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By Frank Firmstone

The piece of spiegeleisen, the analysis of which is given below, was collected by my father, together with various other specimens, while he was manager of the Glendon Iron Works. It bears a label stating that it was taken from a building in the town of Newton, New Jersey, erected in 1765 and torn down in 1863. The building belonged, in 1863, to T. N. McCarter, Esq. The label is in the hand-writing of Mr. McCarter, now deceased, well known as a member of the bar of northern New Jersey. The specimen was, no doubt, given by him to illy father, with whom he had business in 1863 and 1864. It is now in the metallurgical collection of Lehigh University. I know nothing further as to the history of the specimen, but there is no reasonable doubt that it was made from ore from the Andover mine, at the old charcoal-furnace which once stood at the village of Andover, about 5 miles south of Newton, on the Sussex railroad. It was probably broken from one end of a bearer over an open fire-place, is about 6 in. wide by 2.5 in. thick, has been cast in open sand and shows the charcteristic fracture of spiegeleisen rather low in manganese, as shown in Table I. One edge has been white-washed. Table I.—Analyses of Spiegeleisen Made from Andover Ore. 1. 11. Per Cent. Per Cent Graphite,.0.101 0.005 Combined carbon,... 4.529 4.212 Silicon,..0.037 0.294 Manganese,..... 5.760 3.750 Sulphur,.0.003 0.031 Phosphorus,.0.060 0.072 Iron,........ 89.440 91.570 99.920 99.934 I. Spiegeleisen made at Andorer (charcoal) furnace not later than 1765. IT. Spiegeleisen made from Andover ore at Phillipsburg, N. J., anthracire-furnwe, 185-. Both analyses were made by Dr. P. W. Shimer.

Jan 1, 1907

By S. A. LoPilato, J. T. Smith

SEVERAL techniques have been evaluated for cooling the throat area of rocket-nozzle inserts to prevent erosion or fracture of the inserts during exposure to high operating temperatures and pressures. Self-cooled composites, such as infiltrated tungsten, have shown considerable promise for these applications. These composites can be fabricated by infiltrating the refractory matrix with a lower-melting metal or non-metal which is insoluable in tungsten. During firing, the lower-melting substance undergoes a series of continuous endothermic phase changes which absorb sufficient heat to maintain the nozzle matrix material at or below a safe operating temperature. At present, the state-of-the-art has reached a point where the refractory matrix density and microstruc-ture have been established as the critical parameters to be controlled for optimum self-cooled performance.'" Nondestructive testing has been utilized to ensure that porous tungsten billets were of uniform density and free from cracks or other defects prior to fabrication into rocket nozzle inserts. Ultrasonic-velocity techniques have been employed because of their reliability and reproducibility. The purpose of this note is to present and interpret the test data developed for porous tungsten matrices. For evaluation purposes, tungsten powders with Fisher subsieve sizes of approximately 4 and 18 p have been obtained for study from four commercial sources: the General Electric Co., Wah Chang Corp., Fansteel Metallurgical Corp., and Kennametal, Inc. Porous tungsten matrices were fabricated from the powders by hot pressing in induction-heated graphite die assemblies. Typical billets ranged from 3 in. diam, 2 in, high to 5 in. diam, 5 in. high. The ultrasonic-velocity measurement technique employed was through transmission, pulse echo at a frequency of 1.0 mc using matched barium titanate crystal transducers. The testing equipment included a pulsed ultrasonic generator, an amplifier, a specimen holder, and an oscilloscope, as shown in Fig. 1. The porous tungsten thickness was measured to i 0.0005 in, with precision micrometers while the oscilloscope achieved 0.02 psec time measurement accuracy. The time for a sound wave to pass through the billet, the bulk wave velocity, was calculated to 0.5 pct using Eq. [l]: V-} where V = bulk wave velocity, in. per psec, T = specimen thickness, in., and / = time, psec. To develop inspection standards, the bulk density of a porous tungsten billet was determined by the ASTM water-immersion technique.3 The ultrasonic-velocity measurements were completed at seventeen positions for each billet and averaged to develop a characteristic standard velocity for a particular tungsten powder at several density levels. A plot of ultrasonic velocity vs density is presented in Fig. 2 for six different tungsten powders. This graph has been established as

Jan 1, 1967

Jan 1, 1963

By W. F. Hosford

A series of aluminum single crystals was subjected to axially symmetric flow by drawing through dies. The orientation dependence of the drawing stress, which indicates the resistance to this type of flow, compares reasonably with predictions of Taylor and of Bishop and Hill. Measured lattice rotations likewise are generally consistent with theory. The most successful analyses of the plastic behavior of polycrystalline metal and its relationship to single crystal behavior are those of Taylor1-3 and of Bishop and Hill.4-6 The purpose of this paper is to provide a critical test of some of the basic assumptions involved in these theories. Both treatments apply to fcc metals and assume the shape change of each grain in a polycrystal to be the same as that of the polycrystal as a whole. Thus for a randomly oriented polycrystal extended under uni-axial tension each grain is assumed to undergo axially symmetric flow. dey = dez = -1/2dex, deyZ = dezx = dexy = 0 [l] where x, y, and z are a set of orthogonal axes, x being the tensile axis. Although [011.] oriented grains in bcc and fcc metals may depart markedly from this ideal behavior,7,8 the assumption is probably quite reasonable for most grains. Under a uniaxial tensile stress, ox, the work dW per unit volume expended in producing an increment of axial strain dex is, dW=oxdex [21 Since this work is expended in slip, dw =STi dyi 131 where Ti and yi are the shear stress and shear strain on the active slip systems. In both analyses Ti is taken to be the same on all slip systems, and dependent only on the total prior shear strain on all systems, so dw = Tdy [41 where t is the shear stress required for slip and y is the sum of the shear strain yi on all slip systems. Combining 121 and [4] and defining M = oX/T The ratio M is a generalized Schmid factor. It relates the tensile stress required for axially symmetric flow, ox, to the basic shear stress, 7, and it also expresses the ratio of crystallographic strain, y, to the tensile strain, Ex It depends only on the orientation of the crystal. Taylor evaluated M for various orientations by finding the least value of dy/dEx which could satisfy the shape change. Bishop and Hill, on the other hand, found M by considering the relative work (1/T)dW/dEx expended by stress states which could activate enough slip systems to produce the shape changes. The results of both methods appear to be equivalent, although certain omissions were made in Taylor's original work. The orientation dependence of M, calculated by the second method,9 is shown in Fig. 1. Taylor used the average 2= 3.06 for all possible orientations to predict the tensile stress-strain curve (oxvs Ex) for a random polycrystal from the shear stress-strain curve (t vs y) of a single crystal. Changes in M from lattice rotation were neglected so points on the ox vs ex curve were simply taken at ox = 3.06t and e = y/3.06 from corresponding points on the t vs y curve. Recent extension of the analyses of Taylor and of Bishop and Hill to crystallographically textured metals has been used to relate plastic anisotropy to textures, and to predict the potential texture hardening that could result from texture control.9 Unfortunately there have been relatively few experimental tests of the underlying theory. Taylor found that the tensile stress-strain curve of polycrystalline aluminum did agree reasonably well with that predicted from a single-crystal T-y curve. Had the single crystal undergone easy glide, how-

Jan 1, 1965

By Donald J. Knight

HEAT Treatment at 1500' F of a mild steel containing 0.1 pct C, in an atmosphere which is oxidizing to both carbon and iron, results in the progressive oxidation of the metal surface with little or no change in the carbon content of the underlying metal. Further heat treatment of the scaled metal in either a neutral atmosphere or in a vacuum may or may not result in the decarburization of the metal depending upon the physical nature of the scale. It is apparent that if a continuous layer of oxide is present on the steel surface, the reaction OScale + Cmetal Cogas cannot progress since the SO formed gas would be unable to leave the oxide/metal interface. Thus, in order for the reaction to progress, the oxide must be cracked or porous. Vacuum heat treatment at 1500" F of samples with a thick continuous oxide scale showed no decarburization of the steel. However, when cracks were introduced mechanically into the scale prior to the vacuum heat treatment notable decarburization of the metal resulted and a structure as shown by Fig. 1 obtained, i.e., reduction of the crack walls to ferrite. With reference to the diagram of Fig. 2, it would appear that a mechanism of the following type takes place. Carbon atoms arriving at an oxide/metal/void interface, such as 'A', Fig. 2(a), can combine with oxygen atoms from the scale and leave the reaction site as Cogas thereby reducing the oxide to metal. On a greatly magnified scale, Fig. 2(b),this will appear as a ferrite projection along the crack wall. Carbon atoms entering this projection can react with oxygen atoms at point 'C', which is a new interface, and so on leading to a progressive growth of the ferrite along the crack wall and to the surface, Figs. 2 (c) and 1. It would appear that the only means by which thickening of the ferrite film can take place is by a diffusion of oxygen through the ferrite film to react with carbon at the newly formed ferrite/ void interface. Since the diffusion rate of carbon is reportedly much greater than that of oxygen, and since there is a low probability factor of oxygen and carbon atoms arriving simultaneously at the same site on the ferritehoid interface, there will be a tendency for more rapid lengthening than thickening of the ferrite layer, as is observed.

Jan 1, 1962

By Gerald Edmunds

THE liquidus line on the phase diagram for temperature versus composition of a binary alloy system, representing the boundary between the homogeneous melt and the heterogeneous melt plus solid, besides showing the minimum casting temperature, is useful in determining eutectic compositions and the presence of phase changes such as peritectic transformations and intermetallic compound formation. The liquidus often is determined by the cooling curves of thermal analysis, but supercooling frequently occurs, so that the temperature values are low. An alternative method, the one employed here, consists of determining the com- position of samples of the melts from heterogeneous alloys that are at equilibrium. With meticulous attention to fundamentals, this method is capable of yielding values limited in precision only by the temperature control and measurement and analyses. APPARATUS By starting, on the one hand, with a supersaturated solution and allowing the excess solute to precipitate, and on the other hand with an undersaturated solution and allowing more of the solute to be dissolved, both processes being carried out at the same temperature, equilibrium may be said to have been approached from both directions; that is, from above and from below. If the analyses show the solutions to contain the same fraction of solute when equilibrium has been approached from above and from below, one is assured that equilibrium has been reached in both determinations. In order to carry out such determinations, it is necessary to have equipment for obtaining and maintaining the proper temperatures; for holding the melt, measuring its temperature, and stirring, sampling and analyzing it. The present work required temperatures from 420° to 900°C. The equipment consisted of: A furnace, which was a vertical alundum tube, 1 ¾ in. diameter inside and 18 in. long, wound with Nichrome resistance wire, surrounded by a 3-in. i.d. alundum tube wound for 5 in. of length near each end, for compensation of end losses. This muffle was contained in an iron shell with Transite end plates, the intervening space being packed with Sil-O-Cel. The outside dimensions of the furnace were 12 in. in diameter by 18 ½ in. in height. Heating current was supplied by three independent variable-voltage transformers (Variac), one connected to each end compensator winding and manually controlled, and one connected to the main winding through a series resistance of 5 ohms. This resistance was short-circuited for

Jan 1, 1944

By W. L. Phillips

Stress-strain data are reported for sodium chloride, lithium fluoride, and magnesium oxide tested in compression at diffevent strain rates in the telrlperature range from 70° to 873°K. Quantitative equations are given for the stvain-rate dependence of the critical resolved shear stress and the initial rate of work havdening. The properties so determined are compared with results previously reported for metals. ALTHOUGH the effects of strain rate and temperature on the stress-strain characteristics of metals have been extensively investigated1,2 these effects have not been studied in detail in ionic crystals. In the only previous investigations on the effect of strain rate on the deformation of ionic crystals. Gilman and gohnston3 and Hulse and pask4 have shown that the yield stress of lithium fluoride and magnesium oxide at room temperature is proportional to the ninth or tenth root of the strain rate. CRYSTAL PREPARATION Lithium fluoride, sodium chloride. and magnesium oxide single crystals were purchased from the Har-shaw Chemical Co. The compression fixture and sample preparation have been described in detail previously.5 The detectable impurities in MgO were eight parts in 105 of Fe and six parts in 105 of Si; in LiF, six parts in 105 of Mg; and in NaC1, two parts in 105 of Fe and four parts in 10&apos; of Mg. The cleaved samples measured - 0.1 in. by 0.1 in. by 0.3 in. Prior to testing all samples were annealed at -0.8 of their melting point and cooled to room tempera- ture at 50 C per hr.&apos; Samples were strained at rates (<) of 0.1, 0.01, 0.002, and 0.0002 in. per in. per min. EXPERIMENTAL RESULTS Fig. 1 is a plot of the critical resolved shear stress a,. (extrapolation of slope of easy glide region to zero strain) of sodium chloride, lithium fluoride, and magnesium oxide tested at different strain rates as a function of temperature. In all crystals at all strain rates a, decreases with increasing temperature according to an equation of the type397 where uo is a stress constant, K is a constant, and T is the absolute temperature. The points in Fig. 1 are the average of six tests. It is evident that there is a break in the log 0,- temperature plots at a characteristic temperature T,. The constant K of Eq. [I] is dependent on strain rate, Fig. 2. The relationship

Jan 1, 1962

By R. A. Wattenbarger, H. J. Ramey

The trend in gas well testing has been to rely more on the early-time flow data of drawdown and buildup tests than on stabilized flow tests. The stabilized testing methods often are not adequate for complicated modern gas reservoirs because many of these reservoirs have extremely low permeabilities and the transient flow period of a well test can last for days or weeks. It has become common to augment the flow capacity of gas wells by hydraulically fracturing their producing formations. In deep reservoirs the induced fractures are generally vertical and tend to follow a single plane of weakness. The presence of a vertical fracture at the wellbore complicates the transient flow behavior of a low permeability gas well. The flow is further complicated when turbulence occurs near the wellbore. Russell and Truittl published transient drawdown solutions for vertically-fractured liquid wells. They developed methods of drawdown and buildup testing utilizing these solutions, which were based on numerical simulation. Clark2 applied the basic Russell-Truitt solutions to analyze fractured water injection wells by falloff tests. Field examples were given to substantiate the method of analysis. The Russell-Truitt solutions and well testing methods can be extended to gas well flow. Millheim and Cichowicz3 presented the drawdown equations for *Now with Scientific Software Corp., Denver. ideal gas flow, including the effects of formation damage and turbulence. Two actual field cases were presented, both of which exhibited extensive fractures and turbulent flow. For the pressure range of these well tests, the use of ideal gas equations was acceptable. These field cases were significant in being the first published data showing the occurrence of turbulence in fractured gas wells. We, also, observed such cases in practice. Our purpose here is to extend the theory of fractured gas well testing to the flow of real gases. To determine the effects of wellbore storage and turbulence on well test interpretation, we developed a finite-difference model to simulate well test conditions. Since gas wells usually are widely spaced and have high compressibility, the emphasis has been put on the early transient behavior before the effects of the outer boundary are noticeable at the wellbore. The Mathematical Model The geometry of our mathematical model is similar to that used by Prats.4 The well is centered in a circular uniform reservoir. A vertical fracture of infinite flow capacity penetrates the formation and passes through the wellbore. The wellbore itself is not important. Fig. 1 shows a sketch of the problem. Fig. 2 shows the idealized model. The equation for the flow of real gas in a porous medium with uniform porosity, permeability and thickness is5-7

Jan 1, 1970

Jan 1, 1971

CONTENTS PAGE THOENEN, J. R.-Limestone Production as a Mining Problem. Discussed by Oliver Bowles, J. T. Singewald, S. R. Russell 1 GRIGGS, C. C.-Engineering in Limestone Production. Discussed by W. C. Phalen, John Rice, Samuel M. Shallcross, Oliver Bowles, Nathan C. Rockwood, George Milliron 2 WILDER, FRANK A.-Rotary Calciners for Gypsum. Discussed by L. K. Arm-strong 9 PORTER, JOHN J.-Manufacturing Problems of Cement Industry. Discussed by Samuel M. Shallcross 9 KIRKHAM, VIRGIL R. D.-Phosphate Deposits of Idaho and Their Relation to the World Supply. Discussed by F. A. Wilder, S. L. Willis, G. R. Mansfield, R. W. Stone, L. K. Armstrong 9 Limestone Production as a Mining Problem Discussion of the paper of J. R. THOENEN, presented at the New York Meeting, February, 1925, and issued, as Paper 1417-H, with MINING AND METALLURGY, February, 1925. OLIVER BOWLES, New Brunswick, N. J.-I am so thoroughly convinced of the growing importance of underground work in the production of limestone that I had the author make a detailed study of limestone mining for the Bureau of Mines and prepare a report on the principles of limestone mining. Many limestone operators, long accustomed to open¬pit work, are being forced to mining. About 6 months ago I thought there were twenty-five or thirty underground limestone operations in the United States but the author has been finding new ones until his list now runs nearer sixty. Some of these are very extensive; one at least has 4 ½ miles of underground workings. There is an ever-expanding field for the engineer in the operation of limestone mines and quarries. Some of the larger companies realize the need of skilled engineering advice, but many of the companies regard the engineer as an unnecessary expense. Although almost every metal mine, even those handling only a few hundred tons of ore per month, employs a mining engineer, many limestone operations ten times as large employ no mining engineers. Few mining engineers are at all familiar

Jan 6, 1925

By T. S. Lundy, R. E. Pawel

Effects of short-circuiting paths on observed diffusion behavior in real crystalline systems are considered. It is concluded that experimentally measured diffusion coefficients may vary widely from values associated with true lattice diffusion to those appropriate for short-circuiting paths alone depending upon the conditions of the experiment and the sensitivity and completeness of the data. IN 1961 Harrison1 classified experimentally observed diffusion behavior in systems involving both lattice and dislocation-enhanced atomic transport into three categories. His types A and C were limiting cases where the measured diffusion coefficients using the usual serial sectioning techniques were representative of lattice diffusion (with only slight effects of dislocations) and dislocation-network diffusion (with only slight effects from lattice diffusion), respectively. In both cases A and C for a sectioning experiment in which the diffusion couple has the semi-infinite geometry and unidirectional diffusion takes place from a plane source located at the origin of the coordinate system, he pointed out that Gaussian penetration behavior should be observed. For case A the lattice coefficient should be slightly enhanced by dislocation contributions, and the model of Hart2 can be used to predict the amount of this enhancement. For case C the observed coefficient should be that for the dislocation network and have little or nothing to do with lattice diffusion. Hart&apos;s model in its general form is still applicable, but the apparent diffusion coefficient for this case is virtually independent of dislocation density. Harrison&apos;s case B is that for which non-negligible contributions exist for transport by both mechanisms and "the concentration distribution does not approximate to any simple form." With the possible exception of very low temperatures where diffusion distances approach atomic dimensions, any real diffusion specimen will in general show non-Gaussian behavior provided the data are complete enough to uncover it. Thus, a "complete" set of data for any real system cannot be expected to be totally amenable to treatment by a simple mathematical model which does not take into account the relative distribution of transport by the various modes or submodes. For a particular sensitivity of specimen analysis and at a given temperature of annealing if the concentration profile could be observed as a function of time, "the behavior will initially be type C, and will develop into type B. and ultimately type A".1 Thus, it appears that the type of diffusion behavior which is experimentally observed in a given system depends very much upon the particular experimental conditions and the particular tools available to obtain the data. Interpreted in this fashion, Harrison&apos;s classification refers not to the diffusion behavior as a whole but to the relative sensitivity of the method of examination and completeness of the data. In the present paper we will: 1) assume that the measured penetration behavior follows the same general classification as that proposed by Harrison; 2) give, for diffusion in tungsten, examples of the range of diffusion coefficients that it is possible to obtain in a single experiment; and 3) speculate that some arguments which consider the possibility of short-circuiting effects being responsible for "anomalous" diffusion in several bcc metals may have been discarded prematurely.3 Both monocrystalline and polycrystalline tungsten were used in this work. The former was obtained as triple-pass, electron-beam zone-refined 6.0-mm-diam rod from Materials Research Corp.. Orange-burg. N.Y. The latter was swaged, high-purity bar stock which was annealed for 2 hr at 2200°C and 10-9 torr to yield an average grain diameter of about 25 /i. The tracer Nb95 was received in oxalate solution from the Isotopes Division, Oak Ridge National Laboratory. Experimental procedures of specimen preparation, isothermal diffusion annealing, serial sectioning by anodizing-and-stripping, and y counting of the individual sections to determine the tracer penetration profile after a given diffusion anneal have been described elsewhere.4 However, it should be noted that the anodizing-stripping sectioning technique has the particular advantage for this research of permitting sectioning to be accomplished over a wide range of

Jan 1, 1970

By D. L. Ritter, N. J. Grant, B. C. Giessen

The crystal structures of eight of the nine intermediate phases in the Nb-Rh system were investigated by X-ray techniques. The following structures occur: a,Nb3Rh (Cr3O type);o(ofe - cr type) (H.T. phase, structure unknown); Q2 (AuCU type); a, (orthorhombic, analogous to a,, (Ta-Rh)); a (AuCd type); a,, (monoclinic, related to samarium type); a-8 (VCo3 type); a, NbRh, (AuCu, type). Structural relationships between the six close-packed intermediate phases are discussed and a comparison with the Nb-Ir, Ta-Rh, and Ta-Ir systems is made. In the Nb-Rh phase diagram,&apos; nine intermediate phases were encountered. In order to understand the phase sequence in the diagram and to be able to plot atomic volumes, several unknown crystal structures had to be worked out. These and the evi-

Jan 1, 1964

By M. J. Mullikin, J. B. Conway

Several different equation forms were studied to determine the extent to which each particular equation type yielded an accurate representation of a given set of first-stage creep data. Specially developed least-squares computer programs were employed to obtain unique solutions for the creep-equation constants. In studies of creep data for lead at 14.5"C, nickel at 70OCC, and arc-cast tungsten at 2400°C consistently good representations were afforded by a third-degvee polynomial in t113. Other effective correlations were obtained with the Andrade, Cottrell-Aytekin, and de Lacombe equations along with a third-degree polynomial in t112. A newly proposed creep equation involving a hyperbolic-sine term in t1&apos;3 was also found to yield very satisfactory results. This appears to be the first use of such a functional relationship in the analysis of transient creep behavior. In general, the deformation behavior of a material subjected to a tensile load is described in a strain-time plot. Experiments have shown that, following the instantaneous elongation which results on loading, the instantaneous slope (i.e., creep rate) of the strain-time curve decreases gradually with time and approaches what appears to be a constant value. Equations, therefore, which are proposed to provide an analytical representation of such first-stage or transient creep behavior must be consistent with these observations. In other words, at time zero, these equations must yield a finite deformation value corresponding to the elongation on loading. Furthermore, the first derivative of these equations must exhibit a fairly high although finite value at time zero, and then values which decrease with time. It is also preferable, in general, that the derivative eventually assume a constant value at high time values. Although many studies of first-stage creep behavior have been made and numerous equation forms have been proposed for expressing this type of deformation behavior, it is still not possible to state with any assurance which functional relationship will be adequate for a given set of measurements. Parabolic relationships have been employed most extensively although logarithmic expressions have been shown to be applicable in some instances. Combined forms1 have been studied in considerable detail and have on occasion been found to be very effective. One such expression is that of iXndradea and involves a modified parabolic expression: where 1 is the instantaneous length, lo is the length immediately following load application, t is the time, and p and k are constants. Another combined form has been proposed by weaver3 as follows: where E is the instantaneous strain, is is the linear creep rate, t is the time, and a and b are constants.

Jan 1, 1967

By J. A. Faucher

The mining industry has undergone significant technological advances in metallurgical process methods in recent years. The 1000 tpd concentrator of St. Lawrence Colum-bium Metals Corp. portrays the continuing effort made by the industry to achieve economical concentration of new and difficult ores. During the active search for sources of uranium in the early fifties, radioactive minerals were found in the Oka district near Montreal. The compatatively small quantities of uranium which were found occurred in association with widespread columbium (niobium) mineralization which included perovskite, a calcium titanate containing roughly 40% Cb2O5; niocalite, a silicate containing some 20% Cb2O5; and pyrochlore, a calcium niobate containing 45 -70% Cb2O5 as well as fluorine and some water. An idealized formula for one type of pyrochlore is: A typical chemical analysis of pyrochlore is shown in Table I. An important feature of this analysis is the lack of tin, lead, sulphur and P2O5 which conforms with the requirements of most consumers. In general the cerium content varies with sodium content and any increase in Ta2O5 lowers the Cb2O5 content of the concentrate. However, Ta2O5 rarely exceeds 0.5%. The carbonatite host rock of the columbium mineralization has the average mineral composition shown in Table 11. In Table 11, the term "diopside" is used to cover all silicates except mica which is shown separately because of the problems involved with its separation during the concentration process. In some ore zones, small quantities of rare earth minerals, such as monazite are present.

Jan 1, 1964

By Arthur M. Miller

FROM the time of its establishment in 1933, the Tennessee Valley Authority has been active in the field of phosphates. Under the T.V.A. Act it has a broad Congressional mandate to guide a unified development of the resources of the region for the long-range benefit of the people. As one phase of this function, it is directed to co-operate with farmers in the experimental large-scale use of improved fertilizers and development of better fertilizer practices. Following careful study, it was concluded that the objectives of this phase could best be attained by soil rebuilding through the use of phosphatic fertilizer and lime in an improved farm management sys- tem. This activity was launched through a program of test and demonstration on farms and simultaneous technical investigations to develop new and improved phosphatic fertilizers. Phosphorus has since become a keystone of the Authority&apos;s resource development and conservation program. Human effort is being conserved by phosphate utilization on the farm, and mineral conservation has been promoted by technical developments in phosphate mining and manufacturing operations.

Jan 1, 1944

By D. E. Mikkola, G. E. Poquette

X-ray diffraction was used to study the growth of antiphase domains in quenched (or "disordered&apos;? Cu3Au annealed in the range 300" to 385°C. Measurements of the long-range order parameter indicate that a high degree of order is established rapidly at these annealing temperatures. Average domain sizes obtained by Fourier analysis of the superlattice peak profiles show that antiphase domain growth is analogous to classical metallurgical grain growth (i.e.,fol-lows a D2 US kt relation). The activation energy for the growth process, 44 kcal per mole, indicates diffusion control. The anisotropy in the observed effective domain sizes from seven different superlattice peaks can be best accounted for by a configuration involving antiphase domain boundaries on {100 } and (111 ) planes, where the (100) boundary is the low-energy type, {lOO} Type I. The disappearance of the (111) antiphase domain boundary during domain growth is dif-fusion-controlled with an activation energy of 48.5 kcal per mole. On the other hand, the behavior of the parameter representing the amount of (100) Type I boundary indicates that there may be a conversion of the higher-energy boundary types to (100) Type I boundary during the growth process. THE order-disorder transformation in the alloy Cu3Au has been the subject of numerous experimental investigations over the past 40 years, most of which have involved measurements of convenient physical properties such as resistivity and hardness as a function of heat treatment. The interpretation of these data is difficult because measurements of this type have the disadvantage that they yield total changes resulting from several different atomic processes which may be occurring simultaneously. The present study was undertaken to establish by means of X-ray diffraction the kinetic behavior of one of these atomic processes, namely antiphase domain growth. In the completely ordered state Cu3Au has an L12 structure which can be described as an fcc type arrangement of atoms in which the gold atoms occupy the corner sites and copper atoms the face-centered sites. Three other equivalent unit cells can be formed by allowing two gold atoms to occupy opposite face-centered sites and copper atoms to occupy the remaining corner and face-centered sites. These four different unit cells are crystallographically related by a shift of 1/2<110>. Quenching from above the critical temperature (392°C) to room temperature retains the "disordered" structure-a "random" arrangement of copper and gold atoms having the fcc structure. Annealing the disordered alloy below the critical temperature causes ordering to occur through the nucleation and growth of ordered regions at different points throughout the crystal. These small ordered regions, each based on one of the four types of unit cell, grow by consuming the disordered material until they impinge to form a domain structure in which the domains are antiphase by a shift of 4(110). The boundaries between domains are called antiphase domain boundaries (APDB) and they have been found to lie primarily on &apos; {100} planes in highly ordered Cu3Au. Two types of APDB can occur on ( 100) planes. An example of an (001)1/2[110] shear type APDB is shown in Fig. I. Because of the layer of copper atoms separating the domains in this case, there are no near-neighbor violations across the boundary and it has a low surface ener This type of APDB will be referred to as {lOO} Type I. Fig. 2 shows an (001): [011] climb type APDB, (100) Type 11. This type of APDB can be described as resulting from removal of a (200) plane followed by a shift of 1/2<110> to bring the separated regions together. Near-neighbor violations across (100) Type I1 APDB make it a high-energy boundary. There are numerous other possible APDB configurations; however, it is only worth noting that shear type APDB can be produced on the (111) plane by motion of a normal fcc dislocation with Burgers vector 1/2<110> through the ordered structure. A (111); [110] shear type APDB is shown in Fig. 3. Again, because of the near-neighbor violations this type of APDB has a higher energy than the (100) Type I APDB.

Jan 1, 1970

By H. D. Outmans

A method has been developed for determining the relative water wet-tability (fraction of the surface wet by water) of porous media. This method involves the adsorption of methylene blue dye from an aqueous solution onto the solid surfaces of rock contacted by the injected dye solution. Experiments on Berea snndstone cores have shown that water-wet cores adsorb a large amount of dye from solution. In oil-wet cores, however, the injected aqueous dye solution is prevented from contacting the adsorptive surfuces by a film of oil and virtually no dye is adsorbed. This method was tested by experiments on mixtures of water-wet and oil-wet sand. Using the dye adsorption method, it was possible to determine quantitatively the fraction of water-wet and oil-wet sarzd in such mixtures. The dye adsorption test is readily applied to determinitrg the relative water wettability of fresh oilfield cores. The cores are not extracted before testing. Observed values of the wettability of field cores tested to date have varied from 100 to 6 per cent water wet. INTR OD UCTIO N Recent articles1 &apos; have emphasized the important role that wettability plays in almost all phases of reservoir rock behavior. It has been shown that wettability has a profound effect on the interstitial water saturation, residual oil saturation, capillary pressure, relative permeability, waterflood behavior, and resistivity index of oilfield cores. A quantitative investiga- tion of the effect of wettability on these core properties is severely handicapped by the lack of a simple technique for measuring the wettability of a porous medium. If such a technique were available, it would provide investigators with a means of gaining insight into the distribution of phases within a core. A number of qualitative methods of estimating wettability are known. These include contact angle measurements, flotation tests and studies of displacement pressure: imbibition7 and relative permeability data.&apos; Using these tests, it is usually possible to classify a core as water-wet, oil-wet, or some intermediate degree of wettability. One recently proposed method involving measurement of nuclear magnetic relaxatione offers promise of determining quantitatively the fractional wettability of cores. The equipment is rather elaborate and necessary treatment of the cores before testing probably alters the natural wettability. This latter point also applies to most of the cited qualitative methods. This paper presents a new technique for determining water wettability of cores; it is based on measurements of the dye adsorption capacity of the core. This method has the advantage of requiring relatively simple equipment and involves minimum handling of the core before testing. It is important to distinguish between the various concepts of wettability referred to in the literature. The term "wetting" is defined by Bartell as that phenomenon which occurs when a solid and liquid phase come in contact in any manner so as to form a solid-liquid interface. A preferentially water-wet solid is defined by Jennings in terms of the advancing contact angle in the solid water-oil systems. Brown and Fatt regard fractional wettability as the fraction of the total surface area that is preferentially oil-wet or water-wet. However, none of these definitions adequately describes the type wettability measured by the dye test. This calls for the introduction of a new term, "relative water wettability", which we define as the fraction of the total surface area of a core contacted by injected water. DESCRIPTION OF METHOD The ability of a porous medium (especially the clays) to adsorb large quantities of surfactants, dyes, etc., is well known. It is reasonable to assume that a substance can be adsorbed from solution onto a solid surface only if the solution contacts the surface. In this connection Shapiro" has shown by experiments on silica gel that completely dry gel will adsorb methyl red dye from a benzene solution. On the other hand, if a film of water more than several molecules thick is present on the silica gel, the adsorption capacity of the gel for the dye is drastically reduced. Thus, a study of the dye adsorption capacity of cores should give some clue as to the fluid distribution on the surface of the core. TEST OF METHOD As a qualitative check on this theory, dye adsorption tests were run on similar Berea sandstone cores (Table 1, Cores 1-5). Cores saturated initially with water and flooded with 0.01 per cent aqueous methylene blue adsorbed 0.58 mg dye/gm of core. Similar cores saturated initially with water, driven to irreducible water with oil, and then flooded with the same dye solution also adsorbed 0.58 mg dye/gm of core. Another core, treated with a 5 per cent Dri-Film solution, dried and saturated with oil (Soltrol) adsorbed no dye when the dye solution was injected. These tests confirm

By F. A. Seward

A1though the expanding Eltran1 configuration has been used in induced polarization exploration for several years, there has been little application of this method to straight resistivity problems. A comparison of results of resistivity exploration by this technique versus those obtained from Wenner configuration surveys reveals a number of advantages in interpretative resolution as well as in field operation. The application of electrical resistivity to ground-water exploration is well known.= In the past a major portion of this work has been accomplished by use of one or more variations of a technique employing the Wenner3 electrode configuration. With the introduction of the frequency domain technique of induced polarization measurements, used primarily in the exploration for disseminated sulfide deposits, there arose the need for an electrode configuration by which potentials could be measured externally to the current electrode spread in order to minimize coupling between current sending and potential receiving circuits. It was also deemed desirable that the configuration would provide information laterally along profile as well as with depth. To reach these objectives the expanding dipole-dipole configuration (which probably first was used in the electrical transient method of exploration and from which the name &apos;Eltran&apos; was derived) has been adapted to induced polarization exploration. The author has successfully applied the same techniques

Jan 1, 1963

CAPTAIN JOHN H. BALLAMY John H. Ballamy, Captain on the Regimental Staff of the 103d Engineers, was killed near Fismes, on August 9, 1918. Captain Ballamy was born at Plymouth, Pa., in 1886 and graduated from the High School of that town in 1903. In the following year he began work as a coal miner, and at the same time began the study of mining engineering in the evening and any other spare time. He continued this diligent and energetic practice for many years. For sixteen years he continued in the employment of the Delaware, Lackawanna & Western Railroad Company&apos;s coal mining department, first as a practical miner, next as rodman on the survey corps, of which he soon became chief, then draftsman and mining engineer in the company&apos;s office. In January, 1916, he was promoted to the position of district engineer in charge of mining engineering work. He became a member of this Institute in September, 1917. CAPTAIN JOHN H BALLAMY. Captain Ballamy&apos;s military experience began at the same time as his engineering practice. He was a charter member of Company A, Engineers, N. G. P., which was organized ten years ago. He saw service on the Mexican border as First Lieutenant of this Company, and remained in that position until November, 1916. In July, 1917, he was again called into service and was sent to Camp Hancock, Ga., with the 103d Regiment of Engineers. Before joining this regiment he attended a school for officers at Fort Sill, Okla., where he received special training in field fortifications. In December, 1917, he was commissioned Topographical Captain on the Regimental Staff, and in April, 1918, preceded his regiment by about six weeks to France, where he again attended an officers&apos; training school. He rejoined his regiment on July 15, near Chateau Thierry and was killed near Fismes on August 9, 1918.

Jan 11, 1918

By E. Martinez

Samples of chrysocolla, a hydrated copper silicate, from several sources were submitted to differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). Pure samples of chrysocolla are difficult to obtain, but comparison of the thermograms revealed that certain reactions occurred in all the samples and it is believed that these are due to chrysocolla. Endothermic reactions occurred at 50&apos; to 175°C, 350° to 650°C, and 980° to 1100°C each of which caused a weight loss. The first was due to loss of absorbed water, the second to a dehydroxyla-tion, and the last to conversion of cupric oxide to cuprous oxide. In addition, two exotherms were detected at 685° to 695°C and 935° to 950°C. Infrared spectra of heated samples indicated the exotherms were due to changes in the Si-O bonds leading to the formation of cristobalite. The results suggest that thermoanalysis may be a more sensitive and reliable method for detection and identification of chrysocolla than X-ray diffraction, infrared spectroscopy, or optical techniques. The recovery of copper from oxide ores has been the subject of much research in recent years. One of the principal oxide copper minerals is chrysocolla, a hydrated copper silicate. The information available indicates that it has widely varying properties depending on the origin of the sample. Chrysocolla usually is found associated with cuprite, malachite, azurite, and native copper. Most of these other minerals are recoverable by present day flotation practice, but chrysocolla is lost in the tailings.1,2 Reagent combinations that are successful in laboratory chrysocolla flotation with ore from one source have been found to be ineffective with another. 3 The copper segregation process offers an altemative to beneficiation of oxide copper ores.4&apos;5 The process is of particular interest in processing ores that cannot be treated by conventional hydrometal-lurgical methods because of high acid consumption.6 Fuller understanding of the properties of chryso- colla may prove of value in the search for improvements in both the flotation and segregation processes. Chrysocolla samples from Arizona, Nevada, Chile, Australia, and South Africa were studied by differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). In addition, a sample from Miami, Ariz., was submitted to X-ray diffraction, infrared spectrophotometry, and surface area determination. EQUlPMENT Differential thermal analysis (DTA) detects, amplifies, and records exothermic-endothermic reactions occurring in a sample as its temperature is raised at a constant rate, usually 10°C per minute. A unit made by the Robert L. Stone Co. was used in this study. The tests can be run if desired with a gas streaming through the sample. A thermobalance records weight losses or gains in a sample as its temperature is raised at a uniform rate. The gravimetric analyses (TGA) were run on a Chevenard thermobalance converted electronically for graphic recording. A heating rate of 5°C per minute up to 1100°C was used in these tests. A Perkin Elmer Infrared Spectrophotometer, Model 221, was used with sodium chloride optics obtaining IR spectra in the 2 to 15 region. A pressed pellet technique with potassium bromide was used in preparing the samples. DESCRIPTION OF SAMPLES Chrysocolla is found in the oxidation zones of copper deposits commonly associated with malachite, azurite, and limonite. It is described as varying in composition and in color from bluish green to brown or black. Inclusions of other minerals are usual so chemical analysis of chrysocolla samples may be suspect. However, it is considered by many to be a solid solution of CuO, SiO2 and H2O with a general formula of CuO.SiO2.2H2O or 2CuO.2SiO2. 3H20. Chukhrov7 has described a sample from the Urals as CU3,5(OH)2 (A1Si3) O10.nH2O and stated that chrysocolla is a montmorillonite-type mineral. On the basis of X-ray analyses, DTA, and infrared spectra of chrysocolla from the Inspiration Mine, Ariz., Sun8 concluded that there was no substantial evidence to classify it as a montmorillonite mineral. Chrysocolla samples from many sources throughout the world were used in this investigation. The following is a brief description of each:

Jan 1, 1963