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By J. Weertman

The paper of Gifkins and Snowden considers the interesting but difficult problem of determining the stress dependence of secondary (steady-state) creep at low stresses. These authors have concluded that at stresses below 250 psi (2 x 107 dynes per sq cm) the secondary creep rate of lead is proportional to the stress (viscous creep) and is not proportional to the stress raised to about a fifth power. The experimental data considered by them were obtained on tests conducted at room temperature and at 50°C. The lowest stress employed was 50 psi (3.5 X 106 dynes per sq cm). The authors pointed out the main difficulty in determining the stress dependence of creep at low stresses. The creep tests must be run for very long lengths of time. However they made no estimates of when an experimental creep rate determination must be rejected because it does not represent a true steady-state or minimum creep rate. In order to be certain that a creep curve is within the steady-state region, the total creep strain should be of the order of 0.1 to 0.2. For a creep test of a year's duration this requirement implies that a secondary creep rate smaller than about 10-3 per hr cannot be measured reliably. The corresponding creep rate for a 10-year test is 10-6 per hr. The creep rates of the tests that were considered by the authors to prove the existence of viscous creep were of the order of or less than 10-6 per hr. One can conclude reasonably that this data does not prove unambiguously that large strain steady-state creep rate of lead is proportional to the stress in the stress range of 50 to 250 psi (3.5 x 106 to 2 X 107 dynes per sq cm). Another technique can be used to obtain the stress dependence at low stress levels. The creep rate is a very sensitive function of temperature. The creep rate can be increased by very large amounts merely by increasing the temperature. We carried out steady-state creep tests on lead single crystals25 at temperatures up to 320°C. We were able to obtain creep rate data down to stresses as low as 35 psi (2.5 x 10' dynes per sq cm). Our smallest creep rate was 8 x 10-5 per hr. Thus we obtained large strain, steady-state creep rates to even lower stresses than were considered by Gifkins and Snowden. No evidence was seen for viscous creep. The creep rate was proportional to the stress raised to about a 4.5 power down to the lowest stresses. Since there is no reason to believe that changing the temperature should change the stress dependence of steady-state creep, we feel that large strain viscous creep does not occur in the stress range quoted by the authors for lead single crystals or large-grain polycrystalline samples of lead. This conclusion does not imply that viscous creep may nat occur in a lower stress range or in the same stress range for fine grain material or at creep strains very much smaller than 0.1. Support by the U.S. Office of Naval Research is acknowledged. Authors' Reply R. C. Gifkins and K. U. Snowden We thank Dr. Weertman for his discussion and although, as we hope to show, we do not agree with his reservations, we do concur in stressing the importance of ensuring that creep rates are reliably obtained. Dr. Weertman appears to be content to accept n = 1 for low stresses with fine-grained material but not for single crystals. We believe our results show that the former result cannot be accepted without also accepting the latter. We will also show that the probable errors in our minimum creep rates are insufficient to alter our conclusions, that the criterion proposed by Dr. Weertman is arbitrarily restrictive and his alternative experimental approach possibly invalid. 1) A principal result of our Fig. 1(a) is that n = 1 for polycrystalline specimens at room temperature and 50°C for stresses below -250 psi. There was evidence that crystal slip and grain boundary sliding contributed approximately equaily to the overall strain in this low-stress regime. This implies that either a) grain boundary sliding controls slip within the grains or b) both grain boundary sliding and crystal slip independently occur according to mechanisms which give n = 1. Alternative a does not seem acceptable, so we were forced to consider b. This led us to reexamine work on bicrystals by Strutt and Gifkins and plot curves Fig. l(b). Previously Strutt et al. (loc. cit.), had merged these points with others using the Zener-Holloman parameter and thus, we now believe, had been led to overlook the behavior where n = 1. Curves C and D in Fig. l(b) did appear to confirm the hypotheses that n = 1 for crystal slip at these low stresses and the sliding curve F was similarly of the expected form. It was comparatively easy to find a quantitative theory to account for n = 1 for sliding and the similarity of curves C and D to curve F (all obtained from the same set of specimens) led us to feel that the single-crystal curves were valid. 2) We believe the secondary creep rates for both the polycrystalline and single-crystal specimens to be in error by factors c2. In Fig. 6 creep curves for polycrystalline specimens of lead(1) and lead(II) are reproduced as curves a and b, respectively, and curve c is for a single crystal at 100 psi. It is clear that, although the attainment of secondary creep rate takes 2 years for a and 150 days for b, thereafter the curve is linear for periods of 7 and -1 year, respectively. The single crystal has a linear portion commencing after 20 and extending to 90 days. Creep extension was measured directly using a traveling microscope reading to 0.01 mm on gage lengths marked on the specimens; the gage lengths

Jan 1, 1968

By H. I. Aaronson, H. A. Domian, A. D. Brailsford

A current study of the growth kinetics of k (hcp) plates in a Cu-Si (fcc)' has generated a requirement for data 02 the chemical interdiffusion coefficient in a (termed D,) as a function of temperature at the composition of the a/a + k pJase boundary. Rhines and Mehl 2 have determined D, as a function of composition at lower silicon contents by making Matano analyses of concentration-penetration curves. However, the accelerating increase in B, which they demonstrated as the phase boundary composition is approached at constant temperature and the rapidly diminishing accuracy of this analysis as the limiting compositions of a diffusion couple are approached (the silicon-rich component of their couples contained appreciably less silicon than is permitted by the solubility limit) indicate that the required information cannot be safely obtained by extrapolation of their data. Although the quite different method employed in this study is not exact, it will be shown that the approximations made are not serious ones, particularly from the viewpoint of the prgcipal application anticipated for these data. D, was determined from the migration kinetics of the a :k boundaries formed in sandwich-type diffusion couples produced by welding a block of high-purity copper to opposite sides of a cube (* in. on edge) of homogenized high-purity Cu-5.82 wt pct Si alloy. The alloy is pure k in the temperature range employed. The surfaces of the couple components which were normal to the diffusion direction were machined accurately flat and parallel, lightly polished, and carefully cleaned. Welding was then accomplished by means of the vacuum-encapsulated pressure jig technique previously employed.3 Welding was always conducted at the intended diffusion temperature; thus the welding anneal also served as the first diffusion anneal. Subsequent diffusion anneals were performed in evacuated Vycor capsules. Following the welding anneal, one of the surfaces parallel to the diffusion direction was machined, ground, and polished flat; additional material was removed from this surface after each diffusion anneal in order to avoid any effects of composition changes. After etching,4 the average distance between a : k boundaries was measured by means of a traveling microscope with an accuracy (per measurement) of better than 1 p. Satisfactory results were obtained at four temperatures in the range 775° to 655°C; attempts to obtain data at two lower temperatures were unsuccessful, evidently as the result of the interference of surface contamination during the welding process.

Jan 1, 1969

By T. R. Armstrong

Total crude oil production in Mexico in the year 1941 is estimated at approxi- mately 41,000,000 bbl.; a daily average of 112,700 bbl. and a decrease of about 5 per cent as compared with the daily average of 120,000 bbl. produced in the year 1940, and nearly 11 per cent decrease as com-

Jan 1, 1942

By T. R. Armstrong

Total crude oil production in Mexico in the year 1941 is estimated at approxi- mately 41,000,000 bbl.; a daily average of 112,700 bbl. and a decrease of about 5 per cent as compared with the daily average of 120,000 bbl. produced in the year 1940, and nearly 11 per cent decrease as com-

Jan 1, 1942

By L. L. Handy

Solvent floods using slugs of solvent have been found to show continuity in behavior from the vapor pressure of the solvent to the critical pressure for the two-component driving gas-solvent system. In the pressure region between the solvent vapor pressure and the critical pressure for the gas-solvent system, the gar and solvent are only partially miscible. Although complete miscibility cannot be obtained at these pressures, complete oil recovery is possible in principle. In two-phase solvent floods the solvent is propagated tllrough the reservoir, primarily, in the vapor phase. The carrier gas requirements constitute a significant factor in the economics of the process. A qualitative theory is proposed for estimating the amount of dry gas required to move the solvent through the reservoir. The theory shows that for two-phase solvent floods the total gas needed is a minimum at the vapor pressure of the solvent and at the critical pressure for the gas-solvent system, and is a maximum at some intermediate pressure. The predictions of the theory are supported by experimental studies using methane, butane and decane or methane, propane and decane in a natural sandstone core. INTRODUCTION Previously, solvent slug processes have been found effective for oil recovery in two pressure ranges. First, conventional miscible displacements are possible at pressures greater than the critical pressure for the gas-solvent system. Second, Jenks, et al,' have shown that, at pressures slightly in excess of the vapor pressure of the solvent, a solvent slug can be propagated through a reservoir by a gas essentially insoluble in the liquid solvent. The solvent bank displaces the oil ahead of it. Both of these processes, at least ideally, are capable of recovering all of the oil in the swept regions. Slug processes for which the gas and solvent are partially miscible have not been considered; that is, those systems for which the solvent and driving gas form two equilibrium phases in which the vapor phase contains a significant amount of solvent and the liquid phase an appreciable amount of the driving gas. Welge and Johnson' have shown that the gas needed to movc a solvent slug through the reservoir increases with increasing pressure above the vapor pressure of the solvent. It will be shown that solvent slug processes can, theoretically, recover all of the oil at any pressure greater than the vapor pressure of the solvent. But the amount of gas required to move the solvent through the reservoir depends very much on the pressure and temperature. In the present study a maximum in the gas requirements was both predicted theoretically and observed experimentally. This result has not been reported previously, and would not have been predicted from the Welge and Johnson model. The gas requirements are a minimum at the pressures corresponding to the vapor pressure of the solvent and again at the critical pressure for the gas-solvent system, and are a maximum at some intermediate pressure. AN APPROXIMATE THEORY FOR TWO-PHASE SOLVENT FLOODING The differences and similarities between conventional solvent floods and two-phase solvent floods are best understood by referring to concepts developed for miscible displacement in which miscibility is generated in the reservoir. In Fig. 1(A), a ternary diagram is shown for a hypothetical gas-solvent-oil system. To be rigorous the three components should each consist of a single molecular species. The pressure for Fig. 1(A) is greater than the critical pressure for the binary gas-solvent system at the specified temperature. Diagrams of this type are the ones most frequently referred to in discussions of enriched-gas drive and miscible displacement. A limiting tie line is shown tangent to the two-phase envelope and intersecting the gas-solvent line at Point A. To obtain generated miscibility with this type system, others have shown that, for an oil of Composition D, a mixture of gas and solvent must be injected which is richer in solvent than that composition indicated by A. An oil repeatedly contacted with a gas phase richer than A changes toward a composition which would be at equilibrium with the injected mixture, that is, a composition lying on a tie line which passes through the injected-gas composition. Since no such tie line exists, the oil is enriched to the point at which it becomes directly miscible with the injected mixture. At pressures lower than the critical pressure for the gas-solvent system, other types of phase diagrams are observed. The ones of interest in this paper are for pressures greater than the vapor pressure of the solvent, but less than the critical pressure of the gas-solvent system. Such a ternary diagram is shown on Fig. 1(B). In this case, two-phase behavior is observed not only for gas-oil mixtures, but also for certain compositions in the gas-solvent system. If a gas of Composition A (a dew-point vapor) is injected, once again the original oil is enriched by successive

By J. W. Marx, R. H. Langenheim

The authors are to he complimented for a timely presentation of useful information concerning application of heat to oil reservoirs to increase the rate and ultimate recovery of oil. The solution for heated area resulting from constant rate injection of a hot fluid, presented by the authors, and the fluid-flow analogy, solved by Carter,' are particularly interesting in that 110 restriction is placed on the direction of development of the heated area. It is not necessary that the heated area grow radially. Thus the solution could provide useful information for heat injection in any type of well pattern with any specified swept area data. However, it was assumed in the development that the heated region would remain at a constant clevatcd temperature. Vertical heat losses were computed on this basis. Physically. the assumption that the heated region will remain at a constant temperature (independent of distance from the injection point) appears to require that the heat injection medium be stcam, or other condensible gases near the boding point at injection pressure. If a hot liquid below the boiling point or a hot gas considerably above saturation temperature were used, the temperature of the heated region would decrease with distance from the injection well. Lauwerier2 has discussed this problem for a linear system. (See also Jenkins and Aronolsky; and McNiel and Nelson.') Thus, the authors' solution applies more nearly to steam injection than to hot water injection or hot, non-condensable gas injection. Assuming steam as the injection medium, it appears that steam would pass through the constant-temperature heated region and condense upon contact with the unheated sand. The tempcrature in the condensing region would probably be governed by the release of heat of vaporization required for phase equilibrium at the existing pressure distribution. Temperatures in the region would also be influenced by vaporization of hydrocarbon. Thus, it is doubtful that an expression for radial temperature distribution based on heat conduction only (such as the authors' Eq. 9) would have practical significance. As pointed out by Marx and Langenheim, the growth of the heated area under constant rate steam drive will eventually be limited economically by vertical heat loss. The possibility of continuing to move heat economically by cold water injection or by increasing the steam injection rate appears to be a very important consideration. (Movement of liquids away from the injection well should increase injectivity.) Fortunately, the solution presented by the authors may be generalized to thc case of a variable heat injection rate. The general solution is:

By H. G. Landua, Leah L. Naugle, H. H. Lowry

Evidence has been accumulating in recent years, in part from the work of the Coal Research Laboratory, that coals belong to a family of natural polymers and that even in complex reactions the differences between coals are quantitative and not qualitative. This point of view leads to the expectation that if a series of coals were subjected to a closely controlled set of experimental conditions the results obtained should be related to the chemical analyses of the individual coals. The data accumulated over the past 10 years by the Bureau of Mines in its ('Survey of Coke-, Gas-, and By-Product-Making Properties of American Coals," in what has come to be recognized as the Bureau of Mines-American Gas Association (BM-AGA) carbonization assay test,l-l2 offer an unusual opportunity to check this conclusion. The present paper reports an analysis of the data on the first go coals and coal blends— including coals numbered I to 55B, inclusive —which have been carbonized according to a standard procedure at intervals of 100°C. from 500° to 1100° in either or both 13 or 18-in. cylindrical retorts.13 In Table I are given the name of the seam from which the sample was obtained, the analytical data used, and the reference to the original publication of the Bureau of Mines. The coals range in fixed carbon from 46.2 to 79.0 per cent, in volatile matter from 15.4 to 41.3 per cent, in ash from 2.1 to 15.9 per cent, in moisture from 0.8 to 19.7 per cent, and in total sulphur from 0.40 to 4.44 per cent; therefore the entire gamut of bituminous coals is represented. The petrographic nature of the individual coals is not considered in the following analysis, although both "normal" bright coals and splint coals are included in the samples studied. For information on the petrography of the coals and for further information characterizing the coals the original papers should be consulted. Although the coals that are included extend over the whole range of bituminous coals, they do not cover this range entirely adequately. In particular, only 13 of the 90 coals have moisture contents greater than 3 per cent. This concentration at low moisture values means that the effect of moisture, which is an important factor, cannot be determined with as much certainty as would be desirable. All the coals were not tested at every temperature and in both retort sizes. Only the first 30 coals were tested at 1100°, and only about 50 at the other temperatures, except at 900°, where nearly all of them were included. In the accompanying tables the actual number of observations entering into each correlation is given. In this study equations are given for calculating analyses, yields, and properties of coke and by-products from the coal analyses. To decide whether these equations are satisfactory it is necessary to know the accuracy with which these quantities were measured in the assay tests.

Jan 1, 1942

By Leah L. Naugle, H. H. Lowry, H. G. Landua

Evidence has been accumulating in recent years, in part from the work of the Coal Research Laboratory, that coals belong to a family of natural polymers and that even in complex reactions the differences between coals are quantitative and not qualitative. This point of view leads to the expectation that if a series of coals were subjected to a closely controlled set of experimental conditions the results obtained should be related to the chemical analyses of the individual coals. The data accumulated over the past 10 years by the Bureau of Mines in its ('Survey of Coke-, Gas-, and By-Product-Making Properties of American Coals," in what has come to be recognized as the Bureau of Mines-American Gas Association (BM-AGA) carbonization assay test,l-l2 offer an unusual opportunity to check this conclusion. The present paper reports an analysis of the data on the first go coals and coal blends— including coals numbered I to 55B, inclusive —which have been carbonized according to a standard procedure at intervals of 100°C. from 500° to 1100° in either or both 13 or 18-in. cylindrical retorts.13 In Table I are given the name of the seam from which the sample was obtained, the analytical data used, and the reference to the original publication of the Bureau of Mines. The coals range in fixed carbon from 46.2 to 79.0 per cent, in volatile matter from 15.4 to 41.3 per cent, in ash from 2.1 to 15.9 per cent, in moisture from 0.8 to 19.7 per cent, and in total sulphur from 0.40 to 4.44 per cent; therefore the entire gamut of bituminous coals is represented. The petrographic nature of the individual coals is not considered in the following analysis, although both "normal" bright coals and splint coals are included in the samples studied. For information on the petrography of the coals and for further information characterizing the coals the original papers should be consulted. Although the coals that are included extend over the whole range of bituminous coals, they do not cover this range entirely adequately. In particular, only 13 of the 90 coals have moisture contents greater than 3 per cent. This concentration at low moisture values means that the effect of moisture, which is an important factor, cannot be determined with as much certainty as would be desirable. All the coals were not tested at every temperature and in both retort sizes. Only the first 30 coals were tested at 1100°, and only about 50 at the other temperatures, except at 900°, where nearly all of them were included. In the accompanying tables the actual number of observations entering into each correlation is given. In this study equations are given for calculating analyses, yields, and properties of coke and by-products from the coal analyses. To decide whether these equations are satisfactory it is necessary to know the accuracy with which these quantities were measured in the assay tests.

Jan 1, 1942

By P. D. I. Honeyman, P. A. Faust

At the Miami plant of the International Smelting Co., Inspiration, Ariz., there are four reverberatory furnaces, all 120 ft. long. At present only one of these furnaces is in operation. It is operated as a wet-charge furnace, the charge being distributed for about 65 ft. down the furnace length. Usually this charge contains about 12 per cent moisture and runs 25 per cent sulfur, of which there is eliminated in the furnace from 25 to 30 per cent. The furnace is oil-fired, the fuel being burned in a battery of Cananea-type, low-pressure burners. The flame is kept short and conditions so adjusted as to obtain complete combustion within the furnace. The average furnace draft, taken through the verb arch, amounts to only 0.02 in. of H2O. Draft is purposely kept low to cut down infiltration through the flues and boiler settings, and control dampers are regulated to maintain this uniform condition throughout the charging as well as the smelting period. Hot gases discharge from the furnace uptake through a common header flue to the waste-heat boilers. The general layout and dimensions of the plant are shown in Fig. 1. Four Stirling boilers, two of class M-26 (713 hp.) and two class M-31 (850 hp.), serve the furnace. Three usually are sufficient to take care of normal operation, the fourth boiler being used as a spare when necessary. The distribution of hot gases to the various boilers is regulated by the dampers in the boiler exit flues. Normally the boilers closest to the furnace uptake would evaporate more water than do those farther away, but dampers are regulated so as to distribute fairly well the load between the several boilers. Steam from the waste-heat plant is delivered to the adjoining power house of the Inspiration company, where it is used both in the Nordberg blowing engines and for electrical generation. Steam pressures and temperatures recorded are those in the main power-plant header and are thus inclusive of all losses in about 500 ft. of 10-in. line. Steam for smelter heating and auxiliary use is taken from the main waste-heat header, is reduced to 125 lb. and distributed through separate lines. Boiler feed water is supplied by the power plant and consists of returned condensate, augmented to a large extent by make-up water

Jan 1, 1934

By M. Cohen, R. J. Teitel

There is considerable interest in beryllium because of its low density (1.84 g per cu cm), high modulus of elasticity (40 X 106 psi), high melting point (1280°C), and special nuclear characteristics. Moreover, it has fair resistance to corrosion and oxidation. However, the purest beryllium known to the authors is relatively brittle at room temperature, and cannot be fabricated readily. The search for improved properties leads naturally to investigations of beryllium alloys and the phase relationships upon which they are based. The present paper is concerned with the alloys of beryllium and iron, primarily from the standpoint of the equilibrium diagram. Iron was selected (1) because of its all-round importance in metallurgy, and (2) because the beryllium-iron system is known to be quite complex. The most recent diagram in the literature is that of Gaev and Sokolov,' and covers only the iron-rich end up to 16 wt pct beryllium. Beryllium markedly restricts the austenitic field, closing the gamma loop at about 0.4 wt pct (3 at. pct). On the other hand, beryllium is soluble in a-ferrite up to a maximum of 7.5 wt pct (34 at. pct) at the eutectic temperature of 1160"C. The eutectic composition lies at 10 wt pct beryllium (42 at. pct) and corresponds to a mixture of or and FeBez (called j3 in the present paper). The solid solubility of beryllium in the a phase decreases with decreasing temperature, and makes precipitation-hardening possible. These findings substantiate the earlier work of Oester-held,2 Wever and Mueller3 and Laissus.4 In addition to the FeBe2 (ß) mentioned above, Misch6 has reported on FeBes, and indicated evidence for another compound containing still more beryllium. A preliminary diagram by Gordon,5 not hitherto published, is given in Fig 1. Besides the phases previously named, there are shown a solid solution of extended range (e), a compound of limited solubility (t), and a high temperature phase (7). Beryllium is designated as 8. The t field contains the compound composition FeBea, and the f phase undoubtedly corresponds to the beryllium-rich compound found by Misch.6 The region around the { phase was proposed by R. J. Teitel based on Gordon's data. The details of the diagram are self-explanatory. It was the unusual complexity of this system that prompted the authors to undertake the present studies. By the same token, more emphasis was placed on the beryllium-rich than the iron-rich end of the diagram. Exprimental Details RAW MATERIALS The beryllium employed in this investigation was one of the purest grades available. Its chemical analysis after vacuum melting is given in Table 1. The metal assayed 99.4 wt pct beryllium. Vacuum melted electrolytic iron of purity shown in Table 1 was the source of iron.

Jan 1, 1950

By C. G. Dunn

Identification of the kinds of orientation relationships that may exist among crystals is an important problem in the metallurgical field. As an aid to its solution standard orientations of several orders of twins would be very useful for rapid analyses to discover high-order as well as low-order twin relationships. Although data have been published that give orientations for three generations of twins, these data are not readily useful in the form presented; i.e., in a stereo-graphic projection with one pole per orientation.' However, accurate data based on calculations of the positions of all {1001 planes for such groups would be very useful when presented in tabular form. Therefore, calculations have been made for a group of four orders of twins and the data are listed in Table 3. Illustrative applications are considered briefly, with the idea of pointing out what may be done with large groups of orientations. Method of Computing Orientation OF a Twin It is common practice to describe the orientation of a crystal in terms of the positions on a stereographic net of the poles of certain planes of the crystal. A single position on a net may be given in terms of two angle variables, two sets of which appear in the following equations: Polar Net Wulff Net x = , sin ?p cos Fbp x = r COS ?w y = r sin ?p sin Fp y = r sin ?w cos Fw % = r cos ?p z = r sin ?w, sin +, The three numbers z, y and z determine a length r as well as a direction (0, 4) in an X, Y, Z coordinate system. In the present case, r will be set equal to (h2 + k2 + L2)1/2, where h, k and I are the usual Miller indices for a crystallographic plane, a restriction that facilitates determination of the positions of poles of new planes from those of old or known ones,2 as will become evident later. Furthermore, since twinned lattices have certain planes in common, it is an easy matter to determine the orientation of a twin of a crystal if the orientation of the crystal itself is known. We start therefore with a crystal of known orientation (positions of three {Ioo} poles given) and determine where the cube poles occur in first, second, third and fourth-order twins. Methods for identifying twinned lattices and for making the calculations to find the orientation of a twin have been published.3,4' Reference 4 will be illustrated in the calculation of the orientation of a twin, even though this method differs from the one used by the writer in obtaining the following data on four orders of twins. Consider a crystal S and its twin A1, A' being one of the four {112} or {III} type* first-order twills of S. The orientation of S—i.e., the positions of poles of (I00)

Jan 1, 1945

By Nathaniel Arbiter

T. M. Morris (School of Mines and Metallurgy, Rolla, Mo.)—Rate studies promise to help quantify flotation operations. The author's exposition of rate studies is therefore laudable. However his exposition of a second order rate equation rather than a first order rate equation is not convincing. It is important to use the correct equation, otherwise erroneous conclusions may be drawn. The data assembled by the author and plotted according to a second order rate equation can be plotted according to a first order rate equation. As a matter of fact much of the data used reveals that a second order rate equation is not applicable. According to the method used by the author for plotting data, the reciprocal of the slope of the line is the maximum possible recovery. Physically this cannot exceed 100 pct, yet several graphs yield maximum recoveries greater than 100 pct. For example: l—Curve 2, Fig. 1 yields a value of 120 pct; 2—Curve 2, Fig. 2 yields a value of 115 pct; 3—Fig. 7 yields a value of 110 pct. The real test of the graphical method is, as the author points out, whether or not the earliest points agree with a straight line. The second order rate plot does not fulfill this requirement. Fig. 10 shows the data used by the author to obtain Curve 2 in Fig. 1, plotted according to both a second and first order rate equation. Fig. 11 shows the two rate plots made from data published by Ludt and DeWitt.19 In Fig. 10 the first order rate plot gives a very good fit and obeys the boundary condition of passing through the origin. For the second order rate plot a straight line can be drawn through the last three points but the earliest points are not in agreement with this line. The reciprocal of the slope of the straight line gives a value of maximum possible recovery of 112 pct. The maximum possible recovery according to the first order rate plot is 78 pct. In Fig. 11 the first order rate plot again fits all of the points very well and passes through the origin. The second order rate plot shows wide deviation of the earliest point, indicating that the second order rate equation is not applicable. The reason for the fit of data to the second order rate equation during longer flotation times is that R, the cumulative percent recovery, changes slowly toward the end of the flotation operation, so that when t/R is plotted against time, one is, in effect plotting t against t and one would certainly expect a straight line. The author attempts to show that the second order rate equation is correct by citing evidence which shows that recovery is a function of initial concentration. This is a debatable point especially since, in the author's original presentation of this paper at the St. Louis

Jan 1, 1952

By F. W. Davis

This paper deals in a general way with certain of the necessary requirements of refractories for the open-hearth furnace. The refractories in common use for the different parts are discussed both as to the service they are giving and their suitability to withstand existing chemical, thermal and physical requirements. The relation between the service and allowable cost of a refractory is discussed and suggestions are requested on these points. The purpose of this paper is not to report, to the Institute, the results so far obtained in the survey, by the Bureau of Mines, of the metallurgical requirements for open-hearth refractories, but to present an outline that we hope will serve as a basis for discussion. The systematic survey that the Bureau proposes to make has not been outlined, although considerable preliminary work has been done in the way of interviewing open-hearth superintendents in several of the larger steel plants from the Chicago district eastward. At the several conferences so many of the opinions were diametrically opposite, when considering the same point, that it was thought that such an opportunity as the Institute offers in the way of a clearing house for moot metallurgical topics should not be overlooked. For this reason, the paper has been prepared as a basis for a discussion which, it is believed, will be of value in outlining the program of the Bureau. D. A. LYON, Assistant Director. THE importance of securing suitable refractories for metallurgical operations is daily becoming more universally recognized; particularly in the manufacture of open-hearth steel, where the life and earning power of the furnace depends largely on the judgment and care exercised in the selection of the correct quality of refractory for each of the parts. Any innovation that would make available to the steel manufacturers refractories with longer life or better suited to their needs than those now employed, and at a cost that would permit of their use, would be of enormous value to the industry at large. It is quite probable that revolutionary changes would not be necessary. Material now used in some parts of

Jan 3, 1924

By Pol Duwez

IN the course of an investigation of the V-CO system, two intermediate phases were found. One of these phases corresponds approximately to the stoichiometric composition VCo and is isomorphous with the sigma phase in the Fe-Cr system.' The second phase has the composition V3Co; its crystal structure is described in the present note. The alloys were prepared by mixing the two metals in the powder form, pressing a small disk weighing about 5 g at 80,000 psi, and arc melting this disk on a water-cooled copper plate in an atmosphere of pure helium. The details of this technique have been described.' The vanadium powder was obtained from Westinghouse Electric Corp., Bloomfield, N. J. This powder is probably of very high purity, since when it is properly sintered or melted in the above-mentioned arc furnace, ductile specimens are obtained. The cobalt powder, from Charles Hardy, Inc., New York, contained 0.5 pct Ni, 0.1 pct Cr, and traces of Si and Fe. After melting, the V,Co samples were sealed in evacuated quartz tubes and homogenized for ten days at 800°C. Powder diffraction patterns were obtained with a 14.32 cm diam camera, using Ka copper radiation. The patterns were readily indexed on the basis of a primitive cubic lattice with a parameter equal to 4.675A. The density, determined by the immersion method, was 6.71 g per cu cm; hence the number of molecules per unit cell is approximately 1.95; i.e., 2. At this point, the possibility that the structure might be that of beta tungstena became apparent. The beta tungsten structure is described as follows: Space group 03,, — Pm3n 2 Co in (a) : 000; ?4lhYZ (hhl) reflection present only if 1 = 2n. Assuming this structure to be the correct one, intensities were computed by means of the usual eauation: 1 + cos220 I oc p F sin 0 cos 6 where F is the structure factor, 0 the Bragg angle, and p the multiplicity factor. The observed and calculated values of sin 0 and the intensities are given in Table I. The agreement between the observed and the calculated sin 0 is good and there are no flagrant discrepancies between the calculated intensities and those estimated visually. The (hhl) reflections for which 1 is odd are not observed, as required by the space group. In addition, the (410), (430), and (531) reflections are missing as expected, because of the special (a) and (c) positions in0%. However, six reflections—(llo), (220), (310), (411), (422), and (510)—which have very weak computed intensities were not observed. For these reflections, the structure factor is proportional to the difference between the scattering factors of the two atoms in the structure. Since the scattering factors of vanadium and cobalt are not very different, these reflections are weak. However, by using Ka chromium radiation, whose wavelength is just above the absorption edge of vanadium, the effective scattering factor of vanadium may be decreased by one or two units; consequently the difference between the cobalt and vanadium scattering factors is increased. It was, indeed, found that in a powder pattern taken with chromium Ka radiation, the three reflections (110), (220), and (310) were actually present. The three other reflections (411), (422), and (510), with spacings smaller than half the wavelength of chromium Ka, were obviously not obtainable with chromium radiation. All the experimental results appear to confirm the beta tungsten structure for V,Co. In this structure, each cobalt atom is surrounded by twelve vanadium atoms at 2.61A; each vanadium atom is surrounded by two vanadium atoms at 2.34A, four cobalt atoms at 2.61 A, and eight vanadium atoms at 2.86A. Acknowledgment This work was done at the Jet Propulsion Laboratory, California Institute of Technology, under contract number W-04-200-ORD-455 with the Army Ordnance Department, Washington, D. C. The author wishes to thank this agency for the permission to publish the results of this investigation. References 'P. Duwez and S. R. Baen: X-Ray Study of the Sigma Phase in Various Alloy Systems. Symposium on the Nature, Occurrence, and Effect of Sigma Phase. ASTM Special Tech. Pub. No. 110, pp. 48-54. Philadelphia, 1951. 2 C. H. Schramm, P. Gordon, and A. R. Kaufmann: The Alloy Systems Uranium-Tungsten, Uranium-Tantalum, and Tungsten-Tantalum. Trans. AIME (1950) 188, pp. 195-204; Journal of Metals (January 1950). 3 M. C. Neuburger: The Crystal Structure and Lattice Constants of Alpha and Beta Tungsten. Ztsch. fiir Krist. (1933) 85, pp. 232-237.

Jan 1, 1952

By E. A. Nesbitt

The important permanent-magnet alloys 15 years ago contained carbon and depended upon it for their permanent-magnet properties. In recent years great advances have been made in a number of new alloys substantially free of carbon. These include Remalloy,' an alloy of iron, cobalt, and molybdenum, the various iron-nickel-aluminum alloys of the Mishima2 type, and the more recent Alnico V3 in which the best properties are developed by heat-treating in a magnetic field. The Mishima and the Alnico types of alloys are very brittle and after casting must be ground to size. This article describes a permanent-magnet material4 that can be machined as cast, and when handled with some care can be rolled to thin sheet and drawn to fine wire. Optimum magnetic properties are developed by a simple heat-treatment, and at this time the ductility of the alloy disappears. If the cast alloy is heat-treated without cold-working the mag netic energy product is about 1.0 X 106. This material is called Vicalloy I (pronounced vicalloy, V for vanadium, I for iron, and C for cobalt). When the alloy is first hot-worked and then considerably reduced in area by cold-swaging, drawing or grooved rolling, it is found that after heat-treatment the magnetic energy product measured in the direction of previous extension can be increased to 2.0 to 3.5 X 106. These higher values have been obtained only after reductions in area of 75 to 95 per cent, and since the material hardens considerably during working, the reduction ordinarily can be accomplished only in fine wires, although larger sizes can be reduced by the use of powerful machinery. When the material has been cold-worked in such a manner as to improve its energy product substantially, it is called Vicalloy 11. Commercial use of Vicalloy has been made in the recording of speech. Tape 0.002 by 0.050 in. has been found superior in quality to all others tried, and is now used in the Western Electric Mirrorphone 5 In a variety of forms Vicalloy I or I1 is useful in many laboratory instruments, and in experiments in which the sizes and shapes required cannot be obtained with the other more brittle permanent-magnet materials. In 1936, during a study of other age-hardening magnetic systems, it occurred to the author that some of the iron-cobalt-vanadium alloys might be suitable for permanent magnets. The proportions of iron, cobalt, and vanadium were varied and a range of alloys of particular interest was found, as shown by the indicated area in Fig. I. The limits of this range of composition are 30 to 52 per cent iron, 36 to 62 per cent cobalt, and 4 to 16 per cent vanadium. The compositions indicated by points outside this area were also tested. Preparation and Properties OF Vicalloy I The alloys were usually cast in graphite molds into bars 3/4 in. in diameter and

Jan 1, 1946

By E. A. Nesbitt

The important permanent-magnet alloys 15 years ago contained carbon and depended upon it for their permanent-magnet properties. In recent years great advances have been made in a number of new alloys substantially free of carbon. These include Remalloy,' an alloy of iron, cobalt, and molybdenum, the various iron-nickel-aluminum alloys of the Mishima2 type, and the more recent Alnico V3 in which the best properties are developed by heat-treating in a magnetic field. The Mishima and the Alnico types of alloys are very brittle and after casting must be ground to size. This article describes a permanent-magnet material4 that can be machined as cast, and when handled with some care can be rolled to thin sheet and drawn to fine wire. Optimum magnetic properties are developed by a simple heat-treatment, and at this time the ductility of the alloy disappears. If the cast alloy is heat-treated without cold-working the mag netic energy product is about 1.0 X 106. This material is called Vicalloy I (pronounced vicalloy, V for vanadium, I for iron, and C for cobalt). When the alloy is first hot-worked and then considerably reduced in area by cold-swaging, drawing or grooved rolling, it is found that after heat-treatment the magnetic energy product measured in the direction of previous extension can be increased to 2.0 to 3.5 X 106. These higher values have been obtained only after reductions in area of 75 to 95 per cent, and since the material hardens considerably during working, the reduction ordinarily can be accomplished only in fine wires, although larger sizes can be reduced by the use of powerful machinery. When the material has been cold-worked in such a manner as to improve its energy product substantially, it is called Vicalloy 11. Commercial use of Vicalloy has been made in the recording of speech. Tape 0.002 by 0.050 in. has been found superior in quality to all others tried, and is now used in the Western Electric Mirrorphone 5 In a variety of forms Vicalloy I or I1 is useful in many laboratory instruments, and in experiments in which the sizes and shapes required cannot be obtained with the other more brittle permanent-magnet materials. In 1936, during a study of other age-hardening magnetic systems, it occurred to the author that some of the iron-cobalt-vanadium alloys might be suitable for permanent magnets. The proportions of iron, cobalt, and vanadium were varied and a range of alloys of particular interest was found, as shown by the indicated area in Fig. I. The limits of this range of composition are 30 to 52 per cent iron, 36 to 62 per cent cobalt, and 4 to 16 per cent vanadium. The compositions indicated by points outside this area were also tested. Preparation and Properties OF Vicalloy I The alloys were usually cast in graphite molds into bars 3/4 in. in diameter and

Jan 1, 1946

By Gail F. Moulton

The production of petroleum in Illinois in 1928 was approximately 6,500,000 bbl., a decline of about 500,000 bbl. from the previous year and of about 1,500,000 bbl. from 1924. Production increased about 200,000 bbl. in Indiana to slightly less than 1,000,000 bbl. Production for 1929 is estimated at approximately 6,000,000 bbl. for Illinois and 1,000,000 bbl. for Indiana. Illinois Because production from most of the wells in the state has declined to a small daily average and the low prices for crude oil discouraged wildcatting, the number of wells drilled fell below that for any previous year since the development of commercially important production in the state. The Ohio Oil Co. discovered a pool of apparent commercial importance in southwestern Illinois near Dupo, in St. Clair County, and favorable showings of oil were encountered in a well in southeastern Illinois, near Harrisburg in Saline County. New production from the Dupo area is expected to check the rate of decline for the state. Thc following tablel summarizes field developments for 1927 and 1928 (for important detail by counties see notes at foot of table): 1027 1928 Completions........................................... 162 145a Initial production, bbl.................................. 2244 1840b Dry holes........................................,.... 66 58" Gas well completions................................... 13 8d 0111 wells abandoned.................................... 45" a Crawford, 44; Lawrence, 28; Wabash, 40. b Crawford, 501; Lawrence, 403; St. Clair, 165 (4 completions); Wahash, 668. o Crawford, 12; Wabash, 19. d Crawford, 6. b Lawrence, 21; Wabash, 15. The discovery well in the Dupo field in St. Clair County, produced about 150 bbl. per day from the Trenton lime at 660 ft. It is located in a northern extension of the Columbia-Waterloo anticline on which the Waterloo pool was developed in 1921. The best information on the.

Jan 1, 1929

The Colorado Scientific Society, Denver, Colo Charles Henderson, President, 519 U. S Custom House, Denver, Colo. Beginning in 1882, up to. about 1919, the Society published 11 volumes containing many valuable papers From the informa¬tion at hand, the papers in those volumes are now only available in libraries or on file at institutions. Vols 12 and 13 are the current volumes, and the list of the geologic papers contained in them are given here For any information as to price and availa¬bility, address the above. Vol 12 (1929-31) No 1, The geology of the Sangre de Cristo Mountains, by J H Johnson, 2, Relation of the ore deposits of the southern Rocky Mountain region to the Colorado Plateau, by B S Butler; 3, Mosquito Range and the Leadville district, by C H Behre, Jr , 4, Geologic history of the Front Range, by T S Lovering, 6, Revision of geologic structure and stratigraphy in the Ouray district, by W S Burbank, 7, Localization of ore in the schists and gneisses of the Mineral Belt of the Front Range, by T. S. Lovering, 8, Relation of the ore deposits of the southern Rocky Mountain region to the Colorado Plateau, by J. B. Tenney; 9, Preliminary geologic map of the Alma mining district, by Q D. Singewald and B S Butler, 10, The Climax molybdenum deposits of Colorado, by B S Butler and J W. Vanderwilt, 12, Localization of ore bodies at Rico and Red Mountain, by G. F Collins, and Geology of Mount Lincoln and Russia mines, by Q D Singewald and B S. Butler. Vol 13 (1932- ): No. 1, Preliminary geologic notes on Galena Mountain, by J. W Vanderwilt, and High plains of Colorado and New Mexico (Late Tertiary history), by F. M. Van Yuyl and J M. Coke

Jan 1, 1933

By Oliver Bowles

WHILE vast quantities of limestone and dolomite are used in metallurgy, the estimated production in 1926 being 23,860,000 tons, there are many problems connected with their use which have not received adequate study. The literature of metallurgy is notably lacking in comprehensive discussions of fluxing or furnace stone. Approximately 900 lb. of limestone is used for every long ton of pig iron produced in the blast furnace, but this important constituent of the charge receives little attention compared with the intensive study that has been applied to ores and fuels, the other important constituents of the charge. In an effort to elucidate some of the doubtful points, the writer has made a wide review of metallurgical literature, and has had the disappointing experience of finding not more than a paragraph or two on metallurgical stone for each two or three thousand pages of literature reviewed. Furthermore, the limited information supplied is in some instances contradictory and even absurd. For example, a correspondent in a reputable metallurgical magazine classifies magnesia and silica together as impurities in flux "that must be melted and run off as slag." From the furnace operator's viewpoint it is desirable that as complete knowledge as possible be obtained concerning the effects of chemical composition and physical character of the stone on its action in the furnace and on the quality of the metal produced. A better knowledge of these features is advantageous also to the quarry operator in that it enables him to work more intelligently in producing stone that will best satisfy the metallurgists' requirements. The following pages comprise a brief compilation of data now available. Much of the information is well established and probably acceptable to most metallurgists. On some points there is room for debate, and the chief purpose in presenting a paper at this time is to arouse discussion which will throw more light on controversial points and thus assist the author in preparing a more comprehensive and accurate dis¬cussion of metallurgical limestone problems.

Jan 1, 1928

By J. T. Norton, Joseph Gurland

IN spite of the extended use and high state of practical development of the cemented tungsten carbides, the structure of these alloys is still a matter of considerable controversy. The characteristic high rigidity and rupture strength of sintered compacts have been attributed to a continuous skeleton of tungsten carbide grains, formed during the sintering process. This view is based mainly on the work of Dawihl and Hinnuber,1 who reported that a sintered compact of 6 pct Co maintained its shape and some of its strength after the binder was leached out with boiling hydrochloric acid. After leaching, only 0.04 pct Co was reported to remain in the compact. They also showed that the assumed increasing discontinuity of such a skeleton, as the cobalt content is increased, could be made to account for the observed discontinuous increase of the coefficients of thermal expansion, the loss of rigidity, and the impaired cutting performance of alloys of more than 10 pct Co. Contradictory evidence was cited by Sanford and Trent,' who mentioned that a sintered compact was destroyed by reacting the binder with zinc and leaching out the resulting Zn-Co alloy. The skeleton theory also does not account for the observed change of strength of sintered compacts as a function of cobalt content. If the skeleton is responsible for the strength, the latter would be expected to decrease with increasing binder content. Actually, the strength increases and reaches a maximum around 20 pct Co. In addition, tungsten carbide is brittle and undoubtedly very notch sensitive. The highest value found in the literature for the transverse rupture strength of pure tungsten carbide prepared by sintering is 80,000 psi.3 herefore, such a skeleton does not easily account for a rupture-strength value of 300,000 psi and higher, commonly found in sint.ered tungsten carbide-cobalt compacts. In view of the conflicting data present in the literature, experiments were undertaken to determine whether the sintering of tungsten carbide-cobalt alloys leads to the formation of a carbide skeleton or whether the densification behavior and the properties of cemented compacts are consistent with a structure of isolated carbide grains in a matrix of binder metal. The specimens were prepared from powders of commercial grade. Tungsten carbide powder ranged in particle size from 0 to 5x10-4 cm. Mixtures of tungsten carbide and cobalt were ball milled in hexane for 48 hr in tungsten carbide lined mills. After milling, the specimens were pressed in a rectangular die (1x1/4x1/4 in.) at 16 tons per sq in. NO pressing lubricant was used. Sintering of the tungsten carbide-cobalt compacts was carried out in a vertical tube furnace equipped with a dilatometer (Fig. I), by means of which the change of length of the powder compacts could be followed from room temperature to 1500°C. An atmosphere of 20 pct H, 80 pct N was maintained inside the furnace. Decarburization of the samples was prevented by the presence of small rings of graphite inside the furnace tube. The temperature of the sample was measured by a platinum-platinum-rhodium thermocouple, which also was part of a temperature control system able to maintain a constant temperature within ±100C. Pure tungsten carbide compacts were prepared by sintering the carbide without binder or by evaporating the binder from sintered compacts in vacuum at 2000°C. Since complete densification of these samples was not desired, they were sintered only to 60 or 80 pct of the theoretical density of tungsten carbide. The specimens were prepared for metallographic examination by polishing with diamond powders and etching with a 10 pct solution of alkaline potassium ferricyanide. Cobalt etches light yellow and the carbide gray. The amount of porosity is exaggerated since it is difficult to avoid tearing out carbide particles, especially from incompletely sintered samples. Experimental Observations A number of specific experiments were carried out in order to study some particular aspect of the sintering problem. The details of these experiments, together with their results, are as follows: Electrolytic Leaching: The binder was removed by electrolytic leaching from sintered tungsten carbide-cobalt compacts for the purpose of determining the continuity of the carbide phase. The method used was based on the work of Cohen and coworkers4 on the electrolytic extraction of carbides from annealed steels. If the sample is made the anode, using a 10 pct hydrochloric acid solution as the electrolyte, the binder is dissolved, but the rate of solution of tungsten carbide is negligible. A current density of 0.2 amp per sq in. was applied. As shown in Fig.

Jan 1, 1953