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By R. L. Stone

None of the currently used methods of testing bentonites as binders for strengthening iron ore pellets is entirely adequate by itself. Since more knowledge was needed about 1) which properties of bentonite most affect pellet strength, and 2) the precise mechanism by which strengthening is produced, attention was paid to possible new techniques for rating bentonites. With the structural nature of bentonites — in particular, the montmorillonite component — the possibility of rating bentonites on the basis of zeta potential was investigated. These bentonites were also rated by conventional tests and measurements, including colloid content, barrel yield, pH, chemical analysis and physical tests on green and dry pellets. A mechanism for pellet bonding based on electro-kinetic forces between the bentonite and the iron ore concentrate appears to be feasible. In pelletizing, from 6 to 18 lbs of bentonite is added per ton of concentrate to give strength to the green and dry pellets. In some operations even more bentonite than is required for strengthening purposes must be added for moisture adsorption to pennit balling of the concentrate. Since bentonite is thus a major item in pelletizing, more knowledge about the way in which bentonites act as binders and better ways of rating this ability would help in the difficult job of selecting the right bentonite for a given concentrate. The fact of the matter is that although several methods are in current use for testing bentonites, none of these methods are consistently foolproof. For example, a given bentonite may rate high by several standard tests yet turn out to be a poor binder, and of course the reverse also occurs. Actually, more knowledge is needed about 1) which properties of bentonite most affect pellet strength, and 2) the precise mechanism by which strengthening is produced. In this study attention is therefore paid to possible new techniques for rating bentonites. With the structural nature of bentonites as a starting point, we investigated the possibility of rating bentonites on the basis of the zeta potential, i.e., the electrokinetic ootential on the montmorillonite colloids — the main component of bentonite binders. The zeta potential technique was applied to a range of commercial bentonites from several areas in the U.S. and abroad. These bentonites were also rated by conventional tests and measurements, including:

Jan 1, 1968

By A. L. Mowry, John T. Norton

Isothermal sections of the pseudo-ternary carbide systems TiC-VC-ZrC, TaC-VC-ZrC, and NbC-VC-ZrC have been examined. The sections contain an inverted U shaped two-phase field whose maximum extent is 77 molecular pct for Tic, 64 pct for TaC, and 51 pct for NbC. lsoparametric lines were determined which show the curvature of the single-phase field and the direction of tie lines in the two-phase field. It was not possible to show any relationship between atom size and the extent of the two-phase field. REVIOUS work' on the solubility relationship of several pairs of refractory cubic monocarbides from the group Tic, ZrC, VC, NbC, and TaC has shown that, with the exception of the system VC-ZrC, they all form continuous series of solid solutions. It was demonstrated that the limited solubility in the case of VC-ZrC system was primarily a question of the size factor, the size difference between vanadium and zirconium being greater than the limiting value of about 15 pet. It is interesting to consider the results of combining these isomorphous carbides in groups of three and to determine the isothermal section of the pseudo-ternary diagram at, for instance, 2000°C, a temperature that will assure an equilibrium structure in a reasonable length of time. In the ternary systems where the three pairs form complete solid solution series, it is probable that the isothermal ternary section would be a single- phase field, although this is not necessarily the case. However, if one pair of carbides has a very limited solubility, then there must be a two-phase field of some extent, and it is the purpose of the present work to examine the extension of this field and to determine if it can be related to the nature of the third carbide. This condition is fulfilled if the VC-ZrC pair, which has only limited solubility, is combined with Tic, TaC, or NbC. The relative sizes of the metal atoms undoubtedly play a role in the extent of the single-phase field, and the values obtained from the pure carbides, assuming close-packing between metal and carbon atoms and a carbon atom diameter of 1.54A, are

Jan 1, 1952

D. F. HEWETT, Washington, D. C. (communication to the Secretary*).-I am not prepared to discuss the metallurgical use of manganese in the form of alloys. In connection with other work for the U. S. Geological Survey, however, I have been investigating incidentally, for about 5 years, the American as well as other sources of manganese. There are some conclusions that come out of this investigation that may interest those whose greatest interest lies in the use of the alloys. From a geological point of view, most manganese ore deposits may be regarded as concentrated masses of manganese oxides, as there are few masses of the other manganese minerals that are rich enough in manganese and low enough in silica to warrant smelting. The deposits of the Huelva district, in Spain, which are largely manganese carbonate and silicate, are exceptions to this statement. Some deposits of manganese oxides, such as those of Russia and Cuba, are bedded with ancient sediments, and although they are clearly concentrated under unique conditions, the source of the manganese cannot be determined. Probably 60 per cent. of the world's production of manganese ore, or 95 per cent., if that of Russia be excluded, is derived from the superficial parts of deposits that have undergone weathering and enrichment near the surface. In other words, the situation with the manganese ore supply is such as it would be with regard to copper, if instead of being derived largely from deep zones of deposits of deep-seated origin, such as veins, it were derived solely from the zone of secondary enrichment. Manganese oxide occurs in all rocks but is most abundant in igneous rocks, of which, according to Clarke, it forms an average of 0.10 per cent. It also forms 0.05 per cent, of the average limestone, but only traces are present in shales and sandstones. It is interesting that although many commercially important manganese deposits occur in rocks that are but slightly richer in manganese than the average, the most important deposits occur in rocks of unusual character that are much richer in manganese than the average. Thus, the most important deposits of India and Brazil overlie or occur near masses of rocks that contain excessive amounts of manganese garnet and pyroxene.

Jan 5, 1917

Discussion of the paper of E. C. HARDER, presented at the Pittsburgh meeting, October, 1914, and printed in Bulletin No. 94, October, 1914, pp. 2573 to 2586. I. C. WHITE, Morgantown, W. Va.-I have seen some of the great iron-ore deposits described in this paper. -One of these in the State of Minas Geraes appears to be an immense mountain of iron ore about 2,000 ft. in height. All over its surface from bottom to top may be seen large masses of rich iron ore, varying in weight from a few pounds to several tons, and from all that one can judge without exploitation, the quantity of available ore is certainly very large in this particular mountain. Whether it will prove a mere surface deposit or shell, like the famous Iron Mountain of Missouri, is for future exploration to determine. The question of transportation is the main factor in determining the availability for exportation of these Brazilian iron ores. There is no coal in Brazil that can be manufactured into coke without expensive previous treatment, since the best of the raw coal in the States of Rio Grande do Sul, Santa Catharina, and Parana, contains about 35 per cent. of ash, of which about 6 per cent. is sulphur, and coal of this composition cannot be utilized in iron smelting without purification. When I was chief of the Brazilian Coal Commission in 1904 to 1906, I had a cargo of this coal shipped to Balk, Germany, and treated in the great coal-testing plant of the Humboldt Engineering Works, located just across the Rhine from Cologne. It was found that by crushing and washing the Brazilian coal, it yielded 33 per cent. of briquetting coal, containing only 10 to 12 per cent. of ash (of which 1 per cent. was sulphur), and 42 per cent. of slack coal, with 25 per cent. of ash and low in sulphur, so that about 33 per cent. of the Brazilian coal could be converted into coke of fair quality, as shown by the following average of three analyses, using air-dried coal, of briquets made from the Barro Branco coal bed, State of Santa Catharina: Moisture 1.56 Volatile matter 31.66 Fixed carbon 56.73 Ash : 10.05 Total 100.00 Sulphur 1.34 Phosphorus 0.003 B.t.u 13,395

Jan 4, 1915

By H. Rush Spedden, Arvid Thunaes

Pilot plant test work in 1942 and 1943 showed that by a combination of deslim-ing, fine-size classification, and Sullivan deck concentration it is possible to recover heavy minerals such as cassiterite at least as fine as 10 microns in size. This appreciable improvement in gravity concentration practice has been substantiated by several full-sized plants. IN the past, mills treating ores of tin and tungsten by gravity concentration have recovered very little mineral finer than 325 mesh, although some form of slime concentration has been generally attempted by the use of buddies or round tables. This paper describes a series of pilot plant tests made in 1942 and 1943 in which the use of the Sullivan deck was investigated for the recovery of an appreciable amount of the fine values formerly lost. The investigation was initiated by the U. S. Government in an effort to increase the wartime production of tin. Bolivian milling practice at that time included jigging of the coarse sizes, tabling of the intermediate sizes on conventional shaking tables, and the use of buddies or round tables on the finest sizes. Flotation of the pyrite was employed at different stages of the treatment, depending upon the quantity present and the preference of the operator. Usually good recoveries and the bulk of the production were made in the jigging and tabling operations provided that these sections were not overloaded. Buddies and round tables were used for a small additional recovery if it could be shown that they could pay for their high cost of operation. Extensive test work established that by a combination of desliming, classification, and Sullivan deck treatment, cassiterite as fine as 10 microns (1500 mesh) could be recovered when proper conditions were maintained. This test work has been verified by several full-scale installations. The method is generally applicable to the preconcentra-tion of large tonnages of low-grade ores or tailings for the recovery of a small amount of a valuable heavy mineral. The Sullivan deck (or now the Denver Buckman tilting concentrator), which is the essential part of the method, was devised originally for the recovery of tin from tailings of the Sullivan concentrator, Kimberly, B. C. Since the material treated contained only 0.05 pct Sn, it was impractical to attempt to recover cassiterite finer than 500 mesh.*

Jan 1, 1951

By W. A. Boyer

Edward Thomas (U.S. Bureau of Mines, Washington, D. C.)—This excellent article on an ingenious and successful installation of wooden rock bolts loses much of its effectiveness through an attempt by the authors to establish the general adaptability of this type of support. Possibly because they have only local experience as a guide, they imply erroneously in the first paragraph that the Bureau of Mines has been opposed to wooden bolting, although later in the article reference is made to a Bureau publication on the subject. In 1947 the Bureau of Mines decided to sponsor experiments in roof bolting in coal mines because the experience of the St. Joseph Lead Co. had indicated that this type of roof support appeared to be a roof-fall accident-prevention measure that might be adopted and also effect economies in operating cost. Justification for this belief has been borne out, particularly in coal mining. This program has been carried out under the following general program: 1—The Roof Control Section of the Bureau of Mines has advocated and initiated underground experiments under controlled conditions with many different ideas related to rock bolting since 1947. In no instance has cooperation in developing an idea been refused, no matter how ridiculous it may have seemed at first glance, if it has been requested by a mining company. 2—The Bureau of Mines has no police powers over the selection of roof-support devices and seeks none. 3—At the request of an operator, the Bureau of Mines will make comparative tests on various types of bolts underground and will submit resultant data for the operator's consideration. 4—Wherever possible, the Bureau publicizes successful installations, so that others may benefit from this experience; however, it is careful not to discriminate between manufacturers of bolts or bolt-installation equipment. Unsuccessful experiments probably should also be publicized, but from a practical standpoint it is usually not feasible. In other words, the role of the Roof Control Section of the Bureau is in line with the original purpose for which the Bureau was first organized: to serve industry through gathering, analyzing, and disseminating factual data. It would seem to be logical that the starting point for any experimentation on roof bolts in coal mines should be the time-proved practice of the

Jan 1, 1955

By H. Rush Spedden, Arvid Thunaes

Pilot plant test work in 1942 and 1943 showed that by a combination of deslim-ing, fine-size classification, and Sullivan deck concentration it is possible to recover heavy minerals such as cassiterite at least as fine as 10 microns in size. This appreciable improvement in gravity concentration practice has been substantiated by several full-sized plants. IN the past, mills treating ores of tin and tungsten by gravity concentration have recovered very little mineral finer than 325 mesh, although some form of slime concentration has been generally attempted by the use of buddies or round tables. This paper describes a series of pilot plant tests made in 1942 and 1943 in which the use of the Sullivan deck was investigated for the recovery of an appreciable amount of the fine values formerly lost. The investigation was initiated by the U. S. Government in an effort to increase the wartime production of tin. Bolivian milling practice at that time included jigging of the coarse sizes, tabling of the intermediate sizes on conventional shaking tables, and the use of buddies or round tables on the finest sizes. Flotation of the pyrite was employed at different stages of the treatment, depending upon the quantity present and the preference of the operator. Usually good recoveries and the bulk of the production were made in the jigging and tabling operations provided that these sections were not overloaded. Buddies and round tables were used for a small additional recovery if it could be shown that they could pay for their high cost of operation. Extensive test work established that by a combination of desliming, classification, and Sullivan deck treatment, cassiterite as fine as 10 microns (1500 mesh) could be recovered when proper conditions were maintained. This test work has been verified by several full-scale installations. The method is generally applicable to the preconcentra-tion of large tonnages of low-grade ores or tailings for the recovery of a small amount of a valuable heavy mineral. The Sullivan deck (or now the Denver Buckman tilting concentrator), which is the essential part of the method, was devised originally for the recovery of tin from tailings of the Sullivan concentrator, Kimberly, B. C. Since the material treated contained only 0.05 pct Sn, it was impractical to attempt to recover cassiterite finer than 500 mesh.*

Jan 1, 1951

By G. F. Tagg

In an earlier paper1, the author described a method of interpreting earth-resistivity curves, based on the theoretical investigation of a single horizontal underlying stratum. If the four-electrode system of Wenner is employed, the resistivity in a homogeneous soil is given by the formula where a is the electrode separation and R is the resistance of the earth between the two inner electrodes. If the earth is not perfectly homogeneous, the application of this formula gives an apparent specific resistance varying with the electrode separation. In the special case of the single horizontal underlying stratum, there is a surface layer of thickness h and resistivity p1 and a lower layer, extending to infinity, of resistivity pz. It has been shown by Lancaster-Jones2 that the apparent resistivity obtained by an application of equation 1 is related to the true resistivities, the depth h and the electrode separation a by an expression of the formhere pa is the apparent resistivity and F is a function (actually an infinite series), of the ratio h/a, and a reflection coefficient k = (p2 — p1)/(p2 + p1). For given values of h/a and k, the right-hand side of equation 2 can be calculated, and curves drawn showing the relationship between pa/p1, h/a and k. Such a set of curves for the case when p1 > p2 is given in Fig. 1. When pl is less than pz it is more convenient to use conductivity instead of resistivity. Hence, if oa = the apparent conductivity = lip, and a1 = the conductivity of the upper layer = l/pl, it follows that GeophyGical prospecting by earth-resistivity methods is frequently applied to investigation of structural problems in geology. Fig. 1 indicates a scheme of the general arrangement used in these methods of measurements. The battery (or generator) E is connected with two "current electrodes" I1 and I2. The current of intensity J, supplied by this battery, passes through the earth between these elcc- trodes. A potential difference U will be measured between two other electrodes V1 and Vz, called "potential electrodes." According to the configuration of electrodes (Fig. I), the resistivity of a homogeneous soil results from the formula

Jan 1, 1940

By David Donoghue

THE. years 1901, 1910, and 1924 may be considered as the beginning of new eras in the history of the oil industry of the Gulf Coast of Texas and Louisiana. Spindletop, in 1901, with its enormous cap-rock production revealed the possibilities of the salt domes. The lateral sand development at Vinton, in 1910, renewed interest in the then known domes which were non-producing, or were producing from the cap rock or from sands above the cap rock. The discovery of three domes, Nash, Orchard and Long Point, in the year 1924, by means of the torsion balance and the seismograph, is the beginning of intensive explorations of the Gulf coastal plain by geophysical methods. Domes other than those mentioned have no doubt been found during the last few months of the year but tests have not been drilled to confirm the evidence of the instruments. DISCOVERY OF DOMES BY GEOPHYSICAL METHODS The Rycade Oil Corpn. operated the first torsion balance on the Gulf Coast in October, 1922, and the Roxana Petroleum Corpn. brought in one of these instruments and began work in December, 1922. The U. S. Coast and Geodetic Survey made some gravity observations at Damon Mound, in 1923, with a pendulum apparatus. In March, 1924, the Marland Oil Co. placed the first seismograph on the Gulf Coast and the Gulf Production Co. followed with one in May. In June, 1924, the Gulf Production Co. began operations with a torsion balance. The Atlantic Oil Producing Co., The Texas Co., and others have experimented with several types of instruments involving various principles. During the next few years, a great advance in geophysical methods may be expected, especially if one of the newly discovered domes should be productive. The first dome discovered was the Nash, in Fort Bend County, Tex., about 6 mi. east of Damon Mound. A slight elevation and two shallow wells containing sulfurous waters made the locality somewhat interesting from the standpoint of surface indications, and the torsion-balance measurements indicated the presence of a dome. On July 20, 1924, the Rycade Oil Corpn. No. 1 Wisdom encountered lime at a depth of 634 ft. and anhydrite at 639 ft. The hole was abandoned on Sept. 8, 1924, at 769 ft. in anhydrite. A cavity in the anhydrite caused much delay and the final abandonment of this test.

Jan 3, 1925

By John Jan

Iodine is a soft, lustrous, grayish-black non- metallic element with a density of 4.9. It is the least active of the four members of the halogen family. The other members are, in order of increasing activity, bromine, chlorine, and fluorine. Iodine is a solid at ordinary temperatures, while bromine is a liquid and chlorine and fluorine are gases. Iodine melts at 113°C and volatilizes at 184.4°C to a blue- violet gas with an irritating odor. It occurs in nature only as iodates and iodides or other combined forms. It was discovered by Bernard Courtois in France in 1811, who noticed its presence as an unknown substance in crude soda ash obtained from burning seaweed. Gay-Lussac recognized it as a new element and named it iode, from the Greek word "ioeides or iodes" for violet color (MacMillan, 1970). The world production is not known with any great certainty, but it is probably between 20 and 25 million lb per year, of which about 25% is consumed in the United States. Geology and Mineralogy Iodine compounds occur as a minor constituent as a mineral in the Chilean nitrate deposits and in solution in brines and sea- water. According to the U.S. Geological Survey, it is the 47th most abundant element in the earth's crust. The minerals lautarite, Ca (10,) (calcium iodate), and dietzeite, Ca, (10,) , (CrO,) , (calcium iodate-chromate) are found in Chilean nitrate deposits which are located in Antofagasta and Tarapach provinces on the eastern slope of the coast range in a desert area. Various brines contain iodine compounds. Seawater contains about 0.05 ppm of iodine and some seaweeds will extract and accumulate it up to 0.45% on a dry basis. Some coals in West Germany also contain iodine compounds. The known and potential sources of iodine reported in 1968 are given in [Table 1]. Iodine has been recovered from brines in Java, Indonesia, France, England, and the USSR. Iodine has also been recovered from seaweed in Ireland, Scotland, France, Japan, Norway, and the USSR. The indicated re- serves and future resources of iodine are large but have never been adequately measured. Analysis Iodine as the free element can be detected by the characteristic blue color it gives to a starch solution. Quantitatively it is determined as the free element by titration with standard thiosulfate solutions using starch as an indicator. Colorimetric methods are also applicable.

Jan 1, 1975

By G. F. Tagg

In an earlier paper1, the author described a method of interpreting earth-resistivity curves, based on the theoretical investigation of a single horizontal underlying stratum. If the four-electrode system of Wenner is employed, the resistivity in a homogeneous soil is given by the formula where a is the electrode separation and R is the resistance of the earth between the two inner electrodes. If the earth is not perfectly homogeneous, the application of this formula gives an apparent specific resistance varying with the electrode separation. In the special case of the single horizontal underlying stratum, there is a surface layer of thickness h and resistivity p1 and a lower layer, extending to infinity, of resistivity pz. It has been shown by Lancaster-Jones2 that the apparent resistivity obtained by an application of equation 1 is related to the true resistivities, the depth h and the electrode separation a by an expression of the formhere pa is the apparent resistivity and F is a function (actually an infinite series), of the ratio h/a, and a reflection coefficient k = (p2 — p1)/(p2 + p1). For given values of h/a and k, the right-hand side of equation 2 can be calculated, and curves drawn showing the relationship between pa/p1, h/a and k. Such a set of curves for the case when p1 > p2 is given in Fig. 1. When pl is less than pz it is more convenient to use conductivity instead of resistivity. Hence, if oa = the apparent conductivity = lip, and a1 = the conductivity of the upper layer = l/pl, it follows that GeophyGical prospecting by earth-resistivity methods is frequently applied to investigation of structural problems in geology. Fig. 1 indicates a scheme of the general arrangement used in these methods of measurements. The battery (or generator) E is connected with two "current electrodes" I1 and I2. The current of intensity J, supplied by this battery, passes through the earth between these elcc- trodes. A potential difference U will be measured between two other electrodes V1 and Vz, called "potential electrodes." According to the configuration of electrodes (Fig. I), the resistivity of a homogeneous soil results from the formula

Jan 1, 1940

By J. F. Wilson

An experimental investigation has been made of gas-driven slug displacements in a system of high gas saturation to evaluate the process for use in a California reservoir. Fluid compositions, temperature, pressure and core permeability duplicated reservoir conditions as closely as possible. The temperature was above the critical of the slug materials. The slug composition required for 100 per cent oil recovery in the linear flow systems was found to agree with that determined from equilibrium phase studies. A qualitative theory for the slug displacement of two-phase systems is proposed and found to be in general agreement with the observed flow behavior. The theory predicts that the length of the reservoir fluid-slug transition Zone will increase with increased initial gas saturation and decrease with increased oil swelling accompanying the composition change from reservoir oil to the critical composition. The precipitation of small amounts of an asphaltic phase during the formation of the transition zone had no adverse effects on the flow behavior of otherwise miscible systems. INTRODUCTION Despite the large number of recent publications relating to oil recovery by miscible displacement, little information is available concerning the behavior of crude oil-natural gas systems at conditions likely to be encountered in field application. The laboratory data reported here were obtained during an investigation of the possibility of using a gas-driven LPG slug in a partially depleted California reservoir. Seven gas-driven slug displacements employing slugs of different compositions and sizes were made in 26- to 27-ft long sandstone cores. The equilibrium phase behavior of the systems was also determined. The features of primary interest in this study are the following. 1. Data were obtained on the displacement of reservoir fluids at reservoir conditions. 2. A high gas saturation existed in the long cores at the start of the displacements. 3. The temperature of the studies was above the critical of the slug materials. 4. A comparison between the flow behavior and equilibrium phase behavior, as illustrated by a pseudo-ternary phase diagram, is afforded for a system of considerable complexity. THEORY Phase Behavior The use of the pseudo-ternary phase diagram to illustrate the phase behavior in miscible displacements has been discussed by Clark, Schultz and Shearin. Sie-vert, Dew and Conley and Arnold, Stone and Luffel' have presented both phase equilibrium and flow data for true ternary systems. For the true ternary, the application of the theory is straight-forward; for a reservoir system represented as a ternary, the theory undoubtedly gives a qualitatively correct picture. One purpose of this investigation was to see if the pseudo-ternary phase diagram could be used to predict with reasonable accuracy the conditions necessary for miscible displacements with actual reservoir systems. MiscIBLE Displacement of Two-Phase System A large number of papers "I3 have treated the miscible displacement of a single-phase fluid from both an experimental and a theoretical viewpoint. However, the normal field application of the process will be in a partially depleted reservoir. Often the state of the system will be such that the mobility of the gas phase is greater

By G. W. Thomas

Jan 1, 1967

By R. W. Smith

Many industries such as the cement industry handle large quantities of limestone and clay slurries. However, at present very little is known about the flow properties, such as friction loss due to flow of slurries in pipelines. This lack of knowledge has made it often very difficult to calculate the total dynamic head of a proposed slurry handling system, and therefore has often made the selection of correct size slurry handling equipment difficult. Because of lack of knowledge about slurry flow a study of slurry flow theory has been made at the Portland Cement Association's Research and Development Laboratory with the idea of developing a method whereby friction losses due to slurry flow may be predicted for any size pipeline. The flow equations developed have been checked by pilot plant size equipment. DERIVATION OF FLOW EQUATIONS It has been known for some time that limestone and clay slurries handled in cement plants do not flow in the same manner as a Newtonian fluid such as water. When a Newtonian fluid flows the shear stress at any flow velocity is proportional to the rate of shear. This phenomenon can be illustrated by a line (Figure 1). The viscosity of the fluid is the slope of the curve. Thus, the flow properties of the material may be characterized by a single materials constant: viscosity. When a non-Newtonian fluid with the type of characteristics exhibited by limestone and clay slurr-ries flow, a similar curve can be constructed (Figure 2). This graph is a shear diagram of a Bingham plastic non-Newtonian fluid. It should be noted that with the Bingham(1) plastic type of flow viscosity, the slope of the curve, is still an important materials constant. In addition, however, there is another materials constant, namely the yield stress of the material. One way to visualize this constant is to consider it as the amount of energy that must be put into a Bingham plastic material to start it flowing.

Jan 1, 1961

By P. G. Hallof

Only recently has the term Induced Polarization found its way into geophysical literature. Schlumberger first mentioned the possible use of the induced polarization effect in one of his early papers. Later, induced polarization was the subject of several university theses, such as Seigel's at the University of Toronto and Bliel's at the Michigan School of Technology. In addition, a group at the New Mexico School of Mining and Technobgy has done work on induced polarization. There is very little to be found in print on the subject of induced polarization. Several papers have been presented at meetings, the 1958 AIME and SEG* conventions, for instance, on laboratory measurements of the effect and theoretical considerations useful in the interpretation of field results. This paper is the first attempt to present actual field results which show the usefulness of induced polarization as a prospecting technique. There are several phenomena that can cause polarization when electrical current is passed through the ground. In a paper presented at the 1958 SEG* meetings Professor T. R. Madden of M. I. T. demonstrated that only two of these gave rise to appreciable effects. The first is a result of the membrane and diffusion effects in a sandstone that contains appre- ciable amounts of clay minerals. The unbonded charges associated with the clay mineral forma material that passes positive and negative ions with different mobilities. When current is passed through such a system for some period of time, polarization results. The second phenomenon, which gives rise to very much larger polarization effects, is the one used in the new prospecting technique. These effects are a result of the blocking action or polarization of metallic or electronic conductors in a medium of ionic solution conduction. This electrochemical polarization, called "the over-voltage effect" by electro-chemists, occurs whenever electrical current is passed through a volume of rock which contains metallic minerals such as base metal sulphides. This polarization at metallic interfaces in ionic solutions depends upon the chemical energies necessary to allow the ions to continue the flow of current by giving up or receiving an electron from the metallic surfaces. The energy stored in this reaction isanalogous to that stored when a condenser is charged. If a d. c. current flowing through such a system is interrupted, the polarization can be detected as a small, decaying current that flows after the applied current is discontinued. The decaying potential measured is a result of the current flow caused by charges returning to their equilibrium positions from the positions they assumed under the applied potential field. Because of the polarization, there is an excess of change at each metallic interface. There is an alternate method of measurement of the induced polarization effect. The electrical

Jan 1, 1961

By G. S. Cole, G. F. Bolling

A series of Al-Cu alloys has been cast from constant superheat to solidify either with a hot top or with a free liquid/air interface. All the other variables which affect relative fluid motions were kept constant except the imposition of slow rotations m oscillations of the mold. Depending upon the exact circumstances, evi-dence could be found for the nucleation of equiaxed grains from dendrite bits detached from the columnar zone, or from the free surface, or from solid bits induced at pouring; a special experiment showed the solute buildup during ingot solidification and by inference the reality of constitutional supercooling. All methods of grain nucleation are thus supported. When solidification is arranged in a static mold the columnar- to-equiaxed transition occurs by one of these nucleation paths, subject to the natural decay of temperature gradients which promotes nucleation or the survival of nuclei. But when solidification is forced under special fluid flows it may display odd transitions. In one of these the equiaxed zone is synihesized from. dendrite bits detached from the solid/liquid interface. These survive under the concurrent lowering of temperature gradients and eventually cause transition by impeding columnar growth. GRAIN structure control is desired because real experience shows that specific properties are associated with specific cast grain structures. But since control is thus a matter of need and does not require understanding, much of casting remains art. For example, the manipulation of relative fluid motions in simple ingots provides a control of grain structure development,1-4 but theoretical insight is not required in order to broaden its potential applicability. Fortunately, however, once a variable like fluid flow is recognized it can also provide paths toward new insight. New observations using this variable have provided an insight which is curious. All the theories or descriptions of the columnar-to-equiaxed transition (CET) seem to be supported as long as the appropriate experiment is carried out. In order to develop this idea, let us ignore segregation, the chill zone (until a later section of this paper), and the origin and development of the columnar zone.= The details of questioning how equiaxed material forms in a casting may be divided in two. The first part is simply a questioning of the origin for equi-axed grains: are there fresh nuclei from heterogeneous nucleation, or dendrite bits broken off or melted from the columnar zone or elsewhere,6 or other solid bits surviving from the outset of freezing? The second is more complex, a questioning of the CET: does columnar growth slow down and allow the dominance of equiaxed grains, however they are formed, or do equi-axed grains take over and force columnar growth to stop? This "chicken-or-the-egg" second question can be quite useful, especially because it allows us to delineate the ordinary or NATURAL EQUIAXED ZONE and the induced or SYNTHETIC EQUIAXED ZONE. A natural equiaxed zone occurs if solidification proceeds in the absence of disturbances or extraneous forces such as ultrasonics, stirrings, and so forth. Both the CET theory proposed by Winegard and Chal-mers, 7requiring constitutional supercooling, and the CET theory suggested by Chalmers,8 requiring nuclea-tion only on pouring, pertain to the natural equiaxed zone. The best collating evidence to date for both these theories is contained in the work by Biloni and Chal-mers;9,10 the former theory7 is supported by special versions of the unidirectional growth experiment performed by Plaskett and winegardl1 and the latter theory' is supported in detail for the solidification of small ingots. An equiaxed zone can be synthesized when disturbances caused by forced fluid flows2-4 or other artificial means9,10 break off or melt off dendrite tips from an advancing solid/liquid interface,* if (and only if) temperature gradients in the melt are (forcibly) reduced enough to ensure the survival of these bits of dendrites, 2'3 Willful disturbances even so trivial as those produced by rapping a mold might be included here; as will be shown for example, this follows Southin's suggestion that the free liquid/air interface

Jan 1, 1970

By B. C. Allen

Liquid surface tensions of copper and 18 Group IV-A to VIII transition metals (Ti, Zr, Hf, V, Cb, Ta, Mo, W, Re, Ru, Rh, Pd, Os, Ir, Pt, Fe, Ni. Co) have been measured by the static pendant-drop and dynamic drop-weight methods on the same rod sample. The drops were formed by electron-bombardment heating in high vacuum. Application of necessary corrections enabled determination of surface tensions to k2 pct and agreement between methods to * 1 to 4 pct for all the metals studied. Evidence is presented that the liquid surface was well screened by metal vapor, suggesting negligible adsorption of gaseous impurities and that the surface tensions measured are characteristic of the metals involved. Correlations between liquid surface tension and melting point, molar volume, heat of vaporization, and atomic number are presented and discussed. Temperature coefficients of surface tension were calculated using Eötvös' law. SURFACE tension and interface energies of metals are the result of incomplete atomic coordination resulting in a force perpendicular to the boundary, tending to minimize its area. These energies are important in many phases of metallurgy, including microstructure, sintering, joining, electronic emission, and lubrication, which in turn affect many physical and mechanical properties of metals. Liquid surface tension refers to the interface between the liquid and its own vapor or nonreactive atmosphere, and is considered a physical property of the liquid. Since equilibrium shapes can be readily obtained with liquids, the units of surface tension (force per length) and interface energy (energy per area) are interchangeable. Thermo-dynamically, the surface tension ?LV is given by the change in free energy F with surface area A at constant pressure P, temperature T, and composition N: for commercially important refractory metals, vanadium, columbium, tantalum,13,14 molybdenum,14 and tungsten,l5 and none for the rare platinum-group metals and rhenium. Measuring the surface tensions of transition metals is difficult because of their high reactivity and melting points. Of the many techniques available,16-18 the pendant-drop 19-21 and drop-weight methods17,22 are considered superior because they can be modified to eliminate persistent sources of contamination such as supports and capillaries necessary in the popular sessile drop, capillary rise, and maximum-bubble-pressure techniques. The necessary modification is to melt a drop on the tip of a vertical rod, which provides support through a solid of the same composition.13,15 The object of the work was to study the surface-tension behavior of copper and transition metals, having reasonably low vapor pressures. Liquid surface tension of each pure metal was systematically determined by using a combination of the static pendant-drop and dynamic drop-weight methods on the same rod. Liquid drops were formed by electron-bombardment heating in high vacuum. EXPERIMENTAL WORK As indicated in Table I, the metals studied were high purity and generally were obtained in rod form. The exceptions were titanium and zirconium, which were machined from crystal bars, and molybdenum (tot 11, osmium, and ruthenium, which were sintered and arc cast into rods. All the metals were ground or swaged to desired sizes between 1- and 7-mm diam, and centerless ground round and smooth to a finish better than 50 µ in., rms. Each rod was thoroughly cleaned with steel wool, degreased, acid etched, and dried. In a typical run, the rod was vertically clamped in a modified floating-zone electron-bombardment furnace designed after Calverley23 and Carlson.24 The specimen was outgassed and maintained positive at several kilovolts in a dynamic vacuum of 10-5 to 10-7 mm. The bottom end was enclosed by a tantalum pillbox and heated by electrons emitted from a hot concentric tungsten filament mounted on a movable bracket. The bombardment power was slowly raised until melting was observed. Power requirements ranged from 30 w for copper to 1300 w for 4-mm tungsten. The stabilized and out-gassed drop of near-maximum size was photographed at 4. 1X on panchromatic film at desired time inter-

Jan 1, 1963

By G. H. Kesler, J. E. Oberele, C. E. Dryden, J. H. Oxley

Heat-transfer rates were measured in a model of a multifilament vapor-deposition bulb fo the preparation of high-purzty metals. Local transfer coefficients for heat transfer frow the filaments to the circuates process stream were determined as a functiol of gas flow rates and bulb, inlet, and filament, geowzetvies. These results a-e then convertted to n mass-t7,ansfer basis to provide a method of correlating vapor-deposition rates and to predict the performance of commercial urzits. The firm1 cor?,elating equation for mass transfer was found to be- wheve k, is the mass-transfer coefficient; D, is bze gas difficsivity : P is the system pressure; R is the gas constant; T is the gas temperature; Df, DB, and Di ave tlze diameters of the filament, bulb, and inlet, respectively; k is the gas conductivity; C, is the specific heat of the gas, M is the wzolecular zleight of the gas; Npr . N,,, NRe a7'e the Prandtl, Schmidt, and Reynolds numbem of the system, respectively; LB is the height of the bulb; and SB and Sf are the total suyiace area of the bulb and filaments, respectively. ONE of the more conventional methods of preparing very high-purity metals is the vapor deposition of the metal upon heated filaments. The reactions which can be employed in such a process generally fall into two classes: 1) Pyrolysis of a volatile metal compound. Generally because of their instabilities, metal iodides are used; however, other metal halides and hydrides have been employed. These processes are frequently carried out under vacuum conditions, and the filaments are maintained at high temperatures. 2) Hydrogen reduction of a volatile metal compound. A metal chloride is normally the preferred feed for these processes, but other halides are sometimes used under special conditions. These hydro- gen-reduction processes are usually operated at atmospheric pressure. Many of the current processes for the production of semiconductor materials are actually vapor-deposition processes. However, the vapor-deposition process itself is relatively old, and almost all metals can be prepared in a state of very high purity by the use of vapor-deposition techniques. Loonam has recently given an excellent review of the iodide process for metal deposition,' and Owen has started some detailed studies with a carbonyl system.' A more general treatment of all vapor-deposition processes has been outlined by Powell, Campbell, and Gonser.3 Despite the fact that vapor-deposition techniques have been employed since 1890, there is a surprising lack of fundamental information regarding the transport characteristics of even the simplest deposition system, the heated filament. The purpose of the investigation described in this paper was to extend some of the earlier data obtained at Battelle to predict deposition rates and the uniformity of deposition in large-diameter, multifilament deposition bulbs under forced convection conditions.4'5 A number of other investigators have already presented a simplified treatment of the deposition process under non-flow conditions, i.e., pure diffusion.6"9 To obtain information on the transport characteristics of a deposition bulb, a model of a typical plant deposition unit was constructed, and local heat-transfer coefficients from the filaments to a circulating air stream were determined under various conditions of air-flow rates and bulb, inlet, and filament geometries. These results were then converted to a mass-transfer basis, and consequently provided a method to correlate experimental vapor-deposition rates and to design commercial deposition units. EXPERIMENTAL WORK Description of Model. The apparatus which was used in this work was a scaled model of one type of deposition bulb. It was constructed of Lucite and was easily altered to give several combinations of diameter of bulb liner, inlet size and location, number of filaments, and outlet geometry. The model is shown in Figs. 1 and 2. The bulb shell was made octagonal for convenience in construction and observation, and the bulb liners were cylindrical. Air, introduced through one of several different jet inlets, was used as the test fluid in these model studies. Filaments for deposition of metal were simulated by metal rods 1/4-in. in diam. Two of the rods could be heated by passing electrical current through them ¦ while the remaining rods could not be heated. This procedure minimized the amount of heat which was

Jan 1, 1962

By G. R. Speich

The age-hardening of Fe-18 to 21 pct Ni marten-sites containing small amounts of titanium, aluminum, copper, or molybdenum has been studied by hardness measurements, transmission electron microscopy, extraction replicas, and X-ray and electron diffraction. Electyon-probe microanaly-sis of the extracted precipitates was also performed. The effects of temperature and composition on the aging kinetics have been studied in detail for Fe-20 pctNi-Ti martensites. All the martensites hardened on aging at 400" to 500 "C with a single aging peak. In the Fe-20 pct Ni-Ti martensites hardening was associated with the formation of a fine dispersion of NisTi. No precipitation was observed in an Fe-21 pct Ni-2.6 pct A1 alloy, although the hardness increased from 327 to 545 Dph during aging at 500°C. Copper was precgitated from an Fe-20 pct Ni-10.7pct Cu alloy, at least during the later stages of age-hardening. Hardening in an Fe-18 pctNi-5pct Mo alloy was associated with the precipitation of an intemzetallic compound tentatively identified as NisMo. The formation of austenite and the recovery of the defect structure of the martensite occur simultaneously with the normal precipitation processes &ring aging of these alloys. THE age-hardening of substitutional iron-base martensites is an important subject for study since age-hardening is one of the principal means of strengthening the substitutional iron-base martensites in precipitation-hardening stainless steels1 and maraging steels.a~4 In contrast to Fe-C martensites, these martensites are relatively soft and ductile in the as-quenched condition, due to the low solid-solution hardening effect of the substitutional elements as compared to carbon. Also, these martensites are hardened by aging at low temperatures in contrast to Fe-C martensites which generally soften on tempering. Titanium and aluminum, singly or in combination, as well as copper and molybdenum, have been the principal alloying additions to stainless steels to obtain an age-hardening reaction.' Ti-A1 or Co-Mo-Ti combinations have been used in the case of maraging steels.3"4 The present work has been confined to a study of the age-hardening characteristics of an Fe-18 to 21 pct Ni martensite to which small amounts of titanium, aluminum, copper, and molybdenum were added in order to study the effects of each alloying element separately. The age-hardening characteristics of these alloys were studied by hardness measurements, transmission electron microscopy, extraction replicas, and X-ray and electron diffraction. Electron-probe micro-analysis of the extracted precipitates was also performed. The types and dispersion of precipitates, the formation of austenite, and the recovery of the defect structure of the martensite all were studied. EXPERIMENTAL PROCEDURE Alloys. The compositions of the alloys studied are listed in Table I. The level of 18 to 21 pct Ni was chosen to assure complete transformation to martensite on quenching and is the same nickel level used in maraging steels. The concentrations of titanium, aluminum, copper, and molybdenum were chosen after a study of the and Fe-Ni-MO' ternary diagrams indicated how much of each alloying element could be dissolved in austenite. Alloys with 2 and 4 pct Cu were also studied, but these did not show precipitation hardening at the nickel levels studied and will not be discussed further. The alloys were prepared from electrolytic iron and high-purity* nickel, titanium, aluminum, copper, and molybdenum by vacuum melting of 20-lb heats. These were vacuum-cast into two 8-lb ingots. The ingots were hot-rolled at 1100°C to 1/2-in. plate and subsequently cut into 3/8-in. cubes. The cubes were sealed in evacuated quartz capsules and solution-treated for 16 hr at 1100°C, except for the Fe-20 pct Ni-10.7 pct Cu alloy and Fe-21 pct Ni-2.6 pct A1 alloys which were solution-treated for 16 hr at 1300" and at 1250"C, respectively. Metallographic examina-

Jan 1, 1963

By R. W. Heckel, R. L. DeGregorio

The DeHoff method of determining the size distribution of ellipsoid-shaped, second-phase particles has been applied to the spheroidization of cementite in a eutectoid steel. The surface area of Precipitates determined from the various size fractions in the distribution was correlated with surface-area measurements based on the number of intersected interfaces on a random lest line. The precipitate particles were found to be oblate ellipsoids with an axial ratio of about 0.90. The size distributions were found to be log-normal. A method is proposed whereby the shrinkage of small particles and growth of large ones can be determined from the experimental data. The experimental data are compared to previously proposed mathematical models describing diffusion-controlled kinetics and various types of interface-controlled kinetics. The experimental growth and shrinkage rates are considerably slower than those predicted by diffusion-controlled kinetics. The best fit is obtained for a model describing interface-controlled kinetics limited by the rate of formation of cementite at the growing interfaces where the interfacial reaction rate is proportional to the solute thermodynamic activity gradient across the surface. THE subject of spheroidization of second-phase particles has been considered previously by other investigators. Livingston1 has studied the precipitation of the cobalt-rich phase from copper alloys containing 0.7 to 3.2 wt pet Co. His results indicate that the average particle size increases as the cube root of the heat treatment time in accord with diffusion-controlled kinetics.'-' Komatsu and rant' in their studies of the growth of SiO2 in a dispersion-strengthened copper-silica alloy found that the initial growth of SiO2 proceeded by diffusion-controlled growth and later stages were limited by interface-controlled growth. The values of the activation energy obtained for the interface- controlled process led them to the conclusion that the process was limited by the dissociation of SiO2 at the shrinking interface. The transition from diffusion-controlled growth to interface-controlled growth was characterized by a particle size which varied with the heat-treatment temperature. It is also interesting to note that the particle-size distribution as found by Komatsu and Grant exhibits log-normal behavior when replotted on log-probability coordinates. Dromsky, Lenel, and Ansell9 have observed the growth of Al2O3 particles having a mean free path of about 1.5 to 13 µ. Their photomicrographs indicate that the Al2O3 particle sizes were larger than those observed by Komatsu and Grant. Dromsky, Lenel, and Ansell concluded that the Al2O3 coarsened by an interface-controlled growth mechanism limited by the solution of A12O3 at the shrinking interfaces. Bannyh, Modin, and Modin10 have studied the spheroidization of a eutectoid steel (0.83 wt pet C). Their spheroidization (tempering) treatments were carried out in the range from 210o to 700°C for times between 1.5 sec and 20 hr. Measurements of mean particle size as a function of time indicated a cube root of time dependence of size at 700°C, in agreement with previous analyses of diffusion-controlled kinetics.2°7 At lower temperatures, the time dependence was less than the one-third power. It is important to note that, although mathematical models of growth* considering particle-size distribution have been available, measurements of only mean particle size have been carried out. DeHoff11 has presented a quantitative metallography technique which is applicable to the determination of the size distribution of ellipsoids of constant shape. This method is applicable to both oblate and prolate ellipsoids of all ratios of minor to major axis and is based upon an extension of Saltykov's analysis12 of the distribution of spheres of varying size. DeHoff's analysis is based upon measurements of the minor axis of the particles on a random plane of polish in a unit area. This method provides a measure of the number of ellipsoids in various size ranges per unit area. As pointed out by DeHoff, such measurements may be used to obtain surface area and total precipitate volume data. Thus, the accuracy of the distribution analysis may be checked by comparison of the surface and volume

Jan 1, 1965