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By C.A. Zapfee, C. E. Sims

An investigation of the behavior of inclusions in steel several years ago1 led to the conclusion that some of the commonly occurring inclusions in steel have appreciable solubilities, particularly in liquid steel. In the belief that further study and clarification of this matter was warranted, a laboratory study of oxides in liquid steel was started. These oxides are generally the result of deoxidation treatment, and the basis of an understanding of their behavior must be, therefore, the behavior of the deoxidizer in liquid iron. The Fe-Si-O system was selected for the first study, and the apparatus used and experiments conducted are described herein. Apparatus The apparatus is shown in Fig. r and the system is shown by diagram in Fig. 2. Furnace, A lmosphere Commercial hydrogen (1) passes through an orifice (2) into a manometric system that measures the tankside pressure (3) and the back pressure (4) in the system. A water trap (5) guards against excess tankside pressure. A by-pass with stopcocks (6 and 7) is provided, so that the hydrogen can be routed directly from the tank to the furnace if desired. When stopcock 7 is closed and stopcock 6 is open, the gas proceeds through the conditioning train, of which the first unit is a furnace (8) that contains platinized asbestos at 350°C. The temperature is measured by a thermocouple and potentiometer (9) and is controlled by a slidewire resistance (10). In this furnace fres oxygen is converted to water vapor. The exiting gas passes over a water bath (11) kept slightly below boiling temperature by an auxiliary heating unit (12). This unit also heats a surrounding copper coil (13) containing water, and the heated water rises through a collar (14)

Jan 1, 1943

By C. A. Zapfee, C. E. Sims

An investigation of the behavior of inclusions in steel several years ago1 led to the conclusion that some of the commonly occurring inclusions in steel have appreciable solubilities, particularly in liquid steel. In the belief that further study and clarification of this matter was warranted, a laboratory study of oxides in liquid steel was started. These oxides are generally the result of deoxidation treatment, and the basis of an understanding of their behavior must be, therefore, the behavior of the deoxidizer in liquid iron. The Fe-Si-O system was selected for the first study, and the apparatus used and experiments conducted are described herein. Apparatus The apparatus is shown in Fig. r and the system is shown by diagram in Fig. 2. Furnace, A lmosphere Commercial hydrogen (1) passes through an orifice (2) into a manometric system that measures the tankside pressure (3) and the back pressure (4) in the system. A water trap (5) guards against excess tankside pressure. A by-pass with stopcocks (6 and 7) is provided, so that the hydrogen can be routed directly from the tank to the furnace if desired. When stopcock 7 is closed and stopcock 6 is open, the gas proceeds through the conditioning train, of which the first unit is a furnace (8) that contains platinized asbestos at 350°C. The temperature is measured by a thermocouple and potentiometer (9) and is controlled by a slidewire resistance (10). In this furnace fres oxygen is converted to water vapor. The exiting gas passes over a water bath (11) kept slightly below boiling temperature by an auxiliary heating unit (12). This unit also heats a surrounding copper coil (13) containing water, and the heated water rises through a collar (14)

Jan 1, 1943

By A. P., Svenningsen

ECONOMICAL handling of a minimum of 25,000 tons of minus 3/4-in. ore per day, grinding it to 2 per cent on 65 mesh, and effecting a high recovery of the copper at the lowest possible cost were the principal aims in the design of the new Morenci concentrating plant. Dealing with a tonnage of this magnitude, it is obvious that lost motion cannot be tolerated. When ore is carried on a conveyor an unnecessarily long distance or elevated to a greater height than necessary, or when pulp flows in a launder by a circuitous route thereby losing elevation and distance, we have lost motion which is always costly both from the standpoint of construction and operation. In addition to the 25,000 tons of ore which must be handled, 100,000 tons of water per day has to be carried through the plant in the treatment of the ore. Though water is not so difficult to handle as the ore, the combined tonnage represents a figure which could easily run into a considerable monetary loss per day if all phases of the design were not carefully followed with the idea of eliminating any unnessary handing of materials.

Jan 1, 1942

By Edward Keller

(New York meeting, February, 1912.) IN a paper, entitled A Uniform Method for the Assay of Copper Material for Gold and Silver,1 A. R. Ledoux invited the assayers of this country to contribute to a symposium, in which the results of their assays of given samples of copper-matte and metallic copper would be made comparable. This symposium 2 appeared about one year thereafter; and through it and its discussion, first became generally known the fact that the ,gold-yield by the all-fire method of assaying is usually higher than by the so-called combination (wet and dry) method, in which nitric acid is employed as a solvent for the copper. In the publication alluded to, the supposed cause of gold-losses in the latter method was declared to be the solvent action of copper nitrate, or of the reduction-products of the nitric acid, upon the gold. Up to a very recent date, gold has been held to be insoluble in pure nitric acid. (The solvent action of any chlorine present in the nitric acid must here properly be disregarded as belonging in the realm of carelessness. Among later allusions to this topic, W. R. Tan Liew 3 ascribes the solution of the gold in the combination-assay entirely to the action of nitrous acid at the high reaction-temperature of copper and nitric acid ; F. B. Flinn 4 a believes the low result in gold to be due exclusively to mechanical losses-finely-divided gold penetrating through the filter-paper-but presents no experimental data confirmative of this belief; and 0. Pufahl 5 attributes the solubility of the gold in some coppers to the presence of selenium-a view which appears to be shared by many as- 1 Trans., xxiv., 575 (1894). 2 Trans., xxv., 250 (1895). 3 Engineering and Mining Journal, vol. lxix., No. 16, p. 469 (Apr. 21, 1900). 4 Engineering and Mining Journal, vol. lxxxvii., No.11, p. 569 (Mar. 13, 1909). 5 Lunge, Chemische Technische Untersuchungs Methoden, vol. ii., p. 229 (1900).

Jul 1, 1912

No. 345.-Assayer. A man 35 years old, or over, experienced in general mineral assaying, particularly of tin and tungsten ores. To locate in Bolivia with a strongly established house. No. 346.-A firm of consulting and managing engineers, having charge of certain coal-mine properties in Illinois, requires the services of the following: (a) Mine transitman, who has had underground experience and is capable of making accurate surveys. Salary $150 per month to start. (b) Mining engineer, possessing strong personality, and experienced both in surface and underground work, who is capable of taking complete charge of several coal properties. Salary $175 per month. (c) Four rodmen for mine surveying. Salary $85 per month to start. Candidates for the above positions should be able to report to the company's Illinois office at once. No. 347.-A South African development company will shortly require the services of a mill superintendent, who has :a general knowledge .of concentration, particularly of flotation, and is able to take charge of a copper concentrator treating 15,000 tons per month and employing 200 natives and a small number of white men. Salary is £60 per month to start, and the company supplies an unfurnished room or house, including free light, free water and free sanitary service, together with one native house servant. I A contract will be made for six months, and notice of three months by either party will be required to terminate the engagement after six months. An allowance of £75 for travelling expenses will be paid on arrival in South Africa to a single man, or £125 to a man who brings his family. Salary begins upon arrival

Jan 10, 1918

Book Review MANAGEMENT AND MEN. By Meyer Bloomfield, Boston. The Century Co., New York, 1919, pp. 584, H.X. 5 1/2. $3.50. This hook is an exposition of English efforts to solve the problem of labor unrest in England. The first six chapters are reprinted from articles published in the Satur-day Evening Post, for whom the author went to England to study the problem at first hand. These articles deal with housing, increased production, eliminating the internal friction in the industrial machine and a chapter each devoted to the view-point of employer and employee. These chapters are written in the easily readable magazine style and give a complete general survey of the particular solution being tried. Perhaps their greatest., certainly not their least, worth lies in the fact that they form a vehicle for unusually voluminous appendices containing in full the famous Whitley Reports which are the basis of the new movement, together with various reports, which, except for this publication, would be largely inaccessible to those inter-ested in this country. The Whitley scheme considers each industry a unit and proposes to establish therein a Joint Standing Industrial Council composed of representatives of employers and employees to consider appropriate matters affecting the industry at large. There is to be a District Council for each industry which will, as its name implies, deal with the clatters pertaining to that interest in. the particular district. The third and last body in this scheme of Industrial Parliament is the Works Committee, which is com-posed of representatives of the management and of the workers employed in particu-lar plants or mines to act in close cooperation With the district quid national machinery. The Whitley or similar schemes have been tried in many communities in England and the book contains interesting comments on the result obtained, it being notable that most of the objections conic from plants which have not tried the scheme. Meyer Bloomfield, the author; is the specialist in industrial personnel problems who organized the industrial service activities of the United States Shipping Board, Emergency Fleet Corporation. P. E. B.

Jan 10, 1919

By Benjamin C. Craft

As predicted, during 1937 South Louisiana witnessed one of the most active drilling campaigns in the history of the area, resulting in the discovery .of 14 new fields. The economic importance of 10,000-ft. production was far-reaching and the objective depths placed on some wildcats was 12,000 feet. Most of the important discoveries and deep tests were in the delta area between the Atchafalaya and Mississippi Rivers, where the upper Miocene sands were found productive between 10,000 and 11,000 ft. The casing program on these wells usually called for a protection string of 95/8-in. casing at approximately 9500 ft. Drilling barges with the heaviest equipment were used where water transportation was available. The oil production for South Louisiana during 1937 was 62,147,690 bbl., as compared with 51,968,727 bbl. during 1936, an increase of 19.5 per cent. There were 281 oil and gas wells and 172 dry holes completed during 1937 as compared with 262 oil and gas wells and 135 dry holes during the previous period. New Fields Gibson.—The first discovery for the year was in the Gibson area, where Shell Petroleum Corporation's Realty Operators No. 1, sec. 18, 17 S., 15 E., Terrebonne Parish, was completed flowing 780 bbl. of 38° A.P.I. oil daily through a 14/64-in. choke with a tubing pressure of 1700 lb. Production is from upper Miocene sand found from 9461 to 9483 feet. Abbevil1e.—The discovery well for the Abbeville field was Continental Oil Company's Hebert No. 1, sec. 20, 12 S., 3 E., Vermilion Parish, completed flowing 50 bbl. of distillate and 2 million cubic feet of gas through a 3/16-in. choke with a tubing pressure of 2550 lb. The well was plugged back from 12,216 ft. in the Chickisawhay, and is producing through perforations from upper Miocene sand found from 7668 to 7682 ft. Later in the year, the same operators completed Brookshire No. 1, sec. 66, 12 S., 3 E., flowing 366 bbl. of 42° A.P.I. oil per day through a 3/16-in. choke with a tubing pressure of 1800 lb. This well was com-

Jan 1, 1938

By R. B. Adair, J. S. Browning

The laboratory batch and continuous flotation pilot plant tests demonstrated the technical feasibility of recovering high grade mica concentrates from weathered mica pegmatite ores of Alabama and Georgia. The research indicated that combinations of anionic and cationic collectors may be used effectively for flotation of fine size mica from weathered pegmatite ores. In continuous tests, concentrates containing 98.5% mica were obtained from the Georgia pegmatite ore; the Alabama pegmatite ore concentrates contained 98.4% mica. The recoveries were 91 and 89% respectively. INTRODUCTION The principal uses of fine ground mica are as a filler in wallboard joint cement, as a filler and surface coating for roofing, as an ingredient in paints, and in oil well drilling mud. The mineral has other uses in the manufacture of rubber, wallpaper, plastics, welding rods, electric insulation, house insulation, and textiles, and as an annealing agent in metal treatment. In recent years, more than 99% of the domestic mica produced has been scrap and flake mica (mica which does not meet specifications for sheet mica and is used for producing fine ground mica). There has been a continued increase in mica production for several years, the 1963 production of scrap and flake mica totaling 117,251 tons.1 Ground mica is obtained primarily by crushing and milling pegmatites and schists. To a lesser extent, mica is produced as a byproduct of kaolin washing and feldspar and spodumene flotation operations. The processes used in recovering mica by crushing and milling pegmatites are generally simple, consisting of various combinations of alternate roll crushers and trommel screens that separate the mica and gangue at screen sizes coarser than 6-mesh. As these processes are designed to recover only coarse mica, high losses in the plant rejects are common. Large tonnages of tailings from the crushing and screening plants have been accumulated in a number of areas. Methods for treating such products were developed by the Bureau of Mines in 1941,2 but have not been generally applied. More recently, mica flotation research has been completed and published by the Bureau of Mines.3 These methods required complete removal of 150- to 200-mesh materials from the flotation feed with consequent fine mica losses. Later, the Bureau of. Mines investigated methods for-recovering fine size mica from pegmatite ores after desliming sufficiently to remove clay materials, but not so drastically as to remove the fine sands. This report summarizes the results of these studies. The process developed was effective on pegmatite ores from two locations and should be applicable to the commercial treatment of other mica-bearing pegmatite ores and fine rejects that have been accumulated at various mica-milling operations. DESCRIPTION OF ORES The ores used in the investigation were obtained from the Dixie Mines, Inc., Heflin, Alabama, and the Ruberoid Corporation, Hartwell, Georgia. The sample from Alabama contained muscovite and quartz, with a high percentage of clay, and minor amounts of biotite, kaolin, limonite and tourmaline. The mica in the ore was essentially all minus 4-mesh in size and was free of attached mineral grains. The Georgia sample contained muscovite and quartz, with minor amounts of biotite, kaolin, and limonite. The mica in the ore, which was essentially all minus 4-mesh, was liberated. Petrographic analyses of the two samples are given in Table I. THE ANIONIC-CATIONIC MICA FLOTATION METHOD Previous investigators2,3 have reported that complete desliming of mica ores at 150- to 200-mesh was required prior to flotation with cationic collectors to obtain satisfactory selective separation of the mica from the other mineral components. Numerous tests were made at the Tuscaloosa Metallurgy Research Center to determine if some reagent combination could be used to selectively float finer size mica without complete desliming. The investigation led to development of a process using a simple reagent com-

Jan 1, 1967

Section 89 Virginia State Geological Survey, Box 329, University, Va. Arthur Bevan, State Geologist A list of publications will be sent free upon request. Publica¬tions are distributed free to residents of Virginia, and others are asked to pay the cost of postage. Selected Bulletins available are: Bulletin 3-A, Geology of the titanium and apatite deposits, with chapters on the Lower Cretaceous and The economic geology (1913), 4, Physiography and geology of the Coastal Plain Prov-

Jan 1, 1933

By R. F. Mehl, B. Lustman

THE formation of intermediate phase layers in cementation processes has been subjected to extensive qualitative investigation though to relatively little quantitative study; this work has recently been fully summarized by F. N. Rhines.1 It is necessary here only to enumerate the general conclusions drawn concerning the kinetic laws governing the growth of intermediate layers and to state what is known concerning the structural changes accompanying the generation of phase layers. I. When the intermediate phase is protective in type-i.e., when its density is less than that of the base metal, so that a continuous coating is formed and maintained the isothermal growth of the phase follows a simple parabolic equation: X2 = kt [I] where X is the thickness of the alloy layer, k the reaction rate constant, and t the time. The applicability of this equation to diffusion processes is tested by plotting the square of the thickness versus time, or by plotting the thickness versus the square root of time; the resultant achievement of a straight line in such. a plot has been con¬sidered sufficient proof of the validity of this equation. Exceptions have been found where liquid phases are involved in the reaction, where the diffusion layer is cracked,2 and where thin semimetallic oxide and sulphide coatings are formed on metals.3 In the first two cases the thickness increases linearly with time, and in the latter it is a logarithmic function of time. 2. The rate of thickening varies with temperature according to the Arrhenius equation k = Ae-Q/RT [2] where k is the parabolic rate constant of Eq. I, or some other rate-descriptive function, A is the action constant, e the base of natural logarithms, Q the heat of activation, R the gas constant, and T absolute temperature. This equation has been found to be generally valid except when transformations occur during reaction in either the base metal or in the reaction layer; in such instances Eq. 2 is still applicable with different values for the constants A and Q above and below the transformation temperature. 3. All phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two components. In some cases certain of the phases may be too thin to be observed and identified easily. Nonequilibrium phases have never been noted in thick reaction layers; i.e., layers of a thickness that may be discerned microscopically. The relative, thickness of each phase in a diffusion layer is proportional to the concentration gradient and to the rate of diffusion in that phase .4 The reaction layers tend to have a

Jan 1, 1942

A. R. Ledoux,New York City: The so-called combination method " is generally used in assaying bar copper for silver. It has been modified from time to time. Briefly outlined

Jan 1, 1901

By R. S. French

THE purpose of this paper is to present data that have been obtained during the past two years concerning the effects of prior cold-work and temperature and time of anneal upon the recrystallization and grain growth of 70-30 cartridge brass. It was desirable to study certain of these phases so that an accurate picture of the principles of the subject could be shown. The work is not intended to provide explicit annealing data, but to provide material examples that may help to clarify analogous problems concerning this alloy. Specifications often set limitations upon the grain size of annealed materials because of the importance of grain size upon subsequent manufacturing operations. It was, therefore, worth while to study the variables that affect the recrystallized grain size of this material. C. H. Mathewson and A. Phillips,1 W. R. Webster,2 and others have presented annealing characteristic curves of this alloy. A recent typical curve presented by R. S. Pratt3 is shown in Fig. I. The tensile properties and grain sizes are shown as functions of the annealing temperature. Such curves serve as a useful guide in determining the physical properties of annealed material, but as they are made generally under carefully controlled laboratory conditions they do not indicate the performance of metal annealed in a mill muffle, where conditions are different and the amounts of metal require necessarily longer heating times and temperatures. Study of the effect of time and temperature upon grain growth and subsequent recrystallization was made with a coil of metal having the following analysis: 70.04 per cent copper; 0.007 lead; 0.007 iron; 0.00 tin; 0.00 silicon; 0.001 nickel; 0.000 phosphorus; balance zinc. The sample coil was obtained from metal that had been rerolled from hot-rolled mill stock, and was received at 0.228-in. gauge, soft, with a grain size of 0.125 mm. This material was then rolled 43.5 per cent to 0.125-in. gauge and annealed to a 0.053-mm. grain size. In this condition, samples were cut and used in all of the experimental work reported in this paper. TIME The first study was of crystal growth at a constant temperature over a moderate length of time. Material was cut from the stock coil at 0.129-in. size and rolled 75 per cent hard to 0.032-in. gauge. From this piece small samples were cut ½ by 2 in., suitable for grain-size determinations. Twelve samples were placed in an electric furnace uniformly across the width, approximately an inch from the floor, A thermocouple was wired to the center sample, so that the approximate metal temperature could be followed. At various

Jan 1, 1944

By H. H. Stoek

THE fundamental reasons underlying the choice of a method of mining a coal seam are safety of operation, cheapness of producing the product and the character of the product as a saleable article. From the standpoint of safety, open or strip coal mining is always preferable, as many of the dangers inherent to underground work are absent, such as explosions of gas and dust, falls of roof and coal, and also to a great extent those due to haulage and the use of explosives, thus eliminating three of the chief causes of accident from which about 75 per cent. of the underground accidents in coal mines occur. The conditions under which coal is stripped also make the work much safer than ordinary quarry work, as the depth. of the pit is usually comparatively slight. From the standpoint of low mining cost, there is much misapprehension and many of the costs given are misleading in that they do not take into account such items as the destruction of the surface for future use, the full cost of the removal of the overburden, depreciation, amortization, coal depletion, loss of time through floods and from bad weather in winter, etc. Coal is no doubt often put on the cars at less cost by stripping than by underground mining, but by no means always so, as is too generally assumed. In some cases coal must be obtained by stripping or not at all, due to the small amount of overburden that renders underground mining impossible.

Jan 9, 1917

By Leon Eliel

TEN years ago a broad knowledge of aerial mapping, coupled with a smattering of geology, qualified one to speak on the subject of the appli-cation of aerial mapping to geology. Today, with aerial maps a common tool in the hands of expert geologists on every continent throughout the world, it would be nothing short of presumptuous for the author of this paper, who is not a geologist, to give any geological statements on his own authority. Relatively, today we are only purveyors of general geological gossip, with a definite case here and there by way of illustration. But we can present a story of the really marvellous strides that have been made in the evolution of aerial mapping, built around a skeleton of geological tidbits, from which some useful conclusions may be drawn. The average geologist goes about reading his aerial maps much as one would approach the problem of deciphering a cryptogram. To begin with, typical key expressions appear in recurring sequences and under certain conditions. If once the meaning of these isolated bits of infor-mation can be ascertained, the message begins to take meaning. In a similar fashion, the geologist works out his key from aerial maps of territory with which he has some familiarity. He learns that a certain type of thin, white line may mean a vein of quartz. He sees that a certain change in the photographic tone of vegetation on the ground reflects two kinds of soils on opposite sides of, a contact. He sees that a certain type of alignment of topographical features often means a fault. He learns that by the erosion pattern .he can frequently distinguish soft formations from harder ones. And so, bit by bit, he ties together the information of the picture with his experience on the ground until he develops a reasonably creditable capacity of interpretation. Through the complete gamut of surface conditions, ranging all the way from flat, arid, exposed desert terrain to dense jungle, or rugged mountains, the evidence from which the geologist must make his inter-pretation varies with bewildering profusion. The quality of photographs which are obtainable may range from perfect pictures in the desert to almost useless smudges in the steaming jungles. One thing he has learned with certainty-the airplane carrying its mapping camera is a superb reconnaissance tool, only awaiting his ingenuity in correlating the pictures with the ground to simplify most exploratory problems.

Jan 1, 1936

By C. H. Mathewson

THIS paper was prepared upon request as a contribution to a symposium covering the manufacture, properties, and uses of the important non-ferrous metals. In approaching a subject as broad as this, there is a natural desire to build up a comprehensive and finished production which shall constitute a dependable source of information on all questions properly belonging to this branch of metal technology. There are, however, a number of circumstances, apart from the mere routine of labor and thought involved, which operate rather effectively against the possibility of completing such an ambitious program at the present time. First of all, as far as any public record of results is concerned, the commercial rolling, drawing, and forming of zinc with relation to changes of structure and properties-and this we consider to constitute the elements of metal technology-might as well be an unpractised art. We have never seen a published photomicrograph showing the structural characteristics of either hard or soft sheet or strip, although the structure of castings has been frequently described, and other coarse-grained structures resulting from hard-hammering and annealing have been reproduced. Thus, an author in this field must proceed to his task without much assistance from the literature, and the outcome can represent only a personal estimate of principles, facts, or findings, and not a summary

Jan 9, 1919

By L. Leibowitz, M. G. Chasanov, L. W. Mishler

A drop calorimeter system is described for use in measuring enthalpies to 3600°K. Data are presented for tungsten between 2800" and 3600°K. The enthalpy of tungsten in cal per mole between 2000° and 3600°K can be represented by the equation HºT- Hº298 = - 1.7622 X 103 + 5.7772T + 8.9861 where T is in degrees Kelvin. A tabulation of com -puted values is presented for heat capacity, entropy, and free energy function. A drop calorimeter has been constructed to carry out enthalpy measurements at temperatures to 3600°K. Samples are heated by induction1 and dropped into a commercial adiabatic calorimeter, modified for this purpose. The experimental temperature is limited by the melting point of container materials and compatibility of the container and its contents. Several high-temperature drop calorimeters have been described in the literature1-5 but none has been used at temperatures as high as those in the present work; our measurements of the enthalpy of tungsten range from 2800" to 3600°K. DESCRIPTION OF EQUIPMENT An overall schematic view of the equipment is shown in Fig. 1. Power for the induction coil is supplied by a 25-kw 250 kHz Ther-Monic generator coupled to an iron core RF transformer. The Sample capsule is suspended in the work coil by 10-mil diam tungsten wires which are wrapped around a horizontal 5-mil diam tungsten wire. The horizontal suspension wire is clamped between two massive copper electrodes which are fixed in an x-y motion device that allows adjustment of the position of the heated capsule from outside the vacuum chamber. The copper electrodes are connected by flexible copper straps to a 1250-joule (5 kv, 100 pfarad) condenser bank. When it is desired to release the capsule, the condensers are discharged through the horizontal suspension wire causing it to vaporize rapidly. Very reliable and precise release of the capsule is achieved in this manner. Experiments have shown that no heat correction is required for this discharge energy. As part of the temperature measuring system, two prism holders have been incorporated in the apparatus. The upper prism holder is in the main vacuum chamber itself, whereas the lower one is in a side arm attached to the drop tube below the gate valve. The upper prism is mounted on a rotary vacuum feed-through, and may be moved under a protective shield when not in use. This prevents deposition of vapors on the prism surfaces when temperature measurements are not being made. Similarly, the lower prism is mounted on a push-pull vacuum feed-through, and when not in use may be pulled into its side tube. The prism mountings are fitted with guides and stops so that they may be moved precisely into the desired position. The aim throughout is to minimize the time the prisms are exposed to vapors from the hot samples. At the high temperatures reported in this paper, only the lower prism was used. The upper prism holder in these cases was fitted with an additional radiation shield. By using a prism and viewport, the lower surface of the samples can be observed by an optical pyrometer. The measurements discussed in this paper were obtained with a Leeds and Northrup 8622-C-S series manual pyrometer which is estimated to be accurate to 0.5 pct. Pyrometer calibrations and prism and window corrections were carried out in the conventional manner6 using tungsten strip lamps calibrated by the National Physical Laboratory, Teddington, England. Prism corrections were rechecked after each use. All work to date has been done in vacuum, and no measurable change has been observed in the prism correction below -2300°K for the upper prism and below -2800°K for the lower one. The total time of exposure of the prisms is about 50 sec per run. At high temperature, the final temperature reading is corrected by using the final A value for the prism; see Ref. 6 for details of this procedure. The calorimeter is a modified Parr Instrument Co. (Moline, lll.), Series 1230 adiabatic calorimeter with automatic jacket control. Other authors5 have used a similar calorimeter with good results. The calorimeter jacket cover and calorimeter cover are attached to the drop tube which contains a radiation shield. This shield is a gold-plated copper disc which can be operated manually from outside the calorimeter. The receiver is attached below the radiation shield and is lined with tungsten. In a typical experiment, the calorimeter and its jacket water temperatures were adjusted to 0.000°K temperature difference. The sample was allowed to equilibrate in the furnace at the desired temperature for about 20 min. The initial calorimeter temperature was then recorded, the sample dropped, and appropriate shutters closed. After about 3 min, the drop tube and receiver were filled with helium to 60 torr. The final calorimeter temperature was recorded after it had remained constant over a 5-min period. The equilibration time in the calorimeter was about 25 min. Thermistor probes are used to operate a hot and cold water supply system to maintain the jacket temperature equal to the calorimeter temperature. For actual measurements of the calorimeter temperatures, a quartz thermometer was used (Hewlett Packard Dymec Thermometer, Model #2801A). This thermome-

Jan 1, 1970

By P. L. Weston, S. E. Khalafalla

A systematic study was made by the Bureau of Mines on the effect of so me hypothesized accelerators for the process of wustite reduction in carbon monoxide. When small concentrations of promoter materials in the order of 0.69 at. pct were added to the reducible charge, the rate of reduction to iron was increased. Promotion phenomenon prediction was made in light of a suyface reduction mechanism with the aid of Vol'kenshtein's effect regarding the propagation of crystal lattice disturbances by small amounts of relatively larger interstitial ions. The acceleration produced by a typical promotor, such as potassiunl, increases with protnoter concentration up to a maximum, beyond which the reduction rate decreases. Concentration for maximum promotion depends on the nature and physicochemical properties of the promoter. The extent of reduction rate enhancement is found to be directly proportional to the atomic volume and electronic charge of the additive. DESPITE the enormous volume of literature on iron oxide reduction, very little is reported concerning additive or impurity effects on this important metallurgical process. The beneficial effect bf calcium compound additions on the reducibility of iron oxide sinters has been reported by Tigerschiold,1 vor dem Esche,2 and Edstrom. Doi and Kasai~ found that the addition of lime or limestone to iron ores helps to break up any unreducible compounds, such as fayalite or ilmen-ite. and thus free the combined iron for reduction. Schenck et al. 5 suggested that the increased reduction rate obtained when adding lime could be accounted for by the instability of wustite in the presence of lime. Acid-base slagging reactions resulted in wustite disproportionation according to The dicalcium ferrite formed will yield iron and calcium oxide during reduction. Regenerated calcium oxide dissociates more wustite. This mechanism has been used by Seths and white7 to explain their experimental results. Recently, Strangway and ROSS' attributed the calcium carbonate acceleration of iron oxide agglomerate reduction to increased porosity, both initial as well as that developed during reduction. Aside from calcium carbonate, or oxide, no other promoter was noted in the literature, except for a brief mention by Barrett and woodg on the effect of sodium carbonate and aluminate as activators for the hydrogen reduction of magnetite at 600°C. The present investigation systematically studied a host of other promoters, including calcium and sodium, in an attempt to elucidate the mechanism by which promotion takes place and to fit the results into a simple chemical model. To attain this goal, the effect of promoter physical properties, such as atomic volume, electronic charge, and concentration are related to wustite reduction kinetics in this paper. Wustite reduction to iron, rather than the overall hematite reduction, was chosen since this reaction is known to be the slowest, and hence the rate-deter mining step for the overall iron oxide reduction process. EXPERIMENTAL PROCEDURE Raw Materials and Their Preparation. The pure or impregnated wustite pellets were prepared from minus 400-mesh chemically pure hematite powders. A known weight of hematite was thoroughly and uniformly mixed with a calculated weight of the additive. The mixed paste containing 35 wt pct water was gradually heated from 400" to 1200° C and fired at 1200°C for approximately 4 hr in an air atmosphere. After cooling, the sinter was pulverized to minus 100 mesh and pelletized into minus 4- plus 5-mesh spheres. Pellets were fired, similarly to the paste mix, air-cooled, sized, and stored. An appropriate weight of the charge (20 g) was placed in a zirconia reduction tube maintaining a uniform oxide bed height of 1 cm and a cross section of 7.1 sq cm for all of the test runs. The samples were supported in the vertical reaction tube by a bed of fragmented insulating firebrick plus 3- to 6-mesh alumina beads. The hematite was then transformed to wustite by reduction with a 30 pct CO2-70 pct CO gas mixture at 1000°C in a globar furnace. Complete conversion to wustite was ascertained by a continuous infrared gas analyzer recording the CO-CO2 content of the effluent gas until no carbon monoxide was absorbed from the inlet gas, and inlet-outlet gas analysis remained constant for 30 min. The wustite sample was then reduced with 100 pct CO at 100WC. From the recorded data, an initial rate of reduction was determined by the initial slope of the graph percent reduction vs time. In order to estimate the accuracy of the data, five separate determinations of the reduction curve of pure wustite, under otherwise identical conditions, were performed. The maximum deviation from the average reduction at 14 min amounted to 2 2 pct reduction. This deviation corresponds to 3.8 pct variation based on the percent reduction of the sample. Aiiy impurity effect below the limits of this maximum deviation was considered a spurious result. If the effect exceeded + 4 pct, then it was considered as a positive one. Considerable care was exercised in determining the initial rate from the slope of the initial segments of the curve. Each reduction curve was examined separately on large graph paper and the best tangent to the curve at zero time was drawn. The slope of this tangent was taken as a measure of the initial fractional reduction per minute. Although the time required to reach 50 pct reduction may be of special practical significance, initial rate measurements are invaluable in fundamental studies. These rates provide a measure of the process kinetics on the initial

Jan 1, 1968

By John Chipman

HE lecture on 'Thermodynamic Properties of Blast Furnace Slagso prepared in 1959 and published two years later required revision in one particular before it appeared in print. The activity of SiO, was deter mined through studies of the equilibrium: SiO, (in slag) 2C (graphite) = (in Fe) 2C0 (1 atm) The ratio for each experimental temperature was found from the heat of formation of cris-tobalite, the entropies and heat capacities of the re-actants, by virtue of the third law of thermodynamics. Discrepancies between several kinds of data led to investigations regarding other equilibria involving SiO, on the suspicion that there might be an error in the third-law value of its free energy. In particular the equilibrium: was restudied by Kay and Taylor who Confirmed the earlier results of Baird and Tayloron which their SiO, activities depended. The free energy of Sic was also rechecked4 independently. These and other equilibrium measurements led to the conclusion6 that the free energy of SiO, at high temperatures is in error and requires a correction of about -5 kcal. The exact source of the error is uncertain; it could lie either in the entropy of SiO, or in its heat of formation, but it more probably lies in the latter. Adjustment of this free energy lowers the ratio by a factor of approximately 4. Accordingly it will be necessary to multiply by this factor all of the SiO, activities determined by this method.',B Referring to the lecture cited, this correction should be applied in Figs. 8, 9, 10, 19, and 20. It applies also to the experimental data of Fig. 13, bringing these as well as those on the ternary system into good agreement with the work of Taylor and associates. At the same time it eliminates the discrepancy shown in Fig. 11, lowering both lines until the upper

Jan 1, 1962

By P. R. Sperry, P. A. Beck, J. Towers

Dahl and Pawlek1 found that electrolytic copper develops extremely coarse grains at 1000°C after about 90 pct reduction by rolling. This coarsening occurs only under conditions of penultimate grain size, deformation, and alloying which lead to the "cube" recrystallization texture.l,2,3,5 The peculiar angular shapes and straight grain boundaries of the coarse grains were noted by several investigator.1,4,5 On the other hand, coarsening in Fe-containing aluminum or in AI-Mn alloys8 does not depend on a "cube" (or any well developed) recrystallization texture. It is true that increasing deformation by rolling, and, therefore, an increasingly well developed re-crystallization texture, are associated with decreasing incubation periods of coarsening.6-7-8 Nevertheless, coarsening readily develops in aluminum even after only 30 pct reduction by rolling, where the recrystallization texture is very weak.6,8 Also, coarsening was observed by Jeffries9 many years ago in sintered thoriated tungsten, which presumably has no preferred orientation. In all these cases coarsening is associated with grain growth inhibition by a dispersed second phase.8,9 The annealing temperature has to be suficiently high to overcome the inhibition at a few locations. But if it is too high, growth starts at many points, and the resulting grain size becomes much smaller.9 Normally, the coarse grains are more or less equiaxed, and the boundaries have a typical ragged appearance.6.8 Cook and Macquarie4 demonstrated that, in addition to the texture-dependent coarsening previously found at 1000°C,l electrolytic tough pitch copper may also coarsen at 800°C after 50 pct reduction by cross rolling. The coarse grains formed under such conditions have rounded shapes and ragged boundaries, like those in aluminum. When the annealing temperature is higher, the tendency for their formation decreases. All these observations suggest that the coarsening at 800°C is associated with inhibition by a second phase. Actually, coarsening at 800°C after 50 pct reduction by cross rolling was observed only in tough pitch copper,4 which contains Cu2O particles. On the other hand, the texture-dependent 1000°C coarsening occurs in both tough pitch and oxygen-free copper;4 it does not appear to depend on the presence of a dispersed second phase. However, the interpretation of the 800°C coarsening in Cu after 50 pct rolling as an inhibition-dependent process, similar to the coarsening in A1-Mn alloys, is somewhat weakened by the fact that this coarsening was reported4 to occur only after cross rolling, and not after straight rolling. It was, therefore, decided to re-examine this question. A 1 in. diam electrolytic tough pitch copper rod, No. 2 hard drawn, was annealed for 20 min at 700°C, rolled to 0.5 in., annealed 10 min at 700°C, and straight rolled to 0.064 in. It was then given a penultimate anneal of 20 min at 500°C and it was cut into four sections, which were given final reductions by straight rolling as follows: A 30 pct reduction of area B 50 pct reduction of area C 70 pct reduction of area D 90 pct reduction of area Specimens cut from the four sections were finally annealed at 800°C in an oxidizing atmosphere. Strip A remained fine grained up to 10 hr, but the specimen annealed 12 hr consisted of only 2 large grains. Strip B had a few scattered large (1/2 to 3/4 mm) grains after 1 min, although the balance of the specimen consisted of fine grains of about 0.02 mm. After 5 min there were several 10 to 15 mm grains present, and after 1 hr strip B was completely coarsened. The coarse grains had the same characteristics (see Fig 1) as those obtained by Cook and Macquarie at 800°C after cross rolling. Strip C had several grains of 0.05 to 1 mm after 1 min, but it was still largely fine grained after 12 hr. After 48 hr it consisted entirely of grains of about 0.5 to 4 mm, with an extraordinarily large number of twin bands. Strip D remained com- pletely fine grained after 4 hr at 800°C. These results indicate that, in the deformation range of 30 to 70 pct reduction, the incubation period for coarsening as well as the rate of growth and the final size of the coarse grains decreases with increasing deformation. Similar

Jan 1, 1950

By AIME AIME

MONDAY, Feb. 21, evokes memories of the Silver Corridor at the Waldorf to be recalled and reflected upon for time to come when thoughts drift to the Annual Meeting of 1944. Crowded though it was, on occasion there lurked in the mind's eye a vision of what might have been had the 2886 persons who put in an appearance at one time or another milled around in the lobby of 29 West 39th Street. Some confusion resulted from difficulty in locating meeting rooms, but for the most part everyone found what he wanted. The usual bulletin board of members registered was missing this year and rumor has it that tile Waldorf didn't approve. Registration broke all previous records with many a busy engineer realizing that the program had something to offer that would be of use in his particular job. It might be noted here that "Arpad" co-operated nicely, previewing spring days on Monday, Wednesday, and Thursday; Tuesday was a bit damp.

Jan 1, 1944