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By R. W. Gurry, L. S. Darken

The solubility of cementite in austenite is computed by thermodynamic methods from the observed solubility of graphite. It is found that the solubility of cementite is greater than that of graphite in the entire austenite temperature range. Thus the prior discrepancy between this portion of the phase diagram and the observed metastability of cementite is partially resolved. FOR several years it has been apparent that a serious discrepancy exists in certain observations pertaining to the Fe-C system. Direct experimental data indicate: 1-That the curve representing the solubility of graphite in austenite'" crosses that for cementite4 at about 945°C as shown in Fig. 1. 2— That graphite and austenite saturated therewith are stable1 relative to cementite at all temperatures between the eutectoid, about 723°C, and the eutectic, about 1153°C. These observations are mutually incompatible in view of a well-known consequence of the second law of thermodynamics, namely, that the stable phase (presumably graphite at all temperatures) has a lower solubility than the metastable phase (presumably cementite). Hence either 1 or 2 above must be in error; either the measured solubility of graphite or of cementite, or the observation as to the stability of graphite, is in error. Our present purposes are: 1—To collate the available data on cementite and prepare a table of HO — HO° and of (Fa— HO°)/T. This tabular method seems the best and most convenient way to represent the heat and free energy of formation. 2—To determine whether the measured solubilities of cementite and graphite in austenite are in accord with the above table and the measured thermodynamic properties of austenite, in order to resolve, if possible, the existing paradox of these two solubilities. Enthalpy of Cementite The enthalpy of cementite at 273 °K, H279 — HOcem, was computed by integration of the low temperature heat capacity as measured by Seltz, McDonald, and Wells" 68" to 298 °K) and as given by the Debye functions recommended by them (0" to 68°K); the result is included in Table I. At higher temperature HCem — H,,"" is given by Kelley who used the data of Naeser7 (298" to 1037°K) and of Umino8,9 (273° to 1923°K). We have recalculated Hcem — H273 cem from the data of UminoO in the following way. In the equilibrated alloy at temperature the weight fraction of cementite Pct c -Pct cr is PctC -PctCr designated f(C), and the

Jan 1, 1952

By Harold M. Feder, Robert V. Schablaske, Irving Johnson, Ewald Veleckis

The stoichiometry, structure, and stability of the internzediate phases formed between zinc and some of the rare earth (RE) metals were systematically exarnined by means of a recording effusion balance and X-ray diffraction analyses. In the La-, Ce-, PY-, Nd-, and Y-Zu systems, at or below about 600 C, the following sequences of phases (REZnx) were found: La, x = 1, 2, 4.0, 5.25, 7.3, 17/2, 11, and 13.0;' Ce, x = 1, 2, 3, 11/3, 4.3, 5.25, 7.0, 17/2,* and 11; Pr,x = 1,2, 3, 11/3 ,* 4.3, 5.3(?), 7.0, 17/2,* and 11; Nd,x = 1,2, 3,* 11/3,* 4.3, 6.5, 8.5,* and 11; Y,x = 1,2,3, 11/3, 4.5, 5.0, 17/2,* and 12.* The structure types of all these phases were classified. In addition, lattice parameters were obtained for the first time for the pluses denoted by asterisks. In the absence of de tectable valency or electronegativity effects the systesnatic trends in the results have been ascribed to the effects of' the lanthanide contraction. For example, the maximum number of zinc atoms in the coordination polyhedron surrounding the RE atom decreases from twenty-four to twenty-two to twenty as the size of the RE atom decreases. THE structures and compositions of a great many intermetallic phases (e.g., the Laves phases) are known to be based primarily, but not exclusively, on the space-filling efficiency of various modes of packing together atoms of different sizes. The valencies and electronegativities of the constituent atoms are, however, also influential. In extreme cases hypothetical intermetallic phases which fulfill the efficient spacefilling requirements may not be present in the constitutional diagram because of thermodynamic instability brought about by the operation of valency or electronegativity factors. Hence, for a detailed study of the influence of atomic size on alloy structure and composition, it would be desirable to minimize variations of valency and electronegativity. The intermetallic phases formed by the rave earths (RE) with some common partner offer an excellent opportunity for isolating the effects of size from those of valency and electronegativity. The rare earths exhibit a large, but smooth, decrease in size (the lanthanide contraction) in the series from lanthanum to lutetium when inter comparison is made for a common valence state, e.g., isolated atoms or trivalent ions. The elements yttrium and scandium are frequently included as pseudo rare earths; their sizes place them in the vicinity of dysprosium and lutetium, respectively. The electronegativities of RE elements vary by less than 10 pet. The trivalent state is the most common; however, the well-known tendency of cerium, praseodymium, and terbium to achieve higher valencies, and of samarium, europium, and ytterbium to seek lower valencies, requires that caution be exercised in the assumption of equal valencies. In the present study the existence, constitution, and structure of each of the numerous intermediate phases formed by zinc with lanthanum, cerium, praseodymium, neodymium, or yttrium were examined systematically and in detail. The investigation was conducted by a recording effusion balance technique and by X-ray diffraction analysis. The results enrich our knowledge of the phase diagrams of these systems. In addition, they present some clear-cut evidences of the operation of the size factor alone. EXPERIMENTAL PROCEDURE Apparatus. The mode of operation of the recording effusion balance and its application to phase studies have been discussed in detail elsewhere.' In this work, an effusion cell containing a finely divided alloy was suspended within an evacuated tube from the beam of an analytical balance. The tube was immersed in a massive molten salt bath whose temperature was controlled to within 0.5o C during each experiment. The loss in weight of the alloy owing to effusion of zinc* was continuously recorded. Two effusion cells, 1/2 in. diam by 1 in. high, were machined from tantalum rods. Two orifices were drilled laterally into the walls of each cell. The orifice areas were determined by calibration with pure zinc: cell A had a total orifice area of 6.5 x 10-41 sq cm, and cell B an orifice area of 9.8 x 10-3 sq cm. By appropriate choices of orifice area and temperature the wide range of volatilities from pure zinc to pure rare earth metal could be investigated. X-ray diffraction powder photographs were made at room temperature with a 114.6-mm Debye-Scherrer camera with both filtered CuKa radiation and filtered CrKa radiation. Lattice parameters were refined by a computer-programmed least-squares analytical treatment which incorporated appropriate extrapolation techniques.2 Frequent use was also made of a special computer program3 designed to generate a powder pattern from an assumed structure in order to verify structural assignments. Materials. Lanthanum, neodymium, and yttrium were purchased from the Lunex Co., cerium from the Cerium Metals Corp., and praseodymium from the St.

Jan 1, 1968

By M. J. Blackburn

The phasal equilibria in TI':Al alloys has been studied Ry transmission electron microscopy, electron diffraction, and X-ray diffraction. It is shown that three-phase fields exist below the transformation, viz.: a disordered hexagonal solid solution a; an ordered hexagonal phase based on Ti3Al, aa; and a two-phase region. (a + (YZ) , occurring between the single-plzuse fields. The size. disiribution, and morphology of- the a, phase in the two-phase region is shown to be dependent upon the alloy composition and heat treatement. The ordering process in the a, phase leads to the formation of anliphase domain boundary networks; the contrast and stability of these networks is shown to be dependent on alloy composition. A new and relatively simple phase diagralil for the systemm is constructed. The phasal equilibrium at the titanium-rich end of the Ti:Al system has long been the subject of considerable controversy. crossleyl has recently reviewed the phase diagrams that have been advanced for the system and in his turn proposed yet another one. There would seem to be general agreement that a phase exists at a composition at or near Ti& with an ordered hexagonal DO,,-type structure. However, several other phases have been proposed; for instance, Ence and ~ar~olin's' diagram includes two phases, Ti2A1 and Ti3A1, in the region up to 25 at. pct Al. The position of the proposed phase boundaries varies over a considerable compositional and temperature range, a point graphically illustrated in Fig. 1 of Crossley's paper.' It is perhaps germane to briefly examine the techniques used by other workers in the establishment of the phase structure. These fall into three categories: 1) X-ray diffraction, the only limitation of which is the rather low intensity of superlattice reflections in this system.3 Thus, superlattice reflections become increasingly difficult to detect in the more dilute aluminum alloys. 2) A considerable amount of optical microscopy has been performed"2'4 and it will be shown in a later section that many of the obscure mi-crostructures that have been observed can be attributed to hydrogen contamination. It is concluded, therefore, that such observations should be interpreted with considerable care. 3) The variation of some physical property with aluminum content has been measured.5"7 These methods are a useful indication of the existence of a transformation, but are usually insufficient in themselves to identify the transformation. The results using these techniques will be considered in more detail in the discussion. In this paper, the phase structure of alloys containing up to 25 at. pct A1 has been studied by transmission electron microscopy and X-ray techniques, and the results are used to generate a new and relatively simple diagram for the titanium-rich end of the Ti:Al system. EXPERIMENTAL A series of alloys containing 5.05, 10.16, 13.39, 13.99, 14.40, 20.83, and 25.05 at. pct A1 were obtained in the form of hot-rolled sheet 0.02 in. thick. These alloys contained 0.10 to 0.15 pct 0. Thirty-gram arc-melted buttons were prepared from iodide titanium and 99.99 A1 which contained 16.1, 16.9, 18.2, 19.0, 21.6, 22.2, 23.0, and 23.9 at. pct A1 and had an average oxygen content of 0.03 pct 0. The differences in oxygen content did not appear to influence the nature of the phase transformations which were found. Oxygen content may affect the temperature of these transformations, but insufficient samples of the high-purity alloys were examined to answer this question. The heat treatment of alloys was performed in dynamic atmosphere and vacuum furnaces or in helium -filled silica capsules. A special vacuum furnace was constructed to provide a high quenching rate in which rates of 4000°C per sec were obtained using water as the quenching medium. As pointed out by Crossley,' it is important to avoid heat treatment in the a - [} phase field as the resultant segregation of the alloy into the two phases containing different amounts of aluminum can persist through subsequent treatments leading to ambiguous results. It will be demonstrated later that step cooling of specimens from the a phase region can also lead to anomalous effects. Thus, all solution treatments were carried out in either the a or 3 phase fields followed by water quenching and subsequent isothermal annealing at various temperatures. X-ray analyses were performed on a diffractometer on fine-grained bulk specimens. The value of long-range order parameter, S, wa_s calculated from the integrated intensity of the (1211) reflection. In general, the intensity of the (1011) superlattice reflection was compared with that of the (2021) fundamental reflection to correct for experimental differences between measurements. Thin foils for electron microscopical examination were produced by electropolishing using the technique described in an earlier paper.8 Dark-field techniques were employed to a large degree in this investigation using the gun-tilt method. Finally it should be noted that the lattice parameters of the D01,-type superlattice are approximately related to the disordered hexagonal phase parameters by Crf - c, and 2ad - a, where the subscripts s and d refer to the ordered and disordered unit cells, respectively.

Jan 1, 1968

By W. D. Robertson, J. -P. Briant, M. Gell

The distribulion of dislocatiorls genevnted during the propagalion of hydrogen-induced cracks in Fe-Si cryslcrls was studied as a funclion of temperature f-110o lo 243°C) and silicorz conlenl (3.1 and 4.2 pct). It zoas found that the clislocntiotl densily and the size of the plctslic zone increased with increasing tempevalnre and decreasing silicon conlent. Furtheruvzove, there was a correlcrtion in the dislocalion patterns formed around cracks that propagated at different tempevattrt-es in cvyslals of diffevent silicon contents such that a 1 pcl itlcverise in silicon content was equivalent to a lemperaluore redziclion of approximately 120°C. The experimenlal YeSnllS were compaved with the results of an elastic-plastic wodel that relates the size of the pluslic .zone to the cvack length, internal pressure, and yield stress. it was found that the clzunges in the dislocctlion cryrays with lemperature and combosition can be e-kplaincd by the lemperatrnre and composilion dependence of the yield stress. An wmtsual feature of this study was the observation of low -temperature noncrystrrllogruphic cracks. PLASTIC relaxation can occur at the edge of a moving crack by the operation of pre-existing dislocation sources or by the creation of new sources in a region of perfect 1attice.l'2 The amount of relaxation in a given crystal depends on the crack velocity and the temperature, and can determine whether a crack propagates in a brittle or a ductile manner.1-3 Tetelman and Robertson4 observed microcracks m Fe-3 pct Si single crystals that formed on (100) planes by the precipitation of hydrogen gas during electrolytic charging at 23°C. The plastic deformation accompanying crack propagation was observed in the form of dislocation etch pits and an extensive analysis has been made of the size, shape, and crystallography of the dislocation arrays5-7 This paper describes the effect of temperature on the plastic deformation generated around hydrogen-induced cracks in Fe-3.1 pct Si and Fe-4.2 pct Si single crystals. The observations are compared with the results of an elastic-plastic model for yielding around a crack containing an internal pressure. 1) EXPERIMENTAL PROCEDURES The composition of the materials used in this study are given in Table I. Single crystals of alloy A and the 4.2 pct Si alloy were grown by the strain-anneal method; crystals of alloy B and the 5.1 pct Si alloy were cut from an ingot grown from the liquid. he ~ingle-cr~stal metallographic specimens had a Cross section of 0.100 by 0.050 in. with a length of at least 3/8 in. Specimens were annealed for 3 hr at

Jan 1, 1968

By D. Havlena, A. S. Odeh

The use of the straight-line method of solving the material balance equation is illustrated by means of six field cases. Also, the application of statistical criteria to arrive at the most probable answer is shown. The theory underlying the straight-line method of solution and the applicability of the statistical criteria was presented in a previous paper.' The field cases include saturated and undersaturated oil reservoirs with and without water drive. The aquifers discussed are: limited radial, infinite radial, very small aquifer and infinite linear. The field cases also include a gas reservoir producing under water drive. INTRODUCTION In a previous paper,' the authors presented the theory underlying the solution of the material balance as an equation of a straight line. The appropriate equations for various material balance cases as well as the methods of analysis and interpretation with comments and discussion were also included. To illustrate the various theoretical cases treated previously, five field cases are analyzed in this paper by employing the straight-line method of solving the material balance equation (MBE) and one example previously published is referred to. The use of statistical criteria to arrive at the most probable answer is also shown. All the field examples presented, except Case 2, are excerpts from complete reservoir studies. To illustrate the method, only sections specifically dealing with the material balance principles are included. Additional geologic information and basic data are reported to better acquire an understanding of the cases and thus to better follow the reasoning that suggested the successful application of the straight-line method of solving the MBE. The six cases are: (1) saturated reservoir, small gas cap, limited aquifer; (2) saturated reservoir, very small gas cap, infinite aquifer; (3) undersaturated-saturated reservoir, very small aquifer; (4) highly undersaturated reservoir, no water drive; (5) high undersaturated one-well reservoir, limited aquifer; and (6) gas reservoir, infinite linear aquifer. THE D4 SAND, GUICO FIELD, VENEZUELA The D, sand, which was discovered in 1943, is presently in a depleted state. Since its discovery it has produced under water drive, gas-cap-gas expansion, and solution gas drive. In Nov., 1947, water injection was initiated to arrest further pressure decline. When discovered, the D, sand was a saturated reservoir with a gas cap /oil zone volume ratio m estimated volu-metrically at 0.0731, an average permeability of 500 md, a porosity value of 25 per cent, and an oil viscosity at reservoir conditions of 0.3 cp. The volumetrically determined stock-tank oil initially in place was 23.1 million bbl. The volumetrically weighted physical data and production data available until Nov., 1953 are reported in Table 1. In Ref. 1, the effects on the straight-line plot of various values of ro/r for a constant ?to, or of various dimen-sionless times for a constant r8/r10 were theorized and were illustrated in Fig. 3A of that reference. In this field case, the previously theoretically predicted effects are established. Thus, the MBE calculations using Eq. 3c of Ref. 1 were performed for various r6/r10 and dimension-less time values. Eq. 3c of Ref. 1 is:

Jan 1, 1965

By Renato G. Bautista, Theodore D. Tiemann

A kinetic study of the hydrogen reduction of taconite from the Wisconsin Gogebic range was made over the temperature range from 500° to 1000°C on eleven size fractions from 4 to 150 mesh. Two stages of reduction were observed, a rapid initial reaction followed by a slower reaction presumably taking place at an internal receding FexO-Fe interface. Calculated mean activation energies for the two reactions were 7800 and 14,600 cal per mole respectively. In recent years there has been an increased interest in the direct reduction of iron oxide ores to metallic iron by means of gaseous reducing agents such as hydrogen and carbon monoxide.1,2 These investigations have been motivated by the desire to develop a process that will by-pass the blast furnace in the production of steel. The majority of these processes have been developed to produce metallic iron by direct reduction from high-grade iron oxide ores.3"5 Very little work has been done on the low-grade siliceous iron oxide ores.6"8 The work reported here is directed principally towards the fundamental aspect of the reduction reactions of siliceous iron oxide ores, since the practical aspects of the gaseous reductant process were discussed previously. The ore used in the investigation was obtained originally from the United States Bureau of Mines10 trench sample of the Yale member of the Wisconsin Gogebic range iron formation. The Yale taconite has an average analysis of 28.2 pct Fe and approximately 50 pct SiO2. Chemically, these nonmagnetic taconites contain on the average about 53 pct silica and 30 pct Fe. An average analysis calculated fron the USBM10 figures for a composite of the five members (Norrie, Plymouth, Pence, Pabst, and ale) of the iron formation is given in Table I. Mineralogically, based on previous X-ray diffraction and other studies, the principal minerals are hematite (Fe2O3), geothite (Fe2O3.H2O), and quartz (SiO2). Minor amounts of iron containing silicates, siderite (FeCO3) and magnetite (FeO. Fe2O3) are present.10,11 The iron minerals and the quartz are finely disseminated requiring extremely fine grinding for liberation. For the experimental work, the ore sample was screened into a number of size fractions, the analyses and densities of which are given in Table II. EXPERIMENTAL PROCEDURE The reduction experiments were carried out in a 24 in. by 2 in. ID nichrome-wound vertical-tube furnace mounted on a stand. A 1 1/2 in. OD zirconium-oxide combustion tube was used inside the furnace to contain the atmosphere. To the top of this combustion tube was joined a pyrex ground-glass joint to which was attached a glass bulb with a small (1.0 mm) opening at the center, and with two outlets controlled with a stopcock on each side. A pyrex-glass joint with connections to three stopcock joints for introducing hydrogen, nitrogen, and mixtures of hydrogen and nitrogen gas was joined to the tapered bottom of the combustion tube. The sized ore fractions were contained in a 1 in. diameter by 1 1/2 in. 150-mesh nickel screen basket. The basket was suspended in the furnace from a balance by means of a supporting nickel wire which hung freely inside the combustion tube. The furnace temperature was controlled by a Leeds and Northrup Speedomax Type G controller, connected to a chromel-alumel thermocouple placed

Jan 1, 1962

By Richard B. Reese, George R. St. Pierre, Robert A. Rapp

The vapor pressures of pure iron and pure chromium have been measured using a Knudsen cell coupled with a mass spectrometer. The experimental results agree well with some previously reported data; heats of sublimation and vaporization have been calculated. From vapor pressure rr~easurernents, the activities of iron and chromium in their binary alloys have been determined for NcY = 0.10 to 0.65 over a 1400" to 1700~ temperature range. The activity of chromium in the liquid alloys was found to exhibit positive deviation from ideal behavior when referred to solid chromium as the standard state; however, for the activity of chromium referred to nonequilibrium undercooled liquid chromium as standard state, the activity behavior is almost ideal. ALTHOUGH the Fe-Cr system is important as the basic system of alloy steels, the thermodynamic properties of this system have not been thoroughly investigated at elevated temperatures. In view of the potential practical applications of such data as well as their contribution to alloy theory, further study of the Fe-Cr system was undertaken. In addition, further development of experimental techniques for equilibrium measurements at high temperature is required. The present research involved an application of the Knudsen effusion method in conjunction with a time-of-flight mass spectrometer. Belton and ~ruehan' have measured the activities in Fe-Ni and Fe-Co alloys by a similar method. Speiser, Johnston, and lackbburn' have determined the vapor pressure of pure solid chromium between 1283" and 1561°K by a Langmuir free evaporation technique. The vapor pressure of chromium was described by the expression: over the temperature range 1283" to 1561°K. McCabe, Hudson, and paxton3 have measured the vapor pressures of pure iron and pure chromium by the Knudsen cell technique around 1500°K. The vapor pressure and heat of sublimation at O°K, AH,", for pure chromium agreed within experimental error with the measurements of Speiser et al. at 1200°C. Kubaschewski and HeYmer~ determined the vapor pressure of pure solid chromium in the temperature range 1170" to 1400°C by the Knudsen effusion technique combined with a radioactive tracer analysis of crS1. Their results agreed with the work of previous investigators. Edwards, Johnston, and Ditmars5 have measured the vapor pressure of pure solid iron by the Langmuir technique between 1356" and 1519°K. The vapor pressure of solid iron in the temperature range studied was given by: The data of McCabe, Hudson, and paxton3 on the vapor pressure of pure iron around 1500°K by the Knudsen effusion technique were in good agreement with those obtained by Edwards et a~.~ Hultgren, Orr, Anderson, and Kelley give the selected values for the AH: of pure iron and pure chromium as 98,990 *200 and 94,340 * 500 cal per mole, respectively. These values are the average values determined in the several investigations by different methods. The Fe-Cr phase diagram7 is shown in Fig. 1. Previous determinations of activities in this system have been carried out by several investigators, but most of the work has been done on solid alloys. Using a Knudsen effusion method with cr5', Kubaschewski and Heymer4 reported that the Fe-Cr system exhibits positive deviation from the ideal behavior for compositions ranging from NCr = 0.0398 to 0.699 at 1170"

Jan 1, 1969

By J. Spreadborough, D. LaW. King, E. Anderson

Tmzsile tests were performed on Armco iron samples, at various ternpe.ralures and strain rates, ocer a wide range of grain sizes. Analysis of the data suggests that the plot of the lower yield stress, against d-1/2,where 2d is the acerage grain diameter, is not linear (as is often assumed) but is concave toward the d. axis over the range of d-from 7 to 53 . The different values of the parameters obtained by other workers can be explained, in part at least, by the observed curvature. This curvalure is shown to be consistent with a model of yielding based on dislocation pile-ups; however, the values of obtained by fitting our data to this model differ appreciably from the values generally reported. The equation proposed by Cottrell, viz.: is a plausible empirical fit to the experimental results. The purpose of this paper is to comment on the validity of the widely used linear relationship first proposed by all' and Petch and coworkers2"4 between ay, the lower yield stress, and 2d, the average grain diameter, for bcc metals, viz.: Many workers, see Refs. 2 to 7 and Table 11, have fitted this equation to their experimental results and have obtained acceptable fits over the relatively narrow range of grain sizes used by most of them. Indeed, in some cases, so few data points were available that any more sophisticated fit would have been irrational. In most of the interpretations,'-' oi is thought to be a measure of the friction stress accompanying dislocation movement, and ky was originally inter- preted as a measure of the dislocation locking but is now believed by Cottrell" to be a function of the dislocation creation rate. In the "unpinning" theories, k, is equated to where od is the unpinning stress and 1 is the average distance from the boundary of the grain where yielding is taking place to the nearest dislocation source in an unyielded grain. Other considerations (see, for example, Refs. 11 and 12) lead to equations with a similar form to [I] where different meanings may be attributed to the parameters. While there are doubts as to the physical significance of the parameters i and k, they continue to be used by many workers; interpretations of the variations in the behavior of ferrite materials following certain treatments, e.g., aging,'3 neutron irradiation,14 have been given frequently in terms of these parameters. Some theories of the mechanical behavior of bcc metals are based on this relationship. We have investigated experimentally the oy - d-'lZ relationship for Armco iron over a wider range of grain sizes and with more data points than those given in published results. The analysis of our data suggests that the oy—d-'" relationship is not linear but is in fact concave towards the d-'I2 axis. RESULTS AND DISCUSSION The experimental work was carried out on 3-mm-diam Armco iron rods which were prepared by wire drawing from 5-mm-diam rods. By annealing in vacuum at temperatures between 7000 and 1200°C for various times, grain sizes from 7 to 20,000 grains per sq mm were obtained, the grains in all cases being regularly shaped. Grain sizes were measured by lineal interceptand by area methods; only specimens with Amax/A values of 3 to 6 were used in the Petch-Hall plots (where A is the average area of a grain and Amax is the area of the largest grain observed). For all the specimens used, the number of grains in a cross section exceeded 50, which should be adequate to avoid grain size effects.'= Tensile tests were performed at 296", 219, and 17l°K, using

Jan 1, 1969

By Ross Blake

THE St. Joseph Lead Co. became interested in the Tri-State district in 1921 through acquisition of prospecting and development rights on approximately 20,000 acres of land extending northeastward from the Picher mining field, mostly in Kansas. Prospecting with churn drills was begun the same year and the first commercial ore body was found on the Jarrett tract at the then northern limit of the main Picher field. Operations at this mine began in 1923. Kansas Explorations, Inc., was organized in 1923 by the St. Joseph Lead Co. as a wholly-owned subsidiary to carry on its operations in the Tri-State District from an office at Joplin, Mo. As prospecting of the original acreage proved largely negative, attention was subsequently turned to other sections of the district. Numerous additional leases were acquired and prospected. The Company was successful in developing into operating properties the Jarrett, Isherwood, Robinson, Sullivan and Lotson tracts and, in more recent years, the Ritz, Snapp, Buckingham, Gibson and Jasper mines.

Jan 1, 1947

By R. E. Morgan, D. L. Douglass

The determination of phase relationships and solid-solubility limits can be performed by quantitative metallography in addition to the usual X-ray and metallographic techniques. For example, Beck and smith1 redetermined the ß/ß + ?, ß + ?/?, a/a + ß and a + ß/ß boundaries in the Cu-Zn system by measuring the volume fraction of second phase of several alloys and extrapolating the volume fraction-composition curves to 0 and 100 pct. A modification of this technique is suggested for certain alloy systems, in which it is not necessary to use several alloy compositions but merely one. A single two-phase alloy may be used to determine terminal solubilities in the following manner. The method consists of equilibrating samples of the alloy in a two-phase region adjacent to the desired solid solution, at three or more temperatures, quenching, measuring the volume fraction of second phase present, and applying an analytical treatment to calculate the unknown solid solution. However, two restrictions are inherent in this technique. They are: 1) only certain types of alloy systems are amenable to it, and 2) the general features of the system must be known. The first drawback to the new technique, i.e., that only certain types of systems may be studied, necessitates that the composition at one end of the tieline must either be constant with temperature or well established as a function of temperature. Either a pure metal or some intermetallic compounds fulfill the former. If it is assumed that the volume per gram-atom of a dilute solution is unchanged by the addition of element B to element A, the composition of the solid solution in equilibrium with the second phase may be determined by a material balance and is given by where X, = volume fraction of B in a solid solution Xc = volume fraction of B in compound c X = volume fraction of B in alloy f = volume fraction of second phase The composition by weight may then be determined by the use of tables in the Metals Handbook2 when the density ratio of the solid solution constituents is known. A possible alternative treatment involving the use of the lever rule is less precise than the above tech- nique. This may be used when the density of the solid solution is either known or may be calculated from X-ray data for several compositions. The following analysis is then made. The ratio of compound to solid solution (by weight) may be expressed as follows: x0 - x wc = xr-x = x0 - x r2i Xc -X where Wc = weight of compound w = weight of solid solution x, - alloy composition, weight percent x = unknown composition Xe = compound composition but where V, = volume of compound VA = volume of solid solution pc = density of compound p, = density of solid solution fc = volume fraction of compound fB = volume fraction of solid solution and fs = l -fc then If pc and xc are known, and f, is measured, then pB is the only unknown on the right side of Eq. [4]. The known densities of the solid solution can be plotted for various compositions and can then be expressed mathematically as a function of composition. The use of an expression of pB = f(x)reduces the equation to one unknown—the desired solubility. In the event that the densities are unknown, they may be calculated for various compositions from Vegard&apos;s law. The calculated values are then plotted and expressed analytically. The most accurate results are obtained for Eq. [4] when fc<< 1, i.c., when (x, -x,) - 0, &/l-f, - m; but as fc/l -fc - 0, (xl-x,)- (x, - x), and x - x,,. However, the accuracy with which fc can be measured decreases as f, decreases.3 Alloys for investigation must be selected by a compromise, which is based upon an error analysis of Eq. [4] and knowledge of the accuracy of volume fraction measurements. An examination of phase diagrams in the literature showed many which were amenable to the technique described here. The zirconium-copper system was selected in order to determine the solubility of copper in beta zirconium. Pieces of an alloy which was arc-melted three times were wrapped in tantalum foil and sealed under an argon atmosphere in Vycor tubes. The sealed samples were equilibrated at temperatures from 850" to 960°C for 3 weeks and quenched to room temperature by smashing the capsule in water. Several planes of polish were examined, and

Jan 1, 1960

By E. W. Stewart, G. P. Conard, J. F. Libsch

The effects of several additives upon the reduction characteristics of hydrogen-reduced ferrous formate are described. The various additives inhibit sintering of the reduced iron particles by apparently different mechanisms. The magnetic properties of the low density compacts produced from the resulting ultra-fine iron powders were improved markedly. THE permanent magnetic characteristics of ultra-fine iron powder prepared by various means have been a subject of considerable interest and experimentation in the past few years. When such particles are small enough to show single domain behavior, they possess&apos; 1—permanent saturation magnetization, and 2—high coercive force. In the absence of domain boundaries, the only magnetization changes in a particle occur through spin rotation which is opposed by relatively large anisotropy forces. With decreasing particle size, the coercive force tends to increase to a maximum and then decrease because of the instability in magnetization associated with thermal fluctuations. Kittel&apos; has calculated the critical diameter at which a spherical particle of iron can no longer sustain domain boundaries or walls to be approximately 1.5x10-&apos; cm. Stoner and Wohlfarthr in England and Neel4,6 in France have shown from purely theoretical calculations that the high coercive force expected from single domain particles is dependent upon crystal anisotropy, shape anisotropy, or strain anisotropy contributions. Further work by Weil, Bertaut,&apos; and many others has contributed much to the understanding of fine particle theory. Neel and Meikeljohn" have demonstrated that a decrease in particle size below a critical value of approximately 160A leads to a quite rapid decrease in coercive force because of the prevention of stable magnetization by thermal agitation. Lih1, working with powders prepared by the reduction of formate and oxalate salts of iron, has shown the marked influence of powder purity upon magnetic properties. Maximum coercive force was obtained in powders of approximately 65 pct metallic iron content while the maximum energy product, (BxH) occurred in powders of 85 pct metallic iron content. Careful consideration of the preceding theoretical considerations and experimental results has led to the manufacture of permanent magnets from ultra-fine ferromagnetic powders by powder metallurgy techniques. Such work has been done by Dean and Davis," the Ugine Co. of France, and Kopelman." The aforementioned work of Kopelman and the Ugine Co. was concerned somewhat with the effect of various additives upon the properties of hydrogen-reduced ferrous formate. Virtually no work, however, has been published on the effects of additives on the reduction rates of metal formates, although unpublished work by Ananthanarayanan16 howed promise of improved energy product in ultra-fine iron compacts prepared by the hydrogen reduction of a coprecipitated mixture of magnesium and ferrous formate. After consideration of the preceding information, it was hoped that a better balance between the metallic iron content and particle size of the reduced iron powder could be accomplished by a prevention of the attendant sintering of the partially reduced iron powder during the reduction reaction. It appeared possible that magnesium oxide might interpose a mechanical barrier between adjacent iron particles and prevent their sintering together, while metallic cadmium and metallic tin would interpose a liquid barrier which might accomplish the same purpose. The degree to which these materials were effective in accomplishing the foregoing objective and the experimental details associated with the work are reported in the following sections of this paper. Experimental Procedure Preparation of Formate and Oxide Mixtures: To obtain ferrous formate of reproducible reduction characteristics, a slight modification&apos; was made in the technique of Fraioli and Rhoda." A supersaturated solution of ferrous formate was mixed with an equal volume of 95 pct ethyl alcohol and the formate crystals precipitated by stirring and screened to —325 mesh. These crystals were in the shape of elongated hexagons, approximately 4x10 micron in dimension. Various preparations of such ferrous formate, designated as lot 111, were reduced for 2 hr, yielding ultra-fine iron particles of exceedingly reproducible size, metallic iron content, and magnetic properties. The magnesium and cadmium formates were prepared by the reaction of dilute formic acid with their respective carbonates, while the tin formate was prepared by the reaction of dilute formic acid with stannous hydroxide. To evaluate the effect of metallic formate additives in intimate mixture with the ferrous formate, varying amounts of magnesium, cadmium, and tin formates were coprecipitated with the latter. The designations of these materials and their chemical compositions are given in Table I. Due to the differing solubilities of the various formates in aqueous media,

Jan 1, 1956

By W. Bonfield

The temperature dependence of the microscopic yield stress (the stress to produce a plastic strain of 2 x 10-6 in. per in.) and the stress-plastic strain curve of polycrystalline Cu 1.9 wt pct Be have been measured for the solution treated condition, an intermediate condition containing G.P. zones and ?&apos; precipitate and the overaged ? precipitate condition, in the range from -58° to 200° C. A transition in micro -yield behavior and a large temperature dependence were noted for the intermediate condition, which are interpreted in terms of the interaction of glide dislocations with two differently sized zones. In comparison the microscopic yield stresses of the solution treated and overaged conditions were less sensitive to temperature variations and are satisfied by the Mott-Nabarro and dislocation bowing theories, respectively. A determination of the temperature dependence of the yield stress of a precipitation hardening alloy has provided a powerful tool for evaluation of the operative deformation mechanism. There is a marked contrast between the effect of temperature on the yield behavior of a metal containing coherent zones or intermediate precipitates, which can be "cut through" by mobile dislocations, and a metal containing a dispersion of noncoherent particles, through which dislocation "bowing out" is the dominant role of deformation.&apos; These studies have in general been confined to single crystals, as it was considered that similar experiments on polycrystalline material did not produce good data because of the lack of sensitivity with which the yield stress could be determined. However, this objection has been removed by the introduction of mi-crostrain techniques, with which the yield stress in polycrystalline materials can be measured to a strain sensitivity of 10-6. Such measurements have not only shown that the deformation of polycrystalline precipitation hardening alloys can be examined with the same detail as single crystals, but also that some unexpected results are obtained.&apos; In this paper the results obtained from a study of the temperature dependence of the microscopic yield stress (the stress to produce a plastic strain of 2 x 10-6 in. per in.) and the stress-plastic strain curve of a polycrystalline Cu 1.9 wt pct Be precipitation hardening alloy (Berylco 25) are discussed. The temperature dependence of the alloy was measured for three different conditions: 1) The solution treated condition (a supersaturated solid solution of a containing ~12 at. pct Be3) which is obtained by water quenching the alloy from 800° C. 2) The condition of y&apos; intermediate precipitate, to- gether with some G.P. zones,&apos; which is produced after an aging treatment of 2 hr at 315°C from the solution treated condition. (The alloy was cold rolled to 40 pct reduction prior to aging to minimize grain boundary precipitation effects.)4 3) The condition with equilibrium ? precipitate structure2 which is developed after an aging treatment of 24 hr at 425° C. EXPERIMENTAL PROCEDURE Tensile specimens of gage length 1 in. and with rectangular cross section of 0.18 by 0.06 in. were prepared from the solution treated, cold rolled alloy and were either resolution treated for 1 hr at 800°C, followed by water quenching, or aged for 2 hr at 315°C and 24 hr at 425° C to produce the desired precipitate structures. The microstrain characteristics of the aged specimens were determined at temperatures from —58" to 200° C and those of the solution treated specimens from -58° to 30° C. Each temperature was controlled to ± 0.2°C, which was a level of stability sufficient to eliminate thermal expansion effects from the measurements (~1.2°C temperature increase produced an extension of 2 x 10-6 in.). The microplastic behavior of the specimens in the temperature range below 82" C was measured with a standard Tuckerman strain gage,5 while at temperatures above 82°C a modified Tuckerman gage with a reduced strain sensitivity (4 x10-6 in. per- in.) was used. A load-unload technique was used to establish values of the microscopic yield stress. The specimen was strained at a constant cross head speed of 2 x 10-2 in. per min to a given stress level, at which the total strain was measured. Then the specimen was immediately unloaded at the same rate and any residual plastic strain determined. This procedure was repeated for an increasing series of stress levels until the microscopic yield stress was established by a direct measure of the stress to produce a residual plastic strain of 2 x 10-6 in. per in. (It should be noted that, as reversible dislocation motion occurs at stresses less than the microscopic yield stress,2 the plastic strain rate at this level was not constant.) In an ideal test, the microscopic yield stress would be determined from a continuous stress-strain measurement, rather than from a load-unload sequence, in order to eliminate mechanical recovery effects.6 However, it was found experimentally that mechanical recovery was negligible in Cu 1.9 wt pct Be at small plastic strains for all the temperatures investigated, as the microscopic yield stress was independent of the number of load-unload cycles employed (i.e., the values measured for specimens subjected to different numbers of cycles was within the experimental scatter determined for specimens tested in an identical manner). Therefore, it is reasonable to consider the microscopic yield stress determined in the load-unload

Jan 1, 1969

By Werner Goldsmith, Akihiko Kumano

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

Jan 1, 1982

By J. Marvin Weller, M. King Hubbert

Preliminary investigations were undertaken with a Megger Ground Tester in 1931 by Hubbert to determine whether the faults in Hardin County, Illinois, could be located by earth-resistivity surveys. The results of these investigations, which were in part presented before this Institute in 1932,1 were sufficiently promising to warrant a more extensive field program in the same general area the following summer. During the second season an apparatus of the Gish-Rooney type was employed because of its greater sensitivity and to avoid the troublesome correction for resistance of potential electrodes necessitated by the use of a Megger instrument. The discussion of earth-resistivity traverses which constitute the main part of this paper is based entirely upon the results of the second season&apos;s work. All of the traverses were made with a constant electrode spacing of a equal to 100 ft., and the four-electrode technique was employed. Successive stations in these traverses were spaced at intervals of 100 ft. and the line of electrodes was carried parallel to the line of traverse. The graphs of resistivity profiles presented here (Figs. 1 to 3) are plotted with resistivities in ohm-centimeters as ordinates and with distance divided into stations at 100-ft. intervals as abscissas. After the traverses were run by Hubbert the results were computed, the profiles plotted, and tentative interpretations were made by him. These curves and interpretations were then taken into the field by Wellcr, who made a careful geological examination along the lines of traverse for the purpose of checking and supplementing Hubbert&apos;s interpretations. Weller then constructed a geologic cross-section extending along the line of each traverse. The accompanying diagrams graphically illustrate the correlation that can be made between earth resistivity and geology in this area.

Jan 1, 1934

By W. J. McKenna

THE International Smelting Co. concentrator at Tooele, Utah, first operated on a custom basis for the treatment of lead-zinc-iron ores on Nov.&apos; 1, 1924, with a capacity of 500 tons per day. On May 1, 1925, the capacity was increased to 1000 tons per day by the addition of another 500-ton section. The concentrator has since operated on the two-section basis, each treating 500 tons per day entirely by flotation. LABORATORY AND TEST MILL In connection with the concentrator, a well-equipped laboratory and small continuous testing plant are maintained. The flotation equipment in the test plant is of both the Callow and Mineral Separations Sub-"A" types, so that actual concentrator conditions may be duplicated as closely as possible. PURCHASING OF ORE A new shipper usually sends to the plant a 25 to 50-lb. sample, representative of the ore to be shipped. Batch flotation tests are made on this sample to determine its amenability to the concentrator treatment flowsheet and reagent combinations. The results of these tests, which are accurately correlated with those obtained at the concentrator, both as to grades of products and recoveries, determine the actual value of the ore as submitted in the ore purchasing department&apos;s treatment schedule. Hearty cooperation has existed at all times between the ore purchasing and operating departments in the selection of ores as concentrator feed. ORE TREATED The basic tonnages for mixtures on the two sections come from the Park City and Bingham mining districts. The Park City tonnages are received by rail and consist of crude ores and gravity mill products. Those from the Bingham district are received by rail and aerial tramway,

Jan 1, 1928

By Richard Bosustow, Van Dyne Howbert

The Presidio mine of The American Metal Co. is situated in the "Big Bend" region, some 45 miles over state highway south of Marfa, a station on the Southern Pacific R.R. It lies 20 miles by road north of the Mexican border, in semidesert surroundings typical of this general section of the United States and the adjoining part of Mexico. All supplies are hauled in by truck from Marfa under contract. The concentrates and precipitates produced by the mill are carried by the same trucks to Marfa, from whence they are shipped, respectively, to the El Paso and Selby plants. History The mine was discovered about the year 1880 and was soon thereafter taken over for development by some army officers stationed at Fort Davis, Texas. It was later operated by the Presidio Mining Co., which treated the ore in a small pan-amalgamation mill from 1883 until 1913, when a cyanide plant was erected which has been in continuous operation ever since. When the present company, a subsidiary of The American Metal Co., Ltd., took over the mine in April, 1926, the ore-bearing zone had been worked for about 2200 ft. to the east of I the outcrops down the dip of the formation, at which point it is at a I vertical depth of 500 ft. below the surface. Up to that time the mine had produced some 1,150,000 tons of ore averaging about 17 oz. silver. After a development campaign the company started milling again in February, 1927. Since then the production has been approximately 4700 tons per month of ore; of which the yearly average grade has varied from 19.7 to 23.2 oz. silver, $0.20 to $0.50 gold, and 2.0 to 2.5 per cent. lead. No other property in this district has ever produced tonnage of any importance.

Jan 1, 1931

By George Stanley Scott

Many requests for information as to the possibility of washing coals to some predetermined percentage of ash or sulfur have suggested that the producers aim to satisfy some degree of purity set by the user of the fuel, rather than to attain the greatest economic benefit to all concerned. This paper is written to show that the highest economic purity of washed coal can be determined from washability studies of the raw coal, costs of mining and washing coal, and data on the effect of ash and sulfur on the value of the coal for the particular use for which it is intended. Coke fob Blast-fuenace Use For purposes of illustration, we take the case of coal washed for coke to be used in the iron blast furnace. The method outlined can be made general in its application by substituting for the figures used here the actual operating figures for the particular case under consideration. In general, it costs the blast-furnace operation from 8 to 25 c. per ton of pig iron to slag out each 1 per cent. of ash introduced into the blast furnace by the coke. This figure depends on which one per cent. of ash is removed, and decreases with decrease in ash. When blast furnaces and coal mines are considered as a whole, the figure decreases to zero and then becomes negative, on account of low recovery of washed coal. Various figures1 have been given by different investigators. These figures necessarily differ, not only on account of the differences in operating costs but on account of the difference in the respective fuels as well. For the purpose of this paper, which, as explained, is to point out a method of attacking a certain problem, the figures used in the exposition of the method are of secondary importance. It is apparent that no universally applicable figures can be used, because there are none. Each plant has its own coal,2 its own operating cost, and its own conditions.

Jan 1, 1930

By G. W. Jones

THIS paper describes experiments in which eight test samples of gelatin dynamite were fired in three different types of apparatus and the quantity and composition of the gaseous products of detonation determined. The special dynamites were so prepared that the oxygen balance of the samples varied from -35.0 to +6.0 g. per 100 g. of explosive, including the wrapper. By means of this graded series of explosives, the relation between oxygen balance and gaseous products of detonation could be studied explicitly. The effect of varying oxygen balance on explosive strength has been discussed in another paper.1 The apparatus employed in the work described in the present paper included (1) the Bichel gage, a steel bomb of 15-1. volume; (2) the Crawshaw-Jones confined detonation apparatus, a steel cannon from which the explosive is fired into a pipe of 90-1. volume; and (3) the Hercules tank, an apparatus in which the explosive is confined in a quartz block which is placed in a steel tank of about 4500-1. volume. A full description of the apparatus is given later. VARIABLES AFFECTING COMPOSITION OF DETONATION PRODUCTS The character of the detonation products of commercial explosives is governed in part by the same factors that affect the combustion products from explosive mixtures of air with gases or vapors. In either case, combustible materials-namely, carbon, hydrogen, and sometimes sulfur-are present and combined variously. In an exploding gas mixture the combustibles are oxidized by oxygen in the admixed air, whereas with explosives the necessary oxygen is provided by oxygen-carrying materials in the explosive ingredients.

Jan 1, 1928

By H. R. Banks

The Sullivan concentrator has completed 20 years of operation. During this period a considerable amount of data has been accumulated concerning the characteristics of several types of flotation machines in their application to the problem of the differential separation of the lead sulphide, zinc sulphide and, in more recent times, iron sulphide, in the ore from the Sullivan mine. It is the author&apos;s intention to sketch briefly experiences encountered when the several types of flotation machines were introduced into the flow. Original Flotation Equipment and Ore The original flotation equipment consisted of four 18-cell lead-roughing machines, whose concentrate was cleaned in an 8-cell and recleaned in a similar 8-cell machine. Zinc concentration was carried out in four 18-cell machines. One 8-cell zinc re-treatment machine received the reground zinc middling. The 168 cells handled some 3000 tons of original daily feed. These cells were of the standard Minerals Separation type, equipped with 24-in. impellers. Spindles were driven through geared line shaft at a speed of 255 r.P.m. The impellers were the 45&apos; type, except for the last three cells of the zinc-rougher machines, which were of sub-aeration type, with full bottom shroud and half shroud for the top side of the impellers. Four-pound air was introduced. This recognition of the benefit of intensified flotation operation for "gleaning" was an important phase in the early operation and will be discussed further on in this paper. Sullivan ore during this period is described as a finely disseminated mixture of four sulphides, totaling go per cent made up of 13.6 per cent galena, 14.4 per cent mar-matite, I per cent pyrite and 61 per cent pyrrhotite. The specific gravity of the ore was approximately 4.4. There has been a gradual change in the ore content. The 10 per cent of nonsulphide constituents has increased to between IS and 20 per cent and all three sulphides have dropped somewhat. Added equipment and changing technique have made possible the treatment of 8000 tons per day of mill feed instead of the 3000 originally handled. Special Features of Flotation at Sullivan Sullivan flotation differs greatly from customary practice. The very heavy return of lead rougher middling and lead cleaner tailing, totaling at times 125 per cent of the new feed tonnage, has been the subject of much investigation. The practice is still employed. This operating condition is mentioned because it is the author&apos;s belief that the in-

Jan 1, 1947

By H. R. Banks

The Sullivan concentrator has completed 20 years of operation. During this period a considerable amount of data has been accumulated concerning the characteristics of several types of flotation machines in their application to the problem of the differential separation of the lead sulphide, zinc sulphide and, in more recent times, iron sulphide, in the ore from the Sullivan mine. It is the author&apos;s intention to sketch briefly experiences encountered when the several types of flotation machines were introduced into the flow. Original Flotation Equipment and Ore The original flotation equipment consisted of four 18-cell lead-roughing machines, whose concentrate was cleaned in an 8-cell and recleaned in a similar 8-cell machine. Zinc concentration was carried out in four 18-cell machines. One 8-cell zinc re-treatment machine received the reground zinc middling. The 168 cells handled some 3000 tons of original daily feed. These cells were of the standard Minerals Separation type, equipped with 24-in. impellers. Spindles were driven through geared line shaft at a speed of 255 r.P.m. The impellers were the 45&apos; type, except for the last three cells of the zinc-rougher machines, which were of sub-aeration type, with full bottom shroud and half shroud for the top side of the impellers. Four-pound air was introduced. This recognition of the benefit of intensified flotation operation for "gleaning" was an important phase in the early operation and will be discussed further on in this paper. Sullivan ore during this period is described as a finely disseminated mixture of four sulphides, totaling go per cent made up of 13.6 per cent galena, 14.4 per cent mar-matite, I per cent pyrite and 61 per cent pyrrhotite. The specific gravity of the ore was approximately 4.4. There has been a gradual change in the ore content. The 10 per cent of nonsulphide constituents has increased to between IS and 20 per cent and all three sulphides have dropped somewhat. Added equipment and changing technique have made possible the treatment of 8000 tons per day of mill feed instead of the 3000 originally handled. Special Features of Flotation at Sullivan Sullivan flotation differs greatly from customary practice. The very heavy return of lead rougher middling and lead cleaner tailing, totaling at times 125 per cent of the new feed tonnage, has been the subject of much investigation. The practice is still employed. This operating condition is mentioned because it is the author&apos;s belief that the in-

Jan 1, 1947