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By R. L., Fullman

During the past year there have been a number of significant investigations that have furnished evidence on the driving forces governing grain growth and on the role played by boundary impurities. Thus Burke has shown that in high purity alpha brass the rate of grain growth in the earliest stages is approximately inversely proportional to the existing grain size. This relation agrees with one derived by Zener assuming that surface energy was the driving force in grain growth. Also in confirmation of the surface energy hypothesis, Burke found that growth virtually stopped when the grain boundaries or even only the grain corners were melted.

Jan 1, 1949

NORTH AMERICA ALASKA Anchorage.-Strandberg, H. Tuck, R. Coal Creek.-Moore, E. G. Spencer, W. W. College.-Hance, J. H. Henricksen, R. Henton, H. M. Comet.-Albertson, F. E. Cordova.-O'Neill, W. A. Douglas.-Cahill, W. E. Fairbanks.-Crawford, J. D. Earling, R., B. Fowler. D. A.

Jan 1, 1937

By S. C. Carapella, E. A. Peretti

DURING a literature survey of the indium-zinc phase diagram, controversial reports on the composition of the eutectic point were encountered. The value reported in the investigation of Wilson and Perettil and in a later investigation by Valen-tiner' was 4.0 wt pct zinc. The most recent work recorded on this system consisted of an exhaustive survey of alloys by Rhines and Grobe8 in which they indicate a value of 2.8 wt pct zinc for the eutectic composition. To clarify this aspect of the diagram, a series of alloys were prepared by melting the respective constituents in a glass test tube under a covering of mineral oil and slowly cooling the melt in a furnace. The zinc used was Baker's C.P. and had the following analysis: insoluble in H2SO4—0.0l pct; pb—0.001 pct; Fe-—0.001 pct. The indium, which was supplied by the Indium Corporation of America, had a purity of 99.9'7 pet with the following impurities: Cu—0.002 pct; Pb—0.006 pct; Sn—0.01 pct; Zn—0.01 pct. The alloys were prepared for metal-lographic examination using a technique already reported' and a new value of 2.0 ± 0.1 wt pct zinc was observed. An alloy containing 2.00 wt pct zinc was also made by melting the constituents under a vacuum. In both of these methods of alloy preparation the losses can be kept extremely small. Again, the characteristic eutectic structure was obtained, assuring confidence in this value. The accompanying micrographs are presented in support of this point. Fig. la represents an alloy containing 4.00 wt pet zinc, and reveals excess zinc particles, which precludes the value of both Wilson and Peretti, and Valentiner. Fig. lb, gives the structure of an alloy containing 2.2 wt pct zinc, also showing the presence of excess zinc. Fig. lc is a micrograph of a typical structure of the eutectic observed in several sections of the 2.0 wt pct alloy. In the 1.8 pet zinc alloy, fig. id, the definite presence of the primary indium can be noted. From these re-

Jan 1, 1951

By James J. Bean

HE task of measuring the specific gravity of the -*- operating medium in a heavy-media separation system has never presented a particularly difficult problem because the medium is fairly stable and the overflow of the separatory vessel, as well as its underflow, can be sampled easily and accurately and the specific gravity of the suspension determined easily by weighing a known volume. However, while this method is simple and accurate it does require the operator to take the sample by hand and to weigh it and there is considerable temptation to avoid the periodic sampling if everything seems to be going well, or if something is occupying the attention of the operator. Furthermore all operators do not sample in exactly the same manner and considerable practice is required for two operators to be able to "check" each other to the last few hundredths, particularly if the sample is cut underneath the drainage screen where location of the point of sampling and load on the screens tends to influence the determination. While none of the above presents much of a problem, we have all recognized that some mechanical method of continuous measurement and recording would be advantageous since the operator would merely have to glance at the meter to check the gravity and to have an indication of the trend of any changes. Also if the instrument were of the recording type, a permanent record would be available for the guidance of the superintendent. The Eagle-Picher Mining and Smelting Co. was the first heavy-media user to actually install such a recording meter. In 1946 they installed in their Central Mill at Cardin, Okla., a specific gravity recorder manufactured by the Bristol Co. of Water-bury, Conn. R. A. Barnes, of the Bristol Co., working with E. H. Crabtree, Jr. and Elmer Isern, of Eagle-Picher, made the application and worked out the problems of sampling and measuring. Their attempts to measure the specific gravity of the medium in the cone itself were not entirely successful and they resorted to an outside sample tube for actually making the determination. Because of the particular flowsheet used, it was possible to tap off from the medium return pipeline a stream of medium and divert it into the sampling tube, which was provided with a constant level overflow and a spigot underflow, and into which the bubbler tubes dipped. The Eagle-Picher installation was successful and its possibilities were recognized by the Mineral Dressing Laboratory of the American Cyanamid Co. It was decided to install a similar unit in the heavy-media pilot plant to investigate further its possibilities. Chief among these was the continuous record which it was felt would be proof of the steadiness of the gravity in a heavy-media cone, something which is not always appreciated by POtential users. Because the heavy-media pilot plant is required to operate at a wide range of specific gravities, it was realized that the unit would have to record all gravities from 1.25 to 3.50, and do it to the nearest 0.01. It would not be necessary to record all of this wide range on a single chart and the method selected was to have 4 bands, each band range overlapping the other a small amount and calibrated so that with standard charts one division would represent 0.01 sp gr. A shift from one band to another could be arranged without alteration of the instrument itself, being accomplished by a simple change in the bubble-tube lengths, as described later. Accordingly, a recording type instrument was purchased and installed. Because there were some advantages in doing so, the first installation attempted to measure the gravity of the cone proper by placing the bubble tubes in the cone. This was not at all satisfactory and the second scheme utilized a fixed vertical screen at the surface of the cone, and an external sample-tube arrangement. We were particularly anxious to make this work as we felt it would be advantageous to measure the top level of medium where the separation was actually being made, but we were doomed to disappointment because it was impossible to keep the screen clean of float. Since the top gravity of the cone is the most convenient place to sample for control, a launder about 2 in. wide was installed longitudinally beneath the

Jan 1, 1951

By James J. Bean

HE task of measuring the specific gravity of the -*- operating medium in a heavy-media separation system has never presented a particularly difficult problem because the medium is fairly stable and the overflow of the separatory vessel, as well as its underflow, can be sampled easily and accurately and the specific gravity of the suspension determined easily by weighing a known volume. However, while this method is simple and accurate it does require the operator to take the sample by hand and to weigh it and there is considerable temptation to avoid the periodic sampling if everything seems to be going well, or if something is occupying the attention of the operator. Furthermore all operators do not sample in exactly the same manner and considerable practice is required for two operators to be able to "check" each other to the last few hundredths, particularly if the sample is cut underneath the drainage screen where location of the point of sampling and load on the screens tends to influence the determination. While none of the above presents much of a problem, we have all recognized that some mechanical method of continuous measurement and recording would be advantageous since the operator would merely have to glance at the meter to check the gravity and to have an indication of the trend of any changes. Also if the instrument were of the recording type, a permanent record would be available for the guidance of the superintendent. The Eagle-Picher Mining and Smelting Co. was the first heavy-media user to actually install such a recording meter. In 1946 they installed in their Central Mill at Cardin, Okla., a specific gravity recorder manufactured by the Bristol Co. of Water-bury, Conn. R. A. Barnes, of the Bristol Co., working with E. H. Crabtree, Jr. and Elmer Isern, of Eagle-Picher, made the application and worked out the problems of sampling and measuring. Their attempts to measure the specific gravity of the medium in the cone itself were not entirely successful and they resorted to an outside sample tube for actually making the determination. Because of the particular flowsheet used, it was possible to tap off from the medium return pipeline a stream of medium and divert it into the sampling tube, which was provided with a constant level overflow and a spigot underflow, and into which the bubbler tubes dipped. The Eagle-Picher installation was successful and its possibilities were recognized by the Mineral Dressing Laboratory of the American Cyanamid Co. It was decided to install a similar unit in the heavy-media pilot plant to investigate further its possibilities. Chief among these was the continuous record which it was felt would be proof of the steadiness of the gravity in a heavy-media cone, something which is not always appreciated by POtential users. Because the heavy-media pilot plant is required to operate at a wide range of specific gravities, it was realized that the unit would have to record all gravities from 1.25 to 3.50, and do it to the nearest 0.01. It would not be necessary to record all of this wide range on a single chart and the method selected was to have 4 bands, each band range overlapping the other a small amount and calibrated so that with standard charts one division would represent 0.01 sp gr. A shift from one band to another could be arranged without alteration of the instrument itself, being accomplished by a simple change in the bubble-tube lengths, as described later. Accordingly, a recording type instrument was purchased and installed. Because there were some advantages in doing so, the first installation attempted to measure the gravity of the cone proper by placing the bubble tubes in the cone. This was not at all satisfactory and the second scheme utilized a fixed vertical screen at the surface of the cone, and an external sample-tube arrangement. We were particularly anxious to make this work as we felt it would be advantageous to measure the top level of medium where the separation was actually being made, but we were doomed to disappointment because it was impossible to keep the screen clean of float. Since the top gravity of the cone is the most convenient place to sample for control, a launder about 2 in. wide was installed longitudinally beneath the

Jan 1, 1951

By Charles M. Romanowitz

The motivation for the art of dredging for placer mining can be compared in a slight degree to the spread of civilization which started in the Near East and spread both east and west. Dredging started with the "bag and spoon" dredge in the lowlands of Europe reportedly about 1565, went southeast to New Zealand where designs were developed for a bucket-line mining dredge known as the New Zealand type, and westward to the eastern United States where a dredge was developed and used exclusively for excavating. Then it moved to Montana, where it was first used for mining in 1895. The New Zealand-type dredge was imported into California in 1898 (Fig. 1) and was followed shortly by the Montana design. As today, these early dredges were equipped with continuous bucket- line chains, a treatment plant, and a means of waste disposal mounted on a wooden hull. Both types of dredges are complete mining units: they dig the formation, transport the dug materials, and concentrate the valuable ore. After sizing, the fines containing the ore are passed by gravity to the treatment unit, while the barren materials are discharged overboard. By digging the materials to be treated at the bow and depositing all the waste, at the stern, the dredges automatically advance to new reserves without presenting any transportation problems. The main differences between the two types are in the method of holding the dredge in the digging position and in the disposal of the tailings to the rear. The New Zealand type (Fig. 2) uses the headline system with a bow anchor for holding the dredge in the digging position and long tailing flumes or short stackers off the stern for disposal of the barren materials. The California type (Fig. 3) uses box girder spuds projecting into the ground in a vertical position at the stern of the

Jan 1, 1969

By Thomas Harris

This paper. was written in conjunction with the work being undertaken by the Technical Committees on Classification of Coal, and an effort has been made to compile information relative to the use of coal for stationary steam generation in order to use this information to assist the Committee on Classification of Coal for the ultimate purpose of elimination of losses both by the' reduction of indivi-dual effort and waste in the consumption of material. Under the auspices of the National Association of Purchasing Agents, a questionnaire was drawn up to develop this information from stationary steam plants throughout the United States. in order to consolidate the information de-veloped from the many hundreds of boiler tests on coals consumed by various coal¬burning equipment. These questionnaires covered: 1. The company reporting, location and method of delivery to the plant. 2. Complete coal date, including description of coals used (with. sufficient space to- include first, second and third, preference) on--source of coal used,- complete-analysis and factors affecting choice of, coal used. 3. Plant data, divided into - A. Hand fired, B. Overfeed stokers,. . C. Underfeed stokers, D. Traveling grate stokers, E. Pulverized coal, and included complete description of furnace data, draft data, coal-burning rate, type of stoker, type of pulverizer, efficiency date and remarks.

Jan 1, 1933

Jan 1, 1969

By J. A. Eisele

The Bureau of Mines has played an important role in the revival of precious-metal mining underway in the Western United States. During the past 30 years, many techniques used by industry to recover gold and silver were pioneered and developed by the Bureau of Mines. In 1952, technology was developed to strip gold from granular activated carbon and allow the carbon to be reused. In 1969, the heap leaching concept was applied to low-grade gold and silver ores and mine wastes. Heap leaching in conjunction with carbon adsorption-desorption permits very low value material to be economically processed. In 1970, an oxidation treatment based on hypochlorite was developed to increase the recovery of gold from carbonaceous gold ores by cyanidation. In the early 19501s, attempts were made to employ carbon-in-pulp technology to recover gold from ores, but the fixed price of gold and increasing operational costs made the process unprofitable. The Bureau of Mines and Homestake Mining Co. jointly operated a carbon-in-pulp pilot plant, and the technology was used in full-scale production at the Homestake Mine in 1972. In 1973, a pressure stripping method, which decreased the time needed for the stripping step, was developed to desorb gold and silver from carbon. An alcohol desorption method, developed in 1976, also decreased the carbon stripping time. These stripping methods are in commercial use. In 1979, an agglomeration pretreatment was developed that permitted clayey precious metal ores to be heap-leached. Agglomeration-heap leaching technology is being used by at least 30 operations, several of them major gold and silver mines. Almost all precious-metal-mining companies use at least one of the above techniques in production facilities.

Jan 1, 1984

ALTHOUGH the refining period of the heat is generally defined as starting after the charge has been completely melted, it may more properly be considered as beginning with the first efforts to facilitate the shaping up of the slag and the making of corrective additions for the control of slag or metal composition. Such actions may be initiated during the latter half of the lime boil. The early part of the refining period may, then, in essence overlap the latter part of the melting period. The primary aims of the refining period are: (1) to reduce phosphorus and sulfur from the steel bath to levels safely below the maximum contents specified; (2) to eliminate carbon to a specified level as rapidly as possible and still allow time for proper conditioning of the slag and attainment of the necessary bath temperature; and (3) to have the heat ready for tapping or furnace deoxidation, with slag in the proper physical and chemical condition, and with carbon and oxygen contents and the temperature of the steel at the proper levels for the composition and grade of steel being produced. The particular conditions that fulfill these aims are distinctly different, depending upon whether the steel is to be finished according to fully killed. semikilled, or rimming practice and also depending upon the carbon range specified. Regardless of the type of charging practice employed, the object of the refining period is to produce repeatedly the desired finishing and tapping conditions for the grade of steel being produced. The variations and proportions of raw materials used in the charge may cause some variations in the degree of control required during refining, but not in the method of control. The refining period can therefore be discussed from a viewpoint largely independent of charging and melting practice. SHAPING UP THE SLAG In the first helper's vocabulary, refining practice consists in

Jan 1, 1951

By Charles B. Dudley

DEAR SIR: It is now nearly three years since my first report to you on the subject of steel rails was written. That report, as you will remember, dealt principally with the question of the relation between the chemical composition and physical properties of steel rails end their power to resist crushing and fracture in actual service. Other matters were referred to or touched upon in that report, but the main question was, Why do some rails crush or break in service while others do not? Yon will doubtless remember that the principal conclusion arrived at was, that the softer rails are less liable to Crush or break in service than the hard ones. Or, in other words, so far as conclusions could be drawn from the chemical analysis and physical test of 25 samples of steel rails which had actually been in service, these conclusions were that those rails which have the smaller amounts of carbon, phosphorus, silicon, and manganese are less liable to crush or break in service than those which have larger amounts of these elements. Or, again, looked at in the light

Jan 1, 1881

By N. Schapiro, R. J. Gray, G. D. Coe

A petrographic and chemical investigation was conducted to determine the occurrence and distribution of the organic and inorganic forms of sulfur in various size and specific gravity fractions of a high volatile, A-rank, Pittsburgh seam coal. The investigation was conducted to aid in the resolution of the problem of how metallurgical coke of lower sulfur content can be produced from high sulfur coals. The Pittsburgh raw coal contains about 2.4% S in two dominant forms: pyritic and organic. Pyritic sulfur constitutes about 57% of the total sulfur in the raw coal and occurs in macroscopic and microscopic-size particles. A plant cleaning process mechanically separates between 50 and 60% of the pyritic sulfur, mainly the macroscopic particles. The organic sulfur constitutes 41% of the total sulfur in the raw coal and 55% of the sulfur in the washed coal. Thus, organic sulfur is not reduced by physical methods of separation. Organic sulfur occurs in all the coal entities, but in general, increases as the exinoid content of the coal increases. In this study, it was found that carbonizing certain selected low gravity coal fractions containing an average of 0.45% pyritic sulfur and 1.01% organic sulfur produced cokes containing an average of 0.22% pyritic sulfur and 0.91% organic sulfur. However, the organic sulfur in the coke is probably derived in part from the heating of pyrite in the presence of carbon. Thus, the total sulfur in the coal carbonized is the most important factor affecting the sulfur content of the coke produced. Concentration of microscopic pyritic and organic sulfur in the middling-type coal indicates the necessity for rejecting as much of this material as is economically feasible. Most of the sulfur introduced into the blast furnace originates from the coke. Although the sulfur content of the hot metal can be controlled by the addition of flux, the flux used restricts the productivity of the furnace by displacing ore and requires first to be smelted; therefore, low sulfur coke is highly desirable. Since the sulfur content of coke is dependent upon the sulfur content of the coals from which the coke is produced, low sulfur coals are required to produce low sulfur coke. In the western Pennsylvania area, large quantities of good coking coal are available from the Pittsburgh seam, but this coal unfortunately contains relatively large quantities of sulfur. To provide information that might be useful in reducing the sulfur content of this coal in the cleaning process, an investigation was conducted to determine the physical and chemical forms in which this sulfur occurs and with what petrographic components it might be associated. The Pittsburgh seam coal, like most other coals, contains two dominant forms of sulfur: one occurs as the minerals pyrite and/or marcasite and is referred to as pyritic sulfur; the other is combined with the coal substance and is called organic sulfur. Pyritic sulfur is amenable to physical methods of separation, whereas organic sulfur is not. Pyritic sulfur particles must be freed from the surrounding coal if they are to be removed in the washing process. Generally, this requires crushing; the required degree of crushing being a function of the size and distribution of the pyrite. The present investigation was conducted to 1) determine the size, distribution and association of sulfur-bearing minerals in the coal and 2) to determine whether the organic sulfur has a preferential association with specific coal entities. If a preferential association exists, this knowledge may be useful in devising a method for organic sulfur reduction. In addition, a study was made to determine the extent to which pyritic and organic forms of sulfur in the coal contribute to the sulfur in the coke produced from this coal. A representative 3%-ton sample of raw coal was crushed to —3 in. and screened into square-mesh sizes: 3 to 1 in., 1 to % in., % to % in., % in. to 10 mesh, 10 to 35 mesh, and 35 to 200 mesh. Separate samples of the -200-mesh fraction and the all-size composite were also collected. Each size fraction (except the -200 mesh) was fractionated on heavy liquids of the following specific gravities: 1.280, 1.300, 1.325, 1.350, 1.375, 1.400, 1.425, 1.450,

Jan 1, 1963

By Charles T. Holland

IN connection with the problems of bumps in coal mines, much has been written concerning the manner in which roof action and methods of mining enter [ ] into the pressure effects observed but little has been written upon the relationship between the physical properties of coal and associated rocks and the cause of bumps. The question of the strength of bituminous coal, of its elasticity, and the energy it can absorb and store has been neglected to a considerable extent in connection with this problem. STRENGTH OF COAL It is generally agreed that one of the necessary conditions for bumps is a strong [ ] coal.1 Therefore, since the strength of coal is an important factor, a study of this property should be made. Several investigators have conducted laboratory experiments upon the strength of coal, using small cubical or rectangular test pieces. An attempt will not be made to go into all of these investigations, but they are briefly summarized in Table I. Experiments of the U. S. Bureau of Mines8 and of Lawall and Holland (pp. 27 and 34 of ref. 9), however, indicate that regardless of whether the coal is a soft and weak semibituminous (Pocahontas No. 3) or a hard and strong bituminous (Stockton) coal, the maximum ultimate unit stress developed in laboratory tests is higher in small cubes than in larger cubes of the same coal.

Jan 1, 1942

By Thomas Leonard Watson

Introduction,...... Historical Statement,....644 Geology of the District,....645 The Weisner Quartzite,....647 Topography,. .....653 Rock-Weathering,..... The OcheR-Deposits,.....655 Petrography of the Quartzite,..655 Associated Ore-Deposits,....657 Chemical Composition of the Ocher,. 658 Mode of Occurrence of the Ocher,..659 In the Fresh Rock,....660 In the Residual Clays,...661 Origin of the Ocher,....662 Economic Features,..... Methods of Mining,..... Preparation of the Ocher,...664 Uses,........ Introduction. Knowledge of the existence of yellow-ocher deposits in Bartow county, Georgia, dates back to the early mining of manganese- and iron-ores in the vicinity of Cartersville. Systematic mining of the ocher in this area really began, however, probably not longer than a decade back, although the date of its first working is as early as the year 1877. The district has been, for a number of years, one of the principal producers of yellow ocher in the United States; and at no period of its development have mining activities been greater and more successful than at present. Systematic field-study of the ocher- and manganese-deposits of Georgia was begun by me while I was a member of the

Jan 1, 1904

By James Johnston

Synopsis.-A description of the working of the mills of this company and the metallurgical practice in vogue, by which a remarkably. complex silver ore, averaging 54 oz. of silver per ton (run-of-mine ore), is treated to give a 95.66 per cent. extraction. The main features of the, processes are: The cyanide amalgamation of the high-grade ore. The cyanide treatment of the low-grade ore, after extremely fine grinding and close classification, in a caustic soda solution. The use of a wet desulphurizing process to break up refractory silver minerals. The substitution of aluminum dust for zinc dust as a precipitant. The recovery and shipment of over 13,000,000 oz. of silver in bullion at. 997 to 999 fine since this metallurgy was inaugurated, about 2.5 years ago. On the completion and successful operation of the mill to treat their . high-grade ore,1 the Nipissing Mining Co., under the general management of R. B. Watson, started a series of investigations of the possible treatment of the low-grade ore by the cyanide process, so that they would be in a position to market only silver bullion. These tests were run in July, 1911, on a large scale, by G. H. Clevenger, on an average mixture of Nipissing ore. The results obtained by a partial amalgamation followed by cyanide treatment gave an extraction varying from 90 to 93 per cent. and were sufficiently encouraging to warrant Charles Butters, the company's Consulting Metallurgist, in recommending that the new low-grade ore mill under contemplation should be a cyanide mill, instead of a concentrator. The cost of such a mill, capable of treating 200 tons per day, to obtain a 90 per cent. extraction at a working cost of $3 per ton of ore treated, was estimated at $250,000.

Jan 1, 1914

By J. R. Cain

In every process for making steel there are one or more stages where the metal is exposed to gas of one kind or another. Thus, in the open-hearth furnace, the carbon dioxide and water vapor in the products of combustion are oxidizing toward the ferrous and manganous oxides in the slag, tending to convert these to higher oxides; the higher oxides then , oxidize the steel, so that indirectly the products of combustion are oxidizing toward the steel. In the Bessemer process, there is direct contact of air and steel; also, the water vapor in the air blown into the converter is continually decomposed by the molten steel, yielding hydrogen and ferrous oxide, both of which are in part taken up by the metal. In the electric-furnace processes, there is always more or less air in contact with the slag covering the metal, and this air and the gaseous reaction products from it are dissolved in the slag to some extent and thus transmitted in part to the steel. In the crucible processes, there is always entrapped air in the charges and the crucibles are more or less permeable to the gaseous products of combustion from the furnace. In all the processes of manufacture, the molten metal is exposed to air while tapping into ladles and ingot molds and has an opportunity to saturate itself with air or with gaseous or solid products generated by chemical reactions between air and steel. Sievertsl has shown that molten metals requirc but a few seconds to saturate themselves with a surrounding gas. No one familiar with the operations at a steel plant needs to be reminded of the important role that gases play at all stages. The familiar "boil" of open-hearth furnaces, due to evolution of carbon monoxide when iron ore is added to the molten steel; the spectacular operation of the Bessemer converter brought about entirely by a gaseous reagent; the almost magic effect of small quantities of silicon, manganese, or aluminum added to the molten metal in ladle or furnace in quickly preventing bubbling and evolution of gases; the unwelcome phenomena of blowholes in ingots that have not been properly manufactured—these

Jan 1, 1920

By H. I. Aaronson, C. Laird

The kinetics of thickening and of lengthening of ?' plates in an Al-3.93 pct Cu alloy in the temperature range 203" to 300" C were determined by means of transmission electron microscopy. The rate of thickening was found to be less than that allowed by volume diffusion control at all temperatures, by amounts which increased with decreasing temperature, in agreement with the predictions of a general theory of precipitate morphology.1 Thickening was treated on the basis of the ledge mechanism. Ledges were deduced to spread across the broad faces of ?' plates at volume dzjrfusion-controlled rates, as anticipated from the disordered structure of their edges. Lengthening of 8' plates, on the other hand, took Place more rapidly than allowed by volume dzjrfusion. This occurred despite clear morPhological evidence of a bmrier to growth at the edges of these plates. It was concluded that the misfit dislocation structure comprising the barrier requires that lengthening take place by a jog mechanism. The tnisfit dislocations, however, also serve as diffusion short circuits, and allow high overall lengthening rates to be achieved. In Part I' it was shown that, within the range of aging temperatures and times studied, the broad faces of 8' plates formed in Al-4 pct Cu are fully coherent with the a, matrix. Virtually .all of the dislocations present in these faces were found to have developed as a result of plastic deformation in the a phase. Such dislocations are thus "intruders", rather than the more usual misfit-compensating variety. The edges of 8' plates were confirmed, by extension of the earlier studies of Mat-suura and Koda,3 to be made up of edge-type misfit dislocations, in sessile orientation with respect to lengthening of the plates. These interfacial structures should cause 8' plates to thicken and to lengthen at rates less than those allowed under the condition of volume diffusion control, such as would be expected if the interphase boundaries had disordered structures.' The narrow width of 8' plates, the reproducible crystallography of their broad faces, and the appearance of these plates in cross section as octagons rather than as circular discs2 provide qualitative support for these deductions. The present study of the rate of thickening and the rate of lengthening of 8' plates was undertaken in order to examine them on a quantitative basis. I) THICKENING KINETICS OF THE BROAD FACES OF?' PLATES A) Literature Review. The measurements now available on the thickening kinetics of single-phase precipitate plates consist of one plot of the thickening of a proeutectoid ferrite plate in an Fe-C alloy,' showing (as predicted) thickening rates less than those allowed by volume diffusion control. B) Experimental Procedure. Details of the preparation of the 4-3.93 pct Cu alloy used in this study have been previously reported.4 As in Part 1,' transmission electron microscopy was the observational tool employed. A general description of the apparatus and procedures of the electron microscopy studies is given in Section I of Part I. In thin foils, 0' plates tend to form at and parallel to the foil surface.' A direct investigation of the thickening process by means of hot-stage transmission electron microscopy was therefore not feasible. It was thus necessary to use the conventional method of aging individual bulk specimens for a wide range of different times at the various temperatures studied. In each specimen, the thicknesses of a number of plates were measured. Since thin foils prepared from "bulk-aged" material contain a large proportion of grains with orientations near (001) , it was relatively easy to find, near the edges of the foils, the characteristic multifold patterns of intersecting extinction contours which indicate regions where the foil is exactly at an (001) orientation. The thicknesses of large numbers of plates were measured along the (200) branches of the "stars" so that the 8' plates were precisely parallel to the optical axis of the microscope. Wherever possible, intersecting extinction contours were adjusted with the parameter s > 0 to improve the visibility of the plates in bright-field illumination. These precautions, in combination with taking the measurements at the thinnest parts of the foils, minimized the errors in the measurement of the thickness of the plates resulting from inexact parallelism to the electron beam. Since the plates were very thin, it was not easy to measure their thickness on the photographs. The techniques of enlargement and of microdensitometry were employed to minimize errors from this part of the measurement. A further source of possible error, that the plates can appear thicker because of contrast associated with mismatch normal to the plane of the plate, was also considered. The images of the plates were usually thinner than those of dislocations, however, and no anomalous changes in apparent plate thickness were observed when regions of foil containing plates were tilted through various diffracting conditions. Any error from this cause must therefore be small. Other sources contributing errors were: a) the microdensitometer traces per se and the subjective estimates of their peak limits, and b) slight fluctuations in magnification associated with small changes in the current of the objective lens of the electron microscope. The overall error probably amounted to no more than 5 to 10 pct. In order to obtain readily interpretable data on thickening kinetics, it is essential that the diffusion fields of adjacent ?' plates not be allowed to overlap. Calculations'-' showed that this condition is definitely not ful-

Jan 1, 1969

By P. E. Busby, C. Wells

FURTHER study of data used in determinations of 1—rates of diffusion of boron in austenite and 2—solubilities of boron in the a and phases of iron and steel' has provided an equation for the diffusion of boron in a iron. In brief, the previously published data were accumulated from the results of deboron-izing (and decarburizing) experiments carried out in the range of 700° to 1300°C. Diffusion coefficients (D?) for boron in austenite were calculated using the Grube solution of Fick's law. However, only solubility values were estimated from the discontinuous concentration-penetration curves, Fig. 1, which are characteristic of diffusion in two phases. Dr. Carl Wagner' has recently provided a solution for calculating D values from penetration curves of this type as follows: Cl1.1 —C8/C8- C11.1 = vp ? e ? erf (?) and D = ?/4?2 t where C11,12, C8, C11, and E have the values shown in Fig. 1. D is the diffusion coefficient, sq cm per sec; t is time of deboronizing anneal, see; and ? is a di-mensionless parameter. For a given diffusion experiment, the value of ? can be readily obtained by graphical solution from a plot of y vs the right-hand part of Eq. 1. D may then be evaluated from Eq. 2. The avplication of this solution to previously re-ported results, of which excerpts are given in Table I, permits the calculation of diffusion coefficients for boron in a iron. On the basis of these meager data, it is tentatively concluded that the diffusion of boron in a may be represented by the equation Da = 1011 e-92,900/RT where R is the gas constant, cal X 0C-1 X mol-1; and T is the absolute temperature, OK. Although the frequency factor, 106 sq cm per sec, is admittedly several orders of magnitude higher than expected, the value of Q, 62,000 cal per mol, appears reasonable and is, in fact, very similar to that for the self-diffusion of iron. It is pertinent to mention at this point that the value of Q obtained for the diffusion of boron in austenite by means of the Wagner solution is 19,000 cal per mol and is in excellent agreement with the value previously reported1 in the equation DT = 2xl0-3 e-21,000/RT [4] which was determined by the application of the Grube solution to other data. The fact that determined constants A and Q in the equation D? = A e-Q/RT were practically the same, independent of whether the Wagner or Grube solutions were used in determinations of D values, strengthened the authors' belief that the computed values of D (Table I) using the Wagner solution are reliable. The relative values in Eqs. 3 and 4 for the diffusion of boron in the a and ? phases, respectively, suggest that boron forms a substitutional solid solution in a iron and an interstitial solid solution in ? iron. The same tentative conclusion has been reached by McBride et al.3 on the basis of relative solubilities, atom diameter, and the size of the interstitial hole in a and ? iron. In connection with the data for test 14 listed in Table I, it is of interest to calculate the solubility of boron in a iron using the D value given by Eq. 3. As might be anticipated from the small movement of the interface in test 14, proper substitutions in Eqs. 2 and 1 give a low value, approximately 0.0004 pct B, at 850°C. Apparently at 835°C (test 13) it is possible to obtain 0.0018 pct B, and at 850°C only 0.0004 pct B into solution in the a phase before a second phase appears. These observations are consistent with the Fe-B constitution diagram proposed by McBride, Spretnak, and Speiser.3 References P. E. Busby, M. E. Warga, and C. Wells: Diffusion and Solubility of Boron in Iron and Steel. Trans. AIME (1953) 197, p. 1463; Journal of Metals (November 1953). 'W. Jost: Diffusion in Solids, Liquids, Gases. (1952) pp. 69-71. New York. Academic Press Inc. "C. C. McBride, J. W. Spretnak, and R. Speiser: A Study of the Fe-Fe2B System. Trans. ASM (1954) 46, p. 499.

Jan 1, 1955

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

By Frank Firmstone

. In the early decades of the past century the method of starting iron blast-furnaces by " scatlolding-down" seems to have been in universal use for coke-furnaces and, at least in this country, for charcoal-furnaces also. It was likewise used at some of the early anthracite-furnaces, as is stated in the important " Reminiscences" printed by the late Samuel Thomas.' It had been generally superseded in Great Britain as early as 1850, by some variations of the plan now used, and was rarely used when Percy wrote.2 On the Continent it was still followed ill the 60's; and was elaborately described by Valerius in 1852. I have never read any statement as to when and by whom " scaffolding " was first dispensed with, but the following extracts from journals of my father seem to fix an authentic date for an instance in this country: " [Pittsburg] July 12, 1838.—Went with Major Wade to his foundry,etc., and he gave me a letter to D. Tyler, Esq., Farrandsville, Agent Boston Coke & Iron Co." " [Lockhaven, Pa.] July 18, 1838.—Heard there was a flat-boat going to take some gentlemen up to Farrandsville. Got on boat and to Farrandsville, 5 or 6 miles, in 1 hr. 30 min. Dined, and then delivered my letter to Ma Tyler, who showed me much attention, and everything belonging to the furnace, and had the water turned on the wheel that I might see the blowing-cylinders at work. There are two cylinders, 6-ft. stroke, -56 in. in diameter, but they find that one makes more than enough blast for the furnace. The furnace has 16-ft. boshes, 7-ft. tunnel-head, and is 47 ft. high, 3 tuyeres, and 3 heating-ovens [hot blast-ovens]. A

Jan 1, 1908