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By J. B. Cohen

EARLY investigators1-4 reported that additions of beryllium to silver caused embrittlement. The in-termetallic phases which are now known to exist5,' were not known at the time. Solidification appeared to occur by a simple eutectic reation.4,7 (The primary beryllium-rich phase appeared globular, when the liquidus temperature was near the melting point of pure beryllium, and angular when the liquidus was much lower; in discussion of Sloman's work,4 it was suggested that this difference was due to an intermetallic compound which was not revealed by the polishing technique.) In the investigation reported here, it was found that if the compounds now known to exist were avoided, certain beryllium-silver alloys containing large amounts of the primary beryllium phase possessed sufficient ductility to be cold formed. Alloys containing 14 and 20 at. pct Ag were prepared from vacuum-cast beryllium containing 1.0 to 1.2 pct impurities and silver, 99.99+ pct pure. The elements were melted together by induction in beryllia or alumina crucibles under argon at less than 1 atm pressure. The cooling rate was adjusted by regulating the temperature of the melt and by reducing the power to zero without stopping the water flow in the induction coils, which were in contact with the crucible. Ingots were about 0.75 in. in diam with a grain size of 0.12 to 0.25 in. Microscopic investigation of transverse or longitudinal sections of an ingot cast from a temperature well above its melting point showed that, in general, the compounds did not form, presumably because of rapid cooling; the alloys consisted of beryllium-rich particles in a silver-rich matrix as shown in Fig. 1. A eutectic structure was not observed, probably .due to the low beryllium concentration of the eutectic composition and eutectic divorcement. Within a given grain, the small globules of the primary phase were all oriented in the same direction, as indicated by examination under polarized light; the orientation varied from grain to grain. This suggested that the globules were branches of the same dendrites. If cooling was too slow, a third constituent was observed in the microstructure; because it formed around the primary beryllium-rich globules it was Fig. 1—Ag-Be alloy, 18.6 at. pct Ag, as-cast. Bright field illumination. Etched with an aqueous solution of NH,OH and H2O2. X500. Reduced approximately 21 pct for reproduction. probably the 6 compound. A thin ring around an ingot often contained this constituent. When this compound was present in large quantities, or the silver segregated so that large regions occurred with the beryllium-rich globules in contact, sections from the ingot were brittle. When the compound was initially absent, it was possible to carry out reductions in thickness of 50 pct by cold rolling with only limited edge cracking; failure did not occur until reductions of 80 pct. A typical cross section after cold rolling is shown in Fig. 2. After simple bend tests, microcracks were found; these apparently were difficult to propagate in the two-phase structure, as the specimens continued to behave in a ductile manner after the cracks appeared. Similar cracks would probably be closed during rolling. It is apparent in Fig. 2 however, that the primary beryllium particles undergo extensive plastic deformation. Hardness values of the alloys indicated that some work-hardening occurred during cold working. Fig. 2—Ag-Be alloy, 18.6 at. pct Ag, reduced 83 pct in thickness by cold rolling. Bright field illumination. Etched with an aqueous solution of NH,OH and H2O2. X500. Reduced approximately 21 pct for reproduction.

Jan 1, 1961

By J. T. Norton, Joseph Gurland

IN spite of the extended use and high state of practical development of the cemented tungsten carbides, the structure of these alloys is still a matter of considerable controversy. The characteristic high rigidity and rupture strength of sintered compacts have been attributed to a continuous skeleton of tungsten carbide grains, formed during the sintering process. This view is based mainly on the work of Dawihl and Hinnuber,1 who reported that a sintered compact of 6 pct Co maintained its shape and some of its strength after the binder was leached out with boiling hydrochloric acid. After leaching, only 0.04 pct Co was reported to remain in the compact. They also showed that the assumed increasing discontinuity of such a skeleton, as the cobalt content is increased, could be made to account for the observed discontinuous increase of the coefficients of thermal expansion, the loss of rigidity, and the impaired cutting performance of alloys of more than 10 pct Co. Contradictory evidence was cited by Sanford and Trent,' who mentioned that a sintered compact was destroyed by reacting the binder with zinc and leaching out the resulting Zn-Co alloy. The skeleton theory also does not account for the observed change of strength of sintered compacts as a function of cobalt content. If the skeleton is responsible for the strength, the latter would be expected to decrease with increasing binder content. Actually, the strength increases and reaches a maximum around 20 pct Co. In addition, tungsten carbide is brittle and undoubtedly very notch sensitive. The highest value found in the literature for the transverse rupture strength of pure tungsten carbide prepared by sintering is 80,000 psi.3 herefore, such a skeleton does not easily account for a rupture-strength value of 300,000 psi and higher, commonly found in sint.ered tungsten carbide-cobalt compacts. In view of the conflicting data present in the literature, experiments were undertaken to determine whether the sintering of tungsten carbide-cobalt alloys leads to the formation of a carbide skeleton or whether the densification behavior and the properties of cemented compacts are consistent with a structure of isolated carbide grains in a matrix of binder metal. The specimens were prepared from powders of commercial grade. Tungsten carbide powder ranged in particle size from 0 to 5x10-4 cm. Mixtures of tungsten carbide and cobalt were ball milled in hexane for 48 hr in tungsten carbide lined mills. After milling, the specimens were pressed in a rectangular die (1x1/4x1/4 in.) at 16 tons per sq in. NO pressing lubricant was used. Sintering of the tungsten carbide-cobalt compacts was carried out in a vertical tube furnace equipped with a dilatometer (Fig. I), by means of which the change of length of the powder compacts could be followed from room temperature to 1500°C. An atmosphere of 20 pct H, 80 pct N was maintained inside the furnace. Decarburization of the samples was prevented by the presence of small rings of graphite inside the furnace tube. The temperature of the sample was measured by a platinum-platinum-rhodium thermocouple, which also was part of a temperature control system able to maintain a constant temperature within ±100C. Pure tungsten carbide compacts were prepared by sintering the carbide without binder or by evaporating the binder from sintered compacts in vacuum at 2000°C. Since complete densification of these samples was not desired, they were sintered only to 60 or 80 pct of the theoretical density of tungsten carbide. The specimens were prepared for metallographic examination by polishing with diamond powders and etching with a 10 pct solution of alkaline potassium ferricyanide. Cobalt etches light yellow and the carbide gray. The amount of porosity is exaggerated since it is difficult to avoid tearing out carbide particles, especially from incompletely sintered samples. Experimental Observations A number of specific experiments were carried out in order to study some particular aspect of the sintering problem. The details of these experiments, together with their results, are as follows: Electrolytic Leaching: The binder was removed by electrolytic leaching from sintered tungsten carbide-cobalt compacts for the purpose of determining the continuity of the carbide phase. The method used was based on the work of Cohen and coworkers4 on the electrolytic extraction of carbides from annealed steels. If the sample is made the anode, using a 10 pct hydrochloric acid solution as the electrolyte, the binder is dissolved, but the rate of solution of tungsten carbide is negligible. A current density of 0.2 amp per sq in. was applied. As shown in Fig.

Jan 1, 1953

By Emerson F. Heald

A systematic study was made of new and old data on chemical activities in Fe-Pt alloys at elevated ternperatuves. Experimental results may be expressed in terms of the excess free energy using Least-squares analysis of the data gave the following values for the constants: for the temperature range 1130° to 1350°C, and tentatively to 155O°C, B = -3.326564 and C = 0.221051; for the temperature range 650" to 850°C, B = -2.555690, C = 1.762735, and D =0.097196. In the study of iron-containing silicate systems, it is sometimes desirable to have a direct experimental measure of the activity of iron in the system. The well-known solubility of iron in platinum, often a headache in experimental work on iron compounds under reducing conditions, can be used to advantage in this respect. If the activity of iron in an Fe-Pt alloy in equilibrium with the silicate is known as a function of the composition of the alloy, chemical analysis of the alloy will give a knowledge of the activity of iron in all of the phases in the system. The present study was undertaken in order to elucidate the characteristics of Fe-Pt alloys as iron activity indicators. This work is intended to tie together some previous work, which may be summarized as follows. Larson and Chipman1 determined the activity of iron in Fe-Pt alloys at 1550°C by equilibrating platinum metal with calcium oxide-iron oxide-silica melts of known iron activity. Compositions of the resulting alloys were determined by chemical analysis. A similar study was carried out by Taylor and ~uan,' who worked at 1300°C. They brought the Fe-Pt alloys into equilibrium with iron oxide under conditions of known partial pressure of oxygen, and thus, from the work of Darken and ~urr~,~ conditions of known iron activity. Compositions were determined indirectly, by following the change in weight of the sample. Sundaresen et el* used the electromotive force of cells in which the alloy formed one electrode in order to measure the activity of iron in the alloy at 650" and 850°C. These temperatures were chosen to be above and below the first-order phase transition which takes place upon the ordering of Fe3Pt and the second-order transition which occurs upon the ordering of FePt3. EXPERIMENTAL 1) High Temperatures. The starting materials used were thin platinum foil, about 0.002 mm thick, and Fisher Certified reagent ferric oxide, Fez03, which had been heated for 24 hr at 1000°C. An intimate mixture of 80-mesh Fez03 and platinum platelets was placed in a thin platinum foil envelope. The latter was suspended from thin platinum wires in the hot zone of a vertical-tube, platinum-wound furnace of the type described by Muan and ~sborn.~ A capillary gas mixer similar to that used by Darken and Gurry3 was used to prepare a precisely known mixture of carbon dioxide and hydrogen, which was allowed to flow upward through the furnace tube. The partial pressure of oxygen in contact with the sample was thereby fixed at a value which was calculated from the charts prepared by porter? Temperatures were measured with a Pt-10 pct Rh-in-platinum thermocouple, which was calibrated using the melting points of gold (1062 .@C) and diopside, CaMgSizOB (1391.5"C). Temperature control was maintained to within i3"C with a Geophysical Laboratory proportional controller, using the furnace resistance as the sensing element. Samples were quenched by passing a small current through the platinum suspension wires, allowing the sample to drop into a bath of dibutyl phthalate at the bottom of the furnace tube. Prior to chemical analysis the samples were washed with acetone and dried. 2) Chemical Analysis. It proved possible, in almost all cases, to separate the Pt-Fe platelets physically from particles of iron oxide. The platelets were dissolved in a small volume of aqua regia, evaporated to dryness, and redissolved to 0.1 M HC1. In order to determine iron in the platinum alloy potentiometrically, it is necessary first to remove the platinum. A 10-cm column of Amberlite IR-120 cation exchange resin in the hydrogen form provided separation quickly and quantitatively: The mixture of iron and platinum in 0.1 M HC1 was added to the top of the column, and washed with about 100 ml of 0.1 M HC1. Under these conditions, the iron, principally in the form of cations such as FeC1" and FeCl;, is held quantitatively in the uppermost centimeter of the column. The platinum, in the form of anions such as PtC&- , is washed through without being adsorbed. After a qualitative test with stannous chloride indicated all of the platinum was removed, the iron was

Jan 1, 1968

By Shiou-Chuan Sun

THERE are several postulations for the mechanism of slime-coating. Ince1 proposed the electrostatic hypothesis, del Giudice2 suggested the chemical theory; Bankoff3 reported that slime-coating is inhibited whenever the surfaces of the slime particles are ionized sufficiently for Brownian movement to occur, and is facilitated when they are not. These postulations were examined by experiments involving the Burton tube, the cataphoretic cell, and slime-coating. The techniques involved will be described elsewhere in this paper. The electrostatic hypothesis, supported by migration experiments in a Burton tube, was abandoned by del Giudice.2 Experiments of mineral migration in a Burton tube, after the idea of Ince with modification, indicated that this apparatus was inefficient for accurate observation. A cataphoretic cell was constructed. The experimental data, as shown in this paper, enable the correlation and advancing of this hypothesis. Del Giudice's chemical hypothesis considered that slime particles are attached to the galena surfaces by a cement formed as the result of a metathetical reaction between the sulphide and the slime particles. Applying this hypothesis, the calcite slime particles were cemented to the galena surface by the formation of a cementing lead carbonate. In a similar way, lead silicate was considered as the cement of quartz slime coating on galena. Experiments verifying this hypothesis were carried out according to the following procedure: Fresh mineral particles selected from the central part of the broken lumps and examined first under a microscope for ascertaining a clean surface were placed in a small beaker (1.5-in. dia. by 2.5 in. deep) half filled with one kind of slime pulp. The dilution of all slime pulp was 4: 1 and the particle size of slime was minus 400-mesh. After agitation for 5 min. the specimen was removed by a sharp-end tong and washed gently three times in three separate distilled water baths. It was dried before a small electrical fan and examined immediately under a microscope. A photograph was made of the observation. With reference to the published solubilities,4 several of these experiments, which contradict the chemical hypothesis, are listed as following: I. The coating of fluorite slime on the galena surface was light but the coating of galena slime on the fluorite surface was heavy. In a similar way, the coating of quartz slime on the galena was fairly light, but the coating of galena slime on the quartz particle was heavy. According to the chemical hypothesis, using the same constituents and regardless of which is the slime, the density of the coating should be expected to be the same. This, however, as shown above, is not true. Moreover, fluorite (CaF2), having a solubility of 16 mg.[4a] per liter of water, should not be

Jan 1, 1943

By John A. Church

When, in 1879,I examined the mines of the Tombstone Mill and Mining Company, at Tombstone, Arizona, I found a bed of tailings containing 12,000 tons, which had a value of 9 to 12 ounces of silver per ton and some gold. The ore had been amalgamated in pans, in which each charge had been ground for four hours, having been pre viously stamped through rough-punched screens, which gave a pro duct varying from 1-100th to 1-20th of an inch, according to the state of wear of the screen. It was certain that a large proportion of the tailings must be in fine slimes, and the question of recovering their value was difficult. Even now the concentration of slimes is . an unwelcome task, and at that day very little was known about it. Nevertheless, after considering the results of a test by repanning the tailings, I advised the company to concentrate and smelt, although they had to face the difficulty of making a smelting-product from slimes containing only 3 per cent. of lead. Limestone was abundant enough, but no iron suitable for flux was to be had for hundreds of miles. One of the company's claims con tained an argeutiferous manganese-ore, which gave but poor results by amalgamation. This was one reason for recommending smelt ing ; for if manganese would play the part of a precipitant, as iron does, the company could smelt by combining two of its silver ores, without other flux than the small amount of lime that might be needed. At that time no smelter had ventured to trust manga nese as a precipitant, though large quantities of this ore containing silver were bought and used by custom-smelters, who looked upon the manganese solely as a basic flux for silica. I believe that no other furnace has been obliged to trust this metal, and that the man ganese practice of Tombstone remains unique among the records of smelting lead-ores in the shaft-furnace. The bright side of the problem was given by the fact that the mines were shallow and that the enterprise would at least begin with oxidized ores. The tailings contained about 85 per cent. of silica,

Jan 1, 1895

By Lester Guttman

THE connection between short-range order and thermodynamic activities in binary solid solutions has been pointed out by Birchenall1 who calculated approximate values of the energy of interaction of Zn and Cu and of the degree of short-range order in alpha-brass at one composition and two temperatures. The purpose of this note is to call attention to a somewhat more accurate theory than that used by Birchenall and to extend the calculations to a wider range of temperatures and compositions as a means of testing its applicability. This is an example of the well-known general method of comparing measured thermo-dynamic functions of a system with those calculated from a microscopic model by means of statistical mechanics. In this case, mathematical approximations must be used which make difficult any decision about the validity of the model. Birchenall's statistical method resembles closely that called by Fowler and Guggenheim2 the "quasi-chemical" method which has been shown to lead in certain cases to results identical with those obtained by the method of Bethe.3 The quasi-chemical method has been extended by Takagi4 to give general formulae for the free energy of binary solid solutions based on several lattices at all compositions and temperatures. Specifically, he treats the four systems typified by: I. ß-brass; 2. a- brass; 3. AuCu3; 4. AuCu. When the temperature is so high that no long-range order exists, these formulae reduce to the same form for all lattice types, namely: [ ] Here the symbols have the following meanings: [F-Helmholtz free energy E-energy S-entropy k-the gas constant per molecule z-coordination number, (e.g. 12 in. a-brass). N-total number of atoms c-atomic fraction of A] VAA, VBB, VAB-energy per bond of the corresponding bonds log means log, throughout The superscript 0 denotes the thermo- dynamic function in the standard state, which has been chosen to be pure A or B with the same crystal structure as the solid solution. The quantity x is the ratio of the number of A-A bonds to the total number and for minimum F satisfies the equilibrium condition [ ] The free energy may also be written in terms of µA and µB, the chemical potentials or partial free energies per atom:

Jan 1, 1948

By Joseph J. Yancik

From previous work, it was learned that relative strengths of blasting agents can be reasonably predicted from heats of detonation modified by their (D/D*)2 ratio.(1) Bulk Strength = Q x d x (D/D*)2 x K (1) In this equation Q is the ideal heat released during detonation, d is density, D represents actual detonation velocity while D* is ideal velocity. An energy transfer coefficient, K, was used to account for differences among rock strata in response to explosive loading. This equation gave reasonable, field supported strength values for oxygen balanced blasting agents. For aluminized nitrocarbonitrates and slurries which have high Q's the rating system predicted better strengths than were shown in the field. This discrepancy was felt to be related primarily to problems in calculating Q and D*. Theoretical calculations cannot take into account varying energy contributions from particulated aluminums whose reactivities vary substantially with physical properties. One approach to circumventing this problem would be to use a characteristic Q that is dependent on mass reactivity of ingredients as components in explosive formulations. Since the underwater testing method is capable of measuring a functional, relative energy release, it was chosen for study.

Jan 1, 1971

By Alfred H. Bell

IN 1945, Illinois produced 75,210,000 bid. of oil, or 4.4 percent of the total for the United States, and ranked sixth in the nation in oil production for the third consecutive year. Production decreased about 3 per cent from that of 1944, when the total Illinois production was 77,413,000 bbl. This is the smallest percentage of decrease in production in the state for any year since a peak was reached in 1940. Daily average production for 1945 was approximately 206,000 bbl. Daily averages by months were as follows:

Jan 1, 1946

By W. P. Lass

(San Francisco Meeting, October, 1911.) TEE purpose of this article is not only to describe the plant and method of cyaniding the Treadwell concentrates, but to present some of the results of the experimental work obtained in the past three years for the Alaska-Treadwell Gold Mining Co., at Douglas Island, Alaska., under the direction of F. W. Bradley, Consulting Engineer, and Robert A. Kinzie, General Superintendent, of the affiliated companies. At the time the experimental work was undertaken the concentrates were being shipped to the smeltery at Tacoma, Wash., and the cost for treatment of 3-oz. (gold) concentrates was $11.95 per ton, divided as follows: Smelting-charges, . $4.00 Loading, freight, insurance, etc., 2.89 Interest due to time lost in transit and in settlement, . 0.05 Loss due to settlement for 95 per cent. of the gold at $20 per ounce, 5.01 Total, . . $11.95 From the experimental work described later, it was estimated that 96 per cent. extraction could be made by treatment on the ground, and that the cost, when treating 80 tons per day, would be $3.25 per ton, divided as follows; Per Day. Per Ton. Labor, . $66.16 $0.827 Chemicals, . 76.60 0.960 Power and steam-heat, 67.60 0.845 Marketing-, refining- and other charges, 49.36 0.617 Totals, . . $259.72 $3.250 Adding to this total the 4 per cent treatment-loss, which on 3-oz. concentrates amounts to $2.48, gives a total cost of $5.73 per ton. Comparing this with $11.95, the cost when shipping to the smelter, leaves a net gain of $6.22 per ton by the local

Feb 1, 1912

By John B. Hastings

TEN miles from Hartsel, near Antelope springs, in Park county, Colorado, there is a large area of unconsolidated lake beds, which are interesting because at least a part of the lacustrine sands contains in the aggregate an immense amount of gold. During 1906, one of the arms of this dessicated lake was fairly well prospected with shafts and cuts by an Eastern company to test its value, as favorable amounts of gold had in some instances been found upon it. The claims of the company contain about 5,000 acres of the beds; but this is only a small portion of them, a south branch from a main body, which is at least 7 miles in diameter, with other and very wide lateral gulches, paralleling the one herein described on the east and west. A certain amount of digging and sampling was done in the outside areas; but the result was evidently unsatisfactory, since the work was discontinued. his section of Colorado has not been studied geologically, and the age of the ancient lake is unknown. It is probably Quaternary. I spent two weeks on the ground, in September and October, 1906, but was quite absorbed in the sampling. I looked, however, for terraces on the rim-rock and other evidences of movement and erosion, but did not find anything to denote an earlier age than the Quaternary. The granite rim-rock may be Archean; S. F. Emmons says that some of the granites in central Colorado are as old as that. The rim-rock as observed is a gray quartzose biotite-granite, except a small area in Sections 3 and 34, where it is a felsitic (?) breccia. The breccia is silicified by solfataric action at the corner near Shaft No. 7, in Section 34; but this action is older than the sands and does not extend to them. The shaft averaged 50c. per ton, more than twice as much as the rest.

Jan 5, 1908

By Clinton M. Young

(Pittsburg Meeting, March, 1910.) I. INTRODUCTION. THE experiments herein. described were carried on in 1908-9 . by the State Geological Survey of Kansas. Some months before taking up work on black powder the Survey had resumed work on an interrupted investigation of explosions in coal-mines, a subject which is engaging the attention. of numerous investigators. An unusual number of serious disasters has directed to. the subject a study which discloses the disquieting fact that, in the. United States, the ratio of lives lost per ton of coal mined has been on the increase. Methods of coal-mining have changed to some extent with the great increase of output, attained in, comparatively recent years. These changes involve the working of very extensive mines, with increased difficulty of ventilation, increased accumulation of coal-dust, and. a very great increase in the amount of explosive used.. . This last point assumes truly startling proportions when it is carefully observed. In the fields of the Middle. West it is not now uncommon for a miner to use six ,kegs (150 lb.) of black powder in a "pay" of two weeks, while within the memory. of men still active, one keg (25 .lb.) would last two men for a " pay." So. great has . the use of explosives become in some fields that the skilled coal-miner is hard to find, and the coal is not mined, but blasted. A preliminary study of the subject. of explosions in coal-mines has. led to the belief . that the use of, large -quantities of explosives, in some cases by slightly-trained men, had not been * Associate Professor- of Mining Engineering, University of Kansas, Lawrence, Ran.

Aug 1, 1910

By E. J. Duggan

It is a coincidence that the two plants in this country for treating copper ores by ammonia leaching came into existence at almost the same time, that of the Kennecott Copper Corporation at Kennecott, Alaska, in March, 1916, and that of the Calumet & Hecla Mining Co. in July of the same year. The success of both from their very beginning attests the merits of the process under widely different sets of conditions. As would be expected, in the time they have been operating these two pioneers in this field have greatly perfected their methods and improved their technic. The early difficulties inevitably encountered in undertakings of this nature have been largely surmounted and the process may now be considered to be well seasoned and matured. There have been no other commercial plants built in this country and but one elsewhere, the Bwana M'Kubwa in Northern Rhodesia, for the reason that this method of treatment may be employed on comparatively few ores. However, it has certain advantages, some of which are inherent to sand leaching processes generally and some to ammonia leaching in particular. Among these may be enumerated: (1) the avoidance of fine grinding; (2) the small amount of water required; (4) a high-grade product; (5) little likelihood of deleterious gangue constituents and fouling of solutions. It is true that great progress has been made in recent years in the flotation of the ores that come within the province of ammonia leaching. Nevertheless ammonia leaching has its possibilities and these may be overlooked in the present tendency toward the use of flotation for all ores. Probably the chief requisite to its further extension to suitable ores will be a cheap source of steam. Ammonia, the only reagent required, is unlimited in supply, readily transported and the price that is likely to obtain in the future should not make its cost at all onerous. Choice of Method for Kennecott Ores The Kennecott ores are typical limestone replacement deposits. The milling ores have a copper content of approximately 8 per cent in a limestone dolomite gangue. About half the copper occurs as sulfide, mostly chalcocite with some covellite, and the remainder in the form of the two carbonates, malachite and azurite. A comparatively coarse grind followed

Jan 1, 1934

By H. O. Hofman

The object of refining copper in the reverberatory furnace is to obtain a metal which will have the highest attainable degree of malleability, ductility and electric conductivity, and present at the same time a level surface when it solidifies in the mold after casting. These desirable physical properties are governed by the character of the impurities and the forms in which they are present, by the amount of cuprous oxide retained by the copper, by the quantity of gas held in solid solution, by the casting-temperature, and by the thickness of the casting. The effects of impurities, of cuprous oxide and of gases upon the mechanical properties of copper have been studied by Hampe1 in his classical paper " Colitributions to the Metallurgy of Copper." The most recent research into the effect of metals upon the electrical conductivity of copper is that of Addicks. 2 The influence of cuprous oxide upon the electrical conductivity has been investigated by Walker3 and Addick. 4 The absorption of gases has received attention by Hampe: Stah16 and Heyn 7 The effects of casting-temperature have been noted by Stahl.8

Jan 1, 1908

By L. V. Gregor, C. F. Aliotta, P. Balk

The structure of silicon surfaces, thermally oxi&zed in dry oxygen and in steam, was studied using the electron microscope. It was found that the structure on the original (etched) surface is retained at the outer surface of the oxide, whereas the oxide-silicon interface is smoothed out considerably. This supports the idea that, both in oxygen and in steam, the oxidation reaction occurs at the oxide-silicon interface. Mechanical damage of the original silicon surface affects the rate of oxidation. It also changes the chemical properties of the oxide, as shown by the enhanced rate of etching in buffered HF at the locations of damage. However, the oxide at the originally damaged surfaces still exhibits a high electrical breakdown strength. Exposure of thermal oxides to P205 or BzOs vapor, which will yieldphospho- or borosilicate layers, results in complete annihilation of all fine structure on the surface. Reaction of silicon with C02 gives a surface film which probably does not consist of pure SiO,. THERMAL oxidation of silicon yields uniform and strongly adhering oxide films which are normally amorphous and continuous. Contamination and surface imperfections have been reported to cause local crystallization and the formation of pinholes."' The parabolic-rate law of film growth observed by several workers for the oxidation both in steam and in dry oxygen at higher temperatures suggests that diffusion of one or more reactants through the oxide is the rate-deter mining step. One of the dif-fusants is an oxygen species and oxide is continuously formed at the oxide-silicon interface. This was concluded for high-pressure steam oxidation by Ligenza and spitzer5 from an infrared-absorption study of the isotopic exchange of oxygen. Jorgensen arrived at the same conclusion for the oxidation in dry oxygen by measuring during oxidation the resistance change between silicon and a porous platinum marker electrode in the oxide. Recently, Pliskin and Gnall' reported similar conclusions concerning the growth mechanism from controlled etch studies using a phosphosilicate marker. The work communicated in the present paper was aimed at studying oxide growth on locally damaged silicon substrates and relating it to the chemical behavior and electrical breakdown properties of the films. Since etched and oxidized silicon surfaces normally appear to be very smooth when examined by optical microscopy except for some occasional pits, it was decided to use the electron microscope as a tool. In this way, the detection of surface roughness and damage on a scale comparable to or smaller than the thickness of the film is possible. Also, the microstructure of the original substrate surface constitutes a built-in marker which represents a minimum of perturbation to the growing oxide layer, and no foreign material is introduced. Thus information on surface reactions and additional evidence on the location of oxide formation in steam and in oxygen could be obtained. EXPERIMENTAL Electron micrographs7 were obtained using a Philips EM100 electron microscope. Collodion surface replication was used since this is a nondestructive technique and thus permits replicating the same surface at different stages of processing. In order to establish the effect of different treatments it was found essential to make successive observations of the same area by using a reference point. Reference points were conveniently provided by scribing a small v mark on the original surface with a silicon carbide tip. This procedure yields damaged and damage-free areas near the reference point. Upon replication, the samples were thoroughly cleaned before subjecting them to the next process step. Mechanically lapped silicon wafers (Dow-Corning, 100 ohm-cm p-type, cut perpendicular to the (111) direction) were chemically polished in a rotating beaker with a mixture of 1 part HF (48 pct), 2 parts glacial acetic acid, and 3 parts HNO3 (70 pct) by volume. This procedure yields a smooth surface with a faint "orange peel'' structure due to a "ripple" less than 20002i deep. Oxidation in steam or oxygen was carried out in an Electroglas tube furnace. Steam oxidations were always preceded and followed by a brief exposure to oxygen at the same temperattre. The thicknesses of the oxide films under 3000A were determined with a Rudolph Model 436-2003 ellipsometer,' whereas those over 3000A were measured using the VAMFO technique. In the present study, a solution of 300 g of N&F in 25 ml HF (48 pct) and 450 ml water was used to detect areas of increased chemical reactivity in the

Jan 1, 1965

Discussion of the paper of R. J. COLONY, presented at the New York Meeting, February, 1921, and issued With MINING AND METALLURGY No. 169, January, 1921. R. J. COLONY (author's reply to discussion).-The work of Sosman and Merwin on the system lime-ferric oxide, mentioned by Mr. Rankin, was not overlooked. When studying portland cements and portland-cement clinkers petrographically, however, the lime-iron compound was difficult to correlate with the very definite dicalcium ferrite described by those investigators, which possesses such well-defined optical properties. In portland cements, the calcium ferrite (or ferrate?) is an indefinite, fuzzy, and generally amorphous, or apparently amorphous substance that is distributed interstitially with respect to the other grains, from which it was very difficult to derive any satisfactory results. For this reason, the writer, tentatively, chose to regard it as related to the aluminate, and assigned to it the composition 3CaO.Fe203, which may be incorrect, however, as Mr. Rankin suggests.

Jan 8, 1921

By C. S. Matthews, M. J. F. Rosenbaum

The purpose of thir work wax to lcarn it~lzut infori~lation could he obtained from various typs of pilot water floods and to attempt to find the optunum pilot patter11, for a revervoir which had previously been depleted by a solution gas drive. The study was made in the laboratory with mathemetical methods a dynamic analog and a potentiotnetric analog. Results werp tested against the field llistorics of a nrrnlber of pilot water floods. At a reasonable valrre of currzulative injection, the total production rate for the one-injector five-spot should reach about 6.5 per cent of injection rate, and for a four-injector five-spot, about 9 per cent. Accurate estimates of ultimate recovery cannot be made on the basis of such snzall prorluction rates. However, with a pilot composed of nine ir1jector.s and 16 producers the production rate is approximately 50 pcr cent of injection rate at a reasonable value of camulative injection. Sonle inforn~ation for extended performance predictions might he obtained from such a large pilot. These conclusions were drawn on the basis of results obtained for unit mobility ratio, and a sturly using tlre potentiometric analog was made of the effect of other mobility ratios to determine the range of applicability of these predictions. For the four-injector, five-spot pilot with the ratio of production to injection rate (before water breakthrough) is about twice that for with it is about two-thirds; and with M0= 10, it is about one-third For high mobility ratios, it was found that the production rate increased considerably as water-cut increased. These result can be used to modify, qualitatively, the inter.pretntions based on curves for the unit rnobilit\. ratio CaSeS. It was found that the maximum ratio of production rate to injection rate obseriled in field pilot floods was of rhe scime order as that prerdicted by these methods. The time required to reach thisr maximum did not generally agree with the time predicted for a homogeti~orir reservoir. The differcrlce between predicted and observed time of response gives an indication of the permeability profile and of the condition of the producin,g wells. Pilot water floods of the pattern type are generally carried out in reservoirs which have been depleted by solution gas drive and are at low pressure. Under these conditions, oil and water can be considered incompressible. It is assumed that, as the water is injected, an oil bank forms ahead of it and that there is a distinct interface between the water zone (or bank) and the oil zone (or bank) and between the oil zone and the region ahead of the oil zone. It is further assumed that only gas is mobile in the unflooded (gas) region, only oil is mobile in the oil bank and only water is mobile in the water bank. The saturations and the mobilities associated with each zone are assumed uniform. We idealize our reservoir to be homogeneous, horizontal and of constant thickness. Effects of gravity within the producing layer are assumed negligible. If the actual time-dcpendent flow problem is approximated by a acries of steady-state problems. the potential and stream function in the oil bank and water hank satisfy Laplace&apos;s equation in two dimensions. We can therefore use a poteiitiometric analog of this system. Potentiometric models have yielded uscful results in this laboratory&apos; and clsewhere in the study of a variety of secondary recovery problems. For the case where M = I, we generally prefer to use theoretical mcthods as well as a simpler dynamic analog. Except where otherwise noted, the ratio, side of five-spot/wellbore radius. is taken to be 3,600. a figure which corrcsponds to a normal-size wellbore in a 10-acre well spacing. THEORETICAL EVALUATION OF VARIOUS PILOT PATTERNS, Mw0 = 1 <&apos;he theoretical models which we used to examine the performance of various pilots are shown in Fig. 1. Image theory was used to determine the ratio of production rate to injection rate as a function of the volumc of the flood. The ratio of production rate to injection rate was chosen because this is an easily measurable quantity which is characteristic of a pilot

By J. H. Johns, G. R. Stephan

The Climax mine has a history of dealing with ground control problems caused by major stress concentrations in the orebody. These stress concentrations, called weight, can arise in a variety of ways. The general effects of depth, rock type, and mining method give rise to weight problems, but local geologic features and daily cave line management can have even greater effects. Over the years a number of techniques have been developed for identifying weight problems in advance and for cow with them. These techniques all help us to amid interrupting the pace of cave advance and minimize the loss of production.

Jan 1, 1984

Members of the American Institute of Mining and Metallurgica Engineers can now secure copies of the Journal of the Institute of Metals of Great Britain at a special price of $5 for the two volumes issued during the year, postage extra amounting to approximately 25 cents. This Journal is one of the best books dealing with the subject of non-ferrous metals and alloys and this arrangement with the Institute of Metals permits our members to take advantage of this specially low price. Back numbers of the Journal can be purchased on the same basis. The Journal can be ordered directly through the office of the Institute of Metals, Great Britain 36 Victoria St., Westminster, S. W. I., London, England. The letter should be accompanied by an international money order and a copy sent to Secretary of the A. I. M. E. in order that the membership record may be checked.

Jan 9, 1919

Shooting Soot from Stacks In the DuPont magazine of June, 1916, S. R. Russell describes a method of cleaning large smoke or kiln stacks which he calls "simple,. economical- slid-most efficient" and-which- he -says can- be used in either-lined or unlined stacks, brick or steel, without fear of injury to the stack or lining. He gives the following specific directions: "The gun can be made out of air old piece of shafting about 4 in. in diameter and 14 to 16 in. long. Bore a hole 1 ¾ in. in diameter and 10 in. long in the center of the piece. Then bore a small horizontal hole ¼ in. in diameter through the piece-to the bottom of the center bore. This hole serves as a touch hole for inserting the fuse. "The-whole thing can be mounted on a pedestal about 6 in. in diameter so that it will stand in an upright position. "The -method of operation is as follows: Pour some FFF Blasting Powder into the mouth of the cannon to about 2 in. from the top. Tamp to the collar with dry clay. , A short piece of fuse is inserted in the touch hole and in contact with the main powder charge. Open the flue door at the bottom of the stack, set the cannon on the bottom and in the center of the stack, light the fuse and close the flue door. "The explosion shakes and loosens the soot adhering to the sides, causing it to fall to the bottom. It can&apos; then be removed through the flue opening.

Jan 9, 1916

Oct. 8-13, 1917 COMMITTEE ON ARRANGEMENTS H. A. BUEHLER, Chairman, W. E. McCOURT, Secretary, C. J. ADAMI, Southeastern, J. A. CASELTON, Entertainment, F. W. DEWOLF, Book, , E. F. GOLTRA, Finance, L. L. HUTCHISON, Tulsa, E. McAULIFFE, Transportation, P. N. MOORS, Reception, MRS. P. N. MOORE, Ladies, J. D. ROBERTSON, Publicity, VICTOR RAKOWSKI, Joplin., H. A. WHEELER, Excursions, A. THACHER.

Jan 7, 1917