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By B. K. Miller, R. S. Bradley

THE principal producing areas of fire clay in Missouri are: (I) the east central district, which includes Audrain, Callaway, Montgomery, Warren, and Boone Counties [ ] (Fig. I); (2) the St. Louis district, which includes St. Louis and St. Louis County; (3) the north central Ozark district, which includes Franklin, Gasconade, Osage, Maries, Phelps, and Crawford Counties. Most of the semiplastic[$] fire clay is found in Audrain, Callaway, Montgomery and St. Louis Counties, and in St. Louis. Flint fire clay is found in Callaway, Audrain, and Montgomery Counties and in most of the north central Ozark district. High-alumina diaspore clay is found only in the north central Ozark district, except a few deposits found in Montgomery County. This paper is concerned with the semiplastic fire clay that occurs in the east central Missouri district near Mexico, Audrain County, Missouri, which is mined by the open-pit method as practiced by the A. P. Green Fire Brick Co. About one-fourth of the semiplastic fire clay in that district is mined in shaft mines, and three-fourths in open pits.

Jan 1, 1941

By J. B. Dorsey, T. W. Brinkley

Performance of a high-pressure, vaporizing gas-drive project in a volatile oil reservoir is discussed. The project has been in operation for over 8 years. Present recovery from the over-all displaced portion of the reservoir is 40 percent, and an ultimate recovery of 60 percent is indicated. Calculations reflect an over-all displacement volume of 50 percent for the entire reservoir; therefore, ultimate oil recovery will be 30 percent of the entire reservoir oil originally in place. Laboratory vaporization tests conducted prior to project initiation also are presented and discussed, along with an analytical method of determining stock-tank oil production and gar injection requirements related to over-all volumetric displacement efficiency from these data. Introduction The Shoats Creek field is located in Beauregard Parish, La., in the extreme western part of the state (Fig. 1). Discovered in 1956, the field is productive in three Cockfield sand zones, ranging in depth from 8,000 to 9.000 ft. The upper two zones, 1st and 2nd Cockfield, are condensate-bearing gas reservoirs. The lowest zone, the 5th Cockfield, is a volatile-oil reservoir. Laboratory work conducted on crude oil from the 5th Cockfield zone shortly after field discovery demonstrated that, when contacted with dry gas, signidcant volumes of the oil could be vaporized at reservoir temperature and at an appropriately high reservoir pressure. Further study led to the conclusion that early initiation of a crude vaporization project in the 5th Cockfield zone would be superior economically to other methods of reservoir depletion. Consequently, the zone was unitized and gas injection operations started late in 1958. This paper discusses laboratory work performed in conjunction with the project, and project performance to the present. History of Development The 5th Cockfield zone in Shoats Creek is composed of a thin, very shaly, low-permeability sandstone. Oil accumulation is controlled by a structural trap bounded by faults along the north and west and by a water contact on the southern boundary (Fig. 2). The zone covers a productive area of 1,550 acres at an average depth of 9,000 ft. The net sand section is thin, having a maximum thickness of 10 ft and an average thickness of 5.5 ft (Fig. 3). Average reservoir rock properties, as determined from core analysis are presented in Table 1. Shaliness of the zone is illustrated by the typical electric log of the 5th Cockfield section in Fig. 4. Because of the thinness and poor quality of the sand, the 5th Cockfield was developed on a wide spacing. Eleven completions were made in the zone between 1956 and 1961 for an average density of 140 productive acres per completion, with the majority of wells being dually completed in the 2nd and 5th Cockfield. Average initial potential for producers in the 5th Cockfield was 130 BOPD. Oil from the 5th Cockfield has a stock-tank gravity of 50.5" API; with a bubble-point pressure of 3,515 psia, the oil was highly undersaturated at the original reservoir pressure of 4,675 psia. Pertinent properties of the oil as determined in the laboratory are presented in Table 2. Because of the volatile nature of the crude, laboratory studies of its susceptibility to vaporization, as well as a vapor-liquid phase study, were conducted in addition to a standard PVT analysis. The vaporization study was conducted in a visual cell; a stepwise illustration of this work and laboratory measurements are presented in Fig. 5. Field

Jan 1, 1969

By C. J. Rosa, W. C. Hagel

An attempt is made to determine the diffusion coefficients of oxygen ions in hypostoichiometric zirconium oxide. A phenomenological theory is developed for three-phase, unidirectional volume diffusion of a gaseous species from a planar source. Knowledge about oxygen diffusion in a and ß zirconium and experimentally measured rates of movements of interfaces permit the evaluation of oxygen ion diffusivi-ties in ZrO2-x. The results conform to the relationship: sq cm per sec, for the temperature range of 875" to 1050° C. DIFFUSION coefficients of oxygen ions in stoichio-metric oxides have been studied by many investigators. The obtained results not only supplement the knowledge about the lattice-defect structures of oxides and conduction mechanisms but also provide information of technological importance. Rate processes such as oxide sintering, high-temperature creep deformation, and oxidation of metals and their alloys are directly dependent on diffusion phenomena. Unfortunately, diffusion coefficients obtained from studies on stoichio-metric oxides cannot be treated without restraints when applied to oxidation kinetics, if precise evaluations of oxidation rates are desired. Oxides formed on metals are usually nonstoichiometric and exhibit nonuniform distribution of either cation or anion vacancies across their thicknesses. Debuigne and Lehr1 extended Danckwerts'2 mathematical analyses and furnished a semitheoretical treatment for evaluating oxygen diffusion coefficients in zirconium oxide in terms of weight gain measurements during oxidation of zirconium in the temperature range 400° to 850°C. Their calculations are based on theoretical partitioning3 of the total amount of oxygen between a zirconium and its oxide phase. An inherent discrepancy appears to continue throughout their calculations. The amount of oxygen confined to the oxide phase should be corrected by multiplying the calculated oxide thickness by the inverse of Pilling-Bedworth ratio, if expansion of zirconium dioxide is taken into account. The purpose of the present investigation is to provide a new semitheoretical treatment for evaluating diffusion coefficients of moving species in hypostoichiometric oxide. The analyses are relevant to unidirectional volume diffusion. Although the presented method is quite general, its applicability will be discussed in terms of kinetic measurements from oxidation of zirconium at temperatures above the a/ß transition, for reasons stated in the later part of this paper. EXPERIMENTAL Pure, 99.93 wt pct, zirconium samples of approximately 2 by 1 by 0.35 cm were exposed to oxygen for various times at four temperature levels: 875°, 950°, 1000°, and 1050°C. High-purity, better than 99.9 vol pct oxygen was passed through a cold trap and columns containing anhydrous CaSO4 to remove residual water vapor. Before exposing to oxygen at a pressure of 500 Torr, specimens were subjected to wet abrasion on 200- through 600-grit Sic papers and polished with 1—p diamond dust. Prior to oxidizing, all zirconium samples were vacuum-annealed at 10-6 mm Hg for about 15 min at the test temperature. The temperature variation across the uniform heat zone was ±2°C from the preset value. Final polishing, for phase thicknesses measurements, was performed by using 8- and 1-p diamond dust and followed by vibrator polishing with 0.05-µ ? Al2O3 solution. Measurements of phase thicknesses were made by projection on a metallographic viewing screen. Conventional powder X-ray analyses for the oxide were employed. RESULTS Fig. 1 is an example of the cross section of oxidized zirconium. Designations of phases given below this figure are the same as those used in the three-phase diffusion system represented by Fig. 5 in the following section. Zirconium oxidized for longer exposure times showed two types of oxides: white oxide at the surface and an underlaying layer of gray oxide. X-ray powder patterns of these oxides at room tern-

Jan 1, 1969

By Alfred H. Bell

The year 1937 has been outstanding in the history of the Illinois oil industry. During the course of the year the state's daily production has been trebled, increasing from 12,000 bbl. per day at the beginning to 37,000 bbl. per day at the end, and the year's total, 7,426,000 bbl. is 66 per cent above the previous year's production of 4,475,000 bbl. The production in January was 368,000 bbl.; in December it was 1,085,000. Production from the old fields increased slightly. Most of the new production is from fields in the central part of the Illinois Basin, an area that for many years was considered unfavorable to the occurrence of oil and gas. The principal producing horizon of the new fields is the McClosky "sand," an oolitic limestone in the Ste. Genevieve formation of lower Mississippian age. Although development has not yet gone far enough to permit accurate estimates of oil reserves in the new fields, it is believed that they are of the order of 100,000,000 barrels. The following are the oil fields discovered in 1937 listed in order of amount of daily production at the end of the year; Noble (Richland County), Clay City, including Southeast Clay City (Clay and Wayne counties), Patoka (Marion County), New Centralia (Clinton County), Olney (Richland County), Cisne (Wayne County),.Beecher City (Fayette County), and Rinard (Wayne County). One gas field, the Russellville, in Lawrence County, was discovered in 1937. For locations of the new fields see Fig. 1. A generalized geologic column for Illinois, showing producing horizons in the new fields, is given in Fig. 2. The total productive area of the new fields at the end of 1937 was 1712 acres, in which 230 wells were producing. Thisrty-five dry holes were drilled within 1/4 mile of producing wells. At the end of the year there were 19 drilling wells, 28 rigs standing, 18 rigging up and 4 new locations in these fields. In the whole state 447 wells were completed, of which 284 were oil producers and three gas producers. Total initial daily production of

Jan 1, 1938

By C. P. Kempter, H. L. Brown

Recently Chang determined heat content values of tantalum monocarbide and tungsten monocarbide from 325" to985°Kand 326" to 912"K, respectively, and, using other published data, made certain solid-state calculations for these two compounds. Chang expressed his Cp values in units of cal per "g-atom alloy" OK. We consider this poor usage since l) tantalum monocarbide and tungsten monocarbide are not alloys, and 2) an atom of an alloy does not exist. However, one may convert his values to units of cal per mole OK by merely doubling them. For TaC he calculated a Nernst-Lindemann parameter of 9.07 x lo-' "g-atom per cal". We have refined the calculation of this parameter and have arrived at a much lower value. Rather than approximating the true coefficient of volume expansion, a,, as three times the true coefficient of linear expansion, a, we calculated u, from the TaCo.99, lattice expansion data of Fries and Wahman.38 At 25°C a, = 14.3 x 10s per OC. The molar volume was calculated to be 13.32 cu cm per mole at 25°C. From the lattice compression data of Champion and Drickamer~' for "TaC,.,," we determined the room-temperature compressibility to be 3.5 x 10-l3 sq cm per dyne by plotting l/Vo (aV/ap) vs applied pressure. (Since the lowest pressure at which Champion and Drickamer reported a relative volume was 20 kbars, one may calculate an approximate compressibility only. Chang calculated a compressibility of 3.175 x 10-l3 sq cm per dyne from the same data.) We also used twice Chang's value of Cp = 4.38 cal per "g-atom alloy" OK for the molar heat capacity at 25°C. From these four values we calculated a Nernst-Lindemann parameter of 5.8 x 10-l4 mole per erg or 2.4 x lo- ' mole per cal, and a Cdil value of 2.3 x 10' ergs per mole OK. In the case of tungsten monocarbide no isothermal compressibility has been reported; however, one may calculate an approximate Nernst-Lindemann parameter by using the adiabatic compressibility reported by Brown, Armstrong, and Kempter." Using the WC lattice expansion data of Mauer and Bolz~l we calculated a, to be 12., x l0-' per OC. The molar volume was calculated to be 12.5 cu cm per mole. We used twice Chang's value of Cp = 4.18 cal per "g-atom alloy" OK for the molar heat capacity at 25°C. From these four values we calculated an approximate Nernst-Lindemann parameter of 2 x lo-' mole per cal, which is much

Jan 1, 1969

By J. Rourke, F. S. Minshall, E. G. Zukas, C. M. Fowler, O&apos

The Hugoniot curves were determined for Fe-Si alloys containing up to 7 wt pct (13 at. pct) Si. The pressure of the transition increased as the silicon content of the alloy increased. Single crystals of 2.9 wt pct Si-Fe were also studied. The pressure of the transition was not dependent on crystallo-graphic orientation. All of the Neumann bands (mechanical twins) were attributable to (112) planes but not all of the {112} planes showed twin markings. A thorough study of the iron Hugoniot (the relationship between specific volume and pressure) under plane wave shock loading revealed a pressure transition at about 130 kbar shock pressure. The results of this investigation were reported by Bancroft, Peterson, and inshall1 in 1956. At the time of this discovery, it was felt that this was probably the a, to y transition normally found in iron and many of its alloys. Subsequently a number of iron alloy systems were surveyed in which the alloying element has a considerable effect on the normal a, to y transformation. The influence of carbon and nickel and/or chromium have already been reported.2,3 At the present time, there appears to be some doubt that this pressure transition is the usual a, to y transition In this study, Fe-Si alloys containing up to 7 wt pct (13 at. pct) Si were chosen for several reasons. To the present, the transition has been found only in iron-base alloys which were originally in the a, phase (bcc). Secondly, the y loop at atmospheric pressure extends to only about 2.5 wt pct Si. If the transition were a, to y, then one might expect a rather drastic pressure effect for alloys containing more than 2.5 wt pct Si. Finally, single crystals of Fe-Si alloys large enough for shock loading studies are readily available thereby making it quite easy to determine the effect of crystal orientation on the transition pressure and on the twinning behavior of the alloy. EXPERIMENTAL PROCEDURE Fe-Si alloys containing up to 7 wt pct Si were produced by normal vacuum casting procedures. Single crystals of Fe-2.9 wt pct Si were purchased from Monocrystals Co., Cleveland, Ohio. The orientations of these crystals were determined and samples cut so that the shock wave would be parallel (to within 1.5 deg) to either the (loo), (Ill), or (112) principal orientations. Three distinct experimental testing techniques were used. First, the pin technique, described elsewhere,4 was used to determine the transition pressure for the polycrystalline alloys as well as for the (111) and (112) orientations of the 2.9 wt pct Si single crystals. Secondly, the recovery studies, described in detail in an earlier paper,2 were used for determining the effect of alloy composition and crystal orientation on the plastic II compression-plastic I rarefaction interaction zone for several specific shock pressures. Finally, measurements of pressures above the two-wave threshold were made on the polycrystalline alloys so that more complete Hugoniot curves could be constructed for this alloy system. The optical techniques described by Rice et al.5 were used to measure the shock and free surface velocities of the samples from which the Hugoniot data were obtained. This method is applicable only in the single wave region, since velocities are obtained from the measured total transit times of the disturbances through measured sample thicknesses.

Jan 1, 1963

By F. C. Blake

The apparatus which I shall describe in this paper has been in ase for some time at the laboratory of the Pennsylvania Lead Company's works, and has been found to give good results, and to be simple and convenient. Steam Bath.—This steam bath is shown by Figs. 1, 2,3 and 4. It is made of sheet copper, about one-twelfth of an inch thick, the joints being brazed, and is used for heating the bottles in which the silver samples are dissolved,-previous to the fineness determina-

Jan 1, 1882

By M. Cohen, C. Wagner, J. E. Reynolds

If the total volume of a diffusion couple changes during the diffusion, the measurement of distance becomes ambiguous. Use of distance parameters as suggested by Hartley and Crank is discussed. For small concentration differences, the standard form of Fick's second law is retained with conventional length units and the in- terdiffusion coefficient D. It is shown how D can be calculated from experiments involving large concentration differences and analyzed in terms of distance parameters. 'The merits of incremental diffusion couples involving small concentration differences are emphasized. THE conventional form of Fick's second law for one-dimensional diffusion of component B in a binary solution of A and B is where c, is the concentration of component B; x, the distance; t, the time; and D, the interdiffusion coefficient which may depend on ca. Hartley and Crank' have pointed out that Eq. 1 applies only if the total volume of the diffusion couple does not change during the diffusion process; otherwise, the definition of x becomes ambiguous. No change in total volume takes place if the specific volume of the solution is a linear function of the weight fraction Wb, or if the molar volume is a linear function of the mol fraction N. In some alloys, however, these relationships do not hold, and then it is necessary to introduce a modified measure of distance, 4 in order to retain the general form of Eq. 1. The application of Hartley and Crank's suggestions to diffusion in alloys has been discussed by Wagner.' Relation Between Measure of Distance and Units of Concentration The definition of [ depends on the choice of units for the concentration c,, as follows: 1—If the concentration ca is measured as the weight fraction W, (or weight percent), [ = 5, has to be defined so that equal increments of contain equal increments of mass m of the solution, e.g., dm = pSdx = Sdw [2] where p is the local density of the solution, and S is the cross-sectional area in sq cm which is taken to be constant in this problem of one-dimensional diffusion." * da Silva and Mehla have demonstrated the constancy of the cross-sectional area in the usual type of diffusion couple. However, experiments involving diffusion into thin wires4, 5 may exhibit changes in cross-sectional area, and therefore are excluded from the present treatment. Thus and the unit of is gram per sq cm instead of cm. 2—If the concentration c, is the mol fraction N, must be defined so that equal increments of contain equal numbers of mols of solution, e.g., dn= (S/V)dx= Sd [41 where V is the local molar volume of the solution. Thus dt, = dx/V [51 and the unit of is mols per sq cm. 3—If, as may be advisable in the case of interstitial solutions, the concentration C is measured in terms of the molar ratio of components B and A (c,, = Y, = nH/nA, where n and nl are numbers of mols of B and A), = Y has to be defined so that equal increments of contain equal numbers of mols of A, e.g., dnA= (NAS/V)dx = Sdf [6]

Jan 1, 1954

By Roger L. Beals, George A. Tweedy

I. INTRODUCTION. THE results of the cyanide-operations, given in detail in the following paper, show the progress that is being made at the Minas del Tajo. The old pan-amalgamation process, in operation up to and including 1905, while paying a profit on high-grade ores, was no longer able to treat profitably the ores in sight at that time, hence an alteration in the process was imperative. The success of this alteration is eloquently expressed by the following data Pan- Amalgamation. Cyanidation. 1905. 1907. 1903. Tons treated, . . 51,387 53,983 69,300 Value per ton (U. S. currency),. $10.75 $8.39 $8.28 Extraction, per cent., 65.00 88.50 S7.45 Extraction, per ton. .- $7.00 $7.4.; $7.24 Total cost, per ton treated, 6.50 4.311 4.01 Profit, per ton treated, . . 0.50 3.07 3.23.;

Feb 1, 1910

The following additional notes about prices of coal in the early days were collected from the sources shown. Several data about canal tolls and labor conditions are also included. 1796, November: "The inhabitants lay it (coal) in at about 3;d. (83¢) sterling per bushel." (Ref. 73: p. 147.) 1804, March: "In March, 1804, I sent a person accustomed to mining to open the vein of coal, and to load the ark, which was accomplished, and early in the month of April the ark, with the first cargo of bituminous coal passed safely the Conewago falls, and landed her coal at Columbia, Lancaster County. The coal was sold at 31¢ per bushel at Columbia." ($7.75 per ton). This was the first coal from Clearfield County near the town of that name. (Letter from William Boyd: Pa. Senate Jour., 1833-1834, vol. 2, p. 561.) 1807: The following notice appeared in the Bedford Gazette: "Huntingdon, June 4. "Stone Coal.-Such of the farmers as wish to make experiment with stone coal as a substitute for plaster, in manuring their Indian corn, may be supplied with coal gratis upon application to Peter Hughes, at Mr. Riddle's mines, on the Raystown Branch. The proprietor of the mines offers not only to refund the carriage, but to pay the expenses of applying the coal, if upon a fair experiment it is found to be inferior to plaster, which now sells at two dollars per bushel." (Ref. 735: p. 708.) 1809: Coal was delivered in Pittsburgh at 5¢ per bushel or $1.25 per net ton. (Ref. 444: p. 50.) Coal was delivered in Connellsville at 4¢ per bushel or $1.00 per net ton. (Ibid.: p. 185.) 1810: Pittsburgh.-"Coal may be obtained of a good quality, ready delivered at 5¢ a bushel." ($1.25 per net ton.) (Ref. 315: vol. 2.) 1811: "It (coal) costs 6¢ a bushel at your door." ($1.50 per net ton.) (In Pittsburgh.) (Ref. 277: 1811, p. 68.) 1814: At Columbia, now part of Donors, Washington County, Pa., an original sale of lots in 1814 gave the purchaser of each lot the right to mine stone coal gratis from a bank on the property. (Ref. 410: vol. 1, p. 547.) "A laborer is able to dig upwards of 100 bushels per day." (4 tons.) (Ref. 277: 1814, p. 109.) A paper about the early newspapers in West Virginia says: "Collier Wanting. From 10 to 20 steady and industrious men, who understand digging coal, may obtain high wages in Kenhawa for that business, if immediate application is

Jan 1, 1942

By F. N. Rhines, T. E. Leonitis

The oxide scale that forms upon magnesium at elevated temperatures is non-protective in the sense that the rate of oxidation is constant and thus does not decrease with the growth of the scale as it does with other common metals. This generality was first stated by Pilling and Bedworth' and has been verified by Suzuki2 and by ScheiL3 Pilling and Bcdworth argued that the nonprotective characteristic could be predicted from the fact that magnesium oxide occupies less space than does the metal from which it springs, wherefore the scale is not expected to cover the metal so completely as to exclude all direct access to the atmosphere. Linear oxidation is thought by Scheil to be common to all cases where the reaction occurs at the oxide-metal interface. According to Suzuki," he product of high-temperature oxidation in the air is MgO contaminated with no more than traces of a nitride. When the metal is allowed to burn freely a fume composed of cubic crystals of Mg04 is given off. Delavaults observed that excrescences form upon liquid magnesium and alloys in thc course of oxidation. Beyond this it is known that the use of atmospheres containing small quantities of sulphur dioxide6 or carbon dioxide serve to retard the oxidation of solid magnesium and that beryllium' and calciums minimize the oxidation of molten magnesium exposed to the air. Many studies have been devoted to the nature and rates of "protective" oxidation, as exemplified by the cases of copper and iron, wherein the rate is characteristically parabolic. The theory of parabolic oxidation is well developed.~ Linear oxidation, on the other hand, has received but little attention and the theories proposed by Pilling and Bedworth and by Schcil have yet to withstand careful examination. There exists no comprehensive survey of the high-temperature oxidation of magnesium (or of any other metal that exhibits linear oxidation) over a broad range of temperature, under a variety of atmospheric conditions and covering a large group of alloys. It has been the purpose of the present investigation to provide such a survey, with the object of gaining a fuller understanding of linear oxidation, especially as applied to magnesium. Experimental Procedure and Results The experimental studies undertaken were of two kinds: (I) measurement of the rate of oxidation as influenced by the 6c

Jan 1, 1946

By T. E. Leonitis, F. N. Rhines

The oxide scale that forms upon magnesium at elevated temperatures is non-protective in the sense that the rate of oxidation is constant and thus does not decrease with the growth of the scale as it does with other common metals. This generality was first stated by Pilling and Bedworth' and has been verified by Suzuki2 and by ScheiL3 Pilling and Bcdworth argued that the nonprotective characteristic could be predicted from the fact that magnesium oxide occupies less space than does the metal from which it springs, wherefore the scale is not expected to cover the metal so completely as to exclude all direct access to the atmosphere. Linear oxidation is thought by Scheil to be common to all cases where the reaction occurs at the oxide-metal interface. According to Suzuki," he product of high-temperature oxidation in the air is MgO contaminated with no more than traces of a nitride. When the metal is allowed to burn freely a fume composed of cubic crystals of Mg04 is given off. Delavaults observed that excrescences form upon liquid magnesium and alloys in thc course of oxidation. Beyond this it is known that the use of atmospheres containing small quantities of sulphur dioxide6 or carbon dioxide serve to retard the oxidation of solid magnesium and that beryllium' and calciums minimize the oxidation of molten magnesium exposed to the air. Many studies have been devoted to the nature and rates of "protective" oxidation, as exemplified by the cases of copper and iron, wherein the rate is characteristically parabolic. The theory of parabolic oxidation is well developed.~ Linear oxidation, on the other hand, has received but little attention and the theories proposed by Pilling and Bedworth and by Schcil have yet to withstand careful examination. There exists no comprehensive survey of the high-temperature oxidation of magnesium (or of any other metal that exhibits linear oxidation) over a broad range of temperature, under a variety of atmospheric conditions and covering a large group of alloys. It has been the purpose of the present investigation to provide such a survey, with the object of gaining a fuller understanding of linear oxidation, especially as applied to magnesium. Experimental Procedure and Results The experimental studies undertaken were of two kinds: (I) measurement of the rate of oxidation as influenced by the 6c

Jan 1, 1946

By W. A. Backofen, D. Lee

The deformation of textured sheet of titanium and several of its all-a (hcp) alloys was investigated with two kinds of experiments: tension testing along different directions in the plane of the sheet, and combined-stress loading along the principal axes of anisotropy (the rolling and transverse directions). Texture and plastic anisotropy were evaluated with pole figures and by measurement, as a function of orientation, of the tensile transverse-strain ratio, or R parameter. The results as a whole can be rationalized qualitatively with the present understanding of deformation mechanisms in titanium. Quantitative agreement between the orientation dependence of tensile yield strength and the Predictions of continuum ANISOTROPY in the properties of engineering materials is more the rule than the exception because anisotropy in structure is so common, and the one generally follows the other. Two broad categories of structural anisotropy are represented by mechanical fibering and crystallographic texture. The former is important in many aspects of fracture.' The latter has more significance for yielding and plastic deformation, theory, using the R measurements, was relatively poor. However, in tension-tension quadrants of the yield-locus diagrams, the difference between theory and experiment was hardly more than 10 pct. The maximum texture-hardening effect was found in a 4Al-1/4O2 alloy to be nearly 50 pct. In the compression-compression quadrant, {1012} deformation twinning prevented the locus from expanding much beyond the Position predicted for isotropic material. With increasing temperature the trend in R was downwards, approaching unity (isotropy) near the a-transus temperature; an accompanying development was large amounts of neck-free extension. which are of special concern in this paper. The tendency has been to view crystallographic texture more as a liability or curio than as an asset. The prominent exception is found in silicon-ferrite sheet for power-transformer cores, which is processed to develop a new optimum texture for high electrical efficiency. Yet it should be possible to find other examples, involving other kinds of properties. More specifically, there is good analytical reason to expect improved combined-stress yielding resistance in suitably textured material,2,3 and it has now been shown by experiment that texture hardening or softening is a potentially useful phenomenon in certain engineering devices and processes.'-I To date, work has included measurements of the transverse (width to thickness) strain ratios in the

Jan 1, 1967

By John H. Holloman

In recent papers, O'Neill,' Vivian, and Zener and Hollomon3 have reviewed some of the information concerning the relations between stress and strain during plastic deformation. Since further information has been obtained since these reviews were published, this paper attempts to further coordinate and amplify the knowledge concerning the plastic deformation of metals in simple tension. Ordinarily the results of tensile tests of metals are presented as graphs in which the load divided by the original area is plotted as a function of the percentage of elongation measured over some specified gauge length. The interpretation of graphs of this sort is limited, since the stress required to deform the metal at any stage of the deformation is actually the load divided by the instantaneous rather than the original area. Furthermore, each increment of the deformation is performed on metal that has been previously deformed, and, as pointed out by Ludwik,4 the strain could be more effectively defined: where e is the strain and AO and A are, respectively, the original and instantaneous areas. The results of the tensile tests can be more effectively presented and interpreted if the stress* (load divided by actual area) is .lotted as a function of the strain as defined above. A schematic curve of this type is presented as Fig. I. In a previous paper,6 the concept of Ludwik7 concerning the flow and fracture of metals was successfully employed to explain some of the puzzling results of notched-bar impact tests of steel. It appears that the use of this concept ii; very fruitful and should be kept in mind in any study of the deformation charactcristics of metals. Ludwik considered that a flow stress-strain curve of a metal was essentially a locus of points that described the stress required for plastic flow of an infinite numbcr of specimens, each with a different strain history determined by the preceding part of the flow curve Each of these specimens can also be considered to have a fracture strength. Uniortunately (or fortunately depending upon the point of view), all the specimens, except the one deformed to the fracture strain, flow and do not fracture. Even though the metals do not fracture, the concept of a fracture-strength curve seems

Jan 1, 1945

By M. T. Hepworth, A. K. Stewart

Iron containing 0.1 pct A1 and -0.9 pct P by weight was internally oxidized in the temperature range 900° to 1300° C, where the bcc structure is stabilized by phosphorous. By measuring the depth of penetration of oxygen with time in an internally oxidized zone for an imposed surface oxygen potential, oxygen permeability was determined. The dgfusion coefficient of oxygen in iron was then calculated using known solubility data, yielding the expression: where Do is the diffusion coefficient of oxygen in bcc iron in sq cm per sec and T is temperature in OK. RECENTLY Hepworth, Smith, and Turkdoganl measured the diffusivity of oxygen in bcc iron and reported the temperature dependence of diffusivity from data determined in the a, and 6 temperature ranges. Subsequently Swisher and Turkdogan' have measured the diffusivity of oxygen in fcc iron. Internal oxidation techniques were employed by these investigators and in this current study. The analysis of this technique is developed by wagner3 (presented in English by Hauffe4 and Rapp 5). In this present study bcc iron stabilized by phosphorous was used to determine oxygen diffusivity in the temperature range 900° to 1300°C. Meijerin 6 has studied oxygen permeability in this temperature range using bcc iron stabilized with 5 pct Sn. Other inves- tigators who have studied oxygen permeability in bcc iron at other temperatures are Schenck et al., 7 Bohen-kamp and Engell, 8 and Bradford. EXPERIMENTAL Electrolytic iron of 99.99 pct purity was alloyed to contain 0.897 pct P and 0.093 pct Al. The maximum weight percent phosphorous required to stabilize bcc iron between 910" and 1392°C is 0.51 pct as determined by Haughton,10 0.42 pct by Roquet and jegaden," and 0.58 pct by vogel,12 with the latter value preferred by Hansen.13 Microprobe analysis indicated that there was no segregation of the phosphorous either before or after permeability studies; therefore, the quantity of phosphorous added was assumed to be sufficient to stabilize the bcc structure. Furthermore, the permeability results of studies on this alloy agreed substantially with interpolated values from previous data on bcc iron.' An ingot of the Fe-P-A1 alloy was hot-rolled to a l-in.-thick slab. Specimens were machined to dimensions: 13/8 by $ by 1/4 in. The experimental apparatus and procedure used have been described before.' A constant oxygen potential was established by passing argon and hydrogen through a column of oxalic acid dihydrate, which has a water vapor pressure which is well-known as a function of temperature. Slab specimens were exposed to a gas mixture sufficiently lean in oxygen to prevent the formation of a surface oxide for predetermined temperature for selected times. The specimens were then quenched, sectioned, and examined metallo-graphically. All quenched specimens were iron-plated to provide protection from the outside sample edge during polishing. Fig. 1 shows a typical microstruc-ture for a specimen oxidized at 953°C for 48.00 hr at a water vapor-to-hydrogen pressure ratio of 0.20. DISCUSSION AND RESULTS The following equation was derived by Hepworth et al.' from Wagner's kinetic expressions for internal oxidation:

Jan 1, 1969

By R. W. Fountain, J. F. Libsch

ONSIDERABLE time and effort have been ex- pended recently in research designed to provide a better understanding of the solid state transformations leading to the permanent magnet qualities of many commercial alloys. The knowledge derived from these investigations has resulted in the development of new magnetic materials as well as improvements in some of the older materials. The permanent magnet qualities of the newer alloys having high residual inductions and high coercive force values, have been attributed to the precipitation of a second phase or an order-disorder transformation in a solid solution. The ternary Co-Fe-V alloys provide an interesting group of magnetic materials having a wide range of magnetic properties. The low vanadium alloys' possess soft magnetic properties similar to the binary Co-Fe alloys, while at higher vanadium contents (about 10 pct) interesting permanent magnet properties are obtained.2,3 Previous work by Nesbitt' on the ternary Co-Fe-V permanent magnet materials, resulted in the conclusion that the precipitation of a second phase, ?, was responsible for the permanent magnet qualities of these alloys. However, unlike the conventional precipitation hardening alloys, the ? phase, which is stable at high temperatures, is precipitated in the low temperature a phase upon aging. Recent work by Geisler and Martin"." has established that the order-disorder reaction inherent in the binary Co-Fe alloys is also present in the ternary Co-Fe-V alloys. On the basis of their investigation, it was proposed that ordering of the a phase is also a possible explanation of the mechanical and magnetic hardening in these alloys. Thus, it appears that the Co-Fe-V alloys are rather unique in that two solid state transformations are taking place which may account for the properties of these alloys. In view of these facts, the present investigation was undertaken to study the mechanism of mechanical and magnetic hardening in the 10 pct V-Co-Fe alloy with particular reference to the role of the ? phase; and to correlate the results of this study with other magnetic properties. In addition, the influence of increasing vanadium contents on the transformation of Co-Fe alloys was also undertaken to supplement the main objective of the investigation. Experimental Procedure The Co-Fe-V alloys used for study consisted of: 1—a commercial lot of Vicalloy I, a 10 pct V alloy, and 2—alloys prepared by powder metallurgy and containing 52 pct Co and 0 to 14 pct V, balance iron. The commercial alloy was received in the cast and forged condition and was used primarily for the detailed study of hardness, electrical resistivity, and magnetic properties of the 10 pct V alloy. The powder metallurgy alloys were prepared from electrolytic iron, commercial cobalt, and ferro-vanadium powders. The processing cycle was as follows: 1—Elemental powders were weighed and mechanically mixed for 24 hr. 2—Mixed powders were pressed at 60,000 psi into the form of bars 5/8 x 5/8 x 5 in. 3—Bars were sintered in an atmosphere of purified dry hydrogen for 24 hr at temperatures ranging from 1380" to 1340°C, depending upon the vanadium content. The as-sintered bars were cut in half; and one half was machined to 7/16 in. diam for thermal analysis. The remainder of the bar was hot forged to approximately 0.050 in. for X-ray diffraction analysis. Additional details of sample preparation are presented subsequently according to the type of test performed. Thermal Analysis Measurements One of the simplest and most widely used tools for determining phase relations as they change with temperature and composition is to study the rate of change of temperature of a material as heat is supplied or extracted at a constant rate. The thermal analysis method used in this investigation is the inverse-rate method described by Smith.'

Jan 1, 1954

By Robert Goodwin, Frank R. Milliken

IN September 1939, the Ohio Copper Co. inaugurated the treatment of its copper-bearing mill tailings at Lark, Utah. These tailings had been accumulated during the regular operation of the Ohio Copper mine and mill over the period 1907 to 1919. Gravity concentration had been employed except for a comparatively short period in 1919, when flotation was used. The ore milled during that period assayed about 1 per cent Cu. The chief copper mineral, chalcocite, was disseminated in a shattered quartzite, mainly along fracture or cleavage planes. The quartzite gangue was extremely hard and grinding to liberation resulted in excessive sliming of the "sooty" chalcocite, with consequent high tailings losses. Recovery on the seven million tons treated was probably less than 6o per cent of the total copper content. As early as 1918, attempts had been made to sample the dump. In 1928, a complete sampling program was undertaken. The sampling consisted of seventy-four 5-in. post auger holes drilled to the full depth of the dump at regular intervals of 250 ft. Each 10-ft. portion thereof comprised a sample for analysis. Each sample was screened, rolled, divided into three parts, dried and assayed. The reject was retained for testing purposes. From the depth of the auger holes a contour map of the dump was plotted, Fig.1, which gives percentages of tonnage and copper content. The tonnage within the limit of the drill holes was estimated at about five million tons with an average content of 0.42 per cent Cu, 31 per cent of which (0.13 per cent) was acid-soluble. A screen analysis of the composite dump sample is shown in Table I. Flotation tests by several companies and individuals were then made, the results of [ ] which ranged from 62 to 74 per cent recovery. On the basis of these, a Zoo-ton pilot plant employing straight flotation was built and operated for a few months. Operation of this plant was unsuccessful, as no provision had been made to handle the copper-bearing solutions resulting from the water-soluble copper, a point that was overlooked in the laboratory test work. Attempts to decant the copper-bearing solution for precipitation in the usual manner ahead of flotation were not satisfactory because of low water recovery (owing to poor settling characteristics of the pulp) and contamination of the copper precipitate with unsettled slime. Low copper prices in 1931 necessitated the termination of testing. With the stimulus of higher copper prices in 1937, a review was made of metallurgical

Jan 1, 1940

By Harold Roast

THE object of this investigation was to compare the arsenical antimony-lead alloy with some of the regular bearing-metal alloys. With this end in view, the following tests were made: 1. Chemical analyses to show the composition. 2. Thermal analyses. 3. Macroscopic examination of fractures. 4. Microscopic examination. 5. Tensile tests. 6. Crushing tests. 7. Scleroscope tests. 8. Brinell tests, at temperatures from 80° to 400° F. Tests 3 to 8 were conducted on both sand-cast and chill-cast specimens. For the purposes of this paper the alloys have been numbered from 1 to 6; their composition is as follows: LEAD, ANTIMONY, TIN, COPPER, ARSENIC, NUMBER PER CENT. PER CENT. PER CENT. PER CENT. PER CENT. 1 82.64 12.95 4.40 0.01 none 2 27.54 9.94 59.87 2.65 none 3 77.65 20.75 none 0.13 1.47 4 82.95 16.85 none 0.20 none 5 83.78 15.35 none 0.05 0.82 6 0.15 7.87 84.13 7.85 none The analysis, in the case of the antimony, was made by solution in sulfuric acid and titrated with permanganate. For tin, the ferric-chloride method was used; for copper, the alkaline separations, and the thiocyanate methods; for arsenic, volatilization of arsenic and titration with iodine. The lead, with the exception of alloy 6, was taken by difference.

Jan 2, 1922

By M. M. Slotnick

It was once aptly said that a sign of approaching senility is ceasing work on a subject and beginning to talk about it. Perhaps that explains why, after many Years in which Part of my duties has been the training of college men in various branches of petroleum exploration geophysics, I have now begun to talk about it. In making an outline of what I believe ought to be discussed under the general heading of the title, I found it almost impossible to subdivide the ideas into an ordered set of discrete subjects. Rather, the pertinent remarks seemed to interlock almost everywhere. The consequence is that it will be necessary to start with the conclusions and then try to justify them by jumping back and forth. However, based on the types of men with whom I have had to deal, the subject naturally divides itself into two parts. In the first part, I should like to deal with the case of those undergraduates whose natural bent is toward the physical sciences and who may decide to enter the geophysical fold as a career. The other part will deal with those many men, geologists and engineers for the most part, who have drifted into exploration geophysics by one means or another, and whom it is necessary to train for geophysical work while they are occupied in their routine jobs. Here it may be in point to remark that most men in exploration geophysics at Present have been developed from precisely the latter group, and that the problem of training here is of great importance even though, in this paper, it will perforce occupy the secondary place. Training oF a Geophysicist The outstanding reason for the perplexing problem on the training of a geophysi-cist is that ideas differ on the answer to the question: "what is a geophysicistp" ln any of the scientific "specialties," like physics, for example, it is relatively simple to pigeonhole a man as being qualified to call himself a physicist. That appellation applied to an individual does not mean that he has mastered only the branches of intellectual endeavor usually associated under the broad name of "physics." we expect him also to have a more than mere acquaintance with mathematics and chemist~ and some understanding of most of the other sciences. But note this important point—we expect our physicist, whom we have chosen as an example, to be intelligently trained so that, if necessary, he can and will know how and where he can get the proper information on a subject in which he is not a specialist; he will know how to absorb that information and turn it to his uses. It seems to me that this is the outstanding characteristic of a man who can truly call himself a scientist: that he is a specialist in one of the broad branches of science in that he has enough training and discipline in the scientific approach so that, when called upon to do so, he can inteugently absorb knowledge from another bordering science (and all sciences not only border upon one another to some extent, but more often, overlap One another), and

Jan 1, 1946

By M. M. Slotnick

It was once aptly said that a sign of approaching senility is ceasing work on a subject and beginning to talk about it. Perhaps that explains why, after many Years in which Part of my duties has been the training of college men in various branches of petroleum exploration geophysics, I have now begun to talk about it. In making an outline of what I believe ought to be discussed under the general heading of the title, I found it almost impossible to subdivide the ideas into an ordered set of discrete subjects. Rather, the pertinent remarks seemed to interlock almost everywhere. The consequence is that it will be necessary to start with the conclusions and then try to justify them by jumping back and forth. However, based on the types of men with whom I have had to deal, the subject naturally divides itself into two parts. In the first part, I should like to deal with the case of those undergraduates whose natural bent is toward the physical sciences and who may decide to enter the geophysical fold as a career. The other part will deal with those many men, geologists and engineers for the most part, who have drifted into exploration geophysics by one means or another, and whom it is necessary to train for geophysical work while they are occupied in their routine jobs. Here it may be in point to remark that most men in exploration geophysics at Present have been developed from precisely the latter group, and that the problem of training here is of great importance even though, in this paper, it will perforce occupy the secondary place. Training oF a Geophysicist The outstanding reason for the perplexing problem on the training of a geophysi-cist is that ideas differ on the answer to the question: "what is a geophysicistp" ln any of the scientific "specialties," like physics, for example, it is relatively simple to pigeonhole a man as being qualified to call himself a physicist. That appellation applied to an individual does not mean that he has mastered only the branches of intellectual endeavor usually associated under the broad name of "physics." we expect him also to have a more than mere acquaintance with mathematics and chemist~ and some understanding of most of the other sciences. But note this important point—we expect our physicist, whom we have chosen as an example, to be intelligently trained so that, if necessary, he can and will know how and where he can get the proper information on a subject in which he is not a specialist; he will know how to absorb that information and turn it to his uses. It seems to me that this is the outstanding characteristic of a man who can truly call himself a scientist: that he is a specialist in one of the broad branches of science in that he has enough training and discipline in the scientific approach so that, when called upon to do so, he can inteugently absorb knowledge from another bordering science (and all sciences not only border upon one another to some extent, but more often, overlap One another), and

Jan 1, 1946