with its multiple sands, is now believed to be one of South Texas' largest crude-oil reserves. Offshore drilling showed important results during the year, including the discovery of two new submerged fields and the extension of the East White Point field into offshore Nueces County. The new marine fields are: East Flour Bluff) 76

Jan 1, 1941

By Kirtland Marsh

THE manufacture of gas masks by the Chemical Warfare Service, U. S. A., required preparation of the carbon used in the canisters. The largest plant for the production of this carbon was situated at the works of the Astoria Light, Heat and Power Co., at Astoria, N. Y.; this paper will deal1 with the pyrometry equipment at that plant. Commercial charcoal was found unsuitable for use in gas masks because of its low power of absorption and its poor resistance to abrasion. The best raw material for the production of carbon was found to be coconut shells, but any kind of nut shells or fruit pits were used when sufficient quantities of coconut shells could not be obtained. The shells were first carbonized in retorts, the carbon was then crushed and screened between 8 and 16 mesh, and finally submitted to a special heat-treatment in air; steam treatment was later substituted for treatment in air. The production of gas-mask carbon on a commercial scale was begun at Astoria about Aug. 1, 1917. Temperature control was essential during the initial carbonization of the shells, as well as during the air or steam treatment, and pyrometers were installed for this purpose. The installation and maintenance of all pyrometry equipment was done by the pyrometry department, consisting of an officer in charge, an assistant, and two men. A special pyrometry laboratory was maintained in which all repairs were made.

Jan 9, 1919

By Jei Y. Choi, Paul G. Shewmon

The surface self-diffusion coefficient of copper (D,) has been measured between 847° and 1069 "C for six different orientations. These were the(111), (110, (100, and three higher index surfaces. The activation energy for Ds (designated Q s) was found to be about 49 kcal per mol for all six surfaces, and Do about 2 x 104 sq cm per sec. At any temperature Ds varied by no more than a factor of three over these orientations. It is shown that, if the free energy of a surface atom is uniquely determined by its number of nearest neighbors, it follows from the Principle of microscopic reversibility that Qs should have the same value for all surface orientations, and Ds should vary little with orientation. This model also suggests that for clean fee metals Qs ~ 2/3 AH, (heat of vaporization). This is true for copper. ALTHOUGH it has been appreciated for several decades that atoms can diffuse more rapidly on a surface than through the bulk of a crystal, it has only been in the last few years that reliable values of the surface self-diffusion coefficient (Ds) have become available. Tracer studies of Ds had been attempted prior to this period, but when a tracer is placed on a surface, an ever increasing fraction of it is drained off into the lattice. The correction for this loss involves a very difficult, and as yet unperformed calculation. Those who have worked with tracers have not corrected for this loss.1, 2 Thus their results indicate that Ds is greater than the self-diffusion coefficient in the lattice (Dl), but it has not been established that they give quantitative data on Ds. A procedure which avoids the problem of tracer loss is to study the rate of mass-transfer under the effect of surface tension. If the surface asperity being studied is very small, the mass transfer occurs entirely by surface diffusion. The kinetics at which a grain boundary groove forms on an initially plane surface is a well-studied case of this type. The smoothing of a slight scratch in an otherwise flat surface is another procedure that has been studied. If these grooves are up to 20 to 30 µ in width, the dominant mechanism for mass transfer is surface diffusion (at least in the case of metals with low vapor pressures), and the widths can easily be measured with an interference microscope. Of these two, mass-transfer techniques only in the case of grain boundary grooving has a rigorous mathematical treatment been given. This was done by Mullins.3,4 His analysis predicted that in the case of copper in an atmosphere of an inert gas, surface diffusion should be the dominant transport mechanism. This analysis gave an equation for the groove profile and predicted that the width of the groove would increase as (time)1/4. Mullins and Shewmon showed that both of these predictions agreed with experiments.5 Thus the validity of the values of Ds given by this procedure seems to be well established. Gjostein has used copper bicrystals and the grain boundary grooving technique to determine Ds and the activation energy for surface selfdiffusion (9,) in the [001] direction on surfaces ranging between the (100) and (110) planes.= He reported that Qs = 41 kcal per mole and Do = 6.5 x 102 sq cm per sec for all orientations studied. Since the results did not change with the dew-point of the dry hydrogen atmosphere or the type of refractory tube used, he concluded that the surfaces were clean, or at least that the results were not influenced by any impurities chemisorbed from the atmosphere. The work reported here reproduces and extends Gjostein's study in that D s and Q s were determined for copper over a wider range of orientations. To study the effects of impurities, two purities of copper were used as well as cathodic etching to remove any possible electropolishing film. Gjostein postulated that the diffusing atoms on a surface near a low index plane are the few atoms which are adsorbed on the smooth region between ledges or steps in the surface. A more rigorous derivation of the equation relating Ds to the concentration and jump frequency of these adsorbed atoms is given here. Using this treatment, our empirical observation that Q s and D s are essentially the same for all surface orientations can be shown to follow from the assumption that the free energy of a surface atom is uniquely determined by its number of nearest neighbors. The studies of D s using the scratch technique have been carried out by Blakely and Mukura on nickel,' and by Geguzin and Oveharenko on copper. The latter study using copper gives values of D s roughly

Jan 1, 1962

By E. E. Donath

THE coal hydrogenation process is well known as a means for the production of liquid fuels -from coal. In this paper the possibilities of the coal hydrogenation process as a source of chemical raw materials will be discussed. The recovery of chemicals from coal hydrogenation products necessitates some modifications and additions to the equipment used for the production of fuels. The conversion of coal into liquid fuels such as gasoline requires two steps: liquid phase and vapor phase hydrogenation. Intermediate oils obtained in the liquid phase contain oxygen and nitrogen compounds, especially aromatic compounds, since the coal itself is composed mainly of cyclic compounds. These oils are the raw material for the separation of high molecular weight aromatics and of tar acids and tar bases. The relative amounts of heavy and middle oil-boiling above and below, e.g., 325°C-can be influenced by temperature, residence time, and catalyst of the liquid phase hydrogenation. In the vapor phase hydrogenation a solid bed catalyst is used to convert the intermediate oil from the liquid phase operation into hydrocarbons of the gasoline boiling range. Essentially pure hydrocarbons with a low content of sulphur, oxygen, nitrogen, and olefines are obtained. Depending mainly on the catalyst, the high ring compound content of the liquid phase oil can be preserved and gasoline rich in aromatics obtained. However, with other catalysts, these ring compounds can be split into gasoline with a high content of isoparaffins.1 Again, depending on the operating conditions, products of varying boiling range can be obtained. Selection of catalyst and operating conditions therefore makes possible the production of different grades of motor fuel and also variations in the relative amounts of benzene, toluene, and xylene when aromatic hydrocarbons are produced. The schematic flowsheet, Fig. 1, shows the main steps of the coal hydrogenation process, and the product streams used for the recovery of chemicals are indicated. In the liquid phase hydrogenation stage, coal is made into a paste with recycle heavy oil. The coal paste is mixed with hydrogen and preheated at a pressure of 300 to 700 atm in heat exchangers and preheaters. The coal paste and hydro¬gen enter high pressure converters where the liquefaction of coal, conversion of the high boiling liquid materials initially obtained, into intermediate oils is performed at a temperature around 470°C. The reaction products enter the hot catchpot in which lower boiling oil vapors are separated from the residue containing unreacted coal, ash, and heavy oil. This residue, usually called H.O.L.D. (heavy oil let down), is processed to separate solid and liquid material. By thermal treatment of the residue, e.g., a coking process, distillate oil is obtained, which can be recycled as part of the pasting oil. This stream is rich in polynuclear aromatics and can be, and has been, used for the recovery of such material. The oil vapors and hydrogen from the hot catch-pot are cooled in heat exchangers and a cooler, and the condensed oil is separated from the recycle hy-

Jan 1, 1952

By F. Weinberg

The distribution of solute during the progressive solidification of dilute Sn-Ag alloys was determined in both solid and liquid as a jbnction of growth rate, rod diameter, temperature gradient, and solute concentration, using radioactive tracer techniques. The results indicated that partial mixing occurs in the liquid during freezing for most of the conditions investigated, approaching complete mixing for larger rod diameters (>2mm) and slow growth rates. Measured solute distributions were fitted to distribution functions based on diffusion controlled solute transport in the liquid state, by treating the normal solute diffusion constant and distribution coefficient as variable solute transport and segregation parameters. Values of these parameters were determined for the growth conditions investigated. Observations were made to determine whether mixing in the liquid was primarily due to volume changes in freezing or to differences in density between solute and solvent. The former effect was investigated using a selected Sn-Bi alloy as a solvent with zero volume change on fusion, and the density effect was studied using vertical solidifications of Sn-In and Sn-Ag alloys, systems having, respectively, very small and large differences in density between solute and solvent. The result indicate that mixing in the liquid cannot be primarily attributed to either volume changes or density differences. THE solute distribution in progressively solidified rods of dilute alloys, in which there is complete mixing in the liquid, is given by the expression1 where C, is the solute concentration in the solid at the point where the fraction g of the material has solidified, C, is the initial solute concentration and k is the equilibrium distribution coefficient. If it is assumed that there is no significant con-vective mixing in the liquid, then the solute distribution in the initial portion of a semi-infinite rod has been calculated to be2 where t is the time from the start of freezing and x1 is the distance in the liquid ahead of the solid-liquid interface at time t. Expressions [1] and [2] describe the limiting cases of solute distribution in the liquid, i.e., complete mixing, or no convective mixing; in practice it might be expected that the solute distribution would be somewhere between these two cases. pfann3 has suggested that Eq. [I] is applicable for partial mixing, as well as complete mixing, if an effective distribution coefficient k1 is used instead satisfactorily describes solute distributions in rods of magnesium, n-g, and b-sb6 alloys that were progressively solidified from the melt without mechanical mixing. The values of kl were observed to depend on the growth rate4-6 and the temperature gradient.6 The purpose of the present investigation was to measure solute distributions in both the solidified rods and the melt as a function of the solidification variables, and to determine to what extent the observed solute distributions could be described by the above theoretical expressions, keeping in mind that expressions [2] and [3] have been derived solely for the case of diffusion controlled solute transport in the liquid and are not theoretically applicable to

Jan 1, 1963

By M. D. Hassialis

[Surface Areas of Concentrates and Collector Coatings (T.P. 2002, by A. M. GAUDIN and G. S. PRELLER, Min. Tech., May. Discussion by M. D. HASSIALIS and the authors) . I Activation of Minerals and Adsorption of Collectors (T.P. 2082 by J. ROGERS and K. 1'. SUTHERLAND, Min. Tech., Nov. Discussion by A. F. TAGGART and the authors). . . . 3 Correlation between Mineral Behavior in Cataphoresis and in Flotation (T.P. 2005 by A. If. GAUDIN and S. C. SUN, Min. Tech., May. Discussion by M. D. HASSIALIS). . . . . . 8] Surface Areas of Concentrates and Collector Coatings M. D. HASSIALIS.*-In the current flotation theories there exists a common gap spanned by a common assumption pertaining to the arrangement and orientation of the collector ions at the solid surface. Also common is the belief that contact angle and flotation performance are dependent upon the arrangement and orientation of collector ions. This stimulating and informative paper sheds some light upon this general problem. One of the indices of arrangement is the area available per collector ion; in this connection, Gaudin and Preller have applied the B.E.T. method for surface determinations. In a surprising number of cases, their results show a greater specific surface for tailing than for concentrate. This cannot be accounted for by the differences in specific gravity and is attributed to the presence of clay minerals of "primary" sluices in the tailing. This is not a satisfactory explanation, for experience shows that when free slimed clay minerals are present in a flotation cell they will be carried mechanically into the concentrate. A part of the answer to the decreased specific surface of the concentrate would appear to be its usual flocculated condition, yet this should not entirely account for the large spreads reported. The possibility occurs that the nitrogen adsorption isotherms for clean mineral and collector-coated mineral are different. If that were true, and if the coated mineral surface exhibited decreased adsorptive powers, the discrepancy might vanish. In discussing the disposition of collector ions at mineral surfaces, the authors adopt the more consistent viewpoint that there exists some agreement between the ions of the substrate and those of the superstrate. In the case of xanthate ions on galena, a possible arrangement is shown in Fig. 2. This arrangement shows every xanthate ion being shared by two lead ions, whereas the chemical composition calls for two xanthate ions for each lead ion (p. g). This whole discussion is misleading. In the first place, it is known that xanthate ions are not abstracted by unoxidized galena, hence Fig. 2 should show as the substrate not Pbs but PbS„ Om. It would be equally erroneous to use the lattice arrangement of PGSO4, since the surface properties of xanthate-conditioned anglesite differ from those of xanthated galena. It is highly probable that the state of the galena surface exploited in its flotation is ephemeral, since weathered galena is only poorly, if at all, collected by xanthate. Just how a substrate of oxidized galena is to be pictured depends upon one's conception of the transformation from galena to anglesite. This writer is inclined to the following sequence of events. Surface sulphide ions undergo progressive oxidation. As more oxygen is taken up by the sulphide ions they become displaced from their equilibrium positions in the galena lattice, thus accommodating for the larger volume of the S„ Om ions. Concomittant with this change the forces acting on the lead ions

Jan 1, 1946

By George W. King

The yield strength of a dispersion-hardened W-3.8 vol pct Tho,alloy, in both the recovered and recrys-tallized condition, was investigated and cornpared with that ofrecrystallized pure tungsten over the temperature range of 325" to 2400°C. It is deduced that the Orowan mechanism is obeyed in the recrystallized alloy. In the recovered alloy, a further enhancement of the yield strength results from the retained substructure which is stable up to temperatures in excess of 2700°C. Temperature and strain rate cycling tests were also performed, and the apparent activation energy for the deformation process was derived. This activation energy, - 3 ev, for the recovered and also the recrystallized alloy was about the same as that for re crystallized pure tungsten. However, the activation volume of the recovered alloy, -10-2 cu cm, was about an order of magnitude lower than that of the recrystallized alloy or pure tungsten. This fact accounts for an enhancement oj- the temperature dependence of the yield stress of the recovered alloy. A dislocation velocity exponent of about 4 to 13 was deduced frorn the strain rate cycling tests , which is in good agreement with values reported for tungsten single crystals. VARIOUS theories have been developed to explain the enhanced yield strength of a metal containing a dispersed second phase of small hard particles. These theories are thoroughly reviewed by Kelly and Nicholson.' The theoretical models can be separated into two types. The first type assumes direct interactions between moving dislocations and dispersoids. One of the most widely investigated models for this mechanism is the bowing out of dislocations between the dis-persoids and their subsequent pinching off in order to bypass the obstacles. This is the well-known Orowan mechanism.' The second type is an indirect effect of the dispersion because of its ability to stabilize to high temperatures the substructure introduced by cold working. In this instance, the increment in the yield strength is expected to be inversely proportional to the square root of the subgrain diameter. In the present work, a quantitative study was made of the strengthening effect caused by a thoria dispersion in a recrystallized W-3.8 vol pct Thoz alloy over the temperature range 325" to 2400°C. The results are compared with the increment predicted for the Orowan mechanism based on the calculations by ~shb~.~ In addition, the alloy was tested in the recovered state so that any additional strengthening resulting from the substructure produced during fabrication could be measured. The respective contributions can be separated in this manner, provided that the particle size distribution of the dispersion remains the same in both the work-hardened and the recrystallized state. Particle size distribution measurements showed that this condition was met in the present work. I) EXPERIMENTAL PROCEDURES A) Material Production and Fabrication. The alloy investigated is essentially the same as that reported much earlier by ~effries,~ who also found the strength of tungsten to be improved by the thoria dispersion. The procedure for producing the alloy consisted of mechanically blending a thorium nitrate solution in proper concentration with tungsten oxide (WO3) powder, followed by hydrogen reduction to metal powder. After reduction, the dispersed second phase is present as thoria (Thoz). The pure tungsten powder used for comparison was produced in the same manner except that the thoria doping step was omitted. The powders were consolidated by cold pressing and self-resistance sintering in hydrogen. The resulting ingot had a cross section about 0.6 sq in. and a density about 93 pct of theoretical. The ingot was swaged to 0.174-in.-diam rod at temperatures varying from 1650°C initially to -1200°C near final rod sizes. Two intermediate recrystallization anneals were employed during fabrication. Analysis of the swaged rods is reported in Table I. B) Electron Microscopy Techniques. Carbon extraction rrPxcas prepared by a technique reported by ~00' were used to quantitatively evaluate the thoria particle size and distribution. Electron nlicrographs of extraction replicas were taken at 20,000 times but were then enlarged two to three times in printing. The areas photographed were randomly selected. A Zeiss Particle Size Analyzer (Model TGZ3) was used to count and measure the sizes of all particles present on the print. About three thousand particles were counted in determining a distribution curve. Electron transmission microscopy was used to determine the effect of annealing on the substructures of the materials. Thin foils were produced by a two-stage thinning process. The rods were first ground on emery paper to ribbons about 10 mils thick and then a jet of 5 pct KOH was used to electrolytically reduce a portion of the cross section of the ribbon. Final perforation was achieved by immersing the specimen in a 5 pct KOH solution and electrolytically polishing at a current density of about 0.3 amp cm-'. The foils were examined with a Hitachi HU-11A electron microscope. C) Tensile Testing. Tensile testing was performed in an Instron Testing Machine equipped with a radiation-type vacuum furnace which operates at about 1O"S torr at temperatures as high as 2400 °C. The same furnace was used for annealing the tensile specimens.

Jan 1, 1970

By R. E. Holmes, T. W. Leland

The solution to the unsteady-state mass- and heat-transfer equations describing the adsorption of a dilute component from a gas stream flowing through a packed bed is readily applicable to the design of hydrocarbon recovery units. The solution to these equations depends on the assumption of a linear equilibrium equation to relate concentrations on the surface to concentrations in the gas. This assumption is shown to be justifiable for components which are very dilute in the gas stream. This approach permits the prediction of the effects of bed shape and size, cycle time, and gas mass velocity on the recovery of each component. It also allows the time and gas flow rate needed for regeneration to be determined. The equations involve a constant for each component and another constant characterized by the type of adsorbent. These constants must be evaluated from operating data. Values of these constants determined for silica gel are presented. This paper points out the type of experitrrental data needed for a thorough design of hydrocarbon adsorption units. INTRODUCTION The growing importance of adsorption processes to recover hydrocarbons from natural-gas streams has created an urgent need for better methods to design and predict the performance of these processes. Since the original use of solid adsorbents in natural-gas processing was for dehydration, most of the current design methods for hydrocarbon recovery re extensions of those developed earlier for dehydration. These methods are based on an adsorptivity or bed loading factor defined as the amount of a particular component adsorbed per unit weight or per unit volume of the packed bed. The recovery of a given component is then expressed as an empirical function of its adsorptivity on a given adsorbent. In spite of the simplicity and initial utility of these methods, they are not completely satisfactory in that they do not predict the effect of the dimensions of the bed in relation to flow rate and cycle time, and do not predict the distribution of various components along the length of the bed. It is possible, however, to make a considerable improvement in the design of these processes by applying the basic equations of mass and heat transfer applicable to gases containing small concentrations of adsorbing components flowing through granular beds. These equations have been developed and solved by Anzelius,' Furnas,% nd Hougen and Marshall." where G = mass velocity of the inert constituents (assumed to be methane), lb/hr-sq ft, y = weight of an adsorbing component in the gas per unit weight of inert, lb of a given constituent per lb of methane, x = bed length, ft, p, = packed bed density, lb/cu ft, P, = gas density, Ib/cu ft, f = void fraction in the bed, t = time, hours, and w = weight of a given component adsorbed per unit weight of adsorbate free solid, Ib/lb pure adsorbent. The term on the left side of Eq. 1 represents the flow rate per unit bed volume of a component entering less the flow rate per unit bed volume of that component leaving the differential bed length. The terms on the right side represent, respectively, the accumulation rates per unit bed volume on the solid and in the gas phase within the differential bed section. The last term is negligible for this application since pgfv is quite small in comparison with p, and G. The partial differential is determined by the mass-transfer rate between gas and solid in the differential section.

By J. D. Mooney

(San Francisco sleeting, September, 1915) THE accompanying chart has been drawn for the convenience of engineers as a means of quickly determining the correct number of plies of conveyor belts operating under specific conditions. The calculations are based on the average safe strength (factor of safety, 15) of the various standard rubber conveyor belts. The, calculations assume maximum loading conditions; that is, the belt is considered as carrying the greatest load that it will handle without spillage at ordinary belt speeds. This not only produces the most economical operating conditions, but also the maximum tension in the belt. The chart is a graphical representation of the formula: p = kgW (L + 1OH) Where, p = the correct number of plies k = a constant, depending on the type of drive g = the weight in pounds per cubic foot of material handled W = the width of the belt in inches L = the length of the belt in feet (approximately twice the center distance). H = the difference in elevation between the head and tail pulleys, in feet. For a simple drive, with a bare pulley, k = 1/250,000 For a simple drive, with a rubber-lagged pulley, k = 1/300,000 For a tandem dive, with bare pulleys, k= 1/375,000 For a tandem drive, with rubber-lagged pulleys, k = 1/455,000 The chart is drawn for a simple drive, with a bare pulley (k =1/250,000;

Jan 9, 1915

By G. M. Gay, R. L. Perrine

This paper describes a method of numerical computation for three-dimensional, unstable, miscible displacement behavior useful for heterogeneous systems, as well as for more ideal conditions. In the method, flow equations are first linearized by a perturbation approach. The basic flow process is separated and a solution for its behavior readily obtained. The remaining problem of deviations from the basic flow caused by non-ideal conditions is then subjected to numerical analysis. Results obtained from use of the method are also presented. Although conditions assumed in the test cal-culations were severe, results show the type of dispersing flow expected and appear quite satisfactory. The method has eliminated or reduced in importance problems of oscillating values near steep fronts, excessive computer smoothing, etc. A unique advantage of the method is that the source of variations from ideal behavior can be observed. ,The one serious drawback results from the algebraic complexity of the perturbation approach, and the need for second-order terms to be retained in calculations of interest. Fewer array points are available and more computer time is required than would be desired. However, these difficulties are also experienced with other approaches to the solution of three-dimensional dispIacement problems. INTRODUCTION Prediction of behavior of the miscible displacement process within a porous medium for any system of engineering importance is plagued by a number of difficulties. With typical fluid properties the displacing fluid has the lower viscosity, and there is a natural tendency toward flow instability. The problem of predicting instability is compounded by the fact that every real system is heterogeneous. Permeability will vary from point to point — not entirely systematically, and yet not in a random fashion leading to a readily defined average. Furthermore, permeability is unlikely to be isotropic. These permeability properties, which are characteristic of any real porous medium, accentuate the effects of flow instability. Another factor to be considered is that flow dispersion accompanies the displacement process in a porous medium. Mechanistically, dispersion is due to the fact that flow between any two points in the medium follows multiple tortuous paths, each characterized by slightly different flow properties. The fact that the coefficient characterizing dispersive properties of the real medium JS a tensor with variable elements complicates matters. Further difficulties arise because the parabolic influence, while not negligible, is small. Thus, there is a tendency toward steep and uneven displacement fronts along which dispersion smoothing must be represented accurately. Yet frequently used numerical analysis schemes may tend toward either instability, oscillation or excessive smoothing, none of which gives the desired accurate picture of flow behavior. Thus, while many experimental and analytical studies of the process have been made, predictions of actual performance are still subject to considerable uncertainty and possible improvement. This paper reports on part of a study which attempts to develop improved methods for solution of the flow equations describing the miscible displacement process. Of necessity, the calculations were performed on a large digital computer. A three-dimensional system is represented, and the coefficients defining dispersion and permeability can be varied in a manner representative of a real system. Because the differential equations are nonlinear, a first step is to linearize them using a perturbation approach. Objective of this approach has been to separate the basic flow which would occur in an ideal system and for which predictions are readily made. Then the numerical analysis, which is necessarily complex, is directed toward solution of the perturbation equations. These equations state how the basic flow is modified

Jan 1, 1967

By R. A. Wagstaff

Many changes in equipment have had to be made to handle the flotation products at the blast furnace, and these changes have meant an expenditure of considerable money, which has not been compensated by an increase in smelting tonnage. To date, very few new lead mines have been developed, so that the help derived by the innovation of flotation has been directed to old producing properties, where the ratio of concentration is greater now than when gravity concentration was in effect. In some smelting plants there has been an abandonment of complete units due to the introduction of flotation. Flotation Products Difficult to Handle The physical characteristics of the flotation product do not make for economic handling for lead blast-furnace work, either mechanically or metallurgically. The millman or miner do not know what trials and tribulations they have passed on to the smelterman. To the smelterman it is "the everchanging flotation," for little does he know what new reagent will be perfected tomorrow that may completely change the grade and physical characteristics of the product. Even the mining companies who have complete units of mining, milling and smelting have had a hard time to reconcile themselves to the fact that the unit cost per ton of ore smelted must go up with the increase of flotation product on the blast-furnace charge. The "smelterman's burden," for that is what flotation has been for the last few years, has not caused the smelter operator to lag or fall down, but has spurred him on with new zeal. The physical properties of the flotation products are as follows: (1) High moisture content; (2) mucky nature of product; (3) fineness of product, and (4) high metal content. New Mechanical Devices for Handling Furnace Product These characteristics have caused the use of many new mechanical devices in smelting practice, for example: New transportation equipment, such as solid-bottom cars, is required; unloading equipment and sampling

Jan 1, 1928

By BARONJUPTNER VON JONSTORFF, Andrew A. Blair, GUNNAR DILLNER

IT is a well-known fact that the results of different analysts, when operating on the same identical sample of steel or iron, are far from concordant, and it not infrequently happens that great annoyance and trouble in the commercial community are occasioned by these discrepancies. Attempts have been made at various times to investigate the causes of such differences and to obtain more reliable methods of analysis. The most important of these was made by the British Association in 1889: The following gentlemen, with Sir W. Roberts-Austen as Chairman, and Professor T. Turner as Secretary, were constituted as a committee to investigate the question, viz.: Sir F. A. Abel, Mr. Edward Riley, Mr. G. J. Snelus, Mr. John Spiller, Professor J. W. Langley, and Professor Tilden. Average .samples of steel were prepared in America under the superintendence of Professor J. W. Langley. The steels, in the form of turnings, were divided and distributed to sub-committees in Great Britain, America, France, Germany, and Sweden. In Sweden Professor Åkerman acted as Secretary to the Swedish committee. The Government Department of Tests was appointed in Germany; Mr. Ferd. Gautier in France; the British Association Committee in England; Messrs. William

Mar 1, 1905

By M. L. Millican

The objective of this study has been to develop a method of log interpretation in the Delaware sand whereby the effects of the shale contained within the sand can be recognized and accounted for in a quantitative solution for porosity and water saturation. Both theoretical and empirical considerations are discussed. A simplified interpretation chart is presented which provides a means of amending the conventional porosity resolution of the Sonic log to compensate for the presence of shale. The amount of shale within the sand and its degree of lamination may be inferred from a calibrated gamma ray log. The resulting porosity value may then be used in conjunction with a knowledge of the formation resistivity to determine water saturation. Of added interest, particularly in the Delaware sand, is an approximation of permeability which may be derived empirically from the simplified chart. The discussion is illustrated by field examples. INTRODUCTION The performance of the Sonic log in defining the porosity fraction in clean, consolidated formations is well known, particularly in sandstones that are well compacted and free of shale. An approach to Sonic log porosity determination in shaly sands has been recently developed.' This method involves correcting the Sonic log readings by means of an a factor, where a is the ratio of the pseudo-static SP to, the static SP, and is a function of the amount of shale present. This method is dependent upon a contrast between the salinities of the drilling fluid and the connate water in the formation, inasmuch as this contrast produces the SP effect. In wells drilled with salt mud, the contrast, and with it the means of obtaining the a correction, disappear. In the Delaware basin, the large majority of rotary wells drilled to the uppermost sands of the Bell Canyon group employ salt mud as the drilling fluid. These sands have been the objective of most of the drilling exploration in the basin to date. A comparison of porosity values in these sands, as determined by core analysis, to Sonic log readings has indicated that a correction for the shaliness of the sand is needed. In the absence of an SP curve to determine the correction factor, the porosity resolution of the Sonic log in these sands has been questionable.