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By K. Brack, G. H. Schwuttke

Annealing properties of subszerface amorphous lavers produced through high-energy ion implantation in silicon are studied. The buried layers are produced through the implantation of ions (nitrogen), ranging in energy from 1.5 to 2 mev. X-ray interference patterns, transmission electron microscopy, and resistivity profiling are used to study the annealing characteristics of the ion damage. The annealing experiments indicate a low temperature (below 700°C) and a high temperature (above 700°C) region. Significant changes occur in the amorphous layer during the high-temperature anneal. Such changes are corre-lated with the re crystallization of the amorphous silicon and the formation of subsurface (buried) silicon-nitride films. TODAY'S main problems in the field of ion implantation are related to the accurate determination and prediction of 1) the distribution profiles of implanted ions, 2) the lattice sites occupied by the implanted ions, 3) the lattice damage produced through ion implantation, and 4) the annealing characteristics of damage centers in the lattice. This paper reports investigations concerned with the problems listed under 3) and 4). EXPERIMENTAL Our investigations cover the energy range of incident ions from 100 to 300 mev and from 1 to 2.5 mev. The emphasis of this study is on the energy range from 1.5 to 2 mev. The experiments are conducted with single charged nitrogen ions. To implant the ions a van de Graaff generator is used as described by Roosild et al.1 Accordingly, a gas containing the desired ion specie is passed through a thermome-chanical leak into a radio frequency activated source. The positive ions are driven into the van de Graaff with the help of a variable voltage probe. Emerging from the accelerator the ions drift into a magnetic analyzing system and here the desired ion specie is bent 90 deg into the exit port. The ion beam leaving the analyzer is defocused and drifts down a 4-ft long tube to hit the silicon target. At this position the 20 pamp ion beam has a circular cross-section of 2.1 cm. N2 is used as a source gas for nitrogen ions. The implantation target is silicon with zero dislocation density, 2 ohm-cm resistivity, (111) orientation, mechanically-chemically polished, and 1 mm thick. The target is mounted on a water-cooled heat sink and kept at room temperature. A fluence of 1015 to 1016 ions per sq cm is used. RESULTS 1) Silicon Perfection after Bombardment. High-energy ion bombardment of silicon has some striking effects on lattice perfection. Some results were reported in detail previously at the Santa Fe conference2 and are here briefly summarized for the benefit of the experiments described in the following. 1.1) Identification of Surface Films on Silicon. After bombardment all samples are found to be coated with surface films. The films on the silicon surface vary in thickness and color; they can be transparent, slightly brown, or opaque. The films are thicker and darker in the high-intensity area of the beam and they delineate the bombarded surface area of the crystal. The films produce electron diffraction patterns characteristic of carbon and of SiO2. Carbon is predominant. The presence of carbon in these films was confirmed by use of the electron microprobe. Formation of the films occurs independently of the ions used and is attributed to a contaminated vacuum of the high-voltage machine. The carbon is most likely the product of the pump oil which is cracked and polymerized under ion impact. The films stick tenaciously to the silicon surface and burn off in a low-temperature Bunsen flame. 1.2) Mechanical Perfection of the Silicon Surface. The mechanical perfection of the bombarded silicon surface was investigated through optical microscopy, electron microscopy in which the replica technique is used, and optical interferometry. No mechanical damage of the surface was visible after bombardment. However, if a bombarded sample is soaked for several minutes in hydrofluoric acid (HF), gas bubbles may develop in certain spots of the silicon surface. It is also noted that in these areas the surface film starts to peel off. Relatively large patches of film come off if the sample is soaked in HF during ultrasonic agitation. After HF treatment, pits may be present on the silicon surface. The pit dimensions are estimated to be as large as 50 µ. The pits appear in the region of most intense irradiation. 1.3) Lattice Perfection After Bombardment. No lattice damage is found on the silicon surface. Electron transmission micrographs and selected area diffraction patterns of the surface show no difference before and after bombardment. Measured approximately 2 µm down from the surface, the silicon lattice throughout this depth is of good perfection. Well-defined Laue spots and Kikuchi lines are obtained from the surface as well as from the indicated area below the surface. However, some radiation damage is dispersed in this top layer. A sharp boundary line separates this surface layer from a highly damaged layer which extends further downward into the silicon. Typical of this

Jan 1, 1970

By E. T. Dumble

Discussion of the paper of E. T. DUMBLE, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 104, August, 1915, pp. .1623 to 1638. E. L. DEGOLYER, Norman, Okla. (communIcatIon to the Secretary*).-Referring to Mr. Dumble's description of the stratigraphy of eastern Mexico, I should like to question the classification of the ?Papagallos? or ?Mendez? shales as being of Cretaceous age and the so-called overlapping of the Papagallos or Mendez shales by the Alazan shales; the classification of the San Felipe series as Cretaceous, and the correlation of the San Felipe series with the San Juan limestones. Mr. Durable apparently recognizes the continuity of the great shale formation by his use of the terms "Papagallos" and "Mendez," as equivalent and interchangeable, since the Papagallos Hills in the State of Nuevo Leon and Mendez Station in Northern Vera Cruz, localities at which the shale formation outcrops, and from which the formation names are taken, are approximately 250 miles apart and on opposite sides of the Tamaulipas barrier. The Papagallos shales (evidently referring here to the northern extension only) are said to be non-fossiliferous and no reason for .their Cretaceous classification is given, though in a previous article' they are classified as Cretaceous because at their northernmost outcrop they "have the same relation toward the overlying Tertiary that the Escondido (Cretaceous) has through its whole extent." The Alazan fossil locality was found by me and the first collections from it were sent to Dr. Dall; about 17 species of marine invertebrates were recognized by him, the fauna noted as having a distinct Pacific tincture, and the age of the formation from which they cause pronounced lower Eocene. The outcrop of the shale formation has been traced continuously from this point by me and my assistants into the Panuco River region, where Eocene fossils are reported at a depth of 1,810 ft. in a well at Topila.2 From Topila the formation has been traced continuously north to the Padilla-Jiminez region in Central Tamaulipas. Lithologically, the formation is fairly constant and though I am only generally acquainted with it north of the Padilla-Jiminez region, until definite evidence of the Cretaceous age of the Papagallos shale in its type localities, or of an overlap, is available, it seems to me more logical to consider the shale formation a single stratigraphic unit of Eocene age.

Jan 12, 1915

By G. K. Manning, A. R. Elsea, C. R. Simcoe

Boron increases the hardenability of hypoeutectoid steels by decreasing the nucleation rate of ferrite and bainite. It is postulated that concentrations of lattice imperfections, such as exist at the grain boundaries, furnish the necessary energy for nucleus formation. Boron, because of its atomic diameter, will concentrate at lattice imperfections where sites of suitable size are present. Boron will decrease the energy of these local areas by occupying these sites. This mechanism accounts for the large increase in hardenability observed with small amounts of boron. The loss of the boron hardenability effect and the boron precipitate formation are explained on the basis of increased concentration of boron at the grain boundaries either with increasing boron content of the material or with increasing temperature. COMMON alloying elements affect both the nucleation and growth rates of the austenite decomposition reactions.' This effect is largely a result of the slow diffusion rates of these elements. Although a small addition of boron markedly increases the hardenability of steel, the diffusion rate of boron, which is of the same order of magnitude as that of carbon, can hardly account for this effect. An addition of boron in the range of 0.001 to 0.003 pct is about as effective as an addition of 0.30 pct Mo, 0.40 pct Cr, or 1.25 pct Ni in increasing the hardenability of a 0.40 pct C steel;' however, increasing the carbon content of the steel decreases the effectiveness of the boron addition."' The difficulty in understanding why so small an addition of boron can replace much larger quantities of the more strategic alloys, together with the erratic behavior sometimes encountered in boron-treated steels, has interfered with their general acceptance by industry. In the belief that an understanding of the mechanism by which boron increases the hardenability of steel should lead to a more general acceptance of boron-treated steels, a research investigation to determine this mechanism was undertaken at Battelle Memorial Institute under sponsorship of Wright Air Development Center. Experimental Work In order to study the effect of boron on the transformation of austenite to ferrite and bainite, a group of steels was made with a basic composition similar to that of the SAE 8600 series. This base composition was chosen because it has sufficient hardenability to permit accurate measurement of the times required for transformation to start at various temperatures. The chemical analyses of the steels used in the first part of this investigation are listed in Table I. These steels were made as 200 lb heats in an induction furnace. The furnace charge was Armco ingot iron with the alloying elements added as ferroalloys. After the alloy additions were made, the heat was deoxidized with 0.125 pct Al. A 100 lb ingot was cast and an addition of 0.003 pct B, as ferroboron, was made to the metal remaining in the furnace. This metal was cast into a second 100 lb ingot. The ingots were forged to 11/4 in. diam bar stock from which end-quench hardenability specimens were obtained. Part of this material was further reduced by hot rolling to lx¼ in. bar stock from which specimens were obtained for isothermal transformation studies. Studies of Nucleation and Growth: End-quench hardenability tests were performed on these steels, using an austenitizing temperature of 1600°F. The hardenability curves, shown in Fig. 1, indicate that boron treatment resulted in considerable increase in hardenability of the steels. Any such change in hardenability must result from a change in the transformation rate of the austenite, and these rate changes can be established readily by isothermal transformation studies. Isothermal transformation studies were conducted on these steels as follows: specimens were austeni-tized at 1600°F for 15 min, transferred to a lead bath operating at a constant subcritical or intercritical temperature, held for various lengths of time, and water quenched. The specimens were sectioned for metallographic examination to determine the amount and the type of transformation products present. In order to determine the effect of boron on the formation rate of ferrite, isothermal transformation tests were made on the 0.20 pct C steel in both the boron-treated and boron-free condition at an intercritical temperature of 1375°F where ferrite is the only decomposition product of this low carbon austenite. The results of these tests are shown in Fig. 2, where the percentage of ferrite formed is plotted as a function of time at temperature. It is apparent that boron markedly decreased the transformation rate of austenite to ferrite at this temperature.

Jan 1, 1956

By W. M. McKewan, R. G. Olsson

In order to improve the understanding of the iron oxide reduction mechanism, the rate of equal molar diffusion of hydrogen and water vapor was measured through disks of porous iron and alumina. The measuretneizts were made at atmospheric pressure at 800°, 900- , and 1000°C. It is shown tint the reduction of dense hematite pellets with hydrogen at these temperatures and at atmospheric pressure is to a great extent limited by gaseous diffusion between the bulk-gas phase and the iron-wustile interface. THE investigation of the reduction of iron oxides with hydrogen has been the subject of numerous papers. Although the effects of temperature, pressure, and gas composition on the rate of iron oxide reduction have been studied, the actual mechanism of the reduction process has not been definitely determined. As a means of improving the understanding of the mechanism, the rate of equal molar counterdiffusion of hydrogen and water vapor was measured through porous iron and porous alumina disks at reduction temperatures. The alumina was used as a basis of compari-son because its pore structure is homogeneous and independent of temperature. The porous iron was prepared by the reduction of dense hematite disks with hydrogen at the temperature of the subsequent diffusion experiment. The hematite disks were made from pellets that were identical to those used by McKewan1,2 in his study of iron oxide reduction with hydrogen. In these investigations the weight loss and rate of movement of the various interfaces were measured as a function of the reduction temperature and gas composition. With these reduction data and the presently reported diffusion data it is possible to determine the importance of H2-H2O transport between the bulk-gas phase and the Fe/FeO interface to the reduction of dense hematite. APPARATUS AND PROCEDURE A porous iron or alumina sample was held in the base plate of a sealed canister containing porous granular wustite, as illustrated schematically in Fig. 1. The canister was suspended from an automatic recording balance in a vertical tube furnace through which flowed hydrogen and water-vapor mixtures of known composition at atmospheric pressure (0.96 atm). Hydrogen from the gas stream diffused through the porous sample, reducing the wustite in the interior of the canister. The water vapor that was formed diffused back to the gas stream. The rate of diffusion was determined from the recorded weightloss data. The furnace, automatic balance, and gas-metering equipment have been described previously.2 The main body of the canister and the tubing extension were made of stainless steel while the base plate was made of high-purity iron. The main body of the canister was % in. in diam. It held approximately 6 g of porous granular wustite that was prepared by reducing 0.1- to 0.2-cm-diam specular hematite particles at 900°C with an H2-H2O mixture of a composition near the iron-wustite equilibrium value. The upper end of the 1/8-in.-diam tubing extension was sealed with a segment of plastic tubing and a tubing clamp. The temperature at the top of the furnace was sufficiently high so that no water vapor condensed inside the extension. In the experiments with porous iron, iron oxide samples were prepared from reagent-grade hematite that was pressed and sintered in a manner previously described.' The resulting pellets had a density of 5.15 ± 0.05 g per cu cm. Each pellet was centerless-ground

Jan 1, 1967

By H. Foster Bain

THE "miracle of production." which was such an essential element in winning the European war, was nowhere more in evidence than in our Western States. In shipbuilding alone the Pacific Coast States -et a mark never before equaled, and in production of war goods of many kinds, both Rocky Mountain and Coast States accomplished more than their proportionate share if measured by population standards. This was only possible because of the building of immense new plants of many types, largely financed with Government money. Their operation has built up payrolls in the West and brought a measure of prosperity which Westerners are naturally anxious to have made permanent. A widespread doubt obtains, however, throughout the nation and even in the Western States themselves, as to whether, and if so to what extent, this may prove possible. The question has been raised as to whether the national treasury has not been raided to stock the Western ranges with a voracious breed of white elephant .

Jan 1, 1945

By A. Josefsson

The transition temperatures of 0.01 to 0.02 pct carbon steels are shown to be strongly influenced by cooling rate in the a range, quenching from A, causing a very low transition temperature even after strain aging. In a titanium-stabilized steel and in a steel with 0.05 pct C this effect is absent. NORMAL mild structural steels usually show a structure of more or less pure ferrite, as a matrix, in which cementite grains or pearlite are embedded. Of these components, ferrite is by far the most interesting one as far as ductility and brittle (cleavage) fracture are concerned. Obviously, pear-lite and carbide are by no means necessary for a cleavage crack to nucleate and grow in the ferrite, as steels with a very low carbon content (Armco iron with 0.02 pct C) have an impact transition temperature just as high as semikilled steels with 0.26 pct C.1 Although it has been argued that a very embrittling effect is to be expected from cementite, precipitated as continuous films along the ferrite grain boundaries,'. " the micrographic evidence for a direct causal connection between the brittleness and these films does not seem to be very convincing. On the other hand, it has been stated that cementite particles in ferrite are able to stop ferrite cracks.4,5 In any case, the properties of the ferrite itself seem to be of overwhelming importance to the ductility of steels, justifying a thorough study of steels consisting of ferrite of different compositions, but principally free from pearlite, which means a carbon content below 0.02 pct. Such investigations have been carried out using the impact transition temperature as a criterion of the tendency to brittle fracture and have given some rather unexpected results. One result is the profound influence of carbon on the transition temperature of the steel in normalized condition. If the carbon content is reduced from 0.02 to 0.015 pct and below, a nearly discontinuous decrease in transition temperature appears even with high percentages of such elements as phosphorus and nitrogen present. This will be reported elsewhere." The present paper deals with another effect of carbon upon transition

Jan 1, 1955

By Strathmore R. B. Cooke

On the basis of experiments con- ducted on quartz using a bubble pick-up method, it was shown in an earlier paper1 that this mineral will preferentially adsorb hydrogen, calcium, or sodium ions, depending on the relative concentrations of those ions in the solution in which the quartz is immersed. For quartz particles ranging in size from 0.2 to 1 mm, it was demonstrated that the concentration of calcium in solution (assumed present as ions) necessary to completely activate quartz for flotation is given by the expression: In this expression, ionic concentrations are in mols per liter. It was further shown that the pick-up method is apparently more sensitive to changes in reagent concentration than the standard captive-bubble method, and that induction times are apparently much reduced. Since completing these earlier tests, a new type of cell has been constructed; this is shown in Fig 1 and 2. In Fig 1, A is a ground joint, B is a ceutral tube reaching to within a few millimeters of the bottom of the cell, and C is a stopper which may be removed for re- agent addition, and serves the further purpose of excluding carbon dioxide from the air during the test. The entire cell is constructed of Pyrex glass, and does not give the trouble experienced with the earlier cell, in which activating ions were released from the glass at high pH values. The only critical factor in the construction of the cell is the clearance between the central tube and

Jan 1, 1949

By N. A. D. Parlee

The diffusion rate of hydrogen in liquid iron has been measured by a gas-liquid metal diffusion cell technique. The diffusion cell was formed by immersing an alumina tube containing hydrogen gas at 1 atm in a bath of stagnant liquid iron. The change in the composition of the melt in the cell was determined by measuring the rate of absorption of the gas in the cell. The appropriate solution to Fick's second law was used to examine the data and calculate diffusivi-ties. The absorption of hydrogen in stagnant pure liquid iron has been found to be diffusion-controlled. The results show that the chemical diffusion coefficient, D, of hydrogen in pure iron in the range of 1547" to 1726°C can be represented by the following Arrhenius relation: D(sq cnz per sec) = 3.2 x X exp(- 3300 i 1800/RT) where the uncertainty in the activation energy corresponds to the YO pct confidence level. Oxygen in the melt (above 0.015 pct 2) increased the apparent rate of absorption of hydrogen. The importance of diffusion data on liquid metals for predicting the rates of certain metallurgical processes has been recognized for a long time. Moreover, these data are much needed to test and develop theory for diffusion in liquid metals. Despite this practical and theoretical interest, however, relatively little reliable information about diffusion in liquid metals is available in the literature. This is particularly true for gas components such as hydrogen, oxygen, and nitrogen in liquid metals, where almost no data on chemical diffusion coefficients are to be found. This is probably due to a multitude of experimental difficulties particularly associated with high-temperature melts. In an effort to fill this gap in information, a research program was undertaken to study the diffusivities and rates of solution of gases in liquid metals. This paper presents the results of a study of the diffusion of hydrogen in liquid iron. EXPERIMENTAL METHOD Two methods for the study of the kinetics of dissolution of gases in liquid metals are being employed in this laboratory. Both involve the measurement of the volume of gas absorbed by the melt as a function of time and as such both avoid the uncertainties involved in chemical analyses of quenched samples for relatively small amounts of gas. In the first method, the gas dissolves in an inductively stirred melt and, in the absence of a slow surface reaction, the results are often interpreted in terms of mass transport across a liquid "boundary layer" between the homogeneous gas phase and well-stirred part of the melt. Other interpretations of the results of such experiments have also been described in the literature.1'5 In the second method a gas-liquid metal diffusion cell is used.' The gas dissolves in a cylindrical column of stagnant liquid metal and, in the absence of a slow surface reaction, the results are interpreted in terms of a non-steady-state diffusion solution to Fick's second law. The weakness of the first method is that while it gives information on the mechanism of absorption by stirred melts it yields an overall rate constant which even in the simplest cases depends on the nature and the thickness of the "mass transport layer" or "boundary layer". It yields no values of diffusion coefficients. The second method was used in this research because in many cases it is possible to determine the diffusion coefficient of the gas component in the liquid metal. In this research it has been utilized to measure diffusion coefficients of hydrogen in liquid iron. The apparatus used was essentially the same as that described by Mizikar, Grace, and par lee but certain modifications have been introduced to meet the elevated temperatures and special conditions of this research. Fig. 1 is a schematic drawing of the apparatus and Table I gives the identification of various parts in this figure. The diffusion cell, shown in detail in Fig. 2, was formed by immersing an impervious alumina tube (hereafter called absorption tube) in a bath of pure liquid iron contained in an alumina crucible. Two types of tubes were used, Morganite triangle RR and McDanel AP35. The crucible was contained in a vertical impervious alumina combustion tube (32 mm ID by 914 mm long) which was closed at both ends by water-cooled brass heads employing O-ring compression seals, Fig. 1. A protection tube enclosing a Pt, 5 pct Rh-Pt, 20 pct Rh thermocouple was introduced through the lower end of the combustion tube

Jan 1, 1968

By Edward N. Trump

EXTENSIVE beds of rock salt occur in New York, Michigan, Kansas, and Texas. Wells are drilled through the beds, cased, and equipped with a suspended center tube. By circulating water through such a well, the soluble saline is dissolved and a brine produced. Operation of a well results ordinarily in the formation of an inverted conical cavity in the saline, inasmuch as the dissolving action of the fresh water is more rapid at the top of the bed than at the bottom. Under continued operations, the side wall of the cavity becomes so flat that a blanket of mud is deposited thereon and if the bed is overlain with shale or a soft rock caving follows. Three methods of operating wells have been employed-the "Tully plan," "the Detroit plan," and "the Trump plan." Both the Tully plan and the Detroit plan involve the formation of the aforesaid conical cavity with constant caving of shale above and deposition of mud on the side wall; the Trump plan was developed to avoid both these circumstances and thus materially prolong the life of a well. Details of the three plans follow. THE TULLY PLAN In the Tully plan, the water passes down the annular space between the casing and the center -tube, the brine rising in the center tube (Figs. I and 2). An inverted conical cavity is formed, the side wall of which relatively soon becomes so flat that it is blanketed by mud and impurities from the rock salt; this blanket limits dissolving action to the perimeter of the base of the cone, situated at the top of the saline bed. Caving of the overlying strata follows, and the total production of brine from the well is comparatively small. THE DETROIT PLAN In the Detroit plan, the water passes down the center tube, the brine rising in the annular space between the center tube and casing (Figs. I and 2). Initially, this flow forms a pear-shaped cavity in the bottom of the salt bed, but this cavity soon changes in shape to that of an inverted cone, as under the Tully plan, with the attendant disadvantages inherent in that plan. Application of the Detroit plan is limited to salt beds 300 ft. thick as a minimum. This depth of bed is necessary to prevent fresh water of lower specific gravity than the brine from rising in the

Jan 1, 1944

By D. A. Elgillani, M. C. Fuerstenau, J. D. Miller

Adsorption of lead and ferric iron on quartz and alumina is presented as a function of pH. Only the hydrolyzed species of these metal ions, FeOH++ and PbOH+, adsorb significantly on each of these minerals. Zeta potentials of quartz were measured as a function of pH in the presence of various additions of aluminum, lead, and magnesium salts. Sign reversal occurs at the pH values where significant concentrations of hydroxy complexes are formed. Models of adsorption are presented in the absence and presence of collector. The mechanism of adsorption of metal and collector species in the activation of nonmetallic minerals is still the center of considerable discussion in spite of the extensive study given this system. Until recently, the view was widely held that hydrated metal ions were responsible for this phenomenon. This fact is surprising, since it had been shown that the pH range in which flotation is effected corresponds to that in which metal ion hydrolysis occurs.' Additional support of this concept was pro vided by the work of Wolstenholme and Schulman in another system.' Later work has shown that hydroxy complexes of metal ions are the active species. These studies have also indicated that basic aqueous complexes of metal-collector may be necessary for flotation.3-7 Depending on the molecular weight of the collector, formation of these complexes may occur before or after precipitation of the metal-collector salt has occurred. Ion pair formation can occur when low molecular weight collectors are involved because relatively high concentrations of metal hydroxy complex and collector can be present in solution before precipitation occurs. This is not the case when high molecular weight collectors are used. A model of aqueous complex adsorption has been presented6,7 in which it has been assumed that adsorption occurs by the formation of water from adsorbed hydroxyl and hydrogen of the hydroxyl contained in the complex. Other authors8 have suggested that hy-droxy complexes are involved in these systems but that collector adsorption occurs by replacement of the hydroxyl of the adsorbed metal hydroxy complex with a fatty acid anion. All of these investigations have involved mineral surfaces that were negatively charged so that it is not possible to state with certainty whether hydrated metal ions or hydroxy complexes are the active species in this system. Use of a positively charged mineral should be helpful, however, since the hydrated metal ion will be repelled from this surface. On the other hand, if the hydroxy complex adsorbs by splitting out water, surface charge should have no effect because of the free energy decrease that the system will experience when water is formed. In this regard, sapphire is well-suited for study, since its surface is positively charged until approximately pH 9. Electrokinetic studies of quartz in the presence of various metal ions should also be useful in establishing the mechanisms of adsorption in these systems. That is, if the hydroxy complexes adsorb by water formation, drastic changes in the zeta potential should occur in the pH range in which hydrolysis occurs. In this view, adsorption of ions of widely different hydrolysis characteristics on both sapphire and quartz was measured. In addition, zeta potentials of quartz were measured as a function of pH in the presence of various metal ions and compared with flotation responses obtained under similar conditions. Experimental Materials and Techniques Reagent-grade aluminum, ferric and magnesium chlorides, and lead nitrate were used in this investigation. Adjustments in pH were made with reagent-grade HCl or KOH. Conductivity water, made by passing distilled water through an ion exchange column, was used in all of the experiments.

Jan 1, 1971

By E. C. Tveter, R. B. Tippin

The separation of minerals by heavy liquids is a standard laboratory technique which goes back at least 50 years, but commercially economic application of this principal to ore concenfration has been prevented by problems of liquid recovery. Recent investigations which demonstrate the different types of liquid-solid systems on various ores using the two major heavy liquids - methylene bromide and tetra-bromoelhane — are discussed in this article. As a result of these studies, over-all liquid recovery, and especially desorption of heavy liquid from the mineral surface, was improved by the use of surfactants as well as both thermal and mechanical energy. The examples given in the article indicate that heavy liquids which should find major commercial use in ore concentration are now available. The sink-float process using a heavy liquid medium has long been recognized as a nearly perfect method of mineral separation based on the differences in density of the minerals. The use of heavy liquid separation (HLS) offers the potential of an ore dressing method that provides the maximum possible natural concentrate grade and high recovery. In addi- tion the process requires no water, causes no waste disposal problems, and is extremely simple — the crushed ore is merely introduced into a liquid whose density is between that of the minerals to be separated. The minerals lighter than the liquid float while those heavier than the liquid sink. As such, HLS has become a standard laboratory tool but major commercial application has been prevented by the requirement for complete recovery of the heavy liquid, imposed by economics and materials handling hazards. Investigations, both in the United States and abroad, have shown that improved liquid stability as well as improved chemical engineering techniques brighten the future for HLS in ore dressing. The available commercial heavy liquids suitable for mineral separation cost from $2.00 to $20.00 per gallon1 and on this basis alone their complete recovery is economically desirable. Possibly of even greater importance is the fact that any residual heavy liquid remaining on the products could create a serious toxicity hazard. Consequently, to make the process commercially attractive requires (1) essentially complete removal of the liquid from the ore products and (2) optimum recovery of the liquid for reuse. Until recently these two stipulations have remained as obstacles but laboratory and pilot plant research now in progress suggests that these may soon be overcome. Various heavy liquid recovery systems have been proposed to meet these requirements and might be classified into one or more of the following three general classes: Solvent Wash (Fig. 1): The dissolution of the heavy liquid from the ore with a less expensive solvent,

Jan 1, 1969

By Morris Cohen, Robert C. Ruhl

The phases in Fe-C alloys over a wide composition range have been studied after splal quenching from the liquid state. Binary alloys containing 0 to 5.1 wt pel C as /cell as a large number of ternary Fe-C-Si alloys with 2.5 to 5.0 wt pct C and 0.3 to 5.1 wt pct Si were attlong those sludied. Olher Fe-C-X alloys, zcilh X being Co, Cr, ,Wn, Ni, and Ru , were also inrestigated after splat quenching. At high carbon contents, a new hcp phase (designaled 6 phase, but different from e carbide) is retained upon splat quenching. The .fraction of this phase varies up lo 97 pcl for a Fe-4.K-1.9% alloy. The composition of the E phase ranges from about 3.8 10 4.8 wt pet C, and the corresponding laltice parameters increase linearly ulith carbon content, while the c/a ratio remains essentially conslc~nl. The E phrtse appears to he a solulion of carbon in E iron, the latler being nornially found only at high pressures. It is deduced that the unit cell of the E phase corresponds to the formula Fe12C3, and llzal il is relaled to tlie ordered slruclures 0.f 6 iron carbide and c iron nilride. The E phase is compared and contrasted to the olher known carbides and nitrides of iron and nickel. An exlrapolaTion of the atomic volume 1,s carhon conlent of /he E pllase lzcts giz.en a neu7 estitnale jor /he alomic volume of E iron, 11.30 cu A, a1 atmospheric pressure and temperature. Other alomic volume relalionships lead to /he co~zpositioti Fe2.iC tor E iron carbide, /he unit cell fortr~ula being -Fe2rClo The E phase undergoes a lulo-slage decomposition upon healing, .forrning firsl rnarlensile plus E carhide, a/ler 1 hr at 140" lo 200°C, slid then ferr ite Plus cementile, after 1 lir a1 330" to 460°C. A1 carbo,l contents between 1.5 and 3.0 LC/ pcl, (he predo.wirzar/t plzase alley quenching is fcc austenite. The retained carbon content of this phase increases with itlcreasing silicon in certain concentration ranges, reaching a maximum of 2.37 wt pct C itz a Fe-2.6C-4.OSi alloy. This is the highest carbon conten1 reLaitled in austenite to date. These high-carbon aus-tenites can be partially tm?zsforttled lo tnartensile hy severe deformation in the temperature range of — 190 to -50°C. TECHNIQUES for splat quenching from the liquid state have been utilized in numerous recent investigations to produce metastable phases in a variety of alloy systems. Among the several ways of splat quenching, the shock-tube method appears to yield the highest cooling rates1-3, 7, 8 and was adopted here. Estimated cooling rates attained in the present experiments ranged from 10' to 10 80Cper sec.' As a part of a research program on interstitial al- loy phases, the Fe-C system was selected for splat-quenching studies. It was hoped that splat quenching would allow high metastable supersaturations of carbon to be retained in solution. Also of considerable interest were the conditions governing the occurrence of the various intermediate phases upon solidification. The alloys investigated included both binary Fe-C compositions as well as six ternary Fe-C-X alloy systems. The known phases in the Fe-C system are summarized in Table I.* Only the ferrite and graphite are ent investigation.14 and is described in detail herein Table II summarizes corresponding data on Fe-N phases, which are also of interest here because of their similarity to the Fe-C phases. EXPERIMENTAL PROCEDURES Alloys were prepared by melting the elements. 99.9 pct purity, in an inert gas nonconsumable electrode arc furnace. The buttons. weighing about 5 g. were remelted twice. were then fragmented. and their interior surfaces were examined for uniformity: if any doubt existed. they were remelted again. Chemical analyses were performed on all the alloys. the accuracy being about k0.05 wt pct. At high temperatures, carbon-containing alloys react with alumina crucibles as follows: If the atmosphere in the splat-quenching furnace does not contain sufficient carbon monoxide the alloy can be depleted of carbon and contaminated with aluminum. Calculations and experimental observations showed that 50 to 100 torr CO partial pressure effectively blocked the above reaction in all the alloys investigated. The splat-quenching equipment in Figs. 1 and 2 provides for evacuation and back-filling with CO-Ar mixtures. The furnace is capable of operation up to 1650°C. and the gettering action of the graphite heating element reduces the oxygen partial pressure in the furnace atmosphere to below 10-5 torr, thus preventing oxidation of the specimens.

Jan 1, 1970

By T. M. Williams

DURING the year just ended we have had three great fires in the mines in the Wilkes-Barre district. One at the Empire Colliery, one at the Prospect shaft, and the other at the Baltimore old mine. It is proposed in this paper to give a brief history of the fire at the Empire Colliery, and the methods employed in extinguishing it. The fire was first discovered breaking out in the air-stack, alongside what is known as the " Kidder Plane," about one o'clock on the morning of December 31st, 1873. Subsequently it was ascertained that the fire originated in the return airway somewhere near the steam boiler, located inside the mine, near the head of No. 5 slope. The coal from this slope was hoisted to the shaft gangway, at a point nearly four thousand feet distant from the foot of the shaft. As there were from four to five hundred mine cars hoisted per day from this slope the steam boilers were located at this place. The mines being of considerable extent required a large volume of pure air for ventilation, and no fan having been erected at this slope at the time, the heat from the boiler was made use of to assist ventilation, by conveying the return air from No. 5 slope into the large airway made from these boilers to the surface through the old "Kidder slope" to the stack where the fire was first discovered. The length of this slope or airway was about one thousand feet, with a sectional area of about sixty feet. The quantity of air passing through it must have been over sixty thousand cubic feet per minute

By G. A. Merkt

THE Isley furnace control, here presented as a novelty in furnace construction, is, in principle, one of the oldest methods of maintaining furnace heat for industrial purposes. Records unearthed in Egyptian tombs and the primitive methods of melting metal practiced by African tribes today indicate that fanning the fire and forcing the furnace by bellows have been an effective means of regulating heat for man's work during thousands of years. Even today, these cruder forms of mechanical draft production are still nn use within the borders of this most highly developed industrial land. Stacks, as we know them, are of com- paratively recent historical age but their attractive simplicity and seeming effectiveness have made them exceedingly popular. And so we find one of the most important types of furnace the world has even known, the open-hearth furnace, duly and more or less properly equipped with a chimney. The regenerative, or reversing, type of furnace, how-ever, required another mechanism between its hearth and the stack to provide a means for alternately con-necting one side and the other of its system of regen-erative chambers and flues to the stack and to a source of fuel and air supply respectively. Various types of reversing valves were developed, some of which are re-markably well designed for maximum efficiency and ease of installation as well as operation. However, this combination has a number of inherent faults which are so difficult to correct as to make efforts in the direction of improving over-all efficiency almost futile. These inherent difficulties are as follows: (1) The necessarily high temperature at which the gases must be delivered to the stack in order to make it operative. (2) The great temperature difference incidental to the reversal of flue gas and air and consequently the large variation in preheated air and fuel delivered to the furnace dur-ing the cycle. (3) The leakages and resistances created by the reversing apparatus and the complicated flues necessary. (4) The inadequate range of control af-forded by the natural draft system, especially under adverse atmospheric conditions.

Jan 12, 1927

By E. A. Anderson

THIS seems to be the year for superlatives in A.I.M.E. meetings. The programs of the various Divisions and Institute committees offered an abundance of interesting and valuable information in the form of technical papers, symposia. and lectures to large and interested audiences. The Institute of Metals Division may hold up its head with pride for its own program. With six technical sessions, three full-day symposia, and the annual I.M.D. dinner, four meeting days were not enough and many simultaneous sessions were required. The quantity and quality of the paper were equaled by the numbers and interest of those attending.

Jan 1, 1944

By Augustus Locke

I WISH to urge on this Committee the task of evaluating mining geology. -My motive is as follows: It, is a. duty of the Institute from time to5 time, to establish the social perspective of the professions grouped within it, not simply to promote their use, but to determine with engineering definiteness their true powers and functions. This becomes the delegated duty, therefore, of this committee in respect to geology. Be- cause my own subject is mining, I shall confine my remarks to mining geology. But I believe that the evaluation should be made to include all of that geology termed economic. The perspective for such evaluation is shown in the nature of the public support given to geology. The federal Geological Survey, the leading organization on the economic side, is actuated by the zeal of a small group of devoted professionals who consider its work valuable, ' It proceeds, however, on a starvation ration of appropriations, and that implies that neither the corporations, the voters nor the vote getters consider it important. Altogether, in' the public consciousness, geology is negligible. That, at the same moment, .the profession should act with full confidence, while everyone else should act' with opposite motives, is not fitting. For us, as a committee, to remain incurious regarding such a disparity of beliefs is quite impossible.

Jan 1, 1931

By R. H. Tien

The accuracy of the method of steady-state approximation applied to the problems of heat transfer involving phase change (London and Seban's solution) is improved by defining a "modified heat of fusion" which accounts for the effect of specific heat. An analytical expression for this modified heat of fusion is derived in terms of the actual heat of fusion, specific heat, and surface temperature. Numerical solution for the freezing of iron indicates that the ratio of the modified heat of fusion to the actual heat of fusion increases from 1.04 to 1.4 as the surface temperature decreases from 2700° to 1600°F. The heat transfer process accompanying solidification is complicated owing to the moving solid-liquid interface where the latent heat of fusion is released. Exact analytical solution is available only for a few special cases of freezing problems such as Stefan's1 problem. In a commonly used steady-state approximation method, London and seban's2 solution, the effect of specific heat is neglected. This approximation, however, may introduce some degree of error in mathematical analysis when the temperature of the solid surface is much lower than the freezing temperature, as in the case of freezing metals. In a recent work by Robertson and Schenck,3 the problem of freezing a semi-infinite region with finite surface conductance was programed in a digital computer through the finite difference method. A family of curves for the correction of the London-Seban solution was given in a dimensionless plot for different ratios of heat of fusion and specific heat effect; it was shown that the London-Seban solution when applied to the freezing of a mild steel slab under some particular conditions gave results in error by about 10 pct in the solidification rate. Although the Robertson-Schenck computer result has improved the London-Seban solution to a great extent, lack of generality and the tedious computing procedure have restricted its application. In this paper a "modified heat of fusion" which accounts for the effect of specific heat is defined, and is used instead of the actual heat of fusion in the London-Seban solution. An analytical expression of this modified heat of fusion in terms of the specific heat, surface temperature, and actual heat of fusion is derived by comparing the solutions of Stefan and London-Seban for the case of freezing of a semi-infinite region with constant surface temperature. It can also be extended to the case with finite surface conductance, and the results show good agreement with the Robertson-Schenck computer solution. The expression of the modified heat of fusion, the accuracy of the London-Seban solution, and the temperature distribution within the solid are presented graphically in dimensionless form. Numerical solution for the freezing of iron indicates that the ratio of the modified heat of fusion to the actual heat of fusion increases from 1.04 to 1.40 as the surface temperature decreases from 2700° to 1600°F.

Jan 1, 1969

By Robert H. Merrill, Raymond M. Stateham

Recently, the Denver Mining Research Center of the U.S. Bureau of Mines began tests to detect hazardous or potentially hazardous conditions in or around mines with infrared measurement devices. Among the many potential uses of infrared detection techniques are the location of misfires, underground mine fires, combustion in waste dumps, underground water courses and loose rock. However, the primary emphasis has been placed upon the detection of loose rock in roofs, pillars and faces in underground mines. The rock along the edge of an underground opening is subject to two temperature environments: the temperature of the air in the opening, and the temperature of the rock surrounding the opening. Assuming that the rock on the edge of the opening is solid, the rock will reach an equilibrium temperature that depends upon the temperature and flow of the air, the thermal conductivity of the rock and its ambient temperature. Presume that a loose rock exists among this solid rock; because there is a temperature barrier, to some extent, between the loose and the solid, the loose rock will be affected more than the solid rock by the temperature of the air. Therefore, depending upon the temperature differences between the rock and the air, the loose will be warmer or cooler than the solid.

Jan 1, 1970

By W. A., Wasley

THE EL TIGRE MINE is a highgrade silver and gold producer located in the northern part of Sonora, Mexico. It has been worked continuously since 1903, producing 50,000.000 oz. of silver and returning handsome dividends. During 1930 and 1931 falling silver prices compelled the Tigre company to make representations before the Department of Labor in Mexico City showing the necessity for drastic reductions in wages and personnel. The delays in obtaining permission from the Federal Labor Board to make these readjustments caused the company to suffer considerable financial loss during those years. After the reduction in operations was finally effected, the Sonora state government headed by Señor Francisco Elias (former Governor, now Secretary of Agriculture) and Señor Rodolfo Elias Calles (present Governor and eldest son of Señor Plutarco Elias Calles, recently Secretary of War and former President of Mexico) have cooperated with the company to make continued operation possible by revising downward certain state taxes that would have been a factor in forcing the closing of this mine. Also, permission to change our workmen over to another system of mining was essential to continued operation.

Jan 1, 1933

THE following nominations for officers in the, Petroleum Division have been made by the nominating committee, of which Alfred G. Heggem was chairman: Chairman, John M. Lovejoy, Vice-pres., Amerada Petroleum Co., Tulsa, Okla.; vice-chairman for Refinery Engineering, Walter Miller, Vice-pres., Marland Refining Co., Ponca City, Okla.; vice-chairman for Production En-gineering, M. E. Lombardi, Vice-pres., Pacific Oil Co., San Francisco, Cal.; associate vice-chairmen for Produc-tion Engineering, T. E. Swigart, Prod. Engr., Shell Co. of Cal., Los Angeles, Cal.; Joseph B. Umpleby, Vice-pres., Goldelline Oil Corp., Oklahoma City, Okla.; vice-chairman for Production, W. E. Wrather, Cons. Geol., Dallas, Texas; associate vice-chairman for Production, Joseph Jensen, Associated Oil Co., Los Angeles, Cal.; vice-chairman for Transportation Engineering, E. P. Bly, Engr., Pipe Line Dept., Standard of California, San Francisco, Cal..; vice-chairman for Economics., Joseph E. Pogue, Cons. Geol., New York City. The election will take place, at the annual meeting of the Division in New York in February. Any independent nominations received before Jan. 20 and endorsed by ten members, will be announced in MINING AND METALLURGY for February and placed before the meeting for considera-tion. Extensive plans are being made for the meeting and a large number of excellent technical papers have already been received.

Jan 1, 1927