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By F. H. Turan, F. W. Jessen

The gel strength and viscosity of two different suspensions of fractionated montmorillonite clay were measured by using a Stormer viscosimeter and Farm V-G meter. The amount of sodium poly-phosphate (sodium bexametaphosphate, sodium tetraphosphate and sodium acid pyrophosphate) adsorbed by the clay particles was determined. A relationship seems to exist between the amount of polyphosphate adsorbed and the nature of the surface, edge or plate, assumed to be the principal sites for selective adsorption. Reduction in viscosity and gel strength was found to be directly related to the adsorption. Both chemical bonding and physical adsorption seem involved in defloccula-tion Some indication of the axial ratios of particles of .l- to .04-micron average size is possible though study of the adsorption mechanism. INTRODUCTION AND PURPOSE A knowledge of surface areas of clay particles in a suspension and a precise determination of phosphate adsorption should provide a basis for a better understanding of reduction in viscosity and gel strength caused by molecularly dehydrated phosphates. The purpose of this investigation was to study the adsorption of sodium polyphosphates on suspensions of fractionated sodium montmorillonite. Although there is considerable uncertainty regarding details of the structure of montmorillonite, a generally accepted one is that suggested by Hofmann, Endell and wi1m.l The structure shown in Fig. 1 is an idealized one, and Marshall2 has postulated that it is possible for several isomorphous replacements to occur. Thus, aluminum may replace silicon, in which case an exchangeable cation would go along with the aluminum to neutralize what would otherwise be a net negative charge on the structure. There is disagreement among various investigators as to the particle size and shape of montmorillonite clays. Marshall2 reported the following results for the mean lateral dimensions of a Putnam clay (montmorillonite)— 3,730 A° for particles having average diameters ranging from 500 to 1,000 A, and 750 A° for those with an average diameter less than 200 A. The latter particles were estimated at 50A°in thickness, which would correspond to a stack of five unit cell layers. On the other hand, Shaw3 has interpreted micrographs as indicating that particles of montmorillonite ire readilv broken down to the individual cell layers by dispersion in water. Brindley4 and Merings indicate the ultimate particles to be of the order of 300 A° in mean lateral dimension. Van Olphen6 suggested the thickness of particles at four to five unit cell layers. It was suggested also that this number tends to become smaller with increasing dilution. Recently, Kahn and Lewis7 determined the size of sodium montmorillonite particles in aqueous suspension from electro-optical bi-refringence decay curves. The

By R. W. Raymond

Since the foregoing paper (see p. 387) was printed, I have received the decision of Judge William E. Church, of the first District Court of Dakotah, in the case of Michael Duggan et al. v. John H. and Frank J. Dnvey (Silva Terra—Sitting Bull case), published in full in the Black Hills Weekly Pioneer of August 9th, 1584. The journal mentioned gives also several interlocutory decisions rendered in earlier stages of the case; but I shall quote here only so much of the final decision as bears upon the .construction of the Revised Statutes concerning the apex, the end-lines, and the extra-lateral mining right, together with a sufficient statement of the facts of the case to explain the scope of the decision. " This is an action in equity, brought in the first instance to restrain a threatened trespass by the defendants upon certain mining property in the possession of the plaintiffs, known as the ' Silver Terra' claim ; the allegation being that the defendants were about to enter, through underground workings, the ground of the plaintiffs, and remove therefrom valuable bodies of silver ore. " The answer of the defendants, admitting the acts constituting the alleged threatened trespass, further averred that they had, in fact, at the time complained of, reached and passed, in their underground workings, throngh and beyond the vertical side-line of the Silver Terra claim, and therenpon justified the acts complained of, and claimed the right to pursue their workings into and through the Silver Terra ground, by virtue of their alleged proprietorship of a vein, lode, or ledge of rock in place, hearing silver, having its top or apex within the lines of a certain other mining claim called the ' Sitting Bull,' of which they claim to be the owners, which vein, lode, or ledge extended in a continnons body of mineral-bearing rock from such top or apex to the ground in controversy, and constituted the body of ore in dispute; and that it was in the pursuit of this vein, lode, or ledge in its downward course that they had passed beyond the vertical side-lines of the Sitting Bull claim, and for some hundreds of feet beyond, into the ,ground in controversy " Subsequently, a supplemental complaint was filed, setting up the entry into plaintiffs' ground by the defendants, and their claim of right to do so, and asking fnrther relief by a decree restraining the assertion of such claim, and quieting the title of plaintiffs. "The case was tried before the court without a jnry..... " Custer hill, upon which these claims are located, is situated in the village of Galena, in Bare Butte mining district, in this county. The village lies at the base of the western slope of the hill, which presents a lateral face from south to north

Jan 1, 1884

By Jack A. Kanz, Samuel R. Shortes, E. C. Wurst

Zinc diffusion into GaAs from the vapor phase through reactively sputtered SiO, films Izas been inrestigated for various zinc pressures at 1000"C. Diffusions were carried out in evacuated quartz ampules with elemental zinc and with various Zn-Ga alloys. Sputtered films have proved effective in lowering surface concentrations and preventing surface deterioration during diffusion. Approxin.ate complenzentary error-function impurity distributions were found when surface concentrations were reduced to approximately 3 -—4 x 10" atoms cm'3 or less with dilute zinc sources or by diffusion through SiO, films. Zinc difhsions in GaAs tlzrough SiO, films produced more planar diffusion fronts than were observed with uncoated zuafers under identical conditions. A) Surface Deterioration During Diffusion. Device technolorn-- in compound semiconductors has been hampered by several difficult problems not normally encountered with silicon and germanium. 111-V and 11-VI compound semiconductors generally have volatile constituents at temperatures used for diffusion. To achieve specific junction depths in reasonable lengths of time, or to obtain particular impurity distributions and doping levels, it is often necessary to use temperatures which cause surface deterioration and erosion of the wafer. The resultant surfaces are generally unsuitable for devices. The type and extent of surface damage depends to varying degrees on the particular environment of diffusion and on the particular impurity in question. The most common type of deterioration results from simple dissociation of the gallium and the arsenic during diffusin.' The deterioration process is significantly enhanced by thermal gradients in the diffusion zone, usually resulting in vapor transport and condensation at the cooler portion of the system. The resulting damage sometimes appears as a general haziness over the surface or an array of pyramidal etch pits characteristic of the particular orientation. Occasionally, erosion of the surface occurs uniformly over the wafer so that surface loss is not readily apparent. Workers in GaAs usually resort to the sealed-ampule type of diffusion system3"5 rather than the more conventional open system used for silicon and germanium. Another type of deterioration results from direct interaction of the impurity with the surface. The form of deterioration may vary from surface alloying, as in the case of zinc, to direct chemical attack and vapor transport of the reaction products, as in the case of sulfur. Surface alloying with zinc occurs at higher temperatures and source vapor pressures.4 The process is largely controlled by the amount of free gallium on the surface of the wafer in equilibrium with the arsenic lost to the system. The group-VI elements, sulfur, selenium, and tellurium, are commonly used donor impurities for gallium arsenide. These elements are characterized by high vapor pressures and high chemical

Jan 1, 1964

By M. T. Worley

This paper reports investigative work conducted to develop a method of estimating the groundwater influx from a homogeneous permeable formation into a vertical mine shaft during sinking. A method of analysis was developed using data obtained from pumping tests and a modification of the Theis non-equilibrium interpretation technique. Excess influx of groundwater into mine shafts has long been one of the more important problems encountered in the development of a mining property. Much work has been done on methods of preventing such influx and on pumping schemes to control inflow if preventive measures fail. The fundamental aspects of the problem, on the other hand, seem to have been neglected. The purpose of this paper is to review the fundamentals of groundwater flow and to propose a rapid method of analyzing hydrologic data in order to estimate influx from a homogeneous permeable formation into a mine shaft. Such an estimate of the quantity of water to be encountered is of value in planning grouting, pumping and other programs designed to control that influx. It is emphasized that the proposed method of analysis should be regarded only as a tool to be used in evaluating the problem before investing the capital necessary to begin development of a property. FUNDAMENTALS OF GROUNDWATER FLOW In order to effectively approach the problem of estimating influx into a mine shaft, a knowledge of the fundamentals of fluid flow through a porous medium is necessary. Darcy, in 1856, developed an empirical relationship to explain the flow of water through sand filters. This relationship V = k (dh/dl), is the basis for all other flow formulae. It has been shown that Darcy's relation is a solution of the Laplace equation and thus is analagous to other natural phenomena such as heat flow. Theis, using the analogy of heat flow by conduction, developed an expression for determining the transient or time-dependent groundwater flow through a homogeneous, isotropic medium. The resulting equation Was also derived by Jacob using hydrologic considerations alone.' The individual terms in the equation are described in Table I. It is important to understand the assumptions upon which this equation is based. 1) The medium through which the fluid flows is infinite in areal extent, homogeneous and isotropic. 2) The well into which the fluid discharges completely penetrates the medium. 3) The characteristics of the medium remain constant at all times. 4) The initial pressure surface is horizontal. 5) The confining media are impervious and horizontal. 6) Fluid is removed from storage instantaneously by a decline in pressure. 7) The diameter of the discharge well is infinitesimal with respect to the drainage radius of the medium.

Jan 1, 1962

By H. M. Dess, S. R. Bolin

A modifiedl Czochralski technique has been utilized to grow single crystals of YVO, pure or doped with europium or neodymium, from 1 to 2 in. long and 4 to 1/2 in. in dianz. An oxyhydrog-en gas-fired furftace zuas used in this ulork, and melts were contained in iridium crucibles. Successful application of the Czochralski ~vzethod was found to depend upon atmosphere control to prevent crusting and to limit melt decomposition, the establishment of symmetrical thermal gradients in the melt to obtain stable growth, and the selection of high-quality single-crystal seeds to prevent propagation of misorientations during growth and subsequent catastrophic cracking. The suitability of YVO4 as a host for laser-active trivalent rare earth ions has long been recognized. However, the problems associated with the growth of sufficiently large, good-quality single crystals have, until quite recently, seriously hindered satisfactory evaluation of the laser potentialities of this material. Both flux growth and Czochralski growth techniques were investigated at an early stage of interest in YVO,. The former method proved incapable of yielding crystals large enough for practical use,ly2 and the latter was beset with difficulties which took some considerable time to understand and overcome. Recently, however, the Czochralski growth process for YVO, has been improved along separate but similar lines of development by groups working independently in the Crystal Products Department of Union Carbide's Electronics Division and Bell Telephone Laboratories3 so that now good-quality single crystals of satisfactory size can be produced on a routine basis. Stimulated emission from a neodymium-doped YVO4 crystal grown by the Crystal Products Department of Union Carbide was obtained by O'connor4 of MIT, Lincoln Labs. An oxyhydrogen gas-fired furnace was used in this work, Fig. 1, and melts were contained in iridium crucibles. The starting material was 99.9 to 99.99 pct pure YVO4 powder purchased from the Chemical and Metallurgical Division of the Sylvania Electric Products Co. Typical impurity levels, determined by spectrographic analyses, were as follows: Si, 50 to 500 ppm Al, Fe, Mg, 5 to 50 ppm Ni, Pb, Mo, Mn, Ce, Cs, 1 to 10 ppm Initially, YV04 powders predoped with neodymium or europium were obtained from Sylvania. Later, however, because of a desire to grow a series of crystals containing relatively broad concentration ranges of these dopants, it proved more convenient to start with pure YV04 and mechanically admix Nd2O3 or Eu@~ powders plus equimolar amounts of V2O5. The empty crucibles were preheated to 1900" to 1950oC, a temperature range where melting occurred readily. The powdered YVO4 feedstock was then added incrementally. However, a marked tendency toward

Jan 1, 1968

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

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

Jan 1, 1969

AVING started to tell you of working potter's clay for making crucibles and shells, the wish came to me to tell you of the practice of this art also. Although it may seem at first glance to be outside the order and purpose of my writing, he who considers well will see that it is not unrelated to it but proper, since it is wholly dependent on the agency and power of fire if it is to be brought to its perfection. Moreover, the potter's glazes and colors are all substances of various metals or impure minerals and therefore belong to fire. Since it is my intention to treat of fire, minerals, and metals for you, I surely should not have omitted this, particularly because it is a necessary art which enriches and is greatly praised both for its ingenuity and its beauty. The art of the potter has two sources as its principal basis. One comes from the art of design, the other from various alchemical secrets and elemental mixtures. In regard to these, I find that, in my opinion, all this art depends in the last analysis on four things: on good judgment in general, and on the art of design so as to be able to make the vessels beautiful and of good shape, as well as to ornament them with painting; after baking them well the first and second times, the next thing is to know how to make and apply the glaze well and to paint them with varied and appropriate colors. The fourth is to see that you have good, fine clay without small stones or lumps-indeed this is to be considered as the first thing. Now this that I have called clay is what many call cretaceous earth and some call argil. It is found and dug up when the masters wish to make use of it and is put in a container to be moistened. When it is moistened, it is beaten on a bench with an iron rod and very well prepared. Mixing it carefully, every small stone, lump, or other hardness that it contains is removed and cleaned away. Then a shaft [145V] of iron is fitted as the journal in a large wheel. On the other end of the journal a small wheel is made which forms an instrument for working that is called a lathe. Having put some clay on this, it is made to rotate by pushing with one foot, and, by rotating it, vessels are worked into a pleasing shape and size. Then they are taken off and put on a board to dry. After drying artificially or naturally they are painted red,

Jan 1, 1942

Manganese Resources in Relation to Domestic Consumption Discussion of paper by JOHN V. W. REYNDERS, presented at the Cleveland Meeting and issued, as Pamphlet No. 1656-C, with MINING AND METALLURGY, May, 1927. A. G. BETTS, Kinderhook, N. Y. (written discussion).-When a business concern hires an office boy, it takes on the first bright-appearing young chap to apply and pays him the prevailing rate of wages. One of the chief tasks the .office boy is supposed to be competent to perform, is to clean out the office. The manager of the business is highly competent in many lines, but for some reason lacks the ability to keep the office clean. To the steel man, it would seem that manganese is the office boy, and it is purchased just as found and offered to the purchasing agent. The steel mill is competent to perform many functions on a grand scale and with wonderful efficiency, but it is unable to make real steel. It is the function of the office boy, manganese, to do this. It is open to serious doubt if steel mill operators have ever taken seriously the metallurgy of the preparation of crude manganese. It has merely been found that some usable crude manganese may be obtained by running certain manganese ores through an iron furnace when not busy on anything else, or remote from iron ore, or with a lining that is about gone. It is, however, an entirely unwarranted assumption that the metallurgy of manganese has been worked out, or that the supplies of usable raw ore must be limited to materials of some specified analysis. There was a time when ores of copper, lead and zinc, for example, had to be rich and of specified analysis, to be usable, but the commercial raw materials of today bear little resemblance to such ores of the past. The discussions of manganese that I have seen are based on the assumption that the metallurgy of manganese is fully established and that the only usable manganese raw materials are of the kind used today. These discussions contain another error, not so much of statement, but of implication-that the tonnages of manganese materials in the United States are so much in this state and so much in that. When it requires a period of years and the expenditure of millions of dollars for a competent mining company to explore thoroughly a few acres of mining ground, is it not absurd to say that there are so many hundred tons of manganese ore in a certain state? This fact is not apt to be known fully in 10,000, years. I do not charge the mining engineers. who are on record, of making misstatements, because they merely say that so much

Jan 5, 1927

By William B. Stephenson

The paper describes efficient and effective methods of automatically controlling sand pump installations. Particular reference is made to liquid-level controls actuating variable speed pump-driving units. Included is a discussion of various combinations of equipment, with schematic drawings. HERETOFORE many sand pump installations in the mining and metallurgical field involved guesswork as to the size of the pump and then simply direct-connecting it to a constant speed motor which was often large enough to do twice the work required. Considerable thought was given to mill location in an effort to avoid as much pumping as possible. Hillside design of mills with gravity flow of tailing was much to be desired. Power costs were low, construction was relatively cheap, and labor in many places meant nothing in comparison to the values derived from the ores being treated. Today most of these conditions are reversed. Ores are becoming more complex with lower values per ton of ore treated. Power is more expensive, construction is higher, and labor definitely takes a very important place in the profit and loss statement. Each piece of equipment incorporated in the design of a new mill is selected to provide highest efficiency based on careful metallurgical analysis of the ore to be treated both in good and poor markets. Each is designed with its flexibility in mind and with provision for adjustments in its performance to meet actual conditions in the operation of the mill. Sand pumps have taken an important position in mill design. Operators the world over are relying more and more on the performance of a sand pump in the efficient operating of their plant. Many ordinary jobs are being done today with pumps driven through adjustable pitch diameter V belt drives in order that changes in pump speed can be made easily to meet actual operating conditions. Operating costs have long since proved the folly of operating a pump at too high a speed for the volume and head to be overcome. Metallurgical results have shown the benefits derived from a smooth flow as contrasted with a surging flow from an uncontrolled pump. Construction costs have risen to such an extent that surge bins and other means formerly employed must be omitted from today's flowsheet. Several installations of considerable size and involving the use of automatic pump speed control have proved the adaptability of such controls since they were placed in service in recent years. In the following presentation each system discussed and illustrated schematically has been installed in one or more instances and has proved itself reliable and definitely economical from the standpoint of capital investment, operation and maintenance. Variable Volume-Head Speed Control: Probably the most popular, effective and efficient automatic control setup for sand pumping installations is the one shown schematically in fig. 1. Commonly used

Jan 1, 1951

By William B. Stephenson

The paper describes efficient and effective methods of automatically controlling sand pump installations. Particular reference is made to liquid-level controls actuating variable speed pump-driving units. Included is a discussion of various combinations of equipment, with schematic drawings. HERETOFORE many sand pump installations in the mining and metallurgical field involved guesswork as to the size of the pump and then simply direct-connecting it to a constant speed motor which was often large enough to do twice the work required. Considerable thought was given to mill location in an effort to avoid as much pumping as possible. Hillside design of mills with gravity flow of tailing was much to be desired. Power costs were low, construction was relatively cheap, and labor in many places meant nothing in comparison to the values derived from the ores being treated. Today most of these conditions are reversed. Ores are becoming more complex with lower values per ton of ore treated. Power is more expensive, construction is higher, and labor definitely takes a very important place in the profit and loss statement. Each piece of equipment incorporated in the design of a new mill is selected to provide highest efficiency based on careful metallurgical analysis of the ore to be treated both in good and poor markets. Each is designed with its flexibility in mind and with provision for adjustments in its performance to meet actual conditions in the operation of the mill. Sand pumps have taken an important position in mill design. Operators the world over are relying more and more on the performance of a sand pump in the efficient operating of their plant. Many ordinary jobs are being done today with pumps driven through adjustable pitch diameter V belt drives in order that changes in pump speed can be made easily to meet actual operating conditions. Operating costs have long since proved the folly of operating a pump at too high a speed for the volume and head to be overcome. Metallurgical results have shown the benefits derived from a smooth flow as contrasted with a surging flow from an uncontrolled pump. Construction costs have risen to such an extent that surge bins and other means formerly employed must be omitted from today's flowsheet. Several installations of considerable size and involving the use of automatic pump speed control have proved the adaptability of such controls since they were placed in service in recent years. In the following presentation each system discussed and illustrated schematically has been installed in one or more instances and has proved itself reliable and definitely economical from the standpoint of capital investment, operation and maintenance. Variable Volume-Head Speed Control: Probably the most popular, effective and efficient automatic control setup for sand pumping installations is the one shown schematically in fig. 1. Commonly used

Jan 1, 1951

By M. S. Abrahams

Germanium has been rolled in the temperature range of 700o to 800°C. The thickness has been decreased by as much as a factor of four, from a thickness of 0.032 in. to a thickness of 0.008 in. For deformations below 60 pet, the true strain per pass is found to be a constant; from the temperature dependence of this slope, an activation energy of about 2.5 ev is obtained. This energy agrees with that for dislocation climb in germanium . For reductions greater than 60 pet, complete rings are seen in the Lave photographs, new grains are observed in the microstructure, considerable softening occurs, and the hole mobility is very low. This evidence indicates that the recrystallization of gertnanium has occurred. GERMANIUM has been deformed in many ways1 including tension, compression, torsion, and bending since Gallagher2 first described its plastic nature at elevated temperatures. All of these studies indicate that the glide plane in germanium is (111) and that the glide direction is (110). Rolled germanium specimens were used by Kolm, Warekois, and Kulin3 in their X-ray study of deformed semiconductors, but no information is given on the rolling itself. The present experiments deal with the rolling of germanium at various temperatures and for different orientations. In all previous deformation studies, the phenomenon of recrystallization (i.e., the transformation of a single crystal into a polycrystal) in germanium has not been observed4 despite relatively large deformations at elevated temperatures. The proposed reason4 for this was that sufficient energy could not be stored in the deformed germanium lattice. In contrast to the earlier studies this work will present evidence indicating that recrystallization occurs in germanium during rolling at an elevated temperature. I) EXPERIMENTAL PROCEDURE A) Test Specimens. The samples used for rolling were in the form of rectangular parallelepipeds measuring 0.3 in. long, 0.06 in. wide, and 0.035 in. high. They were cut from an undoped single-crystal ingot of p-type germanium with a resistivity of 24.4 ohm-cm, a Hall mobility of 2300 sq cm v-' sec-l, and a hole concentration of 1.1 x 1014 cm"3 at room temperature. The surfaces of the specimens were metallographically polished prior to rolling. The initial dislocation density of the samples was about 10' cm-' as determined by etching in CP4. Two different specimen orientations were used. In the first case, the direction of rolling was parallel to (251), the surfaces in contact with the rolls were of the form (1021, and the normal to the third face was parallel to (211). The corresponding di-

Jan 1, 1964

By Herman Garlichs

The development of the extensive Southeast Missouri deposits greatly preceded that of the Iowa and Wisconsin deposits. It began about 1720 at Mine La Motte and other localities, and has continued uninterruptedly to the present time. It is estimated that this district produced about 184,000 tons of lead in the year 1916, having a value of approximately $25,000,000. This is a new high record. The Southwest Missouri orebodies were hardly known before 1845 and were not extensively developed until 1870. Lead production in Southwest Missouri for 1916 was 38,788 tons. Oklahoma produced 14,399 tons and Kansas 2,345 tons, making a total for Southwest Missouri, and the adjoining districts in Oklahoma and Kansas, of 55,532 tons of lead. The first metallurgists in Missouri were the Indian and the hunter. The early settler learned to procure his bullets either by melting ore in his camp fire or by throwing pieces of galena on an old stump and depending on the usual roasting and reaction method to obtain the metal. A little more refined method was to arrange two flat stones in the form of a, V. Wood and galena were placed in the furnace and ignited.. As heat developed, some of the metal was extracted and molded into bullets. The next step in utilizing the lead ores was the log hearth. All lead in Missouri was smelted in this crude affair before 1820. It was built on sloping ground, and consisted of a hearth of stone, surrounded on the front and two sides by a stone wall. The wall was 7 it. high in front. The top and rear end were left open and in front an arch or opening was made, forming the eye of the furnace. In front of this a pit was dug in the ground, to receive the molten metal. Large logs were rolled in at the back and made to rest upon ledges formed inside, to raise them from the hearth and to give a draft. These logs filled the entire width of the furnace. Small split logs were then set up around the two sides and the front, and the ore was piled on until the furnace was full. Finally, the mass was covered with logs and fuel until the ore was completely surrounded. A gentle heat was started, which was raised very gradually. After 12 hr. the heat was increased and continued for 12 hr. more, 24 hr. being required for each smelting. The furnace treated about 5,000 lb. per 24 hr. and the ore yielded about 50 per cent. of its metallic lead. A considerable quantity of the ore was not desulphurized, and fell between

Jan 1, 1918

By E. P. Abrahamson II

The effect of transitiorz element bitzary solid solution additions upon the recrystallization temperature of columbium has been investigated. The elements Mn, Fe, Co, Ni, W, Re, and 0s OWY the yecystallization tempel-aturye, while Ti, V, CY, zr, Mo, Ru, Rh, Pd, Hf, Ta, W, Ir, and Pt mise it. A correlation is kloted between the rate of chatzge of recyystallization tewaperature with atomic hercent solute and the free atom electron configuration of the solute element. The work of Abrahamson and Grant1 has indicated a correlation between the free atom ground-state electron configuration and the change in brittle-ductile transition temperature per atomic percent solute in chromium base alloys. A similar correlation was observed for the change in the recrystallization temperature of iron base alloys by Abrahamson and Blakeney and Abrahamson. It was also observed that the limit of rapid change in recrystallization temperature also Correlated with the electronic configuration of the free solute atom. A further study by Abrahamson4 established the generality of the phenomenon by yielding similar results for vanadium base dilute alloys. It has been inferred that a peri- odicity might be expected with changes in the free atom electron configuration of the solvent element. This study is the third set of transition base metal systems to be studied. It is the object of this and further studies on transitional metal systems to detect any systematic variations in the observed correlation which might contribute to the understanding of the electron interactions which are evidently exhibiting themselves. PROCEDURE All alloys were made using 99.9 pct Cb with 0.030 Ta, 0.016 0, 0.0025 H, 0.003 Mo, 0.021 Fe, 0.005 C, and 0.002 N. The solute elements were 99.9 pct pure. According to the published binary phase diagrams5 and metallographic examinations at X750, all additions were in solid solution. The alloys were arc melted and remelted 6 times in the form of cubic 400-g buttons under an argon atmosphere. They were then hot forged at 1200oC to 0.6-in. diameter, annealed for 3 hr at 1200o under argon, and furnace cooled. The specimens were then machined to 0.400 -in. diameter. Grain size was checked and found to remain essentially constant at 150 i 30 grains per sq mm. The specimens were then cold swaged to 0.187-in. diameter, yielding 46 i 1 pct cold work. All alloys were chemically analyzed for the major solute. Analyses of random samples indicated that the impurity content remained at the values of the starting material. Tungsten contamination was held to 0.007 pet.

Jan 1, 1962

By Frederick C. Langenberg

IT has been shown1 that copper can be removed from iron-base alloys by solvent extraction with molten lead and sodium sulfide slags. In these processes copper removal is favored by a positive deviation of copper in iron from ideal behavior. Chou' determined the distribution of copper between liquid silver and iron and obtained a value for the activity coefficient of copper in iron at 1600°C, y°, of 9.12. Chipman" calculated the activity coefficient from the Fe-Cu phase diagram to be 12 at 1600°C. More recent work by Koros and Chipman" yields a value at 1600°C for y V equal to 8.0. In this latter work, the distribution of copper between silver and iron was measured at 1600°C, while the activity of copper in the silver phase was determined from calculations based on the Ag-Cu phase diagram. The present work presents another value of based on calculations from the Cu-Pb phase diagram, on the heat of mixing data for the Cu-Pb system, and on an experimental study of the distribution of copper between iron and lead at 1600°C. These experiments were part of a larger research on the removal of copper from iron-base alloys conducted at The Pennsylvania State University. Experimental Procedure—The distribution of copper between pure iron and lead at 1600°C was made in the furnace assembly shown in Fig. 1. The melts were made in high purity alumina crucibles under an atmosphere of prepurified argon. Temperatures were read with an optical pyrometer sighted into a %-in. hole drilled in the inductor. Extensive calibration of the optical readings with immersion readings had been carried out previously. The initial charges consisted of 100 g of electrolytic iron and varying weights of copper. The melts were brought rapidly to 1600°C and 75 g of lead added. The temperature was quickly readjusted to 1600°C, and the melts were held for 10 min at this temperature. A sample was then drawn from the iron layer in a fused silica tube. This sample was analyzed to determine the copper content of the iron layer at equilibrium, while the copper content of the lead layer was determined from a material balance. The validity of the material balance was confirmed by a chemical analysis of the entire lead layer for one heat in which the crucible was removed and quenched after the iron sample was taken. The calculated copper content of the lead-rich phase was 1.18 pct; while the entire lead layer analyzed 1.20 pct Cu. The distribution results are shown in Fig. 2. The distribution constant, N,.'r'"/N, is equal to 3.95. Discussion—From the Cu-Pb phase diagram' it can be seen that lead-rich liquid Pb-Cu solutions

Jan 1, 1957

By Don M. Jackson

The techniques for the growth and controlled, graded doping of silicon epitaxial overgrowth layers were established. Grading of- impurities such as arsenic or boron in arbitrarily chosen profiles oiler four orders of magnitude (from I X 10Lg to 1 X 10L5 cm) was accomplished. The graded structures were grown in a stepwise manner where in the profiles were approximated by growing many separate layers with small doping-level changes between layers. Masked-area growth of silicon through windows in a SiO2 masking film was acconiplished through the simultaneous injection of HCl gas 102th Sic14 in the epitaxial reactor. The HCl served to inhihit the growth of silicon on the Sz02 surface, and also to control the cross-sectional profile of the silicon mesas. silicon from the substrate was etched out through the windows, and then epitaxial material was used to fill the holes hack in to form planar diodes. Simullaneous HCl injection was adapted to control the cross-section profile of the hack-filled regions. Arsenic-huried regions beneath in te- In recent months, the epitaxial growth process in semiconductor materials technology has evolved into a complex system directed at both material improvement for better monolithic integrated-circuit characteristics and the development of new silicon structures for future integrated-circuit needs. The advent of high-temperature HC1 gas etching1 grated-circuit transistors reduced V(SAT) by slightly more than one third, bringing this parame-ter to that of an isolated component transistor. When arsenic was diffused into the starting sub-stvate, it was necessary to remove any excess arsenic in order to avoid excessive audodoping of the subsequent epitaxial layer. Oxide isolation of single-crystal regions in a substrate provided complete electrical isolation of integrated-circuit components, thereby eliminating parasitic capacitance which is inherent in standard integrated-circuit processing. The process involved the etching of deep mesas on silicon Wafers, the formation of an oxide over the mesa surface, and then the deposition of several mils of polycrystalline silicon over the oxide. The original substrate was lapped and polished allay until the mesas were left isolated in the polycrys-talline matrix. The Final components were fabri-cated in the single-crystal islands. Speed and power-handling capabilities of standard circuits were improved through the process. wherein work-damaged material is removed from the surface of the silicon wafer just prior to the silicon deposition step has made it possible to grow silicon films with structural quality that approaches that of the substrate. HBr used in the same volume ratio as HC1 etches silicon at the same rate and with the same results as HC1. Recent developments in epitaxial materials technology have occurred in the areas of precise doping control, buried prediffused regions between over-

Jan 1, 1965

By T. E. Leontis, D. H. Feisel

MAGNESIUM alloys containing rare earth metals have received considerable attention during the past several years because of the need for light alloys having high strength and creep resistance at elevated temperatures. Although much of the work reported earlier has dealt with alloys containing Mischmetal, it has been shown in two previous papersl, V hat distinctly different effects are produced by various rare earth metals and rare earth metal mixtures on the properties of magnesium. For example, much higher strengths are obtained in magnesium alloys containing didym-ium (essentially neodymium plus praseodymium) than in alloys made with Mischmetal, which contains all the rare earth metals in the proportions in which they occur naturally in the monazite ore. Mg-rare earth metal alloys are characterized by a relatively coarse grain size, which greatly impairs castability. The addition of zirconium as a second alloying ingredient has been shown8,7 to refine the grain size, which also produces a distinct improvement in the strength properties. Certain Mg-Mischmetal-Zr and Mg-Mischmetal-Zn-Zr alloy compositions which are currently being produced commercially have been discussed in dytail by Nelson and Strieter,8,4 who also present some in- formation on a Mg-low Ce-Mischmetal-Zr alloy, and by Nelson.8 A patent issued to Jessup, Emley, and Fisher9 emphasizes the superiority of Mg-didymium-Zn-Zr alloys over the corresponding alloys made with Mischmetal. The purpose of this paper is to present the results of an extensive investigation concerned with the effect of increasing amounts of zirconium on magnesium sand casting alloys containing several different rare earth metal mixtures in varying amounts. The effect of the addition of zinc to some of these alloys is also being reported. Preparation and Testing of Alloys The alloys studied in this investigation were prepared in small laboratory melts according to the melting procedures described by Nelson1" as the Crucible Method. Electrolytic magnesium having the composition shown in Table I was used as the starting material. The rare earth metal alloying ingredients used in preparing these alloys were essentially of the compositions listed in Table 11. Some of the didymium-containing alloys were prepared using a Mg-didymium hardener. The rare earth metal content of this hardener analyzed 1.2 pct Ce, 10.4 pct Pr, 80.8 pct Nd, and 7.6 pct La. The zirconium was added in one of three forms: 1) as sponge zirconium obtained from the Bureau of Mines; 2) as a fused salt consisting of 50 pct ZrCl, and 50 pct alkali chlorides from which the zirconium is reduced by the magnesium; or 3) as a Mg-Zr hardener. The alloying procedures and melt hand-

Jan 1, 1958

LIST OF MEMBERS AND ASSOCIATES ARRANGED ACCORDING TO STATES AND TOWNS ALABAMA Aldrich, Aldrich, W F Anniston, Noble, A E, Smith, N B Aibacoche, Bradley, D II Bessemer, Fergusson, V Birmingham, Aldrich, T H, Aldrich, T H, Jr, Bowron, J, Bowron, C E, Davis, F H, Dimmick, F D, Hillman, McCarthy, M E , McCormack, McCrery, Ramsay, E, Shook, A M Bridge¬port, Wheeler, S K Ensley, McDonald, S, Shook, J W Fanbanks, Hamil¬ton, A L Helena, Squire, J Huntsville, Moss Lehigh, Toulmin Oxmoor, Green¬amyer, A G Plasma, Gage Rock Run, Garvin Sheffileld, Miller, D I Tuscaloesa, Lodge, J University, McCalley Woodward, Bukofzer, Woodward, A H ALASKA Dawson, Buck Douglas Island, Corbus, J P , Macdonald, J Hames, Le Wald, E A Jualin, Hoggatt, W B Juneau, Denby, Gaifield, Garside, Hamp¬ton, W H Rodman Bay, Phillpots Snettisham, Tisdale Sumdum, Thane Tel¬ler, Hirshberg, M R Treadwell City, Batcheller, J H , Kinzie Valdez, Esterly, G M Yukon, Dawson, Elmer, J M ARIZONA Bisbee, Clark, G C, Coombs, H L , Douglas, W, Hoatson, Parnall, S A, Pelton, R T, Ricketts, L D, Sherman, G F G, Smith, F W, Smith, H A Black Diamond, Bagge Blanchard, Cummins, Murray, J J Casa Grande, Rich¬mond, A B Clifton, Colquhoun, Grabill, Murray, H T , Plater, Smith, J D A, Veitch, Watson, W S Congress, Goodloe Crown King, Alexander, G E Douglas, Cornell, Kraemer, E L, Lee, G B, Rutherford, F Globe, Berray, Hoar, Snell Harrisburg, Smith, F C Jerome, Clark, W A, Thomas, C A Kingman, Treadwell, Wallace, J P Kirkland, Bretherton, G K Kofa, Lamp¬shire, J O , Pomeroy, H G Mayer, Haggott, E A Metca j, Blumenkranz, M , Forbes, D L H Morenca, Clark, C D, Fleming, J B, Honey man, Mills, C E, Wallace, L R Morristown, Stevens, H W Nogales, Glove, H G, Sandoval, A , Sandoval, P Octave, Rose, G W Phoenix, Armstrong, T , Butler, C E, Defty, Lindsay, L Prescott, Blauvelt, H , Bunker, C E, Claypool, W M , Drescher, F M , Fairbank, Nissen Tombstone, Gage, Poindexter, C L , Staunton, Walker, E W Troy, Cutting Tucson, Blake, W P, Burgess, De Lashmutt, I, McCleary, Mann, Prout, J W , Jr ARKANSAS Fayetteville, Purdue Fort Smith, Bache, F , Denman, H Little Rock, Fordyce, Scholz CALIFORNIA Alameda, Arents, King, L Arnador City, Downs, Tregloan Angeles Camp, Dig¬gles, R N , Kenney, C E Antioch, Belshaw Auburn, Coe, I J Ballarat, Thorns Berkeley, Abadie,, Christy, Dozier, Hall, F F , Hersam, Landfield, Lind¬say, L , Mansfield, N T, Morley, W S , Sharwood, W J Bag Oak Flat, Dron Bodae, Hamilton, W R, Hoover, T, Hoover, T J, Jackson, B L , Nutter , E, H Bullion, Power, H T Callahan, Scott, E H Campo Seco, Baird Cartero,

Jan 1, 1910

A SPRING meeting is to be held at Cleveland this month under the joint auspices of the Iron and Steel Committee and the Ohio Section with the cooperation of the neighboring sections in Pennsyl-vania, Illinois, and the other States of the Great Lakes region. The discussions will be focused on just one subject, that of manganese, but will cover that thor- oughly as is indicated by the following list of papers. TECHNICAL PROGRAM Some Political Aspects of the World Manganese Situa-tion. By C. K. Leith, Professor of Geology, Uni-versity of Wisconsin, Madison, Wis. Manganese Resources in Relation to Domestic Con-sumption. By J. V. W. Reynders, Consulting En-gineer, New York, N. Y. Manganese Deposits of the' Gold Coast, Africa. By Sir Arthur E. Kitson, Director of the Geological Sur-vey of the Gold Coast, London; with Notes on the Petrology of Certain Associated Manganese Silicate-bearing Rocks. By Maj. N. R. Junner. Reserves of Lake Superior Manganiferous Iron Ores. By Carl Zapffe, Manager, iron ore properties, North-ern Pacific Railway Co., Brainerd, Minn. Iron Manganese Alloys Low in Carbon. By. Sir Robert Hadfield, Hadfields, Ltd., London. Manganese in Non-ferrous Alloys. By M. G. Corson, Consulting Engineer, New York, N. Y. Importance of Manganese in the Steel Industry. By H. M. Boylston, Professor of Metallurgy, Case School of Applied Science, Cleveland, Ohio. Minnesota Manganiferous Iron Ore in Relation to the Iron and Steel Industry. By T. L. Joseph, E. P. Barnett and C. E. Wood of the North Central Min-ing, Experiment Station, U. S. Bureau of Mines, Minneapolis, Minn. Representatives of the leading steel companies, the Army, the Navy, the Geological Survey, Bureau of Mines, and leading technical societies will be present and a lively discussion of the various papers is already assured. Nearly 14 pounds of manganese is needed for every ton of steel made. Estimates indicate that the total reserves of ore in this country suitable for making ferro would hardly supply domestic requirements for ten years, even if it could all be mined in that time. The grade of ore called for by present practice must come from abroad. The present tariff policy of this country is stated to cost industry $8,000,000 in order to force production of manganese ore to the extent of $600,000. What is the wise thing to do? Should a stock be accumulated? If so, how? Is it feasible to change practice and use low-grade ore or to beneficiate the ores of this grade and meet our requirements? What progress is being made in this direction? ,These and similar questions are raised in the various papers that have been submitted and will be open for dis-cussion.

Jan 3, 1927

By P. S. Kotval

THE nominal composition of "hconel" alloy 718 is 53 pct Ni-19 pct Cr-19 pct Fe-3 pct Mo-5 pct Cb-0.8 pct Ti-0.6 pct A1-0.05 pct C. The nature of the fine strengthening phase in this alloy has been open to debate. iseelstein' has identified the strengthening phase in the matrix of "Inconel" alloy 718 as a colum-bium-rich fcc y' precipitate. Wagner and Hall2 have noted that the metastable y' precipitate overages to an orthorhombic Ni3Cb precipitate which manifests itself as an acicular phase. These authors thus clarify Kaufman and Palty's earlier suggestion3 that the strengthening phase is orthorhombic NisCb. Wagner and Hall's review also reports work by cometto4 which suggests that the fine strengthening phase is not fcc / but bct with a Ni3V type structure and based on the Ni3Cb composition. Kir man and warringtons have shown by analysis of electron diffraction patterns that the metastable strengthening phase in a 55 pct Ni-15 pct 0-25 pct Fe-5 pct Cb alloy is bct and based on the Ni3Cb composition. Raymond~ has provided electron diffraction evidence which indicates that "y'" in "Inconel" alloy 718 is bct in structure. This note presents unambiguous data on the structure of the strengthening phase in "Inconel" alloy 718* ihe samples of this alloy were provided by courtesy of the ASTM task group on phase identification in 'superalloys. after prolonged aging. The electron diffraction patterns presented show that strengthening phase is not y' but bct as was proposed by cometto,' supported by Raymond,~ and identified by Kirman and warringtons in a similar system. Fig. 1 shows a selected-area diffraction pattern taken from a thin foil of "Inconel" alloy 718. The sample had received a final aging treatment of 1118 hr at 1200°F to precipitate the strengthening phase in the matrix. Fig. 2 is a schematic representation of the features in the diffraction pattern. The matrix orientation is (0i2)~,, as is shown by the indexed zone in Fig. 3. Figs. 4, 5, and 6 illustrate that the pattern, Fig. 1, is composed of three bct zones, viz., (0i4), (2i0), and (i01), respectively. These three zones correspond, respectively, to the alignment of the c axis of the bct unit cell with the [001], [loo], and [OlO] directions of the fcc matrix and serve to illustrate the fully coherent relationship of the precipitate structure with the matrix. The streaking of certain reflections is also consistent with the above orientation relationship. The interpretation of the diffraction effects presented here shows the metastable strengthening precipitate in "Inconel" 718 alloy to be bct in structure and demonstrates that it is not an ordered fcc y' phase.

Jan 1, 1969

By R. W. Guard

ALTHOUGH etching techniques have been developed for revealing dislocation sites in several metals and ionic crystals,h t is valuable to extend the technique to new metals. An etch pit method for nickel has been developed on the basis some suggestions of Dr. John R. Cuthill of the National Bureau of Standards who had observed etch pits in creep specimens of nickel. The etchant used was proposed first by wensch2 for revealing grain size in nickel. The present paper describes the evidence that the technique can be used to reveal dislocations and gives the conditions under which etching can be carried out. The specimens examined were vacuum melted high-purity Ni (99.985 pct Ni) and commercial "A" nickel (99.8 pct Ni). Both materials contained greater than 0.008 pet C and had been annealed in nitrogen or dry hydrogen at 1100o to 1200°C. This gave a grain size of 1.5 mm in the high-purity nickel and 0.050 mm in "A" nickel. Tensile specimens (0.254 in. diam) were deformed from 0.25 to 10 pct at room temperature and then heated for 1/2 hr at different temperatures from 400" to 900°C. The specimens were sectioned longitudinally then polished electrolytically in 60 pct H2SO4 and etched in 35 pct H3PO4 solution at 0.2 to 0.4 v for 30 sec to 3 min. The best method for setting the proper voltage for etching is to increase the voltage until gas bubbles are evolved vigorously from the specimen and then cut it back by 10 pct. It is necessary to heat the specimen above 500°C after deformation in order that etch pits will be formed. This "decoration" treatment permits carbon to segregate to the dislocation rendering them sensitive to etching. It was demonstrated that carbon was the decorating impurity by decarburizing some specimens in wet H2 at 1200°C. The susceptibility to etch pitting was lost following this treatment but could be restored by carburizing in contact with graphite. Some rearrangement of the dislocations in the as-deformed structure occurs on heating at 500oC and above so that the technique can not be used to study the nature of dislocation patterns in deformed specimens. Extended etching does not change the number of pits although the background becomes rough and the pits quite large. The polycrystalline specimens with various strains were examined after annealing at different temperatures. Typical patterns are shown in Figs. 1 and 2. In the unstrained specimen, Fig. 1, the density of pits is 2.5 X 10' per sq cm. All grains show pits regardless of their orientation although there is a

Jan 1, 1961