Search Documents

By J. C. Williams

The operations described in this paper are those of the flotation plant of the Valley Forge Cement Co. at Conshohocken, Pa., and concern the use of a particular cationic reagent—namely, DP-243. The role of this reagent in this plant may be better understood by first considering the purpose of beneficiating cement rock in general and the specific problems at the Valley Forge plant. The ultimate purpose of beneficiating cement rock is to obtain a kiln feed of the desired chemical composition in a form suitable for the most efficient kiln operation. The chemical composition is governed by the type of cement to be made. Before government restrictions (the purpose of which is to simplify operations during wartime) limited the types of portland cement a manufacturer is permitted to produce, five principal types of cement were generally recognized by the industry. They are based upon chemical and physical specifications proposed by the American Society for Testing Materials, federal and other governmental agencies, state highway departments, water boards and other users of large quantities of cement. The physical as well as chemical specifications for any particular type of cement necessitate proper proportioning of the major components—that is, the silica, alumina, iron and lime—and it is necessary to establish and maintain definite limits for each in the raw mix. The manufacturer must then prepare a kiln feed of a composition that will yield a final product that will fulfill the desired specification. This step is further complicated for kilns using coal as fuel, by the amount and analysis of the ash introduced. The amount and nature of the dust lost during burning will also affect the composition of the kiln feed. The problem of preparing a kiln feed of the desired chemical composition is not a simple one, and it is the final product that governs the methods used to obtain such a feed. For example, in starting with a material deficient in lime for the mix sought, it may not be sufficient to raise it to the required lime content. The other constituents must also be present in the proper proportions. In some cases, it may be necessary to raise the lime content to a point greatly exceeding that of the final mix, then, by addition of one or more other materials lower in lime, obtain the mix. The rock used at the Valley Forge plant is a metamorphosed argillaceous limestone of the Jacksonburg formation, the same formation as that of the Lehigh Valley cement rock (which occurs approximately 50 miles north), and its oxide composition is similar to that of the latter. The only practical differences between the two are that, as a result of metamorphosis, crystallization of the Valley Forge rock is considerably coarser and it contains less carbon than the Lehigh Valley rock as well as slightly more magnesia in the form of magnesian mica. The calcium carbonate content of the various strata in the Valley Forge quarry ranges from about 65 per cent to over 85 per cent, the average for the entire quarry being somewhat under the requirement for manufacture of cement, which usually is from 75 to 76 per

Jan 1, 1947

By D. E. Peacock, B. Harris

Thermal-expansion and electrical-resistivity measurements have been carried out below 400°K on niobium and two niobium alloys containing tungsten. For anonaly in the expansion us temperature curve below aboct 300°K. This reslt is consistent with an earlier obsercation that Young's modilus joy Cb-132 lms an unusiully strong -tenperati-e dependence below roon temperature. No anonulous behavior was observed in the resistiuity vs temperature curve for either alloy or in the magnetic susceptibility us tenperature curve for Cb-132. These results are disclssed in terms of various electronic and bonding theories of the transition metals and their alloys, but it has not been possible to reach any definite conclusion as to the cause of the results obtained. ALONG with investigations of the low-temperature mechanical behavior of niobium and its alloys, some of the physical properties of these materials have also been studied. In the work described here, thermal expansion and electrical resistivity were measured below 400°K for niobium and two of its alloys, Cb-132 and D-43. In addition, the magnetic susceptibility of Cb-132 was measured over the same temperature range. The alloys are representative of two distinct tion-hardened alloy such as might find service as a turbine blade, while D-43 (Nb, 5.3 at. pct W, 1.1 at. pct Zr. and 0.08 at. pct C) is a solution- and dispersion-hardened alloy, of considerably lower strength than Cb-132. which is a potential vane material. Their significant common feature is the presence of tungsten as the principal source of solution hardening. EXPERIMENTAL TECHNIQUES Thermal-expansion measurements were made with a quartz-tube dilatometer using baths of liquid nitrogen, liquid bromoethane, and a liquid polyalkylene glycol derivative to cover the range 80 to 400 K. Results are recorded as expansion relative to that of quartz, and the probable maximum error in any value of relative expansion. All, is about il pct. The metallurgical condition of the specimens, which were in rod form. will be discussed in the section dealing with experimental results. Resistivity was measured on recrystallized wires 0.030 in. in diam using a potentiometric technique. The same baths were used for temperatures between 80' and 400°K as were used for the expansion measurements. and in addition the resistance of D-43 and Cb-132 was measured at 4.2 K by immersion in liquid helium. The maximum expected experimental error in any resistivity value is about 3 pct and that in any change in resistivity about i0.05 pct. Temperatures in both sets of experiments were measured with liquid-in-glass thermometers with an accuracy usually better than 1°K. EXPERIMENTAL RESULTS 1) Thermal Expansion. In Fig. 1 is shown the relative linear expansion of recrystallized niobium. D-43. and Cb-132. The curve for Cb-132 is composed of results from several runs on three different samples. Two of the samples were annealed for an hour at 1500°C to cause recrystallization and the third was annealed for an hour at 2000'C to remove some mi-crosegregation of tungsten which was known to be present in the wrought alloy received from the manu-

Jan 1, 1967

By Arnulf Muan, Klaus Schwerdtfeger, L. S. Darken

The equilibrium ratios CO/CO, of. a gas pharse coexislitrg with selected oxide phase assemblages of the system "FeO"-MnO-SiO2 and metallic iron have been determined at 1150°C. The data obtained are combined wilh the thermodynamic data on fayalite (Fe2SiOi) and "FeO"-MnO solid solutions to derive the actiuity-coiHpQsiUon relations for the various oxide components of the olivine (Fe2SiO4-,lIn2Si04) and pyroxenoid (standard free energies of formation of ferrosilile (FeSiO,), tephroite , and rhodonite from their oxides have been evaluated. In the Appendicc~s by Darken and Schivcerdtjeger the ideal solution law for solid deri oed. THE quaternary system Fe-Mn-Si-0 is of interest in many important phases of iron- and steelmaking. For instance, reduction in the blast furnace of ores containing Fe-Mn silicates, deoxidation of liquid steel with Mn-Si alloys, formation and subsequent alterations of oxide inclusions in steels, and the oxidation of manganese- and silicon-containing steels during processing are all governed largely by the thermodynamic relations existing in the system Fe-Mn-Si-O. Although the equilibria between liquid iron and Fe-Mn silicates have been studied in detail previously,' experimental data are lacking for equilibria among the solid phases. The present paper provides such data for a selected temperature, 1150°C. I) PREVIOUS WORK The general feature of subsolidus phase relations in the system iron oxide-manganese oxide-silica under strongly reducing conditions is known.' Fig. 1 represents an isothermal section at 1150°C. The phases present, in addition to silica, are three solid-solution series, viz.. the oxide solid-solution series "Fe0"-MnO (manganowiistite), the orthosilicate solid-solution series Fe2SiO4-Mn2SiO4 (olivine), and the metasilicate solid-solution series FeSi03-MnSi03 (pyroxenoid). The "FeO"-MnO solid solution is continuous between the two end members wustite and manganositeV3 as is the orthosilicate series between the two end members Fe2SiO4 and Mn2 SiO4. 4 The metasilicate solid solution, on the other hand, extends only part way from the MnSi0.l end member toward FeSiO because the latter end member is unstable relative to the phase assemblage fayalite + silica. The letters a through m in Fig. 1 identify end members of the individual solid phases dealt with [for instance, c designates fayalite (FeZSiO4) in equilibrium with wustite, e designates fayalite in equilibrium with silica, and so forth]. In addition to the phase relations there are some thermodynamic data available for the end members of the silicate solid solutions and for the "FeO" -MnO solid solution. The free energy of formation of fayalite (Fe2Si04) from its oxide components has been studied by several investigators. Unfortunately, the data obtained show considerable discrepancies. According to recent tabulations by Kelley, the change in standard free energy Affn for the reaction

Jan 1, 1967

By Thomas O. Ziebold, Robert E. Ogilvie

Experimental analysis of diffusion samples covering the entire Cu-Ag-Au system at 725°C has been carried out. Experimental coefficients are computed at twenty-eight points in the lermary system. It is found that the direct coefficienl for copper is nearly independent of the silver, content for 1ow-silver alloys and that the cross coefficient for silver correlates with the ther-nzodynatnic properlies. This lalter observalion leads to the conclusion that the mobililies of copper and gold are nearly equal. Thermodynarmic actiuilies for Cu-Ag-Au were computed from binary data and adjusted to be consistent with neasured tie lines across the two-phase region which extends into the ternary diagram at 725°C. Application of these therknodynarnic calculaliorls to the dijftcsion data terifies the Onsager reciprocal relations to the extent that experimental uncertainlies will allow. It is jound that diffusion neav the critical point of the 1200-phase field in the isothermal section at 725°C causes the composition gradients for copper and silver to approach infinity while the direct and cross coeficients become equal. From the standpoint of experimental Procedures, it has been shown that microanalysis of ternary samples may be carried out using a simple expression for the conversion of X-ray zntensily to composilion. The accuracy of' this method has been demonstrated by the analysis of standard alloys and by the reproducibility of composition determinations using differed X-ray lines. DIFFUSION in a ternary alloy system is basically and significantly different from diffusion in binary alloys. When only two elements are present there is just one independent composition variable, and the diffusion profile of composition vs distance across a sample must change monotonically through all solid solutions bracketed by the terminal alloys. If two-phase regions are stable for compositions between the terminal values, these must appear as planar interfaces in the diffused sample, with the composition profile exhibiting sharp discontinuities. Adding a third element may alter this picture completely. Because of the additional degree of freedom in the composition, we may see composition profiles which do not change monotonically through solid-solution ranges, and stable, nonplanar phase interfaces. Even though two-phase regions may lie between the terminal compositions of a diffusion sample on the constitution diagram, they will not necessarily appear in the diffusion profiles. In binary diffusion only one coefficient is needed to describe the interdiffusion process. From Fick's law this coefficient relates the diffusive flux of one component to its own composition gradient. In ternary diffusion we must allow for cross interaction between the two independent species. By a linear extension of Fick's law we introduce "cross" or "off-diagonal" diffusion coefficients which relate the flux of one component to the composition gradient of the other independent constituent. Thus, we require four interdiffusion coefficients to describe the transport process in a ternary system. In its most general form,1,2 the rate equation for mass transport by isothermal diffusion in a system of s components states that the diffusive flux of component i, Ji, is a linear summation of all driving forces, Xk, each force being multiplied by an appropriate compliance coefficient:

Jan 1, 1968

By J. L. Lummus, Frank O. Jones

A field procedure for determining graphite in drilling mud is presented which is sensitive to 0.25 lbs/bbl and accurate to 20 per cent. The method, utilizing oil flotation principles, is suitable for use in all oil-free water base muds except those containing ligno-sulfonates, lignites, or surface active agents. INTRODUCTION Graphite was proposed as a drilling lubricant as early as 1940, but has not been used extensively until recently.' Graphite has been substituted for oil in certain instances to avoid oil contamination of core samples since it has been found that graphite does not interfere with routine core analysis. A major difficulty in using graphite is the lack of a satisfactory field test for determining the concentration of graphite in mud. DISCUSSION OF METHOD Several possible methods of analysis were investigated, including chemical separation, density fractionation, radioactive tracers, and oil flotation.', ' The investigation indicated that a satisfactory method for field use could be devised using an oil flotation method. It was found that toluene shaken with a highly diluted mud sample would recover sufficient graphite to be apparent in the oil phase. Refinement and standardization of technique made it possible to detect as little as 0.25 lb/bbl graphite and to estimate graphite content to within 20 per cent by using a visual comparison method. The test is limited to oil-free water base muds. Quebracho, phosphates, or barytes in the mud do not interfere with the test but surface active agents, lignosulfonates' and lignites evidently render !he graphite water-wet so that none may be recovered by oil-flotation. PROCEDURE Instructions for determining graphite in mud: 1. Collect representative one gallon sample.- from mud stream. Transfer immediately 350 ml portions of this Sample into four mixing cans labeled A, B, C, and D. Measure out graphite (same as is used to treat mud) for addition to cans as indicated below, using either a specially designed scoop or a balance. Can: A B C D Grams Graphite to Add: none 2 4 6 Stir samples B, C, and D for 15 minutes with propeller type mixer. 2. Clean and rinse well with water four 250 ml volumetric flasks labeled I, 11, 111, and IV. Using a 5 ml hypodermic syringe, transfer the indicated volume of samples from cans A, B, C, and D into designated flasks as follows: From Can: A B C D To Flask: I II III IV Add This Volume of Mud: 4 ml 2 ml 2 ml 2 ml 3. Measure 100 ml fresh or distilled water to each flask and swirl gently to disperse mud. Add exactly 5 ml toluene to each flask. Stopper and shake each

Jan 1, 1953

By Harry H. Power

WHILE the attention of all engineering branches is focused today on changes and improvements in the several curricula, we are concerned here with the many questions arising in industry and college concerning the preparation for the petroleum engineering profession. The succession of problems confronting the petroleum engineer demands a degree of versatility not ordinarily encountered in other professions. As a consequence, the student cannot acquire mastery of all the several engineering branches represented in field practice, and as an alternative, he has learned to appreciate the value of thorough training in the basic or fundamental sciences as a preliminary foundation for professional work. While our attention is directed primarily to the training of engineers in educational institutions, it is necessary that the ultimate education of the professional engineer be kept in mind. It is apparent that his success as an engineer is limited not only by his educational and job experience, but by his native endowments: mentality, personality and health. The engineer's lack of job experiences often proves as much a handicap as the lack of adequate college training. If the final product proves to be satisfactory, both industry and technical institutions are to be congratulated. However, if the product is found wanting, the one most responsible should be apprehended. FITNESS FOR PROFESSION For the most part, students of engineering colleges have had their interests in applied science awakened at a relatively early age. Many of them entered college as a convenient means of acquiring a technical education, but undoubtedly would have had better prospects in a shorter program offered by institutions of noncollege grade. The activating motive of practical interest is also strong in students suitable for college training, but in many cases an intellectual interest must be awakened in order that it may survive graduation. Numerous engineers believe that this progressive process of selection and determination of career aims is one of the essential services rendered by the engineering colleges. Industrialists, who are more interested in quality than quantity of petroleum engineering graduates, have pointed out the good that should result if more empha¬sis were given to the work of eliminating the misfits. They also point out the protective measures that have been taken by other professions for the betterment of professional standards. Mention has been made of the beneficial results to be obtained by collective determination of the market for the products of engineering schools, particularly in that the students unsuited to the profession would have an opportunity to prepare themselves for employment more suited to their personalities and other qualifications. In the event that such a system of coordinated personnel direction is developed by the

Jan 1, 1941

Discussion of the paper of GEORGE S. Rice, presented. at the Pittsburgh meeting, October, 1914, and printed in Bulletin No. 94, October, 1914, pp. 2459 to 2492. WILLIAM GRIFFITH, Scranton, Pa.-I notice in the discussions and literature that emphasis is placed on rock dust, shale dust, and limestone dust, and I infer that these different. sorts of rock are ground up to produce this dust. -Is that right? MR. RICE.-That is correct, but we do not have to grind the limestone dust we are using in the experimental mine, as that is obtained from a quarry, and is used just as it comes; we can get it very cheaply, as it is a by-product of the quarries. MR. GRIFFITH.-Have any experiments been made with ordinary dirt out of the fields; could not that be used as ground dust? MR. RICE.-If you dry it and powder it enough so it will float in a, strong air current it might be all right for the barriers, but if it is damp there will be a tendency for it to mat together; then it would be quite useless for making a dust cloud. There might also be another disadvantage if used through the whole mine, if it had very much free silica in it, which is bad for the lungs. Limestone and selected shale dust would not affect the health of miners. MR. GRIFFITH.-In order to do very much good with any of those barriers, they ought to be rather extensively used throughout the mines, and there are few mines that have facilities for grinding up this rock into such a fine dust. If the ordinary earth from a plowed field could be used, even if it were not quite so good, it is more accessible and very much cheaper; therefore, in using it, with the universality of the supply through-out the country, it would tend to stop explosions. MR. RICE (communication to the Secretary*).-In closing, it is well to again emphasize that I do not advocate barriers being a "cure-all" for explosions. It will be generally agreed that prevention is best, not only by means of improved methods of using explosives, and ventilation to prevent accumulations of firedamp, but also by either thoroughly wetting the dust throughout the mine, or else so treating it with rock dust or other inert dust that an explosion cannot start. From my observations I believe that rock dusting. is a practicable method, and has the merit of visibility, and remaining effective for considerable periods, whereas the watering method has to be daily followed up, and if neglected for a short period the mine may become in a dangerous condition. The Germans

Jan 4, 1915

By William Klement

THIS note reports the results of some attempts to metastably extend the primary solid solubilities of tin, antimony, and silicon in silver by rapidly quenching these binary alloys from the melt. The procedures employed for alloy preparation, quenching, and Debye-Scherrer X-ray diffraction measurements have been described elsewhere. The lattice parameters obtained for the fcc structures in Ag-Sn and Ag-Sb alloys are presented in Fig. 1, together with the results of Owen and Roberts.4 Alloy compositions are believed to be within ± 0.2 at. pct on the basis of negligible weight losses during preparation and reproducibility of the lattice spacings. Diffraction lines from hcp phases were also detected: the relative visual intensities of the fcc (200) and hcp (10.2) lines were estimated as shown in Table I. The intensities were m for the (200) and w for the (10.2) in a quenched 13.6 at. pct Sn alloy: a lattice spacing for the fcc structure could not be reliably obtained, however. As seen from Fig. 1, the lattice parameters vary linearly with composition up to 8., at. pct Sb and 13." at. pct Sn, respectively, which may be compared with the maximum equilibrium solid solubilities5 of 7.2 at. pct Sb and 11.5 at. pct Sn, respectively. The presence of the hcp phases, which were found together with the fcc phases, is a consequence of the competition1,3 in the nucleation and growth processes during solidification. Both the fcc and hcp phases must be of the same composition for those alloys in the range where lattice parameters increase linearly with solute concentration. Despite much effort with quenched alloys of several silicon concentrations, it has not been possible to obtain lattice spacings of sufficient precision to establish the variation of lattice parameter with composition or the maximum metastable solid solubility: the equilibrium data5 suggest little primary solid solubility of silicon in silver. For alloys containing less than 16 at. pct Si, the Si (111) diffraction line was not observed. For alloys containing 10 to 25 at. pct Si, faint low-angle lines were detected and these could be indexed as the (10.0), (00.2). and (10.1) reflections of an hcp structure with a = 2.87 + 3A. c = 4.52 ± 3A, and c/a = 1.57 ± 2. The 16 at. pct Si alloy was quenched to, and examined at. liquid nitrogen temperatures without any change observed in the proportion of the hcp phase. These experiments were jointly supported by the Atomic Energy Commission and Office of Naval Research under a program directed by Professor P. Duwez. The assistance of H.-L. Luo and A. Abu-Shumays is acknowledged. as is the support afforded

Jan 1, 1965

AS you and anyone else can understand, a great expense and a large supply of things are necessary for parting a quantity of silver by means of aqua fortis. First, as you have seen, it is necessary to have a great abundance of every kind of cucurbit and alembic, of charcoal and wood, and a large number of pounds of a vigorous, well-purified aqua fortis, because for every pound of silver there are of necessity [71v] at least four pounds or more employed from the parting to the coloring of the separated gold. It is also necessary to prove its fineness and to granulate or beat it, to have furnaces and supplies, and to provide for a thousand other necessities which need not be repeated now. The most important thing in this art seems to me to be that it requires continual working night and day with extreme watchfulness and care. For this reason another way, much quicker, less dangerous, and less expensive than the aforesaid one was found by some clever men (alchemists, I believe) in order to avoid such laborious and heavy methods. It produces the substance of the thing exactly as the acid does. If you wish to make use of it in conjunction with the acid it is possible to render great aid to this work although there is a great difference in the techniques of the two. The method used in this parting is as follows: First, make a round or square wind furnace for melting, below ground or above, and of height and size in proportion to the work and as it comes out best for you. Then take a large clay crucible and fill it almost up to the edge with that silver which contains the gold, cut into pieces, and put it to melt with the silver on top of a piece of brick cut to the size of the bottom of the crucible and resting on a grate in the middle of coals that are burning well. When you see that the silver has been made so hot by the fire that it looks white and that it wishes to begin to liquefy, take a little stick of sulphur or a small piece of antimony and put it in. When this is melted, lifting away the charcoal that covers it, put in more sulphur or antimony (for the method is the same with either one) until the silver is very well melted and these materials properly incorporated. Then for every pound of silver that you put in add half an ounce of sheet copper. When this is melted take your crucible out with tongs or pincers and strike the bottom gently on the coals two or three times so that the gold may make a residue on account of

Jan 1, 1942

By Donald L. Katz, Leo B. Bicher

A correlation is presented for predicting the viscosities of light paraffin hydrocarbon mixtures such as natural gases for temperatures from o° to 4o0°F. and for pressures fro1 atmospheric to I0,000 lb. per sq. in. The correlation is based on the viscosity data for the methane-propane system and requires only a knowledge of the molecular weight of the naturaI gas. The viscosities of natural gases reported in the literature up to 2500 lb. were reproduced by the correlation with an average deviation of 5.8 per cent. Introduction The viscosity of a natural gas is required whenever calculations are made of the pressure drop that occurs while the gas flows through pipes or porous media. Methods of predicting the viscosities of gases at the present operating pressures are not available. This paper presents a simple method of predicting the viscosity of a natural gas in the single-phase region from its molecular weight, temperature, and pressure. Viscosity oF Methane-propane Mixtures The viscosity of methane, propane, and four of their binary mixtures, 20,40, 60, and 80 mol per cent, have been determined for pressures from 400 to 5000 lb. per sq. in. and temperatures from 77" to 437 F., with an experimental accuracy of 3.2 per cent.2 The apparatus used in the investigation was a modification of that employed in previous studiesaJ4 on the viscosity of normal paraffin hydrocarbons. It consists of a viscosimeter of the rolling-ball, inclined-tube type,5>k7 with auxiliary equipment for making up and charging binary mixtures into the viscosimeter.~ The viscosity data on the methane-propane mixtures have been plotted as a function of molecular weight with lines of constant pressure, charts of constant temperature in Figs. I to 3. These charts are extrapolated at temperatures below 77°F. and at pressures above 5000 lb. per sq. inch. Prediction OF Viscosity from Molecular Weight of a NaturaI. Gas At atmospheric pressure the viscosity of light hydrocarbon gases increased with increased temperature, contrary to the change of viscosity of liquids with temperature. The atmospheric viscosities of the normal paraffin hydrocarbons have been determincd by several investiga-tors 3,4,9,10,12,15,16,17,19 and are plotted in Fig. 4 as a function of molecular weight, with extrapolation to 896'F. and to 220 molecular weight. Data for isopentane and normal pentane show less than 2 per cent difference in viscosity, indicating that Fig. 4 can be used for isomeric parafin hydrocarbons with an accuracy of approximately 2 per cent. Trautz and Sorg'7 determined the atmospheric viscosities 01 methane-propane mixtures and showed that they are proportional to the molecular weight. The viscosities of these mixtures

Jan 1, 1944

By David R. Mitchell

The mineral pyrite (or marcasite) occurs in coal beds as balls, lenses, veinlets and bands. Several million tons are wasted annually on the refuse dumps from coal mining and coal-preparation activities. Sporadic attempts have been made in the United States to recover this pyrite for manufacture of sulphuric acid but only a few plants have succeeded in recovering it on a commercial scale. Several chemical companies in the East became concerned about supplies of pyrite early in 1943, but by late summer of that year the situation had eased. If for no other reason than national security and self-sufficiency during wartime, methods of recovering pyrite from coal-mine refuse should be worked out and made available to coal-mine operators who are potential producers of pyrite. Eastern sulphuric-acid plants are particularly likely to have their sources of raw material blocked by war conditions, so that special studies to determine where supplies of pyrite can be obtained for these plants from inland sources are desirable. Davis's1 summarization of conditions during World War I gives the following facts: During those years, the shortage of pyrite became acute. Shipments of hand-picked pyrite were made from a number of coal mines in Illinois, Indiana, western Kentucky, Ohio and Pennsylvania. A mechanical concentrating plant for sepa- rating pyrite from picking-table refuse was built at Danville, Ill., and operated for several years, and a small pyrite-concen-trating plant treating washery refuse near Gillespie, Ill., operated for several months in 1918. The Consolidation Coal Co. of Fairmont, W. Va., constructed and operated a sulphuric-acid plant using pyrite recovered from coal-mine refuse. The U. S. Bureau of Mines during 1917-1919 made a comprehensive survey of pyrite-production possibilities from coal mines and estimated that there was a potential yearly production of 435.000 tons from Ohio and Pennsylvania and 928,000 tons from Kansas, Missouri, Iowa, Illinois, and Indiana mines. This estimate included only mines that could produce one per cent or more of their coal production as pyrite containing a minimum of 40 per cent sulphur. PyRite Production According to the Minerals Yearbook,2 approximately 660,000 long tons of pyrite was produced in the United States in 1941, with an average sulphur content of 42 per cent. The average value f.o.b. mines was $3.09 per long ton. Spanish pyrite, 48 per cent sulphur minimum, was quoted at 12 cents a unit c.i.f. U. S. ports, equal to $5.76 a ton for shipments of minimum sulphur content. Most of the pyrite produced in the United States is obtained as a by-product in the dressing of copper and zinc ores. Metal mines in the East making pyrite concentrate for the market or use in company-operated sulphuric-acid plants

Jan 1, 1944

By H. K. Livingston

A technique has been developed which makes it possible to determine the spreading pressure of liquids and solids, for simple systems. Data for surface tensions, interfacial tensions, spreading pressures, and contact angles for water, heptane, and silica are tabulated.' These results can be applied to the evaluation of capillary rise and displacement pressure in a petroleum reservoir. Appropriate equations are presented and the application of these equations is discussed. The presence of surface-active components affects both capillary rise and displacement pressure and also seems to influence the rate of fluid flow. The purpose of this paper is to supplement and bring up to date the last article on the subject of the surface chemistry of petroleum reservoirs, that of Garrison in the 1935 Oil and Gas Journa1.1 A discussion of the "adhesion tension" concept used by Garrison has been presented in another publication,2 together with the reasons for the recommendation that the term "adhesion tension" be abandoned. In view of the fact that some of the data used by Garrison have been superseded by more recent work, it seemed advisable to call attention to this fact and present the more important data currently believed to be correct. In the earlier paper, Garrison set up the equations that 'relate solid-oil and solid-water interfacial tensions to each other, and applied data from Bartell and Miller3 to these equations. However the adhesion tension measurements made by Bartell and Miller involved a confusion of symbols, so that they did not actually measure the spreading pressure, ?s — ?sf.2 The spreading pressure is a convenient method of indicating the amount by which the surface energy of a solid surface is lowered on immersion in a liquid or vapor. Since the initial value of the free surface energy is represented by the symbol ?s and the final value is ?sF, the spreading pressure is ?s — ?SF. A technique has now been developed4 that makes possible the determination of ?s — ?sF for simple systems. This method would be very difficult to carry out with a multicomponent system such as exists in the petroleum reservoir. However, already results have been obtained for ?s — ?sF for water and heptane in contact with silica and graphite. These values will be of the same order of magnitude as those in the petroleum reservoir. Accordingly, it is possible for the first time to discuss the surface-energy relations of the petroleum reservoir on a semi-quantitative basis. Preliminary Generalizations A petroleum reservoir may contain the following four phases: gas, hydrocarbon liquid, aqueous liquid, and solid. The three fluid phases are dispersed through the solid reservoir rock. If gravity were the only force acting, it is obvious that the

Jan 1, 1943

By H. K. Livingston

A technique has been developed which makes it possible to determine the spreading pressure of liquids and solids, for simple systems. Data for surface tensions, interfacial tensions, spreading pressures, and contact angles for water, heptane, and silica are tabulated.' These results can be applied to the evaluation of capillary rise and displacement pressure in a petroleum reservoir. Appropriate equations are presented and the application of these equations is discussed. The presence of surface-active components affects both capillary rise and displacement pressure and also seems to influence the rate of fluid flow. The purpose of this paper is to supplement and bring up to date the last article on the subject of the surface chemistry of petroleum reservoirs, that of Garrison in the 1935 Oil and Gas Journa1.1 A discussion of the "adhesion tension" concept used by Garrison has been presented in another publication,2 together with the reasons for the recommendation that the term "adhesion tension" be abandoned. In view of the fact that some of the data used by Garrison have been superseded by more recent work, it seemed advisable to call attention to this fact and present the more important data currently believed to be correct. In the earlier paper, Garrison set up the equations that 'relate solid-oil and solid-water interfacial tensions to each other, and applied data from Bartell and Miller3 to these equations. However the adhesion tension measurements made by Bartell and Miller involved a confusion of symbols, so that they did not actually measure the spreading pressure, ?s — ?sf.2 The spreading pressure is a convenient method of indicating the amount by which the surface energy of a solid surface is lowered on immersion in a liquid or vapor. Since the initial value of the free surface energy is represented by the symbol ?s and the final value is ?sF, the spreading pressure is ?s — ?SF. A technique has now been developed4 that makes possible the determination of ?s — ?sF for simple systems. This method would be very difficult to carry out with a multicomponent system such as exists in the petroleum reservoir. However, already results have been obtained for ?s — ?sF for water and heptane in contact with silica and graphite. These values will be of the same order of magnitude as those in the petroleum reservoir. Accordingly, it is possible for the first time to discuss the surface-energy relations of the petroleum reservoir on a semi-quantitative basis. Preliminary Generalizations A petroleum reservoir may contain the following four phases: gas, hydrocarbon liquid, aqueous liquid, and solid. The three fluid phases are dispersed through the solid reservoir rock. If gravity were the only force acting, it is obvious that the

Jan 1, 1943

By H. E. Stauss

THE time-to-fracture test has been applied to pure platinum and to two alloys of platinum under the special conditions of small cross-sectional area of the specimens and of a test temperature above the annealing temperature. While the results are similar in character to those secured with large specimens of steel at temperatures below the annealing temperatures, two differences are noted: (I) an upward inflection in the curves for log stress vs. log time for the alloys, and (2) a sharp break in the curve for log stress vs. log time for pure platinum when single crystals filled the wire. The experiments showed that: (I) platinum and 10 per cent rhodium-platinum maintained their strengths at 1100°C. better than did 10 per cent iridium- platinum, and (2) the rhodium-platinum after a time exceeded the iridium-platinum in strength at 1100°C. Platinum alloys in their service at high temperatures encounter conditions some- what similar to those that exist in the usual form of the time-to-fracture "l test with steel. This paper is intended primarily to present results obtained by a "time-to- fracture" test under conditions approximating actual service for platinum (at the temperature 1100°C. under oxidizing conditions) with three materials, pure platinum (99.99 per cent), a platinum alloy with lo per cent iridium, and a platinum alloy with 10 per cent rhodium. The experimental procedure differed from that previously used in this type of measurement in that the samples were of small diameter (0.010 in.), were fully annealed, and were tested at a temperature definitely above their annealing points (600°C., 1000°C. and 1050°C., respectively, for 60 per cent cold reduction and 15 min. heating time2,3). The experimental arrangement was similar to that previously described,4 using as heating unit a small, horizontal, platinum- wound furnace, ½ by 12 in., maintained at constant temperature by an automatic controller. The samples were 0.010-in. wires, which had been annealed at 1200°C. by drawing them slowly through the furnace. The time-to-fracture was measured electrically. Elongation was not determined because of the difficulties inherent in the experimental arrangement. Life-that is, the time-to-fracture-was considered the important property in these first tests. No attempt was made to measure the reduction in area, but the types of fracture were noted qualitatively; in the text they are referred to as (I) the normal, plastic, or necked fracture, (2) the knife-edge fracture, and (3) the brittle or intercrystalline fracture with small reduction of area. Results for different constant applied stresses are plotted in Fig. I. In all cases at least two trials were made for each stress, although they cannot always be indicated separately on the curves. The breaking stresses drop very rapidly to a small frac-

Jan 1, 1943

By Leo B. Bicher, Donald L. Katz

A correlation is presented for predicting the viscosities of light paraffin hydrocarbon mixtures such as natural gases for temperatures from o° to 4o0°F. and for pressures fro1 atmospheric to I0,000 lb. per sq. in. The correlation is based on the viscosity data for the methane-propane system and requires only a knowledge of the molecular weight of the naturaI gas. The viscosities of natural gases reported in the literature up to 2500 lb. were reproduced by the correlation with an average deviation of 5.8 per cent. Introduction The viscosity of a natural gas is required whenever calculations are made of the pressure drop that occurs while the gas flows through pipes or porous media. Methods of predicting the viscosities of gases at the present operating pressures are not available. This paper presents a simple method of predicting the viscosity of a natural gas in the single-phase region from its molecular weight, temperature, and pressure. Viscosity oF Methane-propane Mixtures The viscosity of methane, propane, and four of their binary mixtures, 20,40, 60, and 80 mol per cent, have been determined for pressures from 400 to 5000 lb. per sq. in. and temperatures from 77" to 437 F., with an experimental accuracy of 3.2 per cent.2 The apparatus used in the investigation was a modification of that employed in previous studiesaJ4 on the viscosity of normal paraffin hydrocarbons. It consists of a viscosimeter of the rolling-ball, inclined-tube type,5>k7 with auxiliary equipment for making up and charging binary mixtures into the viscosimeter.~ The viscosity data on the methane-propane mixtures have been plotted as a function of molecular weight with lines of constant pressure, charts of constant temperature in Figs. I to 3. These charts are extrapolated at temperatures below 77°F. and at pressures above 5000 lb. per sq. inch. Prediction OF Viscosity from Molecular Weight of a NaturaI. Gas At atmospheric pressure the viscosity of light hydrocarbon gases increased with increased temperature, contrary to the change of viscosity of liquids with temperature. The atmospheric viscosities of the normal paraffin hydrocarbons have been determincd by several investiga-tors 3,4,9,10,12,15,16,17,19 and are plotted in Fig. 4 as a function of molecular weight, with extrapolation to 896'F. and to 220 molecular weight. Data for isopentane and normal pentane show less than 2 per cent difference in viscosity, indicating that Fig. 4 can be used for isomeric parafin hydrocarbons with an accuracy of approximately 2 per cent. Trautz and Sorg'7 determined the atmospheric viscosities 01 methane-propane mixtures and showed that they are proportional to the molecular weight. The viscosities of these mixtures

Jan 1, 1944

By David R. Mitchell

The mineral pyrite (or marcasite) occurs in coal beds as balls, lenses, veinlets and bands. Several million tons are wasted annually on the refuse dumps from coal mining and coal-preparation activities. Sporadic attempts have been made in the United States to recover this pyrite for manufacture of sulphuric acid but only a few plants have succeeded in recovering it on a commercial scale. Several chemical companies in the East became concerned about supplies of pyrite early in 1943, but by late summer of that year the situation had eased. If for no other reason than national security and self-sufficiency during wartime, methods of recovering pyrite from coal-mine refuse should be worked out and made available to coal-mine operators who are potential producers of pyrite. Eastern sulphuric-acid plants are particularly likely to have their sources of raw material blocked by war conditions, so that special studies to determine where supplies of pyrite can be obtained for these plants from inland sources are desirable. Davis's1 summarization of conditions during World War I gives the following facts: During those years, the shortage of pyrite became acute. Shipments of hand-picked pyrite were made from a number of coal mines in Illinois, Indiana, western Kentucky, Ohio and Pennsylvania. A mechanical concentrating plant for sepa- rating pyrite from picking-table refuse was built at Danville, Ill., and operated for several years, and a small pyrite-concen-trating plant treating washery refuse near Gillespie, Ill., operated for several months in 1918. The Consolidation Coal Co. of Fairmont, W. Va., constructed and operated a sulphuric-acid plant using pyrite recovered from coal-mine refuse. The U. S. Bureau of Mines during 1917-1919 made a comprehensive survey of pyrite-production possibilities from coal mines and estimated that there was a potential yearly production of 435.000 tons from Ohio and Pennsylvania and 928,000 tons from Kansas, Missouri, Iowa, Illinois, and Indiana mines. This estimate included only mines that could produce one per cent or more of their coal production as pyrite containing a minimum of 40 per cent sulphur. PyRite Production According to the Minerals Yearbook,2 approximately 660,000 long tons of pyrite was produced in the United States in 1941, with an average sulphur content of 42 per cent. The average value f.o.b. mines was $3.09 per long ton. Spanish pyrite, 48 per cent sulphur minimum, was quoted at 12 cents a unit c.i.f. U. S. ports, equal to $5.76 a ton for shipments of minimum sulphur content. Most of the pyrite produced in the United States is obtained as a by-product in the dressing of copper and zinc ores. Metal mines in the East making pyrite concentrate for the market or use in company-operated sulphuric-acid plants

Jan 1, 1944

By David R. Mitchell

THE mineral pyrite (or marcasite) occurs in coal beds as balls, lenses, veinlets and bands. Several million tons are wasted annually on the refuse dumps from coal mining and coal-preparation activities. Sporadic attempts have been made in the United States to recover this pyrite for manufacture of sulphuric acid but only a few plants have succeeded in recovering it on a commercial scale. Several chemical companies in the East became concerned about supplies of pyrite early in 1943, but by late summer of that year the situation had eased. If for no other reason than national security and self-sufficiency during war-time, methods of recovering pyrite from coal-mine refuse should be worked out and made available to coal-mine operators who are potential producers of pyrite. Eastern sulphuric-acid plants are particularly likely to have their sources of raw material blocked by war conditions, so that special studies to determine where supplies of pyrite can be obtained for these plants from inland sources are desirable. Davis's1 summarization of conditions during World War I gives the following facts: During those years, the shortage of pyrite became acute. Shipments of hand-picked pyrite were made from a number of coal mines in Illinois, Indiana, western Kentucky, Ohio and Pennsylvania. A mechanical concentrating plant for separating pyrite from picking-table refuse was built at Danville, Ill., and operated for several years, and a small pyrite-concentrating plant treating washery refuse near Gillespie, Ill., operated for several months in 1918. The Consolidation Coal Co. of Fairmont, W. Va., constructed and operated a sulphuric-acid plant using pyrite recovered from coal-mine refuse. The U. S. Bureau of Mines during 1917-1919 made a comprehensive survey of pyrite-production possibilities from coal mines and estimated that there was a potential yearly production of 435,000 tons from Ohio and Pennsylvania and 928,000 tons from Kansas, Missouri, Iowa, Illinois, and Indiana mines. This estimate included only mines that could produce one per cent or more of their coal production as pyrite containing a minimum of 40 per cent sulphur. PYRITE PRODUCTION According to the Minerals Yearbook,2 approximately 660,000 long tons of pyrite was produced in the United States in 1941, with an average sulphur content of 42 per cent. The average value f.o.b. mines was $3.09 per long ton. Spanish pyrite, 48 per cent sulphur minimum, was quoted at 12 cents a unit c.i.f. U. S. ports, equal to $5.76 a ton for shipments of minimum sulphur content. Most of the pyrite produced in the United States is obtained as a by-product in the dressing of copper and zinc ores. Metal mines in the East making pyrite concentrate for the market or use in company-operated sulphuric-acid plants

Jan 1, 1944

By E. F. Sturcken, J. W. Croach

A grain orientation distribution function, P(u,F), was developed for use in predicting physical properties in oriented metals. Examples are given of the use of the function to predict thermal expansion coefficients in rolled uranium rods and plate. The P(u,F) function was synthesized from X-ray difpaction intensity measurements, Ii, norrnally used to plot inverse pole figures. The symbols u and F specify the angles that the crystallographic axes of the grain make with the normal to the sample surface and P(u, F) gives the number of grains oriented in each direction, (u,F). P(u,F) is obtained from a least squares fit of the Ii to an orthonormal set of spherical harmonic functions. The P(u, F) function was also used to define a quantity, J, which is a measure of the departure of the orientation distribution from unifomzity (or "randomness"). The J parameter may be used to follow, quantitatively, the amount of preferred orientation induced as a function of mechanical working or heat treatment. An example is given of the application of the J parameter to prefevred orientation studies of hot- and cold-rolled uranium rods and hot-rolled uranium plate. Because P(u,F) is derived from relative intensity measurements by the powder diffraction technique, it is applicable to material with large absorption coefficients and/or grain size and is particularly suitable for characterizing the preferred orientation of large numbers of samples such as fuel elenzents for a nuclear reactor. IN general the physical properties of an oriented metal depend on the direction in which the properties are measured. Hence to predict physical properties the grain orientation must be known as a function of the direction of the specimen. The conventional methods of expressing preferred orientation measurements are the pole figure1 and the inverse pole figure.2-8 Both methods are difficult to use for predicting physical propertiess because they are graphical and because they are stereographic projections and hence are not "area-true." In the present report a quantitative orientation distribution function, P(u,F), is synthesized from pole density measurements normally used to plot inverse pole figures. For inverse pole figure plots the pole densities, pi, are obtained by powder dif-fractometer intensity measurements of their reflections from a flat surface of the sample, normal to the direction of interest. Each pole density, pi, represents a single orientation, i, and is proportional to the volume of material with orientation, i; hence a set of pi gives an approximation for the general orientation for the sample direction measured. The expression8'7 for calculating the pole densities, pi, from the diffraction measurements was previously

Jan 1, 1963

By Blake M. Loring

Recently the S-curves for 30 to 40 alloy steels have been pub1ished.l.2 These steels show individual characteristics, which make each additional S-curve of great interest. There are important differences in the mechanism of the transformation process, the type of transformation product, and the influence of alloying elements. Steels of the same general alloy composition may possess such variable characteristics with regard to the length of time of isothermal transformation that an S-curve for each heat of steel may be desirable. In the present work the isothermal transformation of a steel having the following composition and grain size was studied: 0.29 per cent carbon; 0.21 manganese; 0.026 phosphorus; 0.017 sulphur; 0.056 silicon; 1.45 chromium; 3.25 nickel; austenite grain size, 7. The progress of the isothermal transformation was followed by several different methods, including hardness measurements, dilatometer observations, and examinations of the microstructure. It was not expected that these methods would be in precise agreement.3 Accordingly, the changes in microstructure and hardness were given additional weight in determining the initial stage of transformation and the dilatometer measurements were relied on in estimating the completion of the process. The beginning of transformation was indicated by I per cent of transformation products and the end of transformation by about 99 per cent. The reproducibility of the various methods in the ranges of highest sensitivity was checked by several observations at each time and temperature. The steel used in this investigation was annealed for 24 hr, at 925°C. Macroetching revealed no serious segregation. The specimens for the metallographic and hardness investigations were 1¼ by ½ by ? in. Wires attached to the samples were used for handling. instead of tongs, to avoid chilling. The specimens were heated at 845°C. for ½ hr. and quenched into constant-temperature salt baths held at various temperatures from 205' to 650°C. The time required to transfer the specimens was found to be about 1½ sec., and nearly 5 sec. more was required for them to come to the temperature of the bath. After various lengths of time in the constant-temperature baths the specimens were quenched in water at 2I°C. The specimens were cut in half for the metallographic examination, to provide a surface free from decarburization. To determine the beginning and end of the transformation the percentage of transformation determined metallographically and by hardness was plotted against time. A planimeter was used in the metallographic determination. The hardness and metallographic determinations made at room temperature were confirmed reasonably well by dilatometer measurements taken during the process of transformation at the various temperatures. Two dilatometers were used to

Jan 1, 1942

By Sage B. H., Lacey W. N., G. W. Billman

The composition of the coexisting phases in the methane-ethane-n-pentane system was determined at 100°F. This was accomplished by withdrawing samples of the coexisting phases under isobaric-isothermal conditions. The relative amount of each of the components present in the liquid and gas phases was determined by conventional analytical fractionation methods. The phase behavior of this system approximates that estimated from generalized correlations which take into account the influence of the nature and amount of each of the components present upon the equilibrium. It was found that for particular pressures and temperatures the equilibrium constant of each of the components was influenced significantly by the composition of the system and this effect was more pronounced at the lower pressures for methane than for the components of greater molecular weight. However, at the higher pressures approaching the maximum two-phase pressure for the system at this temperature the composition markedly influences the equilibrium constants of all the components at a particular pressure and temperature. The results of this study are presented in graphical and tabular form. Introduction The phase behavior of many of the binary systems containing parafin hydrocarbon components from methane through n-pentane has been investigated during recent years. In addition the compositions of the coexisting phases in mixtures of crude oil and natural gas have been studied.' However, these results do not establish the influence of the nature and amount of the other substances making up a multi-component system upon the gas-liquid equilibrium constant of any one component. A preliminary correlation on the basis of values for binary systems was made2 utilizing such experimental information as was available. However, there is need for much additional information regarding behavior in systems containing more than two components. Study of the phase behavior of ternary systems offers a feasible attack upon the determination of the influence of composition as well as of pressure and temperature upon the several equilibrium constants concerned. An investigation of the phase behavior of the methane-propane-n-pentane system at 100°, 160°, and 220°F was reported.".' This work served to illustrate the marked influence of concentration of the other components upon the equilibrium constants. Variations of as much as 50 pct in the equilibrium constants for methane for fixed temperature and pressure were observed in regions remote from the critical state. Likewise there was a marked variation in the equilibrium constants of propane and n-pentane as a result of changes in the composition. These results indicated the desirability of investigating additional ternary systems. The present paper deals with a study of the methane-ethane-n- pen-tane system at 100°F, which is similar in many respects to the work upon the meth-ane-propane-n-pentane system cited above.

Jan 1, 1948