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By J. W. Downey, A. E. Dwight, M. H. Mueller, H. Knott, R. A. Conner

Sixty new ternary equiatomic compounds are reported with a hexagonal crystal structure that is isostructural with or very similar to Fe2P, D3h-P62m. HoNiAl is a typical example, with a, = 6.9893 ± 0.0003Å, C, = 3.8204 ± 0.003Å, and c/a = 0.54 7. Three holmium atoms occupy (g): x,0,1/2 three aluminum atoms occupy (f): x,0,0; one nickel atom occupies (b): 0,0,1/2; and two nickel atoms occupy (c): 4, + , 0. The nonequivalent 1(b) and 2(c) sites give rise to two sets of unequal interatornic distances (i.e., Ho-Ni and Al-NL in the case above), which account for the prevalence of Fe2P-type tertmry compounds and the scarcity of binary examples. Unit-cell constants are presented for the sixty compounds and density measurements on the compounds HoNiAl and UFeGa confirm that three formula weights are present per unit cell. Neutron and X-ray powder diffraction intensity measurements were made on CeNiAl and HoNiAl, respectively. The atomic posiLiotml parameters in CeNiAl were determined from neutron data to be x = 0.580 5 0.001 for cerium and 0.219 5 0.001 for aluminum. An investigation of the quasibinary section between the binary compounds CeNi2 and CeA12 revealed a new ternary compound CeNiAl. The compound has a hexagonal structure and is isostructural with the prototype compound Fe2P. Additional examples discovered or confirmed in this investigation provide a total of sixty ternary compounds that are isostructural with or closely related to Fe2P. Previous investigators1'2 reported the unit-cell constants for the hexagonal compounds UFeA1, UCoAl, UIrA1, ZrNiAl, ZrNiGa, HfNiAl, and HfNiGa and the present investigation has confirmed that the compounds are isostructural with Fe2P. Independently, Steeb and petzow3 reported the same structure type for UCoAl, UIrA1, and UNiA1. However, the present results suggest a different atomic site occupancy for the component atoms in the three compounds. A detailed investigation of the relative positions of the three kinds of atoms in the compounds CeNiAl and HoNiAl will be discussed. EXPERIMENTAL PROCEDURE The equiatomic alloys were prepared from elements of 99.9+ pct purity by arc melting under a helium-argon atmosphere. After homogenization at temperatures from 700" to 900' C, a metallographic examination was performed by conventional methods, and density measurements were carried out by the immersion method in CCl4. A powder sample was prepared for diffraction studies by crushing a portion of the annealed button. X-ray diffraction patterns were obtained with a Debye-Scherrer camera, in which the annealed powder was glued to a quartz filament, and indexed with the aid of a Bunn chart. Unit-cell constants were calculated from the computer program of Mueller, Heaton, and Miller4 and d spacings were obtained by the program of Mueller, Meyer, and Simonsen.5 The intensity values were calculated from the relation I, ~ (m)(L.P.)F2 by a computer program written by Busing, Martin, and Levy.6 The absorption and temperature correction factors were neglected. An X-ray study of HoNiAl was carried out to take advantage of: large differences in atomic scattering factors for holmium and aluminum, X-ray patters free of background darkening, negligible oxidation at room temperature, and negligible weight loss in the preparation of this alloy. The neutron diffraction studies were made on a powder sample of CeNiAl contained in a -in. diam V tube and a pattern was obtained with neutrons of wavelength The neutron scattering factors employed (x 10-12 cm). In contrast to the scattering amplitude for X-rays, cesium does not have the largest cross section, however, there is a sufficient difference in the neutron scattering amplitudes to distinguish between the atomic species. The neutron transmission was high, 86 pct; therefore, absorption corrections were not necessary for the cylindrical sample. Most reflections could not be observed individually, because of the relatively large unit cell (a = 6.9756 and c = 4.0206Å) and relatively short neutron wavelength; therefore, the intensity of grouped reflections was considered. The Kennicott modification7 of the Busing-Martin-Levy program6 was employed to determine the identity of the atoms at the various lattice sites and the positional parameters. RESULTS A structure for the prototype compound Fe2P was first reported by Hendricks and Kosting;8 however, the structure was in error. The correct structure, as reported by Rundqvist and Jellinek,9 is as follows. The unit-cell constants and volumes per formula weight (V/M) are given in Table I for the sixty compounds examined in this investigation and classified as Fe2P-type compounds. The structure type was determined initially from a comparison of the unit-cell constants of HoNiAl with other known examples of this structure type1' and from the density of HoNiAl, given in Table 11. The density indicated that three formula weights comprised a unit cell, as in the prototype compound Fe2P. The assignment of the three species to lattice sites was made initially on the basis of atomic size. The large holmium atoms were assigned to the 3(g) sites that have a relatively large interatomic distance to nearest neighbor positions, the small nickel

Jan 1, 1969

By W. F. Stowasser

downdraft traveling grate process to agglomerate pelletized iron ore concentrates has been successfully demonstrated in a pilot plant at Carrollville, Wis. Work there followed several years of development in the Allis-Chalmers Mfg. Co. laboratories, and the pilot plant phase was carried out in cooperation with Arthur G. McKee & Co., consultants and engineers to the iron and steel industry. End result of the process is conversion of iron ore concentrates into a form which can easily be transported and smelted in the blast furnace. Process Description The first of two process steps incorporates the art of balling and prepares the concentrates for burning. The second step consists of burning the green balls on the grate machine to the hardness required for shipping and handling purposes and for reduction in blast furnaces, see Fig. 1. Facilities are provided at the pilot plant to receive carload quantities of concentrate. The concentrates are loaded into a 50-ton bin direct from railroad cars. Because of the variable moisture content of the concentrates after shipment in an open railroad car it is necessary to repulp and refilter the concentrates to maintain a uniform and proper moisture content for the balling operation. Concentrates are conveyed to slurry tanks, and the slurry, at 50 to 60 pct solids, is pumped to a 4x4-ft drum filter. The filter provides feed of uniform moisture to the plant. Magnetite concentrates are normally filtered to produce a cake containing about 10 pct moisture, a necessary requirement for the following balling operation. The filtered concentrate is conveyed to a rotary bin table feeder which acts as a surge bin for the filter cake and delivers a steady flow of concentrates to the balling drum. It is often desirable to make additions to the concentrates as they are fed to the balling drum. These additives, such as bentonite, increase the strength of the finished green pellet and improve ballability of the concentrate. A vibrating feeder supplies additive to the feed belt, and the additive is mixed with the concentrate in the balling drum. The balling drum, shown in Fig. 3, is 8x3-ft diam. An oscillating cutting bar maintains the lining in the drum by trimming off the buildup of excess concentrate as it forms. The drum is operated in closed circuit with a lx4-ft rod-deck vibrating screen. Undersize pellets or seed pellets from the screen are returned to the balling drum until they grow to the desired size. Size of pellets is controlled by the opening in the screen deck. The formation of pellets in the balling drum is affected by many variables. Some of these are: the size distribution of the feed, the particle shape of the concentrate, the feed rate to the drum, the moisture in the concentrate, the speed of rotation of the drum, the slope of the drum, and the type of trimming obtained with the cutting bar. In this process, attempts are made to control the pellet size within the limits of % to 5/8 in. diam. The screened oversize pellets are conveyed under a coal feeder where sufficient powdered coal is added to the belt to produce desired results in the burning process. The top size of the coal successfully used has been 20 mesh, and anthracite was used in the test program. Fig. 4 illustrates the vibrating screen and the coal feeder. The pellets and free coal are conveyed together to the 5x3-ft diam- reroll drum that rolls the coal onto the surface of the pellets. This drum is also equipped with a cutting bar. The prepared pellets, containing bentonite, water, and surface coal, are elevated to the traveling grate, which consists of a continuous strand of 37 pallets. Each pallet, with a grate bar area 2 ft wide by 1 1/2 ft long, has 14-in. high side plates, Fig. 5. Feeding and distribution of the green balls to the grate is handled by a short conveyor which oscillates back and forth across the 2-ft width of the grate. An adjustable vertical plate located several inches in front of the head pulley of the oscillating conveyor controls the height of the bed and levels the moving bed of pellets. This method of feeding prevents segregation of various size pellets as well as fines and produces a uniform, permeable bed. The pallet train moves under the furnace and across four windboxes, located beneath the pallet frames, see Fig. 2. As the green pellets are deposited on the grate, partial drying of the pellets begins over a 2-ft long updraft windbox. The low temperature air reduces the moisture in the pellets in the lower level of the bed and this operation is essential to prevent sagging of the bed during later stages of the Process. The air used for this drying is recuperated from cooling the pellets on the grate, and supplemental heat, required for starting the Process, is obtained from an auxiliary burner. The pellets are then moved by the grate into the furnace and over an 8-ft windbox, designated as the downdraft waste windbox. Products of combustion are exhausted from this windbox to atmosphere. The furnace, shown in Fig. 6, is constructed with three chambers to provide downdraft drying, preheating, and ignition, respectively, to the pellet bed as it passes through. Overall length of the furnace is 5.57 ft; however, the exterior wall ends may be moved to reduce the length and also adjusted to Obtain the bed height desired, The drying, preheating, and ignition sections of the furnace are supplied with medium temperature

Jan 1, 1956

By D. T. Van Zandt

IN the late 1920's rotary drills began to replace the churn drills in the petroleum industry, but until the middle 1940's the churn drill was the only widely accepted means of drilling large-diameter blastholes for quarry operations. The Calcite plant of the Michigan Limestone Div., U. S. Steel Corp., was one of the first to experiment with rotary drills for quarry blasthole drilling, and the first to employ compressed air on a fully rotary rig to cool the bit and raise the cuttings to the collar of the blasthole. The Calcite plant operates a limestone quarry near Rogers City, Mich., in the northern part of the lower Michigan peninsula. The formation quarried, a portion of the middle Devonian series, is the Dundee limestone, which is uniform, seldom massive, and characterized by definite bedding planes. The dip is southeast, 40 ft to the mile. Quarry faces vary from 20 to 116 ft in height. Vertical blastholes are used entirely, from three to five rows of holes being drilled parallel to the working face, spaced 18 ft apart with 18-ft burden and drilled 6 to 8 ft below shovel grade. Quarry operations coincide with the navigation season on the Great Lakes, as the bulk of the stone is transported by lake carrier. The normal operating season runs from April to December, the remaining time being devoted to stripping operations and plant and equipment maintenance. In the followirig discussion drilling rates mentioned refer to overall drilling time and include all operations such as moving from hole to hole, penetration and extraction of tools, and routine maintenance. Time consumed by such factors as power delays and major machine repair is not included in drilling time unless otherwise stated. Figures cover only operations at this one plant in the formation mentioned. Needless to say, a very different set of figures could be obtained in a different formation. However, the comparison of footage obtained with churn drills and rotary rigs in this particular formation has been used as an indication of what might be the expected performance of rotary rigs in other formations. Prior to 1950 the bulk of the blasthole drilling at the Calcite plant was done by electrically powered churn drills. Both crawler and wheel-mounted rigs were used. These machines, which mounted a 22-ft drill stem of 4½ in. diam and a spudding type of bit 2 to 4 ft long, drilled a hole of 5 ?-in. diam. Average drilling rate of these rigs in the Rogers City formation was 8 % ft per hr. In 1946 one of the first rotary blasthole drills offered to the quarry industry was put into use on an experimental basis. This machine, known as the Sullivan Model 56 blasthole drill, Fig. 1, was on 16-in. crawler pads and electrically powered at 440 v. The drill bit, a Hughes Tri-Cone roller bit of 5?-in. diam, Type OSC, was threaded into the end of the 4-in. square hollow drill rod or stem. These drill rods were 20 ft long with female threads on one end and male on the other to allow for addition of the desired number of rods for drilling holes of various depth. Rods were handled by a single drum hoist geared to the main drive motor and racked by a 30-ft derrick or mast when not in use. The cable from the hoist drum fed through a crown block on the top of the derrick back to the water swivel mounted in the top end of the drill stem in use. This cable remained attached during drilling operations and was used to hoist the tool string from the hole. Down pressure was applied to the tool string by means of a pair of 4-in. diam hydraulic cylinders acting on the drill chuck holding the drill rod. The first chuck consisted of flat jaws which gripped the flat sides of the stem. These jaws were controlled by set screws forcing them into contact with the drill stem. As these set screws had to be loosened and tightened by hand with each stroke of the hydraulic feed cylinders, there was great delay. For this reason the semi-automatic chuck was developed which automatically gripped the stem on the downward stroke but released for retraction of the hydraulic feed cylinders. Rotation was imparted to the tool string by a rotary table acting on the chuck and geared to the main drive motor through a separate gear train and clutch. A positive displacement water pump, mounted on the drill, fed water through a system of pipes and hose into the water swivel mounted on the top of the drill rod and through the rod and bit, washing the drill cuttings to the collar of the hole. Where water was scarce, provision was made to settle out the cuttings coming from the collar of the hole and re-use the water. Where water was abundant the stream coming from the hole was wasted. Drilling rate with this machine was about 20 ft per hr and bit life 1600 ft of hole. While this rate was more than twice that obtained with the churn drills employed, the problem of water supply and drill cuttings disposal rendered the machine impractical from an operating standpoint. Consequently it was used only in that part of the operation for which water was easily supplied, when the character of the formation made it least difficult to wash cuttings away from the collar of the hole. In October 1949 it was suggested that drill cuttings be removed by compressed air, long used for this purpose on pneumatic drills, and collected at the collar by suction. Thereafter, the water pump on the Sullivan 56 was replaced by a 500-cfm air compressor and a trial run made. Air pressure at

Jan 1, 1955

"The Washoe Smelter is situated about two miles east of the City of Anaconda. The smelter site includes about 240 acres and peculiarly adapts itself in topography to the efficient handling of material. By reason of its being on a hill side it is possible to make the level of delivery of the product of one building the level of the charge floor of the next succeeding one.THE ORES: The ore treated comes principally from the Butte district and is hauled by the Butte, Anaconda & Pacific railway, a distance of twenty-eight miles, in trains of fifty 50-ton bottom-dump cars to the railroad yards at East Anaconda. At this point these trains are• split up according to their destination,—that is, as to whether they go to the concentrator and sampling mill ore bins, or to the storage bins. In each case they are made up into trains of eight or sixteen cars, according to the size of engine to be used, and are carefully weighed before delivery to their respective bills.Some idea of the magnitude of the works may be obtained from the following figures:Amount of ore that can be treated in 24 hours…12,000 tonsLime rock from adjacent quarries…2,300 tonsCoke used…500 tonsCoal for reverberatory use…500 tonsCoal for power use…50 tonsWater, per minute, 35,000 gallons.Men employed in and around Anaconda, 3,000. Monthly payroll for above, $300,000.00."

Jan 1, 1913

By Chas. H. Behre

MINING geology, both theoretical and practical, continued to make noteworthy progress during 1938. Mining companies generally, stimulated especially by the improvement in economic conditions during the latter part of the year, extended their workings and developed new ore bodies. Federal and state surveys expanded their search for favorable localities and actual ore bodies, with corresponding enlargement of regional knowledge. Theoretical investigations covered geochemistry of ore deposition, structural control of mineralization, and mineralogy of the ores (chiefly aided by the microscope). More geochemical work is greatly needed: ore searching is still too purely empirical, based on features that have been recognized else- where. Thus, clearer understanding of the conditions essential to transportation of metal salts is needed. Jean Verhogen has suggested that solubilities

Jan 1, 1939

By Sherwin F. Kelly

MANY baffling problems of crustal geology-of warping and folding, elevation, subsidence, and great dislocations of the earth's surface-may now be on the verge of yielding to the science of geophysics. Electric, magnetic, gravitational, geothermal, and seismic methods are being turned to the gathering of geological evidence buried by deep layers of rock, or lying beneath the waters of the oceans. In this hope, B. L. Miller expresses the opinion that these geophysical studies will sup- ply useful data bearing-on some of the more theoretical problems of North American geology. Among these for example, is the explanation of how Appalachia disappeared. This ancient land mass is supposed to have foundered beneath the Atlantic Ocean after the close of the Paleozoic era and the question arises, was it warped or faulted downward? The geophysical data, though meagre, indicate that the surface of the dense, basal rocks, the probable remnant of ancient Appalachia now underlying the Continental Shelf, slopes downwards to a depth of some two miles below sea level at a distance of 140 mi. from shore: thus suggesting that the subsidence was the result of warping downward rather than abrupt faulting.

Jan 1, 1938

President H. M. Howe, Boston, Mass. (communication to the Secretary): Le Chatelier's pyrometer is certainly a most convenient and accurate instrument for the laboratory, and one that may be used under some conditions in the mill. I have used it for several years and with great satisfaction. Like Prof. Roberts-Austen and unlike Herr Blass, I have always found that its indications remain constant over long periods. Like Prof. Roberts-Austen, also, I find it possible, in a quiet place, to read with extreme accuracy ; and, by the use of a telescope, I can read temperatures to within a degree, for some delicate determinations which I have in hand. Variations in the temperature of the room affect the readings of the instrument far less than one would expect. When the current is cut off, the mirror does not always return exactly to the same place; in other words, the zero shifts appreciably, and must be determined often, indeed every few hours if accuracy be desired. In some cases I have had it determined within a very few minutes of every important reading. To this end a switch should he introduced, so that the circuit may be broken readily. With this arrangement we can determine accurately the position of the zero within a very few seconds of the time of taking any especially important reading. The chief causes of the variation of the zero which I have noticed are as follows: a. The suspension may not be tight enough, so that the momentum of the galvanometer frame as it swings makes its supporting wires slip in their bearings. b. Changes in the position of neighboring iron objects may deflect the mirror. c. Changes in the temperature of the room may, perhaps, change the torsion of the suspension wires, and so shift the mirror. d. Dust may attach itself to the galvanometer frame, and by friction against the surrounding fixed parts of the galvanometer, may

Jan 1, 1895

By George F. Kunz

THE recently discovered occurrence of diamonds near Murfreesboro, Pike county, Ark., was brought to. our attention by Mr. Samuel W. Reyburn (Trustee for Messrs. C. S. Stifft, A. D. Cohn, August Zinsser, Jr., and himself, owners of the property), through whose courtesy we investigated the locality of the deposit. Prospecting with the diamond-drill is now in active progress ; but mining operations on a large scale have not yet been ordered. Geology.-The geology as well as the petrography of this interesting locality has been well described by Messrs. J. C. Branner and R. N. Brackett.1 Briefly summarized, the igneous rock in which the diamonds are found is a vitreous peridotite, forming a stock or volcanic neck, which has broken up through the Carboniferous and Cretaceous quartzites and sandstones. After an extensive period of erosion, during which an unknown portion of the neck and presumably a previously existent volcanic cone have been removed, the surface was covered with thin beds of Post-Tertiary conglomerate. The volcanic intrusion was accompanied by the formation of several small dikes of a rock much like that of the main body. One of these dikes cuts across the stock, while another cuts the Cretaceous sandstone, but is overlain by the conglomerate, thus giving a datum for the period of intrusion. So far as known, there was little, if any, metamorphism of the country-rock by the igneous magna, which probably followed an approximately vertical course, so that a more or less vertical extension downward of the igneous body to indefinite depths may be expected.

Mar 1, 1908

By W. M. Ross

AMONG the comparatively few A radical changes in mining equipment in recent years is the introduction and use to an ever greater degree of detachable bits for rock drills. Just how great the possible field for economic application of this innovation is, and to what ex- tent detachable bits are used instead of the conventional type of drill steel, are matters of conjecture. Just as a rough approximation, one might conceive that at least three-quarters of the drilling done in mines today could better be performed by steel with detachable bits, instead of only about one-quarter as at present.

Jan 1, 1939

Elected Died 1895 *ABBOTT, AI ATTHUR 1908 1882 *ABBOTT, ARTHUR V 1906 1905 * ABE, MASAYOSHI 1909 1903 * ADAMS, CHARLES C. 1905 1906 * ADAMS, JOHN C. 1913 1905 * ADAMS, WILLAMS 1909 1903 * ADAMS, W. EDWARDS 1910 1884 *ADDY, MATTHEW 1896 1906 * AFFLECK, WILLIAM A. 1911 1889 * AKERS, WILLIAMS A. 1906 1905 * ALABASTER, RUPPERT C. 1911 1899 * ALBERGER, LOUIS R. 1911 1894 *ALLEN R B 1896 1905 * ALLEN, R. SCOTT 1906 1874 * AMIOT, H. 1892 1886 *AMSLER, CARL 1894 1898 ** ANDRSON, JOHN W 1905 1895 *ÅNGSTROM, CARL 1901 1887 * ARCHBALD, JAMES 1910 1900 * ARLETT, GEORGE H 1906 1895 *ARMSTRONG, JOHN F 1898 1882 *ARNOLDS, HUGO 1886 1875 *ASHBURNER, CHARLES A 1889 1872 *ASIIBURNER, WILLIAM 1887 1883 *ATKINS, C M , JR 1885

Jan 1, 1917

By Augustus Locke

WHY should I, a geologist, be coming before you to talk about finding ore? Certainly, the great discoveries of the past have not been made by geologists, but by men of very different tastes and training. If, in the year 1800, the course of ore discovery could have been foreseen, there would have been no reason to put it into the hands of geologists or other men of technical preparation. It was not geologists but explorers, Indian fighters, prospectors, manual laborers, and hardy financiers, who initiated the American mining industry. Then why this association of geological technique with ore finding? Why this feeling that the way to find ore is to apply to the problem what we call geo- logical principles? Well, to put it broadly, the old method has run out on us. It no longer works. Or, to put it another way, the cost of finding ore by the old method has mounted so high that one old district after another has become, practically speaking, dead, and various other old districts that are still going apparently at full strength are actually beginning to limp, and, with the cost of discovery mounting yearly, to fear, more than they will acknowledge, that the end is approaching.

Jan 1, 1926

By E. T. Turkdogan, L. S. Darken

Calcium ferrite melts were equilibrated with sulfur and oxygen-bearing gases at temperatures within the range 1290°C to 1620°C. The results show that at oxygen partial pressures below 10-4 atm the sulfide-reaction occurs and at higher oxygen pressures the sulfur dissolves in the melt principally as sulfate ion. It is also observed that when the product increases, sulfate ions are converted to pyrosulfate ions and the results permit the evaluation of the pyrosulfate/sulfate ratio. It is shown that the ratio y CaSO,/rCaO increases with decreasing concentration of calcium oxide in calcium ferrite, silicate and aluminate melts. Indications are that oxy-acids, e.g. silica, alumina and ferric oxide, increase yCaS0,. A few experiments were carried out within the sul-tide range and the results are in accord with those obtained by other investigators on aluminate and silicate melts. BECAUSE of the industrial importance and theoretical interest, many investigators have studied the reactions between molten oxides, silicates or alumi-nates, and gases containing oxygen and sulfur. The early work reviewed by Schenckl and studies made by Bardenheuer and Geller2 indicates that solution of gaseous sulfur in an oxide melt resulted in the replacement of the oxide ions by the sulfide ions. Measurements made by Grant and Chipman3 on the equilibrium partition of sulfur between molten iron and complex silicate melts also demonstrated that, for a given temperature and silicate composition, the distribution of sulfur between slag and metal increased with decreasing oxygen content of the metal. Fincham and Richardson4 studied the effects of temperature and partial pressures of sulfur and oxygen on the solubility of sulfur in simple silicate and alumino-silicate melts. They observed that at oxygen partial pressures below about 10-5 atm sulfur in the gas dissolved in the melt as sulfide ions, replacing an equal number of oxide ions of the melt. At oxygen partial pressures higher than 10-3 atm, sulfur entered the melt as sulfate ions. Similar studies were made by St. Pierre and Chipman5 using calcium ferrite and calcium silico-ferrite melts. The experimental data presented in this paper were obtained in this Laboratory about 10 years ago; this is the first formal presentation although a preliminary report was given previously.6 In each of these experiments, a pure synthetic CaO-Fe2O3 melt in a platinum crucible was equilibrated with a gas mixture (SO2-O2, SO,-air, SO2-CO, or SO2-CO2-CO) at a temperature ranging from 1296°to 1620°C. The experimental technique was essentially the same as that reported by Darken and Gurry,7 the main difference being that the atmosphere in the reaction chamber contained sulfur dioxide together with oxygen, or carbon dioxide-carbon monoxide

Jan 1, 1962

By L. J. M. Smits

A theoretical equation is developed describing membrane potentials of shaly sands as a function of the cation-exchange capacity per unit pore volume of the rock and saturating water salinity. This equation is based on the same simple physical model as that employed earlier7 describing the electrical conductivity of shaly sands. Experiments conducted with NaCl solutions showed that the equation is obeyed, except in the case of saturated salt solutions where minor deviations were observed. A possible explanation is given for this discrepancy. As the clay content and the porosity of shales may vary appreciably, shale membrane potentials also vary. It was found that membrane potentials of shales can be calculated accurately with the aid of the same theory. Consequently, changes in membrane potentials can be accounted for by simple measurement of cation-exchange capacities per unit pore volume of both shales and shaly sands. Charts are given to facilitate interpretation of the electrochemical part of the SP in terms of cation-exchange capacities and the salinities of mud filtrate and formation water. INTRODUCTION A spontaneous potential (SP) log is a record of the way in which the electrical potential of a sonde varies as it passes down a borehole. Such variations frequently reflect rock texture, e.g., permeable beds intercalated in an impermeable series often are indicated by a sharp change in potential. Nowadays it is recognized that SP logs may be interpreted in terms of formation-water salinity and formation shaliness. The four sources of the SP are illustrated in Fig. 1. El and E4 represent streaming potentials generated by the flow of mud filtrate through mud cake opposite permeable formations and through shale, respectively. An extensive review of the literature on the evaluation of these streaming potentials is given by Lynchl and will not be discussed here. The remaining part of the SP generally is called the electrochemical potential, which is divided into two parts: a membrane potential across the shale (E3, Fig. 1) and a membrane potential in the permeable sand at the diffusion boundary between formation water and mud filtrate (E2, Fig. 1). It was found by wyllie2 that the membrane potential across the shale, E3, is the most important contribution to the electrochemical potential, the shale acting as a semi permeable membrane. When the sand is clean it does not influence the diffusion process, so E2 equals the value of the so-called liquid-liquid junction potential observed when the two solutions diffuse freely into each other. When the sand contains clay, however, this interferes with the diffusion process and affects the diffusion potential generated. The greater the proportion of clay, the stronger this effect will be. Wyllie,3 Doll4 and Poupon et al.5 took this effect into account theoretically, starting from a physical

Jan 1, 1969

By K. M. Kolobova, E. Z. Kurmayev, A. Z. Menshikov, S. A. Nemnonov, V. A. Trapeznikov

The present work represents a review of our intestigations into the X-ray spectra of solids, which have been carried out by us along two lines of upproach: 1) St@ of the electronic structure of high -rnelting compounds of transition metals; 2) stzddy of the interatomic binding forces by the fine structure of absorption spectra under varying temperature and concentration conditions. With this in mind, int>estigations hare been made into the emission and absorption spectra of the K-series of atoms of transition elements in alloys and compounds. In the problem concerned with the electronic structure of high-melting compounds of transition metals, considerable importance is attached to the question of ascertaining the role played by 3d4sp electrons of metal and 2p electrons of metalloid in the formation of chemical bonds and of giving, on the strength of this data, an explanation of the properties which seem to be contradictory at first sight: good conductivity inherent in metals and high brittleness and high-melting characteristics typical of covalent compounds. Over the last few decades this question has attracted the attention of many investigators whose studies were devoted to this type of compound. Many works, both of theoretical1-3 and experimental4- l5 nature , have contributed much to the elucidation of the physical character of the phenomenon referred to. Alongside the investigations in the field of electric resistance, Hall effect, paramagnetic susceptibility, electronic heat capacity, and the temperature of transformation into a superconducting state, we should particularly emphasize the studies on X-ray spectra, which have played a significant role in the development of the zonal theory for high-melting compounds. This fact has become highly evident after the theoretical calculation of the energy spectrum has been made and the density of states curve in Tic, TiN, and Ti0 has been plotted by Ern and Switendick3 who used the method of augmented plane waves. Correlation of the results of the theoretical calculation of the band structure in the compounds listed above with the data obtained by X-ray spectroscopy studies showed that X-ray spectra can be a source of valuable information on the electronic structure of high-melting compounds within a wide range of ener- gies. It is well known that X-ray emission spectra basically give a direct picture of the occupied excited states above the Fermi level of a solid (valence band, conduction band) and that the absorption spectra (region of initial absorption) give a similar picture of states corresponding to the unoccupied levels near the Fermi surface. Full information on the density distribution of electronic states by energies can be obtained by combining the emission and absorption spectra. Such an opportunity arises from investigation

Jan 1, 1970

By J. G. Morlet, A. R. Troiano, H. H. Johnson

Delayed failure in steel occurs by controlled initiation and growth of a crack. The incubation period for crack initiation was measured. Crack initiation and Propagation are controlled by interaction between hydrogen concentration and triaxial stress state. The incubation period results from stress-induced diffusion of hydrogen to the point of crack initiation. THIS paper describes the phenomenon of delayed failureland the kinetics of crack initiation and propagation in uniformly hydrogenated steel. The investigation was prompted by service failures of high-strength-steel components at applied stresses far below the conventional yield strength, after the part had successfully sustained equal or higher stresses for an extended time interval. This delayed failure phenomenon, often termed static fatigue, is associated1 with the presence of hydrogen. This is not surprising, since the voluminous literature on flaking and hydrogen embrit-tlement demonstrates that hydrogen may exert a potent embrittling influence. Flakes, or internal hairline cracks in alloy-steel forgings, are related to the presence of hydrogen retained from the steel-making process.2 On the other hand, embrit-tlement arises from hydrogen introduced during surface treatments such as acid pickling or electroplating. Laboratory delayed failures have been induced in notch specimens of 4340 steel by electrolytic charging of the specimen surface with hydrogen and subsequent static stressing.l,4,5 Static fatigue was observed over a wide range of applied stresses; however, failure did not occur below a critical applied stress, designated as the static fatigue limit. In this instance the extended time for failure resulted primarily from the macroscopic redistribution of hydrogen. A crack formed to the depth of the hydrogen enriched "case* upon loading; further crack growth naturally awaited diffusion of hydrogen into the material ahead of the crack. The crack-propagation rate was therefore controlled primarily by the macroscopic diffusion of hydrogen into the specimen interior during the test. Thus, in this instance static fatigue was associated with the movement of a gross concentration gradient. However, delayed failure in steel of uniform hydrogen concentration is of greater fundamental interest, as well as commercial significance. With a homogeneous hydrogen distribution a different mode of delayed failure might be expected. As the heterogeneous hydrogen distribution became more uniform,4,5 the initial crack-propagation rate decreased markedly and, in fact, what appeared to be an incubation period for crack initiation was observed. However, the macroscopic concentration gradient precluded an accurate evaluation of these observations. Although the existence of an incubation period, up to this time, has not been established definitely, it is not amiss to point out some implications of the concept. It is of interest in all hydrogen-induced embrittlement phenomena, such as flaking, delayed failure, and hydrogen embrittlement. Much discussion has centered around the possibility of an

Jan 1, 1959

By E. P. Polushkin, Henry L. Shuldener

This paper describes the results of microscopic examination of a series of brass pipes removed from apartment and office buildings in New York City, adjacent localities on Long Island, and Philadelphia. They were selected as typical of approximately four hundred pipe specimens obtained over a period of five years during an investigation of corrosion in hot-water installations. A part of the investigation is reported in this paper and includes a brief history of the pipes, a description of their inside surface and microstructure, and a study of the effects of corrosion, with particular reference to the structural aspects of local and selective dezincification. Although the bibliography on the corrosion of brass pipes is quite extensive, it refers almost entirely to corrosion in sea water. The authors believe that their examination of this series of pipes, which had been subjected to the corrosive action of fresh water for various lengths of time, may throw some additional light on the problem of corrosion. Pipes Examined The pipes were made by different manufacturers and their sizes range from 3/4 in. to 4 in. nominal inside diameter, the majority being within I to 2 in. They can be divided into two groups according to chemical composition: (I) with a copper content of 60 to 62 per cent and (2) with a copper content of 65 to 68 per cent. The first group (pipes made of Muntz metal) comprises 22 pipes and the second (pipes made of high brass) comprises 18 pipes. The pipes had been in service in various locations in the hot-water systems of the buildings involved. Some were taken from horizontal lines in the basement, some from overhead distributors and some from vertical risers. The distance, in terms of feet of pipe, of the specimens from the hot-water generator was no less than 75 ft. and often IOO to 300 ft. In the majority of cases the water-heating equipment was provided with a regulator to limit the temperature of the hot water supply. The normal range of temperature in pipe systems of this kind is Ioo° to 160°F. Water Supples The average chemical composition of the water supplies carried by the pipes is shown in Table I. In evaluating the corrosiveness of a natural water, four factors are considered of prime importance: namely, hardness, alkalinity, pH and silica content. The waters listed in Table 1 are characterized by relatively low hardness, 10, alkalinity, low pH and low silica content. The waters of lower pH and higher CO2 content are more corrosive. A characteristic of all of these waters is that they do not deposit a protective mineral coating as do waters with high bicarbonate of lime content, which would be reflected

Jan 1, 1945

By M. R. Pickus, I. W. Pickus

Ordinarily age-hardening is thought of as being associated with a limited solubility of one metal in another. Much less has been written about the type of age-hardening that attends the formation of superstructures. Solid solutions generally have a disordered or random arrangement of atoms; that is to say, in a unit cell, such as that of the face-centered cubic lattice, there is no distinction between atomic sites. Atoms of a given metal may occupy cube corners or face centers. Under certain conditions, however, some alloys develop what is known as an ordered structure. In this case, cube corners would be occupied by only one type of atom and face centers by another type. Associated with this ordering process are many interesting changes in physical and electrical properties. Moreover, in many instances the alloys become susceptible to age-hardening. From the evidence now to be described, it appears that age-hardening in 14-carat gold alloys is due to the formation of both a superstructure and a precipitate. Alloys of the metals gold, silver and copper were known in antiquity. The available knowledge regarding their constitution has been ably summarized and extended by Sterner-Rainer,' Jänecke,2 Carter,3 Wise,4 and Coleman.5 Despite the long familiarity with these alloys and the numerous investigations of their properties that have been made, there is still much that remains unexplained. It has been known for a long time that the hardness of these alloys is closely related to the rate of cooling. Similar changes have been observed in the binary gold-copper systemI6 one alloy of which corresponding to the formula CU³AU, has been the subject of a careful and competent report by the English investigators, Sykes and Evans.7 They have established the fact that the shift of atoms from the ordered to the disordered condition takes place in some critical temperature range. At temperatures above the critical range the structure is random, and at temperatures below it the structure is ordered. No difference between these two structures is revealed by the microscope. Both have a face-centered cubic lattice and complete solubility, so that there is no evidence to suggest that the changes in properties are associated with a phase change. The more slowly the alloy is cooled, the higher is the degree to which the ordering process proceeds and the more marked is the increase in hardness. As experimental data were accumulated on I4-carat gold alloys, several contradictions arose. Certain observations tended to confirm the existence of a superstructure, while other observations seemed to be inconsistent with such a transformation. Present Investigation As a focal point about which to develop this subject, it is expedient to consider first

Jan 1, 1943

By M. R. Pickus, I. W. Pickus

Ordinarily age-hardening is thought of as being associated with a limited solubility of one metal in another. Much less has been written about the type of age-hardening that attends the formation of superstructures. Solid solutions generally have a disordered or random arrangement of atoms; that is to say, in a unit cell, such as that of the face-centered cubic lattice, there is no distinction between atomic sites. Atoms of a given metal may occupy cube corners or face centers. Under certain conditions, however, some alloys develop what is known as an ordered structure. In this case, cube corners would be occupied by only one type of atom and face centers by another type. Associated with this ordering process are many interesting changes in physical and electrical properties. Moreover, in many instances the alloys become susceptible to age-hardening. From the evidence now to be described, it appears that age-hardening in 14-carat gold alloys is due to the formation of both a superstructure and a precipitate. Alloys of the metals gold, silver and copper were known in antiquity. The available knowledge regarding their constitution has been ably summarized and extended by Sterner-Rainer,' Jänecke,2 Carter,3 Wise,4 and Coleman.5 Despite the long familiarity with these alloys and the numerous investigations of their properties that have been made, there is still much that remains unexplained. It has been known for a long time that the hardness of these alloys is closely related to the rate of cooling. Similar changes have been observed in the binary gold-copper systemI6 one alloy of which corresponding to the formula CU³AU, has been the subject of a careful and competent report by the English investigators, Sykes and Evans.7 They have established the fact that the shift of atoms from the ordered to the disordered condition takes place in some critical temperature range. At temperatures above the critical range the structure is random, and at temperatures below it the structure is ordered. No difference between these two structures is revealed by the microscope. Both have a face-centered cubic lattice and complete solubility, so that there is no evidence to suggest that the changes in properties are associated with a phase change. The more slowly the alloy is cooled, the higher is the degree to which the ordering process proceeds and the more marked is the increase in hardness. As experimental data were accumulated on I4-carat gold alloys, several contradictions arose. Certain observations tended to confirm the existence of a superstructure, while other observations seemed to be inconsistent with such a transformation. Present Investigation As a focal point about which to develop this subject, it is expedient to consider first

Jan 1, 1943

By R. E. Miner, J. K. Jackson, T. L. Wilson

THE nature of the decomposition reactions producing hardening in aluminum-rich A1-Ag alloys is now fairly well understood. The silver is not uniformly dispersed even at temperatures above the solvus line: rather, it is clustered into zones and associated with dislocations.' During quenching, nearly all of the silver segregates into zones' and some is attracted to dislocations, producing stacking faults. Growth of these faults produces the semicoherent y precipitate.1 During aging, the larger zones and the y precipitates grow at the expense of the smaller zones. The large zones persist up to about 350°C; where they redissolve in favor of the y' and y precipitates.' The equilibrium hcp y precipitate occurs both by a cellular reaction at the grain boundaries1 and by growth of the Y' plates to a critical size where incoherency results. Damask and Nowick 4 observed an internal friction peak in an A1-6 at. pct Ag alloy at about 140°C (0.25 cps). The peak was found to exhibit a systematic instability. After aging at successively higher temperatures between 155' and 23Z°C, the peak first migrated to higher temperatures while increasing in height, then returned to lower temperatures and decreased in height. After aging at temperatures above about 200°C, the peak position remained constant while the height decreased very slowly. In quenched specimens, elastic after-effect measurements inhcated a rapid initial transient in peak position from low temperatures up to 155°C. The authors concluded that a stress induced growth and resolution of the clusters and the 7' was the most reasonable mechanism to account for the behavior. It would seem, however, very unlikely that both the clusters and the y' precipitate would provide damping contributions whose relaxation time and activation energies were identical, which is required for them to produce the same internal friction peak. The present investigation was motivated by this apparent anomaly and the development of a very low thermal inertia torsion pendulum5 capable of monitoring transient behavior. Low frequency internal friction measurements were made on four binary A1-Ag alloys nominally containing 5, 10: 15, and 20 at. pct Ag. The results of measurements made on a 10 at. pct Ag alloy in the quenched condition are shown in Fig. 1. There are two peaks apparent in the spectrum, one centered at about 160°C, the second at about 210°C. The two peak spectrum was observed in each alloy, but it was best resolved in the 10 pct Ag specimens. Because of the instability in the internal friction, 4 it seemed possible that the second peak was not a peak at all, but simply a manifestation of a single, sharply transient, peak. This effect has been observed in Au-Ni alloys.6 The existence of the higher tempera-

Jan 1, 1970

By G. K. Manning, A. R. Elsea, A. B. Westerman

A considerable number of high-tem-perature alloys, that is, alloys which have load-carrying ability at elevated temperatures, have been developed on an empirical basis. In order to determine why these alloys possess this particular ability, a project was started at Battelle Memorial Institute on the fundamental factors promoting high-temperature strength of alloys. .4t the time of inception of this study, the cobalt-base alloy, Vitallium, was widely used because of its good high-temperature properties. One phase of this study was to include an investigation of the structures observed in vitalliurn after various heat treatments. Howcver, before investigating the structural features of Vitallium, it appeared logical to examine the phase diagrams of the related binary systems in order to develop information as to which phases might be present in Vitallium. A preliminary survey of the pertinent alloy systems was made, with particular emphasis on the cobalt-chro-mium system, which is the base for the Vitallium series of alloys. The early work of Lewkonja and Guertler2 indicated that cobalt and chro-mium are completely miscible in the liquid state, and, within a narrow temperature range, in the solid state; that the liquidus shows a minimum; and that the alloys containing 45 to 85 pct chromium undergo a transformation at [zoo to 12 50 c More recently, Wever and Haschimoto,3 Wever andLange,4and Matsunaga5 carried Out experimental work which led to the diagrams shown in Fig I and 2. Both diagrams are based on thermal analysis, metallogra~hic, magnetic, and dilatation data; in addition, X ray diffraction results were used by Wever and Haschimoto, and electrical resistance measurements by Mat-SUnaRa. It is apparent from a comparison of the two diagrams that there was a difference of opinion as to the locations of the boundaries of the various phases, and as to the existence of a phase containing approximately 47 pct chromium. With these excep-tions noted, it might be pointed out that the two diagrams are similar, and that, in general, any particular reaction which is shown on both diagrams occurs at a lower temperature on the Matsunaga diagram than on that of Wever-Haschimoto-Lange. Thus, in view of the gaps in the data arid the questionable features in the published diagrams, it appeared desirable to start the fundamental study of Vitalhum by deter-mining the diagram for the cobalt-chro-mi~m system- Experimental Work For the convenience Of the reader, the diagram as determined by the present investigation is presented in Fig 3. The liquidus and solidus data for the low-chromium alloys were taken from the work of Wever and Haschimoto,3 while the melting point for pure chromium is the

Jan 1, 1949