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By D. E. Wolfson, D. A. Reynolds, F. W. Smith

IN 1948 the U. S. Bureau of Mines began a three- phase program to evaluate the extent and quality of U. S. coking coal: 1) a factual appraisal of known recoverable reserves in beds of mineable thickness, 2) a study of preparation characteristics, and 3) a study of carbonization properties. A previous paper presented the methods used in assessing reserves.' Although this investigation is only partly completed, data on coking properties of the Pittsburgh district coals are now available. The results are presented in this article. When coals are selected for manufacture of metallurgical coke more factors must be considered than for any other major use, as no basic industry requires coal of such high quality and uniformity. This is particularly true in the Pittsburgh district, where blast furnace practice is based on use of cokes from high quality coals. Although it is true that inferior coals are carbonized in other industrial areas, both here and abroad, the Pittsburgh coals are the best economically obtainable in the required tonnages, even though they are not the most desirable for metallurgical use.

Jan 3, 1957

By John B. Gayle

PRESENT flotation processes depend almost entirely on the buoyant properties of air bubbles to effect separations of mineral and gangue, but there is no convenient method for measuring aeration in flotation cells. Consequently the relation between aeration and cell performance has not been definitely established. In connection with a comparative study of kerosene and froth flotation processes, a modification of the displacement method' was developed in which air escaping from the cell surface is measured with a wet-test meter. The arrangement shown in Fig. 1 is satisfactory for use with a number of cells and is not critical, except that care must be taken to use connections and tubing large enough to avoid excessive back pressures. Attempts to use smaller tubing resulted in back pressures that caused displacement of the liquid level in the receiver, so that some air was lost around the sides, an occurrence readily visible when measurements were taken with only water passing through the cell. With the arrangement shown, the manometer indicated an average reading of about ½ -in. water pressure. No loss of air was evident.

Jan 7, 1958

By P. K. Lucke

One of the interesting features connected with the great continental uplift, which formed the table land of Mexico, is the great depth to which oxidation and secondary enrichment of orebodies occurred. This table land lies at altitudes ranging from 4000 to 7000 ft. (1219 to 2133 m.) above sea level. Several cases could be cited of oxidized zones in copper and lead mines which reached depths of upward of 1500 ft. (457 m.) below the surface, and it is universally admitted that the oxidized zone in a mine is limited by the permanent water level. Mexico, however, like many other countries in which deserts occur, is visited at rare intervals by tremendous floods, which sometimes cause variable water levels over long periods. The following cases bear out the idea, and lead to interesting conclusions of commercial value. My paper demonstrates that carbonates of ores may occur below water level and sulfides above, and I will endeavor to explain the causes of the phenomena in certain specific instances. Case I.—Fig. 1 in this case shows that sulfides of lead remained

Jan 1, 1920

By Erwin Zodrow

An elaborate model for the magnetite distribution and genesis in the Smallwood mine, Labrador, based on factor analysis with orthogonal and oblique rotation of the factors, was proposed in an earlier paper. However, it is implicit in that model that variances of one variable shared with all others (communality) are estimated. To avoid the problem of communality estimation in the present investigation, a different type of factor analysis is used which (1) emphasizes the shared variances, and (2) attempts to eliminate, as much as possible, errors associated with the estimation of communality and sampling (unique variance). The samples for the present analysis are not the commonly employed oxide percentage variables, but counts of mineral species in specified areas of thin sections from drill core in the Smallwood mine: quartz, magnetite, calcite, and specular-hematite minerals. The counting procedure for mineral species is similar to modal analysis differing from it principally in the aspect of texture recognition. The constant area in which mineral species are counted is dependent primarily on

Jan 1, 1975

By G. L. Coleman, D. S. Hutton, W. C. Leslie

The occurrence of twins in a iron, generated during cooling through the ?-a transformation, is well established,1-8 but this phenomenon has been nearly ignored during the past 20 years. It is the purpose of this note to call attention to the prevalence of such twins and to illustrate their appearance. The work of paxton7 and Kelly8 has demonstrated beyond reasonable doubt that for Neumann bands (mechanical twins) in a iron the twinning plane is (112) and the twinning direction <III>. The agreement with McKeehan&apos;s earlier work4 on transformation twins indicates that both types of twins in ferrite follow the same twinning law. There is little doubt of this conclusion, but it could be strengthened by a microbeam X-ray determination of the orientation relationship between a single ferrite grain and a transformation twin within that grain, as in the technique used by Kelly8 on Neumann bands. RESULTS AND DISCUSSION Transformation twins, identified by their appearance on a polished and etched section, were found in

Jan 1, 1960

I HAVE already described to you many kinds of fusions and fires and still have many to describe if1 am to guide you, as I intend, among the operations of these processes. In all these, quantities of charcoal and various kinds of it must be handled continually and it therefore seems to me necessary to tell something about charcoal for aiding you in these processes. Without it artificers could scarcely bring their works to an end, because it is the food that nourishes the fire both for smelting and for softening the metals, or for calcining or drying things out. [61] It is a very powerful means and not only is its fire used for many more works than other fires, but it is also essential. Although there are many other things that make fire and would make it, I do not know of any that are better adapted for this purpose, or that can be more easily procured in large quantities, than wood and charcoal. For, as you can see, very great forests are found which make one think

Jan 1, 1942

By D. Kelly Campbell

Cleveland-Cliffs Conveyor System Uses Twisted Belt To: 1 -Beat Upper Peninsula Weather 2- Solve Underground Transportation Problems

Jan 7, 1953

By H. Bernstein

Grain coarsening tests were carried out on AI-4.5 pct Cu and AI-4.5 pct Si alloys. The effects of three variables, melt composition, pour temperature, and mold temperature, were determined. It was found that the macrostructure generally coarsened with increased pour and mold temperatures. Coarsening was extreme in the unrefined alloys but was retarded by the active grain refiners like titanium and columbium. The effect of boron was spectacular in suppressing coarsening tendencies. The results of the investigation support the carbide theory of nucleation as opposed to the peritectic theory. A REVIEW of prior work on the subject of grain refinement in the light metals indicated that, for the most part, it had been concerned with the positive effects of addition agents upon structure. This work produced various theories of refinement. Prominent among them were the peritectic theory and the transition element carbide theory. Certain inadequacies in the former theory appeared to be explained satisfactorily by the transition element carbide theory. In order to appraise these theories further, a study was undertaken of the permanence of grain refinement effects when subjected to thermal or chemical variations. It was considered that a study of this kind would be of practical value, since the light metals are exposed to thermal and chemical variations in the normal course of foundry operations. Accordingly, two alloys of commercial importance were selected for this investigation, the A1-Cu and A1-Si alloys. Experimental Procedure and Results Raw Materials: The base alloys, A1-Cu and A1-Si, were prepared from virgin aluminum and hardeners, induction melted, and pigged for remelting. The grain refiners, including titanium, columbium, zirconium, and boron, were added as master alloys. Analyses of the raw materials and base alloys are listed in Table I. Melting and Casting Practice: The metals were melted in clay-graphite crucibles in a Hevi-Duty pit-type resistance furnace, equipped with a Leeds and Northrup Micromax Recorder and Controller. After melt down of the base alloys, the additions were made. For each casting, approximately 80 grams of metal were poured into a preheated graphite mold held in a transite flask. The mold (Fig. 1) weighed 320 grams. To determine the effect of superheat upon structure, a set of melts was heated successively to four temperature levels, 705°, 775°, 845°, and 915°C, and test specimens were cast at each level. Prior to each pour, the furnace temperature was held constant for 20 min. Next, a set of melts was put through a superheat cycle and test specimens were cast at melt temperatures of 705" and 915°C successively. The crucibles then were cooled in air to 705°C as deter-mined by immersion thermocouple and additional test specimens were poured. The cooling interval was approximately 1 min. Another set of melts was furnace cooled with the cover slightly ajar and test specimens cast as before. The interval in this case was 15 to 20 min, varying with the superheat temperature. The mold temperature for all these tests was 400°C. To determine the effect of cooling rate without superheat upon structure, a set of melts was heated to 705°C, and castings were poured at mold temperatures of 205", 400°, and 540°C. An interval of 15 min elapsed between each pour. Mold temperatures were measured by a direct reading millivolt-meter, using a chromel-alumel thermocouple located at midwall thickness of the mold. To demonstrate the phenomenon of chemical coarsening, agents such as chromium and beryllium, which had acted as coarseners in a previous investigation,&apos; were added to the A1-Cu alloy. Test speci-

Jan 1, 1955

By Merlon C. Flemings, Theodoulos Z. Kattamis

Examination was made of the distribution of tnanganese and nickel in colutrrnar dendrites of a cast low-alloy steel; more limited work was corzducted on chromium. Corresponding "segregrction ratios" were calculnted and shown to be relntivelv insensitive to cooling rate (&apos;&apos;segregation ratio" is defined (Is the ratio of maximum to minimum concentrations within a volume whose dimensions are the order of the dendrite-arm spacing). Isoconcentratiorl curves were determined by the electron micropvobe and by rt7etallografihic studies on specimens subjected to isothermal-transformation treatments. From construction of isoconcentration curves, morphology of columnar dendrites is descvibed as intermediate between Perfect rodlike and sheetlike morphologies. The study is extended to equiaxed dendrites and it is shown that the strcture of these dendrites is sittlilar in many respects to that of columnar dendrites. On the basis of tlze sheetlike morphology of dendrites, a simple model is pvoposed for calculation of honzogenization kinetics. Results of trzatllevlatical analysis brcsed on this utzodel are given. This analysis relates residual segregation to time at homogenization temperature; it is in agreement with experiment. Calculations are given which show that even for relatively rapidly cooled material (of 1-ine dendrite-artn spacing) treatmets at 1200°C or above are necessary to achieve slgxificant Izomogenization of elenlents other than carbon itz reasonable time (e.g., rnangclnese, nickel). Conlplete homogenization of carbon is obtnined at much lowev tenlperatures (below 870°C). IN dendritic solidification of castings and ingots, solute redistribution during freezing results in mi-crosegregation of most alloy elements. The micro-segregation is such that minimum solute concentrations occur at the center of dendrite arms and maximum concentrations occur between dendrite arms. Residual segregation after subsequent therma1 processing (homogenization) depends on maximum and minimum initial concentration, on the detailed geometry of the isoconcentration surfaces within interdendritic regions, on the diffusion coefficient of the solute, and on time of thermal processing. The objective of this work was to determine, for a low-alloy steel, maximum and minimum concentrations, and the geometry of isoconcentration surfaces, primarily in order to permit calculation of homogenization kinetics. Most of the work reported was conducted on Samples from a unidirectionally solidified, fully columnar ingot. This type of ingot is made by extracting heat during solidification from one face; techniques for accomplishing this have been discussed.&apos; Samples were taken at several locations, up to 5.75 in. from the mold chill face; the bulk of the work was performed on samples at 5.75 in. Alloy cast was, nominally, 0.4 pct C, 1.8 pct Ni, 0.8 pct Cr, 0.7 pct Mn, 0.25 pct Mo, 0.3 pct Si, and the balance iron. Brief study was also made on samples from an ingot which solidified with equiaxed grain structure. SAMPLE PREPARATION AND ANALYSIS Samples for electron-microprobe analysis were incorporated in mounts that included pieces of electrolytic nickel, chromium, and manganese, in order to normalize the intensities of these solutes in the specimens; also, a piece of electrolytic iron was included to measure the background. All specimens were polished in the usual metallographic manner. After the microprobe traces were made, the path was revealed by etching the specimens with picral. All microprobe analyses were made by point counting, integrating for 30 sec. The distance between points was fixed from 2 to 10 p, according to the precision desired in each case, the fineness of the structure, and the concentration gradient existing in a given area. (The distance was chosen 2 to 5 p near the maximum-concentration regions and 5 to 10 p near the minimum concentration.) The "take-off" angle for the A.R.L.-Model No. 21000 microprobe employed was 52.5 deg. Samples for metallographic analysis of isoconcentration curves were prepared by austenitizing at 1540°F for 20 min, quenching to the nose of the TTT curves (1200°F), heat treating isothermally at this temperature for a given time 0, and then quenching to room temperature. Due to concentration gradients existing in a dendritic structure, no transformation will take place for a given time 0 of isothermal heat treatment in the regions where the a.lloy concentration is higher than a given limit. Thus, the dendrite appears limited by an isoconcentration curve and can be made to appear to grow by varying the time of isothermal heat treatment.

Jan 1, 1965

By H. C. Gatos, J. T. A. Pollock, V. Sadagopan

PREVIOUS investigations on the effect of neutron irradiation on the superconducting properties of bulk transition metals indicated that little or no change occurred in poly crystalline disordered materials, particularly if cold-worked prior to irradiation. Only the superconducting properties of ordered intermetal-lic A15 compounds were found to be sensitive to irradiation, and the observed reduction in Tc and increased magnetic hysteresis or critical current densities were attributed to the introduction of flux pinning vacancy clusters and disorder in the lattice. Since the former would also be expected to be present after irradiation in disordered alloys, the general conclusion was that the disordering effect of the irradiation was the primary reason for the changes observed. The present note reports some unusual effects of neutron irradiation on cold worked Nb(Cb)-Ti-V alloys. Specimens with nominal composition as given in Table I were prepared by repeated arc melting, taking the usual precautions, and homogenized at 1000°C for 24 hr prior to a reduction of 15:l by cold rolling. Samples of size 1 by 1 by 25 mm were sliced from the rolled strips. The sarmples chosen for irradiating were sealed in a cadmium tube (wall thickness 1 mm) prior to exposure in a fast neutron flux of 3.7 x 1019 neutrons per sq cm in the swimming pool reactor of Union Carbide Corporation&apos;s Sterling Forest Reactor. During irradiation the temperature of the samples was maintained below 70°C. The irradiated samples were stored at room temperature for approximately 1 year allowing the radiation levels to reach a safe handling value. Tc measurements were made employing a self-inductance coil technique. Jc data at 4.2"Kwere obtained using a four lead resistivity method. The latter measurements were made at the Francis Bitter National Magnet Laboratory by setting the perpendicularly applied field and increasing the direct current through the sample until a potential of about 10-6 v was detected. Tc values for the nonirradiated samples are listed in Table I together with the change in Tc after irradiation. A decrease in Tc of 0.25 or 0.3"K was measured for three of the four samples, the exception being the Nb-30 at. pct V-20 at. pct Ti alloy which showed a decrease of 0.5K. Jc vs applied field data are plotted in Fig. 1 for the Nb-20 at. pct V-30 at. pct Ti alloy. These curves are typical of the four alloys and surprisingly indicate that a degradation occurred in all the samples after irradiation. Hc2 values, obtained by extrapolation to zero current, are 8 to 15 pct lower than those measured for the nonirradiated specimens. The reasons for the degradation of Tc and jc ob-served in the alloys on exposure to neutron irradiation are not immediately apparent. The temperature at which the samples were maintained during bombardment (<70°C) and stored (20°C) make it highly unlikely that any significant change in the dislocation density of the materials through thermally activated migration and annihilation would occur. The explanation must lie in the type of damage produced by the bombardment. McEvoy et a1. reported no change in superconduct-

Jan 1, 1970

By N. Mungan

Laboratory water floods were performed in oil-wet and waterwet alundum and Torpedo cores, displacing a refined oil with n-hexylamine or Triton X-100 solution. Also, some floods were performed in which a sucrose solution was displaced with n-butyl alcohol. The Purpose ot the tests was to see if the oil recotlery could be increased and to examine what role the inter-facial tension reduction and wettability change play in the recovery mechanism. it was found that the chromatographic transport of amine was influenced by core wettability. In oil-wet cores, the rate of advance of the amine band could be predicted from equilibrium chromato-graphy, while in water-wet cores the amine band moved faster than predicted, indicating a non-equilibrium process. By reducing the interfacial tension to 1.1 dyne/ cm, oil recovery was increased. More oil was recovered from Dri-filmed cores than from water-wet cores. Reversing the wettability of the porous media from oil-wet condition also resulted in some additional oil recovery. Neutral wettability floods did not increase oil recovery. INTRODUCTION Interfacial forces in petroleum reservoirs are responsible for retention of large quantities of residual oil. Increasing exploration costs have created an incentive to attempt recovery of this residual oil by new and novel processes. One novel process involves changing the interfacial forces by introducing a chemical into the reservoir during water flooding. Recently, several investigators have carried out laboratory displacement tests using amines. lt3.4 The amines adsorbed onto initially water-wet core surfaces, changing them to oil wet. Additional oil was recovered when the cores were flooded in a manner reversing the. wettability from oil-wet conditions. In all these studies, the wettability reversal was considered responsible for increased oil recoveries although it was noted that amines also reduced oil-water interfacial tension. In the present study, displacement experiments were performed in water-wet and Dri-filmed cores. The purpose was to separate the effects of lowering the interfacial tension from changing the wettability. LABORATORY STUDY All experimental data given in this paper have been obtained at a temperature of 70F + 1 and prevailing atmospheric pressure. FLUIDS AND MATERIALS The oil used in these experiments* was washed with H2S04 and passed through two 100-200 mesh silica-gel beds to remove unsaturates and surface active impurities. Normal hexylamine** of practical purity was used, and the alundum cores*** were composed of nearly pure A1203. Fused quartz (SiOi) and Lucalox (A12 )t plates were used in the contact angle measurements. DISPLACEMENT TESTS Displacement tests were performed in alundum and Torpedo cores. Before displacement runs, cores were acidized with 0.1 normal HCI, flushed with distilled water and fired at 1,200F to make them water wet. This procedure also reduced water sensitivity of the Torpedo cores. Oil-wet cores were prepared from water-wet cores by flowing several pore volumes of 1 per cent by weight Dri-film SC-87 solution in heptane through the cores, flushing the cores with nitrogen, evacuating, and finally heating the cores at 300F for 4 or 5 hours. Between floods, cores were cleaned by conventional procedures and treated again as above.

Jan 1, 1965

By F. O. Jones

The capabilities of small proportions of divalent cations, such as calcium or magnesium, for controlling clay blocking are reported. Potentially sensitive formations can be exposed to fresh water if at least one-tenth of the salts dissolved in both the native water and invading fresh water are calcium and magnesium salts. Often, even less suffices. The behavior evidently depends upon the cation exchange properties of the clays, which favor adsorption of calcium and magnesium over sodium. Clays having sufficient adsorbed calcium and magnesium resist dispersion by water and consequent blocking of permeability. An allied phenomenon, the dependency of clay blocking on salinity contrast, is also reported. Abrupt change from highly saline to fresh water can cause blocking which may not occur if salinity is lowered slowly. A process related to osmosis is thought responsible for this behavior. Applications of findings to drilling, fracturing and water flooding are discussed. INTRODUCTION Many formations, when exposed to fresh water, can lose permeability through clay effects.&apos;,&apos; For example, drilling-mud filtrate can cause oil permeability decreases, which persist long enough to interfere with drill-stem testing and well completion.3 Ultimate productivity may suffer when clay damage is severe, especially if drawdown pressures are low.&apos; The injection pressures and the time required for water flooding can increase if clay blocking occurs. Earlier work indicates that clay blocking is caused by obstruction of flow channels by clays or other mineral fines dispersed by fresh water.&apos;!" It is well known that increasing salt concentrations in water tends to prevent clay blocking. Also it is well established, although perhaps not as widely known, that the nature of the dissolved solids is also important. If, for instance, formation clays are exposed to calcium chloride solution and then exposed to weaker solutions of calcium chloride or distilled water, considerably less permeability damage results than if the clays had been exposed instead to sodium chloride solutions. The reasons for this behavior are: (1) clays are cation-exchange, or base-exchange, materials similar in this respect to zeolites or exchange resins, and (2) clays in the calcium form do not disperse easily in fresh water, whereas clays in the sodium form do. The base-exchange form of a clay is easily altered by flowing a solution through it. For example, a sodium clay can be changed to a calcium clay simply by passing a calcium chloride solution through the clay bed. There is general agreement that the reason calcium and magnesium clays do not disperse easily in fresh water is because the calcium ions do not ionize easily from the clay surfaces.&apos; Sodium clays, however, are believed to allow the sodium ions to ionize from the clay particle surfaces. In fresh water, this allows the particle to accumulate a net negative electrical charge great enough for the particles to repel one another and, therefore, disperse more easily. The foregoing suggests that, even in the presence of a large excess of sodium, a relatively small ratio of divalent cation, such as calcium or magnesium, might serve to prevent clay dispersion. The divalent ion probably adsorbs to a disproportionately large extent, because of being adsorbed more tightly, with the result that the proportion of divalent cation on the exchange positions of the clay might then be great enough for the clays to resist dispersion. Consequently, an investigation was conducted to find how mixtures of salts in solution influence clay blocking. APPARATUS AND PROCEDURE Water permeability tests were conducted using conventional techniques. The equipment is illustrated schematically in Fig. 1. Flow rates of solutions driven through small core samples at known temperatures and pressures were measured. Regulated compressed air, usually at 10 to 15 psig, was used to drive the solutions. Core samples 0.75 in. in diameter and 1 in. long were used for the most part. Cores were saturated by evacuating and then admitting a de-aerated solution. Tight core samples were first saturated with carbon dioxide gas and then evacuated and saturated with the test solution. After saturation, 140 psig pressure was imposed for several hours. Cores were tested to insure absence of gas saturation by a Boyle&apos;s

Jan 1, 1965

By N. E. Rogen, N. J. Grant

WHILE direct measurements of the growth of precipitate particles during aging is of fundamental value, few such measurements have been made. Direct measurements by means of optical or electron-microscopy and X-ray techniques are preferred, however, many of the aging studies have been based on indirect methods such as electrical resistivity and hardness. Because of the minute size of most precipitate particles (less than 1000A) the light microscope is of limited use while electron microscopy is subject to slowness, etching problems and consequent resolution problems. It is fortunate that alloys of the Nimonic type, based on Ni-Cr-Ti-Al, lend themselves to accurate and relatively easy particle size measurements. With proper balance of titanium and aluminum, the only aging precipitate is the gamma prime (r&apos;) Ni3,(Al, Ti)2 phase and this phase is the basis of the high-temperature strength of these allos.3-6 The Ni3(Al, Ti) phase is a face-centered-cubic, ordered structure with nickel atoms occupying the cube faces. Titanium atoms can replace three out of every five aluminum atoms and when substituting do so preferentially.2 Electron microscopy has shown that during aging of most of the commercial alloys of this type, precipitate particles are unusually uniform in size and distribution, and that the volume of (r&apos;) phase is large (20 pct).4,7 The aim of this investigation was to measure the growth of (y&apos;) phase during aging. In so doing, it was hoped that a clearer understanding of the aging process would be attained. X-ray line broadening was used as the measure of precipitate particle size. This technique was selected because it can measure and average the diameter of thousands of particles in one operation. The variations in hardness and matrix lattice parameter with aging were also studied and related to the particle size. EXPERIMENTAL PROCEDURE An alloy of the following composition was studied: Cr Ti A1 C Ni Wt pct 20.71 2.98 1.43 0.04 bal. At. pct 22.06 3.47 2.95 0.18 bal. The alloy, a 15- lb vacuum melt, was forged to 1/2-in. diam at a temperature of 1900" to 2200°F; was solution heat treated for 4 hr at 2000°F and water quenched; and was then aged in various ways. The ASTM grain size was 4 to 5. No (7&apos;) phase could be detected by X-ray analysis after solution treatment and electrolytic extraction. Aging was performed on 2-in. long specimens at 1400°, 1500°, and 1600°F for increasing times. One-half inch sections were removed after each time increment and were then electropolished in a solution of H3P04 saturated with chromium trioxide at a potential of 30 v and rectified with a tantalum electrode. Rockwell hardness measurements were taken using one side of the polished specimen. Matrix lattice parameter determinations were made on the other side using filtered chromium radiation references with the position of the (220) line of a silicon standard. To enable the precipitate particles of the (y&apos;) phase to be measured using X-ray line broadening techniques, it is first necessary to separate and concentrate this phase by electrolytic extraction. Extraction is necessary because the difference between matrix and precipitate lattice parameters is only approximately 0.5 pct and intensities of.the (y&apos;) phase lines are very weak relative to those of the matrix. The extraction techniques employed have been described before and found to produce a reasonably quantitative separation.398 A water solution of 15 pct H3Po4 is used at a current density of 0.5 amp per sq in. at 6 v. The precipitate particles are separated from the liquor by centrifuging and decanting and are then washed, dried and repowdered. A plot of the X-ray intensity vs diffraction angle for the (111) line of the precipitate particles was used as a measure of particle size. The intensity curve approximated the shape of Gaussian distribution function and its breadth was measured at the half height. The (220) line of a silicon standard was used to correct the measured line breadth for instrumental and other broadening errors. The Scherrer formula was used to calculate particle

Jan 1, 1961

Edward Keller, Baltimore, Md. (communication to the Secretary): When, at the New Pork meeting, February, 1899, Mr. Douglas gave an abstract of his highly interesting paper on the Copper Queen mine, he invited the members of the Institute, in his usual progressive spirit, to make a full scientific investigation of the region of that mine during the prospective excursion to Bisbee, Arizona. I volunteered to examine some of the metallurgical processes and products of the works, and obtained from Mr. Douglas a valuable series of samples. Upon the issue of his paper, however, I found that he had already a considerable volume of analyses of those products, and that little was left for me to do in that respect, except to duplicate his results, the importance of which work would not have been commensurate to the time and labor involved. I selected, therefore, only some points which he had not made entirely clear, or concerning which I was skeptical. The details of most of my work will appear in a future paper. From Mr. Douglas&apos;s figures I have calculated the values for the elimination of impurities in the so-called Leghorn converter, introduced by him at the Copper Queen works, and have found them to be as follows: Percentage of Elimination of Impurities in Pour Blows of a Converter. No of &apos; Selenium Sulph&apos;r Iron. Zinc. I Nickel. Lead. Antimony Arsenic. and Blow- ! Tellurium .. 1.......... 99.4 99.6 88.0 92.6 94.4 81.6 83.8 40.3 2.......... 99.0 99.6 98.1 92.5 96.8 71.9 76.6 38.1 3.......... 98.8 99.5 93.5 91.4 96.3 63.8 80.6 25.3 4.......... 99.8 99.5 95.8 95.8 97.5 65.3 76.9 36.3 Average 99.2 99.6 93.8 93.1 . 96.2 70.6 ! 79.5 35.0

Jan 1, 1900

By T. J. Koppenaal, M. E. Fine

A yield point effect attributed to short-range ordevi?g (SRO) occurs in Cu base Al. At at 296°K varies with heat treatment, decreasing as the annealing ternperature is raised .from 433Oto 598°K. Davies aid Cahn&apos; observed a corresponding decrease in SRO. (523 °K anneal, measured at 77°K) is approximateZy proportional to the variations of A7 with strain rate and testing temperature are also Consistent with the idea that is associated with SRO. A preliminary investigation of the tensile properties of a Cu-Al single crystals showed the presence of a rather strong yield-point effect (drop in flow stress after initial yielding). The object of this research was to investigate its origin and behavior. a Cu-Al alloys are particularly interesting because diffuse X-ray scattering measurements by Davies and Cahn,&apos; Houska and Averbach,&apos; and Borie established the presence of short-range order. The degree of local order may be changed with heat treatment.&apos; cottrel14 suggested that the presence of local order might result in a yield-point effect, and thus the possibility exists here for experimentally ascertaining the importance of short-range order with respect to yield points in these alloys. Since a 12 pct difference exists between the atomic sizes, elastic or Cottrell locking5 must also be considered. Further, Howie and swanne have shown that the stacking fault energy of copper is reduced by aluminum additions. The width of extended dislocations should thereby increase. hus the conditions appear attractive for Suzuki locking.&apos; Finally, the possibility of stress-induced order at dislocations, schoeck locking,&apos; must also be examined, EXPERIMENTAL PROCEDURE Alloys up to 14 at. pct Al were prepared by induction melting high-purity (99.999 pct) Cu and (99.996 pct) Al in a graphite boat under a dynamic vacuum of 5 X 10o mm of Hg. After homogenizing the ingots at 900°C for at least 24 hr under vacuum, they were rolled with intermediate anneals to strips 1.55 mm thick. Single crystals 10 in. long were grown by lowering strips, contained in a split graphite mold sealed in fused quartz at 5 X lo-&apos; mm of Hg, through a single coil induction heater at a constant rate of 1/2 in. per hr. Tensile specimens 1.25 in. long were cut from the single crystal strips and reduced cross sections about 0.7 in. long and 3.0 to 3.5 mm2 in area were introduced by filing and abrading.8 To remove the worked portion about 10 pct of the cross-sectional area was removed by etching. Back-reflection Laue photographs of a filed and etched specimen were taken before and after annealing at 900°c for 24 hr. Small, well defined Laue spots were obtained with no visual difference in the two photographs. Further, specimens with and without the reduced sections began yielding at about the same stress. Hence, for our purposes, filing and abrading did not affect the structure of the specimens. Each single crystal specimen was annealed at 900° c in vacuum for at least 24 hr and furnace cooled; while cooling through the range of 250o to 200°c, the rate was about 55°C per hr. Orientations were determined by the usual back-reflection Laue

Jan 1, 1962

By T. E. Leontis

ONLY a limited amount of information has been published on the effect of thorium as an alloying ingredient in magnesium. McDonald13&apos;2 showed that the addition of thorium in amounts up to 3 pct increases significantly both the ductility and the strength of rolled magnesium sheet. A recent publication by Sauerwald" indicates that thorium contributes strength and creep resistance at elevated temperatures to magnesium in both the cast and wrought states. The observations of Sauerwald are confirmed in this paper, which presents the results of a systematic study of the effects of compositional variation on the tensile properties, creep resistance, conductivity, density, and metallography of Mg-Th alloys containing up to 50 pct Th both in the sand-cast and in the extruded states. The effect of the addition of cerium to Mg-Th alloys is also reported. Experimental Methods The alloys studied in this investigation were pre.pared in small laboratory melts according to the melting practice described by Nelson4 as the crucible method. Electrolytic magnesium was used as the starting material to which the thorium* was introduced in metallic form. It was observed that the behavior of thorium in molten magnesium with respect to reaction with protective fluxes is similar to that of rare-earth metals. In order to obtain the highest possible alloying efficiency, it is necessary to use non-MgC1, fluxes and to apply all the precautions described by Marande6 for melting, alloying, and casting magnesium-rare-earth alloys. .Under these conditions it is possible to obtain an alloying efficiency in the range of 85 to 95 pct. The Mg-Th-Ce alloys were made with cerium of the highest purity available, not with the commercial product "misch-metal" which contains approximately 50 pct Ce. The total rare-earth content of this material was 97.1 pct, of which 0.3 pct was rare-earth metals other than cerium; the major impurities comprising the balance were iron and magnesium. The thorium and cerium contents of each alloy were determined chemically. Test bars 6% in. long with a 2% in. long reduced section of % in. diam were cast in sand molds using a four-baf pattern. In most cases, a 3 in. diam extrusion billet 10 in. long was cast in a steel mold from the same melt used for making the sand-cast test bars. For the higher thorium alloys, it was necessary to remelt the foundry scrap from the test bars in order to make the extrusion billets. The billets were scalped to a diameter of 2 15/16 in. and the ends faced to a length of 9% in. as limited by the size of the extrusion container. The alloys were extruded into % in. diam rod on a 500-ton direct-extrusion press. The details of the extrusion process are as follows: Billet preheat 925°F (2 to 16 hr) Container temperature 900 °F Die temperature 900°F Extrusion speed 10 ft per min Reduction ratio 36:1 Percent reduction 97.3 Alloys containing up to 10.2 pct Th were preheated at 925°F for 2 hr; all alloys with higher thorium contents were preheated for 16 hr. In order to establish the effect of extrusion temperature, billets of

Jan 1, 1953

By J. R. Hornaday, A. E. Morris, N. A. Parlee, D. C. Carmichael

Rates of absorption and effusion of hydrogen in solid iron were measurede by a Sieverts type of apparatus. With clean a iron these rates are diffusion controlled down to 420°C and are represented by the equation D = 6.70 x e-&apos;100&apos; crn2 sec-I Certain surface impurities can affect these rates at all temper-atuves. Thin oxide films lower, the apparent diffusivity of annealed iron markedly. Cold-worked iron (75 pct) annealed at 430°C has practically the same solubility and diffusivity as anealed iron. THE mechanism of absorption and evolution of hydrogen in solid iron alloys is not fully understood despite the large number of investigations on the subject. While there appear to be many instances of simple solid-state diffusion control of rate, there are many cases where investigators have either concluded that surface reactions are rate controlling or that some "nondiffusible" hydrogen resides in discontinuities. The purposes of this research were 1) to develop a sound method for studying this absorption and evolution behavior, 2) to examine it in pure annealed iron, and 3) to determine the effects of important variables, such as cold work, surface condition, and composition. This paper relates the progress toward these objectives. Much of the present knowledge of the movement of hydrogen through iron alloys comes from permeability studies which involve the measurement of the rate of passage (under steady state conditions) through membranes of the order of 1 mm in thickness. This method is open to question on various grounds. If surface reactions are involved, two different surfaces operating under two different conditions must be considered. The presence of defects in the membrane even of microscopic dimensions may lead to erroneous results. A few people have studied evolution of hydrogen into vacuum, under carefully controlled (unsteady state) conditions, and some of the best diffusivity data come from these sources. Most of these methods measure rates of evolution only and thus do not make a rigorous test for reversibility of behavior. It appeared that an "unsteady state" method that would permit the measurement of both rates of evolution and absorption under controlled temperature, pressure, and other conditions would offer several advantages. Accordingly the modified Sieverts apparatus described below was designed and built. APPARATUS This apparatus is shown in Fig. 1. The sample bulb is detailed in Fig. 2. Hydrogen of 99.5 pct purity and argon of 99.99 pct purity were used. The hydrogen was deoxidized and dried by means of a Deoxo unit followed by a "Dri-erite" tower. The argon was only dried. The gas burette was graduated in tenths of a cubic centimeter, and, with the aid of a travelling magnifier, readings could be estimated to the nearest 0.01 cc. The level of mercury in the burette was adjusted by means of a leveling bulb operated by a fine screw adjustment. An electrical system, consisting of two slightly separated platinum electrodes inserted in one leg of the manometer and a small light bulb was used to obtain rapid accurate adjustment of the pressure. The capillary tubing of the Vycor sample bulb was 3 mm bore as was all tubing back to the gas burette. The samples were discs made from vacuum-melted Ferrovac-E iron of greater than

Jan 1, 1961

By F. E. Jaumot, A. Sawatzky

IT as long been recognized that there is a need for accurate systematic data on diffusion in solids. Originally, such data were needed to check existing theories but, more recently, it would appear that it could be used most advantageously as a guide to, or a check for, much needed extensions of the theory of diffusion. The awareness of the conditions which are important to experimental accuracy, the availability of the materials for accurate experiments, and the techniques have improved to the extent that it would now seem to an experimentalist that, unless extensions of the theory are made which take into account the fundamental parameters of the atoms, the electrons, and the lattice in some detail, the field of diffusion will rapidly become an empirical or semi-empirical field. The present series of experiments was designed to provide accurate data on the diffusion of the elements of the IB and IIB subgroups in silver; that is, to provide data on the diffusion in silver of three face-centered-cubic elements with roughly similar chemical properties, but with different atomic or ionic sizes and, similarly, for three noncubic elements. The elements of these two subgroups have different valences, so that the data will not give any significant information on differences due to the crystal structure of the solute. The present paper reports data on the diffusion of copper and mercury in single crystals of silver; the data for the other elements of the IB and IIB subgroups were reported previously by the authors1&apos;2 and by Tomizuka and Slifkin.8 Experiment The general technique used was identical to that previously described1,2 and will not be repeated here. In all cases, the sectioning technique and high specific activity isotopes" were used. The short half-life of Cu64 made decay corrections more important than for the other isotopes, and necessitated around the clock shifts while data were being taken. Each section was counted at least twice (as was true for all longer half-life isotopes) and a monitor was counted along with each sample. Data for the diffusion of mercury in silver are presented at a greater number of temperatures than for the other solutes. This is a result of two circumstances. First, six (of 30) samples had to be discarded because of pitting or recrystallization which occurred during the diffusion runs, even though the samples had sustained high temperature prediffusion anneals. Either of these was a very rare phenomenon in the other experiments, and their occurrence in this case is considered in more detail below. Second, the curves of the logarithm of the activity of the sections vs the square of the penetration deptht were, in general, quite good, but frequently seemed to show one point to have high activity and the next point to have slightly low activity in terms of the best straight line. When this occurred, there was remarkable regularity of the high-low sequence. In any event, the results, as far as diffusion coefficients are concerned, were not affected by this amalgam effect. In fact, the mercury data had the highest internal consistency of any of the data. Results Diffusion of Copper in Silver—-Diffusion runs were made at eight temperatures In the temperature range from 700° to 950°C, for times ranging from 5 to 45 hr. A linear curve of the logarithm or the activity vs the square of the penetration depth was obtained for all samples. Table I summarizes the results for individual samples and Fig. 1 gives a plot 02 the logarithm of the diffusion coefficients as

Jan 1, 1958

By A. E. Dwight, A. F. Berndt

ThE published U-Ru equilibrium diagram indicates the existence of six intermetallic compounds in this system.&apos; The structure of only two of the compounds, u2Ru2,3 and URU3,4 have been identified. This communication reports on the crystal structure and density of Uau3, which is formed by a peritectoid transformation at 1025° ± 5°C: U3Ru4 + U3Ru5 = U2Ru3. An alloy with the stoichiometric formula U2Ru3 was prepared by arc melting electrolytic uranium and ruthenium of 99.9 pct purity on a water-cooled copper hearth under an argon atmosphere. After homo-genization at 1000°C for 3 days, a metallographic examination revealed that the peritectoid transformation was complete and less than 5 pct of a second phase was present. A powdered sample, obtained by crushing the brittle compound, was annealed for 1 hr at 1000°C and air-cooled. Debye-Scherrer patterns were obtained with filtered CrKa, FeKa, CoKa, or CuKa radiation. The X-ray patterns of U2Ru3 weFe indexed as an fcc structure with a. = 12.895 0.00lA. The unit-cell constant and its standard deviation were calculated by a computer program described by Mueller, Heaton, and Miller.5 The density, measured by an immersion method, was 14.45 g cm-3. A calculated density of 14.48 g cm-3 was obtained on the assumption that twenty-four formula units (120 atoms) comprise a unit cell. The space group is either oh7 Fd3m, or the less symmetric, T4h, Fd3, since reflections indexed as hk0 with h + k + 4n are absent. All values of h2 + k2 + 12 permitted by both space groups are listed in Table I together with dc, do, and I. values. The calculated d spacings were obtained by the computer program of Mueller, Meyer, and simonsen.6 The observed d spacings above 0.77A were obtained from X-ray" patterns prepared with CuKa radiation, above 0.90A with CoKa radiaaion, above 0.98A with FeKa radiation, and above 1.16A with CrKa radiation. An attempt was made to identify the crystal structure of U2Ru3 by comparison with published data on other A2B3 compounds. A recent compilation7 of intermetallic compounds lists thirty-two structure types with the A2B3 stoichiometry. Only two of the structure types are fcc and they are Sb2O3(r), senarmontite, with 16 Sb2O3 per unit cell, and In2Te3 for which several structures have been proposed.8 However, the two cases cited do not have twenty-four formula units in the unit cell. We therefore, cannot identify UPRU3 with any of the other known A2B3 compounds. Ternary alloys were made in which 5 at. pct Os, Rh, or A1 were substituted for 5 pct of the Ru in U2Ru3. The osmium substitution increased the unit cell constant to 12.899 * .001A, which is to be expected since the atomic volume of osmium is slightly larger than

Jan 1, 1969

By G. W. Nabor, A. S. Odeh

The effect of production history of a well on the results of two-rate flow tests, and conventional build-up analyses was investigated. The effect was examined by means of digital computers and an R-C network model, respectively, for wells with infinite and finite radii of drainage. For systems which behave as infinite, it was found that production history and the duration of production at constant rate prior to the initiation of the test have important effects on the results. During build-up time equal to about one-fourth of the stabilized time, correct permeability-thickness product calculations can be made. For wells with finite radii of drainage, the time was determined during which the straight line can be satisfactorily used for permeability-thickness product calculations in case of drawdowns and build-ups. On build-ups, the dimensionless time (based on the external radius) during which the straight line gives reliable results was detertriined to be about 1/12. This is one-fourth as long as that of the drawdown. The investigation was done theoretically, and subsequently was verified by R-C network model runs. General interpretive rules were formulated which, if not followed, could lead to serious errors. Moreover, a recommended testing procedure is reported. INTRODUCTION The method used by most reservoir engineers for estimating formation characteristics in a producing well is the analysis of pressure build-up data. The method originally devised by Horner&apos; makes use of the point source solution to the diffusion equation. This solution is approximated by a logarithmic function and the superposition principle is employed to arrive at the well known pressure build-up equation:where q, the flow rate, is in reservoir B/D; ft is in cp; kh is in md-ft; At is the shut-in time; and t is the producing time. At and t are in any consistent time units. Ey. 1 is applicable to a well of unlimited drainage radius which produces at a constant rate q from zero to time t and is then shut in. Such a constant production rate seldom obtains in practice. Therefore. a correction term must be applied to Eq. I to account for the varying rate. Two theoretically accurate methods are available for treating the variable rate case. The first, originally derived by Horner,&apos; is based on the application of the superposition theorem. It requires knowlege of production history of the well as a function of time and results in lengthy and laborious calculations. The second t*q* niethod is suited for short production tests and requires that the shut-in time be at least one and one-half times the production time. A third method which is not based on any theoretical justification and which was suggested by Horner as a "good working approximation" is the one used by the majority of reservoir analysts. especially when the well has been producing for a long time and the t*q* method is not practicable. The key to this method is in choosing or determining the t that appears in Eq. 1. Horner suggested using a corrected time t, in place of t. t, is calculated by dividing the total cumulative production by the last established rate. Therefore, a normal procedure of pressure build-up testing is to stabilize the well at a constant rate for at least 24 hours before shut in and to use the stabilized rate to calculate t,. The analysis is then made by plotting either or P. and examining the resulting plot for the expected straight line to calculate kh and the original reservoir pressure. Recently, Russell" proposed a method for determining formation characteristics from two-rate flow tests. His method reduces to pressure build-up if the second flow rate is zero. Russell uses the Horner simplified procedure for calculating a corrected t,. His method also requires the stabilization of the well at a constant rate q which is used to calculate t,. Theoretically, the above procedure is valid for a well with an unlimited radius of drainage or with a limited radius as long as the boundary effect has not been felt by the well. Several authors&apos;&apos; derived formulas which allow the estimation of time during which limited reservoirs behave as infinite ones and, thus, can be treated by unsteady-state mechanics. One equation derived by Swift and Kiel&apos; terminates the application of unsteady-state theory when the drainage radius reaches one-half the reservoir radius. Thereafter, steady-state behavior obtains. Another equation derived by Jones&apos;" initiates steady-state

Jan 1, 1967